Comparison of analytical charge-form and equilibrium thermodynamic speciation of certain radionuclides

International Nuclear Information System (INIS)

Jenne, E.A.; Cowan, C.E.; Robertson, D.E.

1984-01-01

Calculating trace element speciation with a thermodynamic model is often challenged on the basis that the existing thermodynamic data are not sufficiently reliable. Water quality data and corresponding analytical charge-form speciation analysis were available for radionuclides occurring in a low-level radioactive groundwater. This offered an opportunity for comparing the results of an equilibrium thermodynamic model with the results of analytical charge-form speciation. The charge-form speciation was determined using the Battelle Large Volume Water Sampler, which contains consecutive layers of cation resin, anion resin and activated aluminum oxide for retention of cationic, anionic and non-ionic dissolved chemical species, respectively. The thermodynamic speciation of Cs, Cr, Fe, I, Mn, Mo, Na, and Zn was calculated using the MINTEQ geochemical model. Ce, Co, Tc, Np, Pm, and Sb were speciated by hand calculation. Excellent agreement between the analytically determined charge-form and the thermodynamic speciation was observed for 54 Mn, 144 Ce, 131 I, 24 Na, 137 Cs, 99 Mo, 99 Tc, 151 Pm, 239 Np. Organic complexation by natural and/or synthetic organics in the waters may be important in the speciation of 65 An, 60 Co, 131 I, 59 Fe and possibly 51 Cr. Both 124 Sb and 125 Sb appeared to be in redox disequilibria with the groundwater. 29 references, 2 tables

High-level waste disposal, ethics and thermodynamics

Science.gov (United States)

Schwartz, Michael O.

2008-06-01

Moral philosophy applied to nuclear waste disposal can be linked to paradigmatic science. Simple thermodynamic principles tell us something about rightness or wrongness of our action. Ethical judgement can be orientated towards the chemical compatibility between waste container and geological repository. A container-repository system as close as possible to thermodynamic equilibrium is ethically acceptable. It aims at unlimited stability, similar to the stability of natural metal deposits within the Earth’s crust. The practicability of the guideline can be demonstrated.

Thermodynamics of Crystals

Science.gov (United States)

Navrotsky, Alexandra

Thermodynamics of Crystals is a gold mine of a references bargain with more derivations of useful equations per dollar, or per page, than almost any other book I know. Useful to whom? To the solid state physicist, the solid state chemist working the geophysicist, the rock mechanic, the mineral physicist. Useful for what? For lattice dynamics, crystal potentials, band structure. For elegant, rigorous, and concise derivations of fundamental equations. For comparison of levels of approximation. For some data and physical insights, especially for metals and simple halides. This book is a reissue, with some changes and additions, of a 1970 treatise. It ages well, since the fundamentals do not change.

Thermodynamic assessment of the Cu–Fe–Ni system

International Nuclear Information System (INIS)

Dreval, Liya A.; Turchanin, Mikhail A.; Agraval, Pavel G.

2014-01-01

Highlights: • The thermodynamic description of the Cu–Fe–Ni system has been updated. • The new experimental data have been used to refine thermodynamic model of the system. • The four-sublattice model has been adopted to predict the equilibria involving the ordered L1 2 phase. • A significant improvement in comparison with the previous assessments has been achieved. • The liquidus and solidus projections have been presented. -- Abstract: The thermodynamic description of the Cu–Fe–Ni system has been updated considering the newly available experimental data, as well as compatibility of the present modeling with those used for the Cu and Fe systems. All of the experimental data available in the literature have been critically reviewed, and the inconsistent information has been excluded. The thermodynamic parameters have been evaluated in order to properly describe the thermodynamic properties of the liquid phase and miscibility gap in the solid state. A significant improvement in comparison with the previous thermodynamic descriptions has been achieved. Additionally, for the ordered L1 2 phase the four-sublattice model has been adopted to predict the ternary phase equilibria involving this phase. A set of thermodynamic parameters for the phases is given

Atomistic-level non-equilibrium model for chemically reactive systems based on steepest-entropy-ascent quantum thermodynamics

International Nuclear Information System (INIS)

Li, Guanchen; Al-Abbasi, Omar; Von Spakovsky, Michael R

2014-01-01

This paper outlines an atomistic-level framework for modeling the non-equilibrium behavior of chemically reactive systems. The framework called steepest- entropy-ascent quantum thermodynamics (SEA-QT) is based on the paradigm of intrinsic quantum thermodynamic (IQT), which is a theory that unifies quantum mechanics and thermodynamics into a single discipline with wide applications to the study of non-equilibrium phenomena at the atomistic level. SEA-QT is a novel approach for describing the state of chemically reactive systems as well as the kinetic and dynamic features of the reaction process without any assumptions of near-equilibrium states or weak-interactions with a reservoir or bath. Entropy generation is the basis of the dissipation which takes place internal to the system and is, thus, the driving force of the chemical reaction(s). The SEA-QT non-equilibrium model is able to provide detailed information during the reaction process, providing a picture of the changes occurring in key thermodynamic properties (e.g., the instantaneous species concentrations, entropy and entropy generation, reaction coordinate, chemical affinities, reaction rate, etc). As an illustration, the SEA-QT framework is applied to an atomistic-level chemically reactive system governed by the reaction mechanism F + H 2 ↔ FH + H

Thermodynamics of Radiation Modes

Science.gov (United States)

Pina, Eduardo; de la Selva, Sara Maria Teresa

2010-01-01

We study the equilibrium thermodynamics of the electromagnetic radiation in a cavity of a given volume and temperature. We found three levels of description, the thermodynamics of one mode, the thermodynamics of the distribution of frequencies in a band by summing over the frequencies in it and the global thermodynamics by summing over all the…

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

Science.gov (United States)

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.

Exergetic and thermodynamic comparison of R12 and R134a as vapour compression refrigeration working fluids

Energy Technology Data Exchange (ETDEWEB)

De Rossi, Filippo; Mastrullo, Rita; Mazzei, Pietro [Naples Univ. (Italy)

1993-05-01

A software package for both the computation of thermodynamic properties and the analysis of the usual vapour compression plant schemes is a useful tool for air conditioning and refrigeration researchers and manufacturers. At present, it could make an important contribution to the search for CFC substitutes; in fact, comparisons between two or more working fluids could be accomplished more easily. A program created by the authors is presented by means of some demonstrative diagrams referring to a comparison between the ''ozone killer'' R12 and its substitute R134a. An R134a exergy-enthalpy chart is also provided. (Author)

A Numerical Comparison of Soave Redlich Kwong and Peng-Robinson Equations of State for Predicting Hydrocarbons’ Thermodynamic Properties

Directory of Open Access Journals (Sweden)

B. Hussain

2018-02-01

Full Text Available Mixture phase equilibrium and thermodynamic properties have a significant role in industry. Numerical analysis of flash calculation generates an appropriate solution for the problem. In this research, a comparison of Soave Redlich Kwong (SRK and Peng-Robinson (PR equations of state predicting the thermodynamic properties of a mixture of hydrocarbon and related compounds in a critical region at phase equilibrium is performed. By applying mathematical modeling of both equations of states, the behavior of binary gases mixtures is monitored. The numerical analysis of isothermal flash calculations is applied to study the pressure behavior with volume and mole fraction. The approach used in this research shows considerable convergence with experimental results available in the literature.

Thermodynamic calculations in ternary titanium–aluminium–manganese system

Directory of Open Access Journals (Sweden)

ANA I. KOSTOV

2008-04-01

Full Text Available Thermodynamic calculations in the ternary Ti–Al–Mn system are shown in this paper. The thermodynamic calculations were performed using the FactSage thermochemical software and database, with the aim of determining thermodynamic properties, such as activities, coefficient of activities, partial and integral values of the enthalpies and Gibbs energies of mixing and excess energies at two different temperatures: 2000 and 2100 K. Bearing in mind that no experimental data for the Ti–Al–Mn ternary system have been obtained or reported. The obtained results represent a good base for further thermodynamic analysis and may be useful as a comparison with some future critical experimental results and thermodynamic optimization of this system.

Thermodynamic assessment of the zirconia-urania system

International Nuclear Information System (INIS)

Yashima, Masatomo; Koura, Toshiaki; Du, Y.; Yoshimura, Masahiro

1996-01-01

An optimal thermodynamic data set for the zirconia-urania system is devaluated by the CALPHAD (CALculation of PHAse Diagrams) method. A regular solution model is applied to all phases of the cubic, tetragonal, and monoclinic solid solutions and the liquid. Comparisons between calculated and measured phase diagrams show that most of the experimental information is satisfactorily accounted for by thermodynamic calculations

Thermodynamic approach to rheological modeling and simulations at the configuration space level of description

NARCIS (Netherlands)

Jongschaap, R.J.J.; Denneman, A.I.M.; Denneman, A.I.M.; Conrads, W.

1997-01-01

The so-called matrix model is a general thermodynamic framework for microrheological modeling. This model has already been proven to be applicable for a wide class of systems, in particular to models formulated at the configuration tensor level of description. For models formulated at the

Thermodynamics and economics

International Nuclear Information System (INIS)

Mansson, B.A.

1990-01-01

Economics, as the social science most concerned with the use and distribution of natural resources, must start to make use of the knowledge at hand in the natural sciences about such resources. In this, thermodynamics is an essential part. In a physicists terminology, human economic activity may be described as a dissipative system which flourishes by transforming and exchanging resources, goods and services. All this involves complex networks of flows of energy and materials. This implies that thermodynamics, the physical theory of energy and materials flows, must have implications for economics. On another level, thermodynamics has been recognized as a physical theory of value, with value concepts similar to those of economic theory. This paper discusses some general aspects of the significance of non-equilibrium thermodynamics for economics. The role of exergy, probably the most important of the physical measures of value, is elucidated. Two examples of integration of thermodynamics with economic theory are reviewed. First, a simple model of a steady-state production system is sued to illustrate the effects of thermodynamic process constraints. Second, the framework of a simple macroeconomic growth model is used to illustrate how some thermodynamic limitations may be integrated in macroeconomic theory

A thermodynamic-like characterization of Colombia’s presidential elections in 2010, and a comparison with other Latin American countries

Science.gov (United States)

Campos, Diógenes

2011-05-01

A thermodynamic-like characterization of Colombia’s presidential election is presented. We assume that the electoral system consists of citizens embedded in a political environment, and that this environment can be considered as an information bath characterized by the entropic parameter q ( q∈[0,∞]). First, for q=1, the electoral outcomes of 2010 are translated into a set of probabilities (relative frequencies of the events) P={P1,P2,…,PN}, with N possible independent results. Then, for 0≤q<∞, the electoral system is characterized by using the thermodynamic-like method for probabilistic systems proposed in a previous article. Some general considerations of the macro-description of a probabilistic system and a comparison of presidential elections in five countries are also included.

JNC thermodynamic database for performance assessment of high-level radioactive waste disposal system

Energy Technology Data Exchange (ETDEWEB)

Yui, Mikazu; Azuma, Jiro; Shibata, Masahiro [Japan Nuclear Cycle Development Inst., Tokai Works, Waste Isolation Research Division, Tokai, Ibaraki (Japan)

1999-11-01

This report is a summary of status, frozen datasets, and future tasks of the JNC (Japan Nuclear Cycle Development Institute) thermodynamic database (JNC-TDB) for assessing performance of high-level radioactive waste in geological environments. The JNC-TDB development was carried out after the first progress report on geological disposal research in Japan (H-3). In the development, thermodynamic data (equilibrium constants at 25degC, I=0) for important radioactive elements were selected/determined based on original experimental data using different models (e.g., SIT, Pitzer). As a result, the reliability and traceability of the data for most of the important elements were improved over those of the PNC-TDB used in H-3 report. For detailed information of data analysis and selections for each element, see the JNC technical reports listed in this document. (author)

Stochastic thermodynamics

Science.gov (United States)

Eichhorn, Ralf; Aurell, Erik

2014-04-01

theory for small deviations from equilibrium, in which a general framework is constructed from the analysis of non-equilibrium states close to equilibrium. In a next step, Prigogine and others developed linear irreversible thermodynamics, which establishes relations between transport coefficients and entropy production on a phenomenological level in terms of thermodynamic forces and fluxes. However, beyond the realm of linear response no general theoretical results were available for quite a long time. This situation has changed drastically over the last 20 years with the development of stochastic thermodynamics, revealing that the range of validity of thermodynamic statements can indeed be extended deep into the non-equilibrium regime. Early developments in that direction trace back to the observations of symmetry relations between the probabilities for entropy production and entropy annihilation in non-equilibrium steady states [5-8] (nowadays categorized in the class of so-called detailed fluctuation theorems), and the derivations of the Bochkov-Kuzovlev [9, 10] and Jarzynski relations [11] (which are now classified as so-called integral fluctuation theorems). Apart from its fundamental theoretical interest, the developments in stochastic thermodynamics have experienced an additional boost from the recent experimental progress in fabricating, manipulating, controlling and observing systems on the micro- and nano-scale. These advances are not only of formidable use for probing and monitoring biological processes on the cellular, sub-cellular and molecular level, but even include the realization of a microscopic thermodynamic heat engine [12] or the experimental verification of Landauer's principle in a colloidal system [13]. The scientific program Stochastic Thermodynamics held between 4 and 15 March 2013, and hosted by The Nordic Institute for Theoretical Physics (Nordita), was attended by more than 50 scientists from the Nordic countries and elsewhere, amongst them

Thermodynamic properties of water solvating biomolecular surfaces

Science.gov (United States)

Heyden, Matthias

Changes in the potential energy and entropy of water molecules hydrating biomolecular interfaces play a significant role for biomolecular solubility and association. Free energy perturbation and thermodynamic integration methods allow calculations of free energy differences between two states from simulations. However, these methods are computationally demanding and do not provide insights into individual thermodynamic contributions, i.e. changes in the solvent energy or entropy. Here, we employ methods to spatially resolve distributions of hydration water thermodynamic properties in the vicinity of biomolecular surfaces. This allows direct insights into thermodynamic signatures of the hydration of hydrophobic and hydrophilic solvent accessible sites of proteins and small molecules and comparisons to ideal model surfaces. We correlate dynamic properties of hydration water molecules, i.e. translational and rotational mobility, to their thermodynamics. The latter can be used as a guide to extract thermodynamic information from experimental measurements of site-resolved water dynamics. Further, we study energy-entropy compensations of water at different hydration sites of biomolecular surfaces. This work is supported by the Cluster of Excellence RESOLV (EXC 1069) funded by the Deutsche Forschungsgemeinschaft.

Thermodynamic description of the C-Ge and C-Mg systems

Directory of Open Access Journals (Sweden)

Hu B.

2010-01-01

Full Text Available The thermodynamic modeling for the C-Ge and C-Mg systems is performed by the CALPHAD method. The enthalpy of formation for Mg2C3, the experimental value of which is not available in the literature, is obtained via first-principles calculation to refine the thermodynamic modeling of the C-Mg system. A comparison of the thermodynamic calculations with the available literature data shows that the presently obtained two sets of thermodynamic parameters for the C-Ge and C-Mg systems can well describe the these two systems.

Thermodynamic analysis of biochemical systems

International Nuclear Information System (INIS)

Yuan, Y.; Fan, L.T.; Shieh, J.H.

1989-01-01

Introduction of the concepts of the availability (or exergy), datum level materials, and the dead state has been regarded as some of the most significant recent developments in classical thermodynamics. Not only the available energy balance but also the material and energy balances of a biological system may be established in reference to the datum level materials in the dead state or environment. In this paper these concepts are illustrated with two examples of fermentation and are shown to be useful in identifying sources of thermodynamic inefficiency, thereby leading naturally to the rational definition of thermodynamic efficiency of a biochemical process

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

Science.gov (United States)

Pekař, Miloslav

2018-01-01

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

Comparison of the applicability of commercial computer programs to study the thermodynamic stability of metal oxides

International Nuclear Information System (INIS)

Koukkari, P.; Olin, M.; Laitinen, T.; Sippola, H.

1999-04-01

The oxide films formed on primary circuit surfaces incorporate radioactive species from the coolant and influence different corrosion phenomena in nuclear power plants. One approach to improve the understanding on the formation and properties of these oxide films is to evaluate their thermodynamic stability. The aim of this work was to compare and demonstrate the applicability of different commercial thermodynamic computer programs to model the deposition of oxides containing iron, chromium and/or nickel in various nuclear power plant environments. The programs considered in this evaluation comprised the EQ3/6 program and a product group including such products as ChemSage, HSC (including SOLGASMIX and GIBBS), H+PLUS and ChemSheet. In the group the transfer of data between different products is relatively easy. The goal was to find out which programs can be applied to evaluate the stability of oxide films, but not to assess the absolute accuracy of the calculations. The evaluation was done by means of applying the programs to calculate the stability of pure and mixed oxides of iron, nickel and chromium on stainless steel both in WWER and BWR conditions at different temperatures and coolant compositions. The comparison showed that EQ3/6 is suitable for most thermodynamic calculations. EQ3/6 can be characterised as a professional tool, for which no commercial training is available. ChemSage is a versatile and reliable program, which can be well used together with HSC and H+PLUS. ChemSage is mainly a professional tool, while HSC is easier to operate by an occasional user. Commercial training and support is available for both ChemSage and HSC. ChemSheet has been designed to utilise the properties of ChemSage in a user-friendly spreadsheet environment. All the products tested calculate thermodynamic equilibrium. Thus they are suitable to characterise such conditions in which the formation of a certain phase is or becomes possible. On the other hand, the modelling of the

Restoring NAD(+) Levels with NAD(+) Intermediates, the Second Law of Thermodynamics and Aging Delay.

Science.gov (United States)

Poljsak, Borut; Milisav, Irina

2018-04-26

The hypothesis regarding the role of increased nicotinamide adenine dinucleotide (NAD+) levels with reference to the fundamental concepts of ageing and entropy is presented. Considering the second law of thermodynamics, NAD+ seems the appropriate candidate for reversing many aging-associated pathologies. NAD+ is presented as an essential compound that enables organisms to stay highly organized and well-maintained, with a lower entropy state.

Thermodynamics of excited nuclei and nuclear level densities

International Nuclear Information System (INIS)

Ramamurthy, V.S.

1977-01-01

A review has been made of the different approaches that are being used for a theoretical calculation of nuclear level densities. It is pointed out that while the numerical calculations based on the partition function approach and shell model single particle level schemes have shed important insight into the influence of nuclear shell effects on level densities and its excitation energy dependence and have brought out the inadequacy of the conventional Bethe Formula, these calculations are yet to reach a level where they can be directly used for quantitative comparisons. Some of the important drawbacks of the numerical calculations are also discussed. In this context, a new semi-empirical level density formula is described which while retaining the simplicity of analytical formulae, takes into account nuclear shell effects in a more realistic manner. (author)

Improving Students' Chemical Literacy Levels on Thermochemical and Thermodynamics Concepts through a Context-Based Approach

Science.gov (United States)

Cigdemoglu, Ceyhan; Geban, Omer

2015-01-01

The aim of this study was to delve into the effect of context-based approach (CBA) over traditional instruction (TI) on students' chemical literacy level related to thermochemical and thermodynamics concepts. Four eleventh-grade classes with 118 students in total taught by two teachers from a public high school in 2012 fall semester were enrolled…

Entropy, related thermodynamic properties, and structure of methylisocyanate

International Nuclear Information System (INIS)

Davis, Phil S.; Kilpatrick, John E.

2013-01-01

Highlights: ► The thermodynamic properties of methylisocyanate have been determined by isothermal calorimetry from 15 to 298.15 K. ► The third law entropy has been compared with the entropy calculated by statistical thermodynamics. ► The comparisons are consistent with selected proposed molecular structures and vibrational frequencies. -- Abstract: The entropy and related thermodynamic properties of methylisocyanate, CH 3 NCO, have been determined by isothermal calorimetry. The entropy in the ideal gas state at 298.15 K and 1 atmosphere is S m o = 284.3 ± 0.6 J/K · mol. Other thermodynamic properties determined include: the heat capacity from 15 to 300 K, the temperature of fusion (T fus = 178.461 ± 0.024 K), the enthalpy of fusion (ΔH fus = 7455.2 ± 14.0 J/mol), the enthalpy of vaporization at 298.15 K (ΔH vap = 28768 ± 54 J/mol), and the vapor pressure from fusion to 300 K. Using statistical thermodynamics, the entropy in this same state has been calculated for various assumed structures for methylisocyante which have been proposed based on several spectroscopic and ab initio results. Comparisons between the experimental and calculated entropy have led to the following conclusions concerning historical differences among problematic structural properties: (1) The CNC/CNO angles can have the paired values of 140/180° or 135/173° respectively. It is not possible to distinguish between the two by this thermodynamic analysis. (2) The methyl group functions as a free rotor or near free rotor against the NCO rigid frame. The barrier to internal rotation is less than 2100 J/mol. (3) The CNC vibrational bending frequency is consistent with the more recently observed assignments at 165 and 172 cm −1 with some degree of anharmonicity or with a pure harmonic at about 158 cm −1

Thermodynamic approach and comparison of two-step and single step DME (dimethyl ether) syntheses with carbon dioxide utilization

International Nuclear Information System (INIS)

Chen, Wei-Hsin; Hsu, Chih-Liang; Wang, Xiao-Dong

2016-01-01

DME (Dimethyl ether) synthesis from syngas with CO_2 utilization through two-step and single step processes is analyzed thermodynamically. The influences of reaction temperature, H_2/CO molar ratio, and CO_2/CO molar ratio on CO and CO_2 conversions, DME selectivity and yield, and thermal behavior are evaluated. Particular attention is paid to the comparison of the performance of DME synthesis between the two different methods. In the two-step method, the addition of CO_2 suppresses the CO conversion during methanol synthesis. An increase in CO_2/CO ratio decreases the CO_2 conversion (negative effect), but increases the total consumption amount of CO_2 (positive effect). At a given reaction temperature with H_2/CO = 4, the maximum DME yield develops at CO_2/CO = 1. In the single step method, over 98% of CO can be converted and the DME yield can be as high as 0.52 mol (mol CO)"−"1 at CO_2/CO = 2. The comparison of the single step and two-step processes indicates that the maximum CO conversion, DME selectivity, and DME yield in the former are higher than those in the latter, whereas an opposite result in the maximum CO_2 conversion is observed. These results reveal that the single step process has lower thermodynamic limitation and is a better option for DME synthesis. From CO_2 utilization point of view, the operation with low temperature, high H_2/CO ratio, and low CO_2/CO ratio results in higher CO_2 conversion, irrespective of two-step or single step DME synthesis. - Highlights: • DME (Dimethyl ether) synthesis with CO_2 utilization is analyzed thermodynamically. • Single step and two-step DME syntheses are studied and compared with each other. • CO_2 addition suppresses CO conversion in MeOH synthesis but increases MeOH yield. • The performance of the single step DME synthesis is better than that of the two-step one. • Increase CO_2/CO ratio decreases CO_2 conversion but increases CO_2 consumption amount.

Thermodynamic properties of xanthone: Heat capacities, phase-transition properties, and thermodynamic-consistency analyses using computational results

International Nuclear Information System (INIS)

Chirico, Robert D.; Kazakov, Andrei F.

2015-01-01

Highlights: • Heat capacities were measured for the temperature range (5 to 520) K. • The enthalpy of combustion was measured and the enthalpy of formation was derived. • Thermodynamic-consistency analysis resolved inconsistencies in literature enthalpies of sublimation. • An inconsistency in literature enthalpies of combustion was resolved. • Application of computational chemistry in consistency analysis was demonstrated successfully. - Abstract: Heat capacities and phase-transition properties for xanthone (IUPAC name 9H-xanthen-9-one and Chemical Abstracts registry number [90-47-1]) are reported for the temperature range 5 < T/K < 524. Statistical calculations were performed and thermodynamic properties for the ideal gas were derived based on molecular geometry optimization and vibrational frequencies calculated at the B3LYP/6-31+G(d,p) level of theory. These results are combined with sublimation pressures from the literature to allow critical evaluation of inconsistent enthalpies of sublimation for xanthone, also reported in the literature. Literature values for the enthalpy of combustion of xanthone are re-assessed, a revision is recommended for one result, and a new value for the enthalpy of formation of the ideal gas is derived. Comparisons with thermophysical properties reported in the literature are made for all other reported and derived properties, where possible

Statistical thermodynamics

International Nuclear Information System (INIS)

Hwang, Jeong Ui; Jang, Jong Jae; Jee, Jong Gi

1987-01-01

The contents of this book are thermodynamics on the law of thermodynamics, classical thermodynamics and molecule thermodynamics, basics of molecule thermodynamics, molecule and assembly partition function, molecule partition function, classical molecule partition function, thermodynamics function for ideal assembly in fixed system, thermodynamics function for ideal assembly in running system, Maxwell-Boltzmann's law of distribution, chemical equilibrium like calculation of equilibrium constant and theory of absolute reaction rate.

Thermodynamic and economic analysis on geothermal integrated combined-cycle power plants

International Nuclear Information System (INIS)

Bettocchi, R.; Cantore, G.; Negri di Montenegro, G.; Gadda, E.

1992-01-01

This paper considers geothermal integrated power plants obtained matching a geothermal plant with, a two pressure level combined plant. The purpose of the paper is the evaluation of thermodynamic and economic aspects on geothermal integrated combined-cycle power plant and a comparison with conventional solutions. The results show that the integrated combined plant power is greater than the sum of combined cycle and geothermal plant powers considered separately and that the integrated plant can offer economic benefits reaching the 16% of the total capital required

Quantum thermodynamics of nanoscale steady states far from equilibrium

Science.gov (United States)

Taniguchi, Nobuhiko

2018-04-01

We develop an exact quantum thermodynamic description for a noninteracting nanoscale steady state that couples strongly with multiple reservoirs. We demonstrate that there exists a steady-state extension of the thermodynamic function that correctly accounts for the multiterminal Landauer-Büttiker formula of quantum transport of charge, energy, or heat via the nonequilibrium thermodynamic relations. Its explicit form is obtained for a single bosonic or fermionic level in the wide-band limit, and corresponding thermodynamic forces (affinities) are identified. Nonlinear generalization of the Onsager reciprocity relations are derived. We suggest that the steady-state thermodynamic function is also capable of characterizing the heat current fluctuations of the critical transport where the thermal fluctuations dominate. Also, the suggested nonequilibrium steady-state thermodynamic relations seemingly persist for a spin-degenerate single level with local interaction.

A Comparison of Local and Global Formulations of Thermodynamics

Science.gov (United States)

DeVoe, Howard

2013-01-01

Several educators have advocated teaching thermodynamics using a"global" approach in place of the conventional "local" approach. This article uses four examples of experiments to illustrate the two formulations and the definitions of heat and work associated with them. Advantages and disadvantages of both approaches are…

New perspectives in thermodynamics

International Nuclear Information System (INIS)

Serrin, J.

1986-01-01

The last decade has seen a unity of method and approach in the foundations of thermodynamics and continuum mechanics, in which rigorous laws of thermodynamics have been combined with invariance notions of mechanics to produce new and deep understanding. Real progress has been made in finding a set of appropriate concepts for classical thermodynamics, by which energy conservation and the Clausius inequality can be given well-defined meanings for arbitrary processes and which allow an approach to the entropy concept which is free of traditional ambiguities. There has been, moreover, a careful scrutiny of long established but nevertheless not sharply defined concepts such as the Maxwell equal-area rule, the famous Gibbs phase rule, and the equivalence of work and heat. The thirteen papers in this volume accordingly gather together for the first time the many ideas and concepts which have raised classical thermodynamics from a heuristic and intuitive science to the level of precision presently demanded of other branches of mathematical physics

Workshop on Teaching Thermodynamics

CERN Document Server

1985-01-01

It seemed appropriate to arrange a meeting of teachers of thermodynamics in the United Kingdom, a meeting held in the pleasant surroundings of Emmanuel College, Cambridge, in Sept~mber, 1984. This volume records the ideas put forward by authors, the discussion generated and an account of the action that discussion has initiated. Emphasis was placed on the Teaching of Thermodynamics to degree-level students in their first and second years. The meeting, a workshop for practitioners in which all were expected to take part, was remarkably well supported. This was notable in the representation of essentially every UK university and polytechnic engaged in teaching engineering thermodynamics and has led to a stimulating spread of ideas. By intention, the emphasis for attendance was put on teachers of engineering concerned with thermodynamics, both mechanical and chemical engineering disciplines. Attendance from others was encouraged but limited as follows: non-engineering acad­ emics, 10%, industrialists, 10%. The ...

Comparison of the thermodynamic and correlation criteria for internal standard selection in laser-induced breakdown spectrometry

International Nuclear Information System (INIS)

Labutin, Timur A.; Zaytsev, Sergey M.; Popov, Andrey M.; Seliverstova, Irina V.; Bozhenko, Sergey E.; Zorov, Nikita B.

2013-01-01

The use of the reference line of an internal standard in LIBS is a usual way to eliminate or reduce the fluctuations of plasma parameters from pulse to pulse as well as from sample to sample. Thermodynamic criterion, i.e. closeness of excitation potentials of the analytical line and the reference one, is often used to select an appropriate reference line. In this work, we propose an alternative criterion based on searching the best correlated pairs of lines under the variations of laser energy. Two criteria were compared for high-alloy steels and soils of different origins. The discrepancy among the values of plasma temperature calculated from Fe I, Mn I and Cr I transitions was found under the conditions of slightly changed laser fluence on steel samples. On the other hand, the agreement between plasma temperatures, obtained for Fe I and Mn I transitions, was demonstrated in plasma on soil samples. Calibration results obtained for manganese in steels and lead in soils show that thermodynamic criterion can be an appropriate way for choosing an internal standard only under LTE conditions. Two lines of Mn I at 403.07 nm and 404.14 nm and Pb I at 405.78 nm were the analytical lines for the quantification of manganese in steels and lead in soils, respectively. The use of the correlative criterion seems to be suitable for internal standardization under LTE or non-LTE conditions. Probable limitations of the correlative criterion and its possibilities to identify weak lines are discussed in the article. - Highlights: • Novel criterion for internal standard selection, based on the correlation of analytical line and reference one • Comparison of correlation and thermodynamic criteria • Correlation analysis of the spectrum can be useful for atomic line identification. • Correlation approach can be used in LTE and non-LTE conditions

Onsager's reciprocity theorem in extended irreversible thermodynamics

International Nuclear Information System (INIS)

Garcia-Colin, L.S.; Velasco, R.M.

1992-01-01

In this paper we shall discuss the Onsager relations for the transport coefficients in a dilute monatomic gas described by the extended irreversible thermodynamics. Our discussion is based on a 26 variables description of the system and its corresponding comparison with the kinetic reciprocity between coefficients is shown (Author)

Is applicable thermodynamics of negative temperature for living organisms?

Science.gov (United States)

Atanasov, Atanas Todorov

2017-11-01

During organismal development the moment of sexual maturity can be characterizes by nearly maximum basal metabolic rate and body mass. Once the living organism reaches extreme values of the mass and the basal metabolic rate, it reaches near equilibrium thermodynamic steady state physiological level with maximum organismal complexity. Such thermodynamic systems that reach equilibrium steady state level at maximum mass-energy characteristics can be regarded from the prospective of thermodynamics of negative temperature. In these systems the increase of the internal and free energy is accompanied with decrease of the entropy. In our study we show the possibility the living organisms to regard as thermodynamic system with negative temperature

Thermodynamics

CERN Document Server

Fermi, Enrico

1956-01-01

Indisputably, this is a modern classic of science. Based on a course of lectures delivered by the author at Columbia University, the text is elementary in treatment and remarkable for its clarity and organization. Although it is assumed that the reader is familiar with the fundamental facts of thermometry and calorimetry, no advanced mathematics beyond calculus is assumed.Partial contents: thermodynamic systems, the first law of thermodynamics (application, adiabatic transformations), the second law of thermodynamics (Carnot cycle, absolute thermodynamic temperature, thermal engines), the entr

Comparison of energy performance requirements levels

DEFF Research Database (Denmark)

Spiekman, Marleen; Thomsen, Kirsten Engelund; Rose, Jørgen

This summary report provides a synthesis of the work within the EU SAVE project ASIEPI on developing a method to compare the energy performance (EP) requirement levels among the countries of Europe. Comparing EP requirement levels constitutes a major challenge. From the comparison of for instance...... the present Dutch requirement level (EPC) of 0,8 with the present Flemish level of E80, it can easily be seen that direct comparison is not possible. The conclusions and recommendations of the study are presented in part A. These constitute the most important result of the project. Part B gives an overview...... of all other project material related to that topic, which allows to easily identify the most pertinent information. Part C lists the project partners and sponsors....

Systematic vibration thermodynamic properties of bromine

Science.gov (United States)

Liu, G. Y.; Sun, W. G.; Liao, B. T.

2015-11-01

Based on the analysis of the maturity and finiteness of vibrational levels of bromine molecule in ground state and evaluating the effect on statistical computation, according to the elementary principles of quantum statistical theorem, using the full set of bromine molecular vibrational levels determined with algebra method, the statistical contribution for bromine systematical macroscopic thermodynamic properties is discussed. Thermodynamic state functions Helmholtz free energy, entropy and observable vibration heat capacity are calculated. The results show that the determination of full set of vibrational levels and maximum vibrational quantum number is the key in the correct statistical analysis of bromine systematical thermodynamic property. Algebra method results are clearly different from data of simple harmonic oscillator and the related algebra method results are no longer analytical but numerical and are superior to simple harmonic oscillator results. Compared with simple harmonic oscillator's heat capacities, the algebra method's heat capacities are more consistent with the experimental data in the given temperature range of 600-2100 K.

Perturbative string thermodynamics near black hole horizons

International Nuclear Information System (INIS)

Mertens, Thomas G.; Verschelde, Henri; Zakharov, Valentin I.

2015-01-01

We provide further computations and ideas to the problem of near-Hagedorn string thermodynamics near (uncharged) black hole horizons, building upon our earlier work http://dx.doi.org/10.1007/JHEP03(2014)086. The relevance of long strings to one-loop black hole thermodynamics is emphasized. We then provide an argument in favor of the absence of α ′ -corrections for the (quadratic) heterotic thermal scalar action in Rindler space. We also compute the large k limit of the cigar orbifold partition functions (for both bosonic and type II superstrings) which allows a better comparison between the flat cones and the cigar cones. A discussion is made on the general McClain-Roth-O’Brien-Tan theorem and on the fact that different torus embeddings lead to different aspects of string thermodynamics. The black hole/string correspondence principle for the 2d black hole is discussed in terms of the thermal scalar. Finally, we present an argument to deal with arbitrary higher genus partition functions, suggesting the breakdown of string perturbation theory (in g s ) to compute thermodynamical quantities in black hole spacetimes.

Comparison of Ablation Predictions for Carbonaceous Materials Using CEA and JANAF-Based Species Thermodynamics

Science.gov (United States)

Milos, Frank S.

2011-01-01

In most previous work at NASA Ames Research Center, ablation predictions for carbonaceous materials were obtained using a species thermodynamics database developed by Aerotherm Corporation. This database is derived mostly from the JANAF thermochemical tables. However, the CEA thermodynamics database, also used by NASA, is considered more up to date. In this work, the FIAT code was modified to use CEA-based curve fits for species thermodynamics, then analyses using both the JANAF and CEA thermodynamics were performed for carbon and carbon phenolic materials over a range of test conditions. The ablation predictions are comparable at lower heat fluxes where the dominant mechanism is carbon oxidation. However, the predictions begin to diverge in the sublimation regime, with the CEA model predicting lower recession. The disagreement is more significant for carbon phenolic than for carbon, and this difference is attributed to hydrocarbon species that may contribute to the ablation rate.

The thermodynamic-buffer enzymes.

Science.gov (United States)

Stucki, J W

1980-08-01

Oxidative phosphorylation operates at optimal efficiency if and only if the condition of conductance matching L33/L11 = square root 1-q2 is fulfilled. In this relation L11 is the phenomenological conductance of phosphorylation, L33 the phenomenological conductance of the load, i.e. the irreversible ATP-utilizing processes in the cell, and q the degree of coupling of oxidative phosphorylation driven by respiration. Since during short time intervals L11 and q are constant whereas L33 fluctuates in the cell, oxidative phosphorylation would only rarely operate at optimal efficiency due to violation of conductance matching. This paper demonstrates that the reversible ATP-utilizing reaction catalyzed by adenylate kinase can effectively compensate deviations from conductance matching in the presence of a fluctuating L33 and hence allows oxidative phosphorylation to operate at optimal efficiency in the cell. Since the adenylate kinase reaction was found to buffer a thermodynamic potential, i.e. the phosphate potential, this finding was generalized to the concept of thermodynamic buffering. The thermodynamic buffering ability of the adenylate kinase reaction was demonstrated by experiments with incubated rat-liver mitochondria. Considerations of changes introduced in the entropy production by the adenylate kinase reaction allowed to establish the theoretical framework for thermodynamic buffering. The ability of thermodynamic buffering to compensate deviations from conductance matching in the presence of fluctuating loads was demonstrated by computer simulations. The possibility of other reversible ATP-utilizing reactions, like the ones catalyzed by creatine kinase and arginine kinase, to contribute to thermodynamic buffering is discussed. Finally, the comparison of the theoretically calculated steady-stae cytosolic adenine nucleotide concentrations with experimental data from perfused livers demonstrated that in livers from fed rats conductance matching is fulfilled on a

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-12-15

We have applied a new stochastic simulation approach to predict the metabolite levels, energy flow, and material flux in the different 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 equations of state 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 selforganization 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, such as biofuels.

Statistical thermodynamics

International Nuclear Information System (INIS)

Lim, Gyeong Hui

2008-03-01

This book consists of 15 chapters, which are basic conception and meaning of statistical thermodynamics, Maxwell-Boltzmann's statistics, ensemble, thermodynamics function and fluctuation, statistical dynamics with independent particle system, ideal molecular system, chemical equilibrium and chemical reaction rate in ideal gas mixture, classical statistical thermodynamics, ideal lattice model, lattice statistics and nonideal lattice model, imperfect gas theory on liquid, theory on solution, statistical thermodynamics of interface, statistical thermodynamics of a high molecule system and quantum statistics

Thermodynamic and Quantum Thermodynamic Analyses of Brownian Movement

OpenAIRE

Gyftopoulos, Elias P.

2006-01-01

Thermodynamic and quantum thermodynamic analyses of Brownian movement of a solvent and a colloid passing through neutral thermodynamic equilibrium states only. It is shown that Brownian motors and E. coli do not represent Brownian movement.

On Thermodynamics Problems in the Single-Phase-Lagging Heat Conduction Model

Directory of Open Access Journals (Sweden)

Shu-Nan Li

2016-11-01

Full Text Available Thermodynamics problems for the single-phase-lagging (SPL model have not been much studied. In this paper, the violation of the second law of thermodynamics by the SPL model is studied from two perspectives, which are the negative entropy production rate and breaking equilibrium spontaneously. The methods for the SPL model to avoid the negative entropy production rate are proposed, which are extended irreversible thermodynamics and the thermal relaxation time. Modifying the entropy production rate positive or zero is not enough to avoid the violation of the second law of thermodynamics for the SPL model, because the SPL model could cause breaking equilibrium spontaneously in some special circumstances. As comparison, it is shown that Fourier’s law and the CV model cannot break equilibrium spontaneously by analyzing mathematical energy integral.

Principles of hyperplasticity an approach to plasticity theory based on thermodynamic principles

CERN Document Server

Houlsby, Guy T

2007-01-01

A new approach to plasticity theory firmly routed in and compatible with the laws of thermodynamicsProvides a common basis for the formulation and comparison of many existing plasticity modelsIncorporates and introduction to elasticity, plasticity, thermodynamics and their interactionsShows the reader how to formulate constitutive models completely specified by two scalar potential functions from which the incremental responses of any hyperplastic model can be derived.

Optima and bounds for irreversible thermodynamic processes

International Nuclear Information System (INIS)

Hoffmann, K.H.

1990-01-01

In this paper bounds and optima for irreversible thermodynamic processes and their application in different fields are discussed. The tools of finite time thermodynamics are presented and especially optimal control theory is introduced. These methods are applied to heat engines, including models of the Diesel engine and a light-driven engine. Further bounds for irreversible processes are introduced, discussing work deficiency and its relation to thermodynamic length. Moreover the problem of dissipation in systems composed of several subsystems is studied. Finally, the methods of finite time thermodynamics are applied to thermodynamic processes described on a more microscopic level. The process used as an example is simulated annealing. It is shown how optimal control theory is applied to find the optimal cooling schedule for this important stochastic optimization method

Thermodynamics, core-level spectroscopy, morphology, and work function study of different TiCl3 crystalline phases: A theoretical approach

International Nuclear Information System (INIS)

Guo, Lei; Li, Wenpo; Feng, Wenjiang; Zhang, Zhipeng; Zhang, Shengtao

2014-01-01

Highlights: • Three TiCl 3 polymorphs materials were systematically investigated. • Structural results agree well with experimental and available theoretical data. • Morphological and thermodynamic properties were computed and analyzed. • Core-level spectroscopy and work function were obtained. - Abstract: Computer simulation has been widely applied in many research fields owing to its superiority in revealing an insight understanding of the phenomena. In this work, the thermodynamics, core-level spectroscopy, morphology, and work function of TiCl 3 with three different crystalline phases (α, β, and γ) have been comprehensively computed employing the Materials Studio package. Our computational DFT-D approach gives a structural description of the TiCl 3 phases in good agreement with experiment. The core-level spectroscopy confirmed that α, β, and γ modifications for TiCl 3 have lightly affected on the valences of the constitutional elements. A series of possible growth faces (h k l) were deduced using the classic Bravais–Friedel–Donnay–Harker (BFDH) model. We conclude that the sequence of work function for (0 0 1) surface was α > β ≈ γ

Basic Thermodynamics

International Nuclear Information System (INIS)

Duthil, P

2014-01-01

The goal of this paper is to present a general thermodynamic basis that is useable in the context of superconductivity and particle accelerators. The first part recalls the purpose of thermodynamics and summarizes its important concepts. Some applications, from cryogenics to magnetic systems, are covered. In the context of basic thermodynamics, only thermodynamic equilibrium is considered

Basic Thermodynamics

Energy Technology Data Exchange (ETDEWEB)

Duthil, P [Orsay, IPN (France)

2014-07-01

The goal of this paper is to present a general thermodynamic basis that is useable in the context of superconductivity and particle accelerators. The first part recalls the purpose of thermodynamics and summarizes its important concepts. Some applications, from cryogenics to magnetic systems, are covered. In the context of basic thermodynamics, only thermodynamic equilibrium is considered.

Experimental thermodynamics experimental thermodynamics of non-reacting fluids

CERN Document Server

Neindre, B Le

2013-01-01

Experimental Thermodynamics, Volume II: Experimental Thermodynamics of Non-reacting Fluids focuses on experimental methods and procedures in the study of thermophysical properties of fluids. The selection first offers information on methods used in measuring thermodynamic properties and tests, including physical quantities and symbols for physical quantities, thermodynamic definitions, and definition of activities and related quantities. The text also describes reference materials for thermometric fixed points, temperature measurement under pressures, and pressure measurements. The publicatio

Misuse of thermodynamic entropy in economics

International Nuclear Information System (INIS)

Kovalev, Andrey V.

2016-01-01

The direct relationship between thermodynamic entropy and economic scarcity is only valid for a thermodynamically isolated economy. References to the second law of thermodynamics in economics within the context of scarcity ignore the fact that the earth is not an isolated system. The earth interacts with external sources and sinks of entropy and the resulting total entropy fluctuates around a constant. Even if the mankind finally proves unable to recycle industrial waste and close the technological cycle, the economic disruption caused by the depletion of natural resources may happen while the total thermodynamic entropy of the ecosystem remains essentially at the present level, because the transfer of chemically refined products may not increase significantly the total entropy, but it may decrease their recyclability. The inutility of industrial waste is not connected with its entropy, which may be exemplified with the case of alumina production. The case also demonstrates that industrially generated entropy is discharged into surroundings without being accumulated in ‘thermodynamically unavailable matter’. Material entropy, as a measure of complexity and economic dispersal of resources, can be a recyclability metric, but it is not a thermodynamic parameter, and its growth is not equivalent to the growth of thermodynamic entropy. - Highlights: • Entropy cannot be used as a measure of economic scarcity. • There is no anthropogenic entropy separate from the entropy produced naturally. • Inutility of industrial waste is not connected with its thermodynamic entropy. • Industrially generated entropy may or may not be accumulated in industrial waste. • Recyclability is more important than thermodynamic entropy of a product.

Surface thermodynamics

International Nuclear Information System (INIS)

Garcia-Moliner, F.

1975-01-01

Basic thermodynamics of a system consisting of two bulk phases with an interface. Solid surfaces: general. Discussion of experimental data on surface tension and related concepts. Adsorption thermodynamics in the Gibbsian scheme. Adsorption on inert solid adsorbents. Systems with electrical charges: chemistry and thermodynamics of imperfect crystals. Thermodynamics of charged surfaces. Simple models of charge transfer chemisorption. Adsorption heat and related concepts. Surface phase transitions

Calculation of the thermodynamic properties of liquid Ag–In–Sb alloys

Directory of Open Access Journals (Sweden)

DRAGANA ZIVKOVIC

2006-03-01

Full Text Available The results of calculations of the thermodynamic properties of liquid Ag–In–Sb alloys are presented in this paper. The Redlich–Kister–Muggianu model was used for the calculations. Based on known thermodynamic data for constitutive binary systems and available experimental data for the investigated ternary system, the ternary interaction parameter for the liquid phase in the temperature range 1000–1200 K was determined. Comparison between experimental and calculated results showed their good mutual agreement.

Black Hole Thermodynamics in an Undergraduate Thermodynamics Course.

Science.gov (United States)

Parker, Barry R.; McLeod, Robert J.

1980-01-01

An analogy, which has been drawn between black hole physics and thermodynamics, is mathematically broadened in this article. Equations similar to the standard partial differential relations of thermodynamics are found for black holes. The results can be used to supplement an undergraduate thermodynamics course. (Author/SK)

Quantum Thermodynamics at Strong Coupling: Operator Thermodynamic Functions and Relations

Directory of Open Access Journals (Sweden)

Jen-Tsung Hsiang

2018-05-01

Full Text Available Identifying or constructing a fine-grained microscopic theory that will emerge under specific conditions to a known macroscopic theory is always a formidable challenge. Thermodynamics is perhaps one of the most powerful theories and best understood examples of emergence in physical sciences, which can be used for understanding the characteristics and mechanisms of emergent processes, both in terms of emergent structures and the emergent laws governing the effective or collective variables. Viewing quantum mechanics as an emergent theory requires a better understanding of all this. In this work we aim at a very modest goal, not quantum mechanics as thermodynamics, not yet, but the thermodynamics of quantum systems, or quantum thermodynamics. We will show why even with this minimal demand, there are many new issues which need be addressed and new rules formulated. The thermodynamics of small quantum many-body systems strongly coupled to a heat bath at low temperatures with non-Markovian behavior contains elements, such as quantum coherence, correlations, entanglement and fluctuations, that are not well recognized in traditional thermodynamics, built on large systems vanishingly weakly coupled to a non-dynamical reservoir. For quantum thermodynamics at strong coupling, one needs to reexamine the meaning of the thermodynamic functions, the viability of the thermodynamic relations and the validity of the thermodynamic laws anew. After a brief motivation, this paper starts with a short overview of the quantum formulation based on Gelin & Thoss and Seifert. We then provide a quantum formulation of Jarzynski’s two representations. We show how to construct the operator thermodynamic potentials, the expectation values of which provide the familiar thermodynamic variables. Constructing the operator thermodynamic functions and verifying or modifying their relations is a necessary first step in the establishment of a viable thermodynamics theory for

Thermodynamic tables to accompany Modern engineering thermodynamics

CERN Document Server

Balmer, Robert T

2011-01-01

This booklet is provided at no extra charge with new copies of Balmer's Modern Engineering Thermodynamics. It contains two appendices. Appendix C contains 40 thermodynamic tables, and Appendix D consists of 6 thermodynamic charts. These charts and tables are provided in a separate booklet to give instructors the flexibility of allowing students to bring the tables into exams. The booklet may be purchased separately if needed.

A thermodynamic evaluation of the Ti-Mo-C system

International Nuclear Information System (INIS)

Shim, J.H.; Oh, C.S.; Lee, D.N.

1996-01-01

A thermodynamic assessment of the Ti-Mo-C system has been made, employing a two-sublattice regular solution model for the solid solution and carbide phases and an ordinary subregular solution model for the liquid phase. A set of thermodynamic parameters describing the Gibbs energy of each individual phase in the Ti-Mo-C as well as the Ti-Mo systems was evaluated from thermochemical and phase equilibria information available in the literature through a computer-aided optimization procedure called the CALPHAD method. The comparison between the calculated and experimental results was made and practically important phase diagrams are also presented

Thermodynamically self-consistent integral equations and the structure of liquid metals

International Nuclear Information System (INIS)

Pastore, G.; Kahl, G.

1987-01-01

We discuss the application of the new thermodynamically self-consistent integral equations for the determination of the structural properties of liquid metals. We present a detailed comparison of the structure (S(q) and g(r)) for models of liquid alkali metals as obtained from two thermodynamically self-consistent integral equations and some published exact computer simulation results; the range of states extends from the triple point to the expanded metal. The theories which only impose thermodynamic self-consistency without any fitting of external data show an excellent agreement with the simulation results, thus demonstrating that this new type of integral equation is definitely superior to the conventional ones (hypernetted chain, Percus-Yevick, mean spherical approximation, etc). (author)

Elementary statistical thermodynamics a problems approach

CERN Document Server

Smith, Norman O

1982-01-01

This book is a sequel to my Chemical Thermodynamics: A Prob­ lems Approach published in 1967, which concerned classical thermodynamics almost exclusively. Most books on statistical thermodynamics now available are written either for the superior general chemistry student or for the specialist. The author has felt the need for a text which would bring the intermediate reader to the point where he could not only appreciate the roots of the subject but also have some facility in calculating thermodynamic quantities. Although statistical thermodynamics comprises an essential part of the college training of a chemist, its treatment in general physical chem­ istry texts is, of necessity, compressed to the point where the less competent student is unable to appreciate or comprehend its logic and beauty, and is reduced to memorizing a series of formulas. It has been my aim to fill this need by writing a logical account of the foundations and applications of the sub­ ject at a level which can be grasped by an under...

Thermodynamic assessment of the Pb-Sr system

Directory of Open Access Journals (Sweden)

Zhang H.

2017-01-01

Full Text Available The Pb-Sr system has been critically reviewed and modeled by means of the CALPHAD (CALculation of PHAse Diagrams approach. It contains seven stoichiometric compounds, i.e. SrPb3, Sr3Pb5, Sr2Pb3, SrPb, Sr5Pb4, Sr5Pb3 and Sr2Pb, in which the SrPb3 and Sr2Pb phases melt congruently, and the other five phases form via peritectic reactions. The enthalpies of formation for the intermetallic compounds at 0 K are provided by first-principles calculations. The liquid, fcc and bcc phases are modeled as substitutional solution phases. Both Redlich-Kister and exponential polynomials are used to describe the excess Gibbs energy of the liquid. Two sets of self-consistent thermodynamic parameters are obtained by considering reliable experimental data and the computed enthalpies of formation. Comprehensive comparisons between the calculated and measured phase diagram and thermodynamic data show that the experimental information is satisfactorily accounted for by the present thermodynamic description.

Extended thermodynamics

CERN Document Server

Müller, Ingo

1993-01-01

Physicists firmly believe that the differential equations of nature should be hyperbolic so as to exclude action at a distance; yet the equations of irreversible thermodynamics - those of Navier-Stokes and Fourier - are parabolic. This incompatibility between the expectation of physicists and the classical laws of thermodynamics has prompted the formulation of extended thermodynamics. After describing the motifs and early evolution of this new branch of irreversible thermodynamics, the authors apply the theory to mon-atomic gases, mixtures of gases, relativistic gases, and "gases" of phonons and photons. The discussion brings into perspective the various phenomena called second sound, such as heat propagation, propagation of shear stress and concentration, and the second sound in liquid helium. The formal mathematical structure of extended thermodynamics is exposed and the theory is shown to be fully compatible with the kinetic theory of gases. The study closes with the testing of extended thermodynamics thro...

Glass formability in medium-sized molecular systems/pharmaceuticals. I. Thermodynamics vs. kinetics

Energy Technology Data Exchange (ETDEWEB)

Tu, Wenkang; Li, Xiangqian; Chen, Zeming; Liu, Ying Dan; Wang, Li-Min, E-mail: simone.capaccioli@unipi.it, E-mail: Limin-Wang@ysu.edu.cn [State Key Lab of Metastable Materials Science and Technology, and College of Materials Science and Engineering, Yanshan University, Qinhuangdao, Hebei 066004 (China); Labardi, Massimiliano [CNR-IPCF, Sede Secondaria Pisa, Largo Pontecorvo 3, I-56127 Pisa (Italy); Capaccioli, Simone, E-mail: simone.capaccioli@unipi.it, E-mail: Limin-Wang@ysu.edu.cn [CNR-IPCF, Sede Secondaria Pisa, Largo Pontecorvo 3, I-56127 Pisa (Italy); Department of Physics, Pisa University, Largo Bruno Pontecorvo 3, I-56127 Pisa (Italy); Paluch, M. [Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice (Poland)

2016-05-07

Scrutinizing critical thermodynamic and kinetic factors for glass formation and the glass stability of materials would benefit the screening of the glass formers for the industry of glassy materials. The present work aims at elucidating the factors that contribute to the glass formation by investigating medium-sized molecules of pharmaceuticals. Glass transition related thermodynamics and kinetics are performed on the pharmaceuticals using calorimetric, dielectric, and viscosity measurements. The characteristic thermodynamic and kinetic parameters of glass transition are found to reproduce the relations established for small-molecule glass formers. The systematic comparison of the thermodynamic and kinetic contributions to glass formation reveals that the melting-point viscosity is the crucial quantity for the glass formation. Of more interest is the finding of a rough correlation between the melting-point viscosity and the entropy of fusion normalized by the number of beads of the pharmaceuticals, suggesting the thermodynamics can partly manifest its contribution to glass formation via kinetics.

Glass formability in medium-sized molecular systems/pharmaceuticals. I. Thermodynamics vs. kinetics.

Science.gov (United States)

Tu, Wenkang; Li, Xiangqian; Chen, Zeming; Liu, Ying Dan; Labardi, Massimiliano; Capaccioli, Simone; Paluch, M; Wang, Li-Min

2016-05-07

Scrutinizing critical thermodynamic and kinetic factors for glass formation and the glass stability of materials would benefit the screening of the glass formers for the industry of glassy materials. The present work aims at elucidating the factors that contribute to the glass formation by investigating medium-sized molecules of pharmaceuticals. Glass transition related thermodynamics and kinetics are performed on the pharmaceuticals using calorimetric, dielectric, and viscosity measurements. The characteristic thermodynamic and kinetic parameters of glass transition are found to reproduce the relations established for small-molecule glass formers. The systematic comparison of the thermodynamic and kinetic contributions to glass formation reveals that the melting-point viscosity is the crucial quantity for the glass formation. Of more interest is the finding of a rough correlation between the melting-point viscosity and the entropy of fusion normalized by the number of beads of the pharmaceuticals, suggesting the thermodynamics can partly manifest its contribution to glass formation via kinetics.

Mechanical properties of protein adsorption layers at the air/water and oil/water interface: a comparison in light of the thermodynamical stability of proteins.

Science.gov (United States)

Mitropoulos, Varvara; Mütze, Annekathrin; Fischer, Peter

2014-04-01

Over the last decades numerous studies on the interfacial rheological response of protein adsorption layers have been published. The comparison of these studies and the retrieval of a common parameter to compare protein interfacial activity are hampered by the fact that different boundary conditions (e.g. physico-chemical, instrumental, interfacial) were used. In the present work we review previous studies and attempt a unifying approach for the comparison between bulk protein properties and their adsorption films. Among many common food grade proteins we chose bovine serum albumin, β-lactoglobulin and lysozyme for their difference in thermodynamic stability and studied their adsorption at the air/water and limonene/water interface. In order to achieve this we have i) systematically analyzed protein adsorption kinetics in terms of surface pressure rise using a drop profile analysis tensiometer and ii) we addressed the interfacial layer properties under shear stress using an interfacial shear rheometer under the same experimental conditions. We could show that thermodynamically less stable proteins adsorb generally faster and yield films with higher shear rheological properties at air/water interface. The same proteins showed an analog behavior when adsorbing at the limonene/water interface but at slower rates. Copyright © 2013 Elsevier B.V. All rights reserved.

Theory and practice in engineering thermodynamics

International Nuclear Information System (INIS)

Polak, P.

1983-01-01

The book is a new approach to engineering thermodynamics for students of mechanical engineering at diploma and degree levels. There is an explanation of the basic principles of thermodynamics, followed by several chapters illustrating these principles as applied to piston engines, the gas turbine, steam power, and refrigerators and heat pumps. The book aims to introduce some key features of theory and current practice in a way that students will find interesting

Thermodynamic assessment of NdBr3 unary and LiBr-NdBr3 binary system

International Nuclear Information System (INIS)

Gong Weiping; Gaune-Escard, Marcelle

2006-01-01

Phase diagram and thermodynamic properties calculations were carried out on the NdBr 3 unary and the LiBr-NdBr 3 binary systems over the entire temperature and composition range, respectively. The Gibbs energy of NdBr 3 was evaluated using an independent polynomial to fit the experimental thermodynamic properties. The liquid phase in the LiBr-NdBr 3 system was described by the two sub-lattice ionic solution model (Li + ) P : (Br - , NdBr 6 -3 , NdBr 3 ) Q . Comparisons between the calculated phase diagram and thermodynamic quantities show that all reliable experimental information was satisfactorily accounted for by the present thermodynamic description

Liquid Nitrogen (Oxygen Simulant) Thermodynamic Vent System Test Data Analysis

Science.gov (United States)

Hedayat, A.; Nelson, S. L.; Hastings, L. J.; Flachbart, R. H.; Tucker, S. P.

2005-01-01

In designing systems for the long-term storage of cryogens in low-gravity (space) environments, one must consider the effects of thermal stratification on tank pressure that will occur due to environmental heat leaks. During low-gravity operations, a Thermodynamic Vent System (TVS) concept is expected to maintain tank pressure without propellant resettling. A series of TVS tests was conducted at NASA Marshall Space Flight Center (MSFC) using liquid nitrogen (LN2) as a liquid oxygen (LO2) simulant. The tests were performed at tank til1 levels of 90%, 50%, and 25%, and with a specified tank pressure control band. A transient one-dimensional TVS performance program is used to analyze and correlate the test data for all three fill levels. Predictions and comparisons of ullage pressure and temperature and bulk liquid saturation pressure and temperature with test data are presented.

Nuclear thermodynamics below particle threshold

International Nuclear Information System (INIS)

Schiller, A.; Agvaanluvsan, U.; Algin, E.; Bagheri, A.; Chankova, R.; Guttormsen, M.; Hjorth-Jensen, M.; Rekstad, J.; Siem, S.; Sunde, A. C.; Voinov, A.

2005-01-01

From a starting point of experimentally measured nuclear level densities, we discuss thermodynamical properties of nuclei below the particle emission threshold. Since nuclei are essentially mesoscopic systems, a straightforward generalization of macroscopic ensemble theory often yields unphysical results. A careful critique of traditional thermodynamical concepts reveals problems commonly encountered in mesoscopic systems. One of which is the fact that microcanonical and canonical ensemble theory yield different results, another concerns the introduction of temperature for small, closed systems. Finally, the concept of phase transitions is investigated for mesoscopic systems

A thermodynamic counterpart of the Axelrod model of social influence: The one-dimensional case

Science.gov (United States)

Gandica, Y.; Medina, E.; Bonalde, I.

2013-12-01

We propose a thermodynamic version of the Axelrod model of social influence. In one-dimensional (1D) lattices, the thermodynamic model becomes a coupled Potts model with a bonding interaction that increases with the site matching traits. We analytically calculate thermodynamic and critical properties for a 1D system and show that an order-disorder phase transition only occurs at T=0 independent of the number of cultural traits q and features F. The 1D thermodynamic Axelrod model belongs to the same universality class of the Ising and Potts models, notwithstanding the increase of the internal dimension of the local degree of freedom and the state-dependent bonding interaction. We suggest a unifying proposal to compare exponents across different discrete 1D models. The comparison with our Hamiltonian description reveals that in the thermodynamic limit the original out-of-equilibrium 1D Axelrod model with noise behaves like an ordinary thermodynamic 1D interacting particle system.

The Thermodynamic Machinery of Life

CERN Document Server

Kurzynski, Michal

2006-01-01

Living organisms are open thermodynamic systems whose functional structure has developed and been kinetically frozen during the historical process of biological evolution. A thermodynamics of both nonequilibrium and complex systems is needed for their description. In this book, the foundations of such a thermodynamics are presented. Biological processes at the cellular level are considered as coupled chemical reactions and transport processes across internal and the cytoplasmic membrane. All these processes are catalyzed by specific enzymes hence the kinetics of enzymatic catalysis and its control are described here in detail. The coupling of several processes through a common enzyme is considered in the context of free energy or signal transduction. Special attention is paid to evidence for a rich stochastic internal dynamics of native proteins and its possible role in the control of enzyme activity and in the action of biological molecular machines.

Thermodynamics in Curved Space-Time and Its Application to Holography

Directory of Open Access Journals (Sweden)

Yong Xiao

2015-03-01

Full Text Available The thermodynamic behaviors of a system living in a curved space-time are different from those of a system in a flat space-time. We have investigated the thermodynamics for a system consisting of relativistic massless bosons. We show that a strongly curved metric will produce a large enhancement of the degrees of freedom in the formulae of energy and entropy of the system, as a comparison to the case in a flat space-time. We are mainly concerned with its implications to holography, including the derivations of holographic entropy and holographic screen.

Organogels thermodynamics, structure, solvent role, and properties

CERN Document Server

Guenet, Jean-Michel

2016-01-01

This book provides a physics-oriented introduction to organogels with a comparison to polymer thermoreversible gels whenever relevant. The past decade has seen the development of a wide variety of newly-synthesized molecules that can spontaneously self-assemble or crystallize from their organic or aqueous solutions to produce fibrillar networks, namely organogels, with potential applications in organic electronics, light harvesting, bio-imaging, non-linear optics, and the like. This compact volume presents a detailed outlook of these novel molecular systems with special emphasis upon their thermodynamics, morphology, molecular structure, and rheology. The definition of these complex systems is also tackled, as well as the role of the solvent. The text features numerous temperature-phase diagrams for a variety of organogels as well as illustrations of their structures at the microscopic, mesoscopic and macroscopic level. A review of some potential applications is provided including hybrid functional materials ...

Simulating metabolism with statistical thermodynamics.

Science.gov (United States)

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.

Thermodynamics of the hot BIon

DEFF Research Database (Denmark)

Grignani, Gianluca; Harmark, Troels; Marini, Andrea

2011-01-01

We investigate the thermodynamics of the recently obtained nite temperature BIon solution of arXiv:1012.1494, focusing on two aspects. The first concerns comparison of the free energy of the three available phases for the finite temperature brane-antibrane wormhole configuration. Based on this we...... propose a heuristic picture for the dynamics of the phases that involves a critical temperature below which a stable phase exists. This stable phase is the finite temperature analogue of the thin throat branch of the extremal brane anti-brane wormhole configuration. The second aspect that we consider...

Thermodynamic and transport properties of sodium liquid and vapor

International Nuclear Information System (INIS)

Fink, J.K.; Leibowitz, L.

1995-01-01

Data have been reviewed to obtain thermodynamically consistent equations for thermodynamic and transport properties of saturated sodium liquid and vapor. Recently published Russian recommendations and results of equation of state calculations on thermophysical properties of sodium have been included in this critical assessment. Thermodynamic properties of sodium liquid and vapor that have been assessed include: enthalpy, heat capacity at constant pressure, heat capacity at constant volume, vapor pressure, boiling point, enthalpy of vaporization, density, thermal expansion, adiabatic and isothermal compressibility, speed of sound, critical parameters, and surface tension. Transport properties of liquid sodium that have been assessed include: viscosity and thermal conductivity. For each property, recommended values and their uncertainties are graphed and tabulated as functions of temperature. Detailed discussions of the analyses and determinations of the recommended equations include comparisons with recommendations given in other assessments and explanations of consistency requirements. The rationale and methods used in determining the uncertainties in the recommended values are also discussed

Rational extended thermodynamics

CERN Document Server

Müller, Ingo

1998-01-01

Ordinary thermodynamics provides reliable results when the thermodynamic fields are smooth, in the sense that there are no steep gradients and no rapid changes. In fluids and gases this is the domain of the equations of Navier-Stokes and Fourier. Extended thermodynamics becomes relevant for rapidly varying and strongly inhomogeneous processes. Thus the propagation of high­ frequency waves, and the shape of shock waves, and the regression of small-scale fluctuation are governed by extended thermodynamics. The field equations of ordinary thermodynamics are parabolic while extended thermodynamics is governed by hyperbolic systems. The main ingredients of extended thermodynamics are • field equations of balance type, • constitutive quantities depending on the present local state and • entropy as a concave function of the state variables. This set of assumptions leads to first order quasi-linear symmetric hyperbolic systems of field equations; it guarantees the well-posedness of initial value problems and f...

Classical and statistical thermodynamics

CERN Document Server

Rizk, Hanna A

2016-01-01

This is a text book of thermodynamics for the student who seeks thorough training in science or engineering. Systematic and thorough treatment of the fundamental principles rather than presenting the large mass of facts has been stressed. The book includes some of the historical and humanistic background of thermodynamics, but without affecting the continuity of the analytical treatment. For a clearer and more profound understanding of thermodynamics this book is highly recommended. In this respect, the author believes that a sound grounding in classical thermodynamics is an essential prerequisite for the understanding of statistical thermodynamics. Such a book comprising the two wide branches of thermodynamics is in fact unprecedented. Being a written work dealing systematically with the two main branches of thermodynamics, namely classical thermodynamics and statistical thermodynamics, together with some important indexes under only one cover, this treatise is so eminently useful.

Thermodynamics and statistical mechanics of some hydrides of the lanthanides and actinides

International Nuclear Information System (INIS)

Mintz, M.H.

1976-06-01

This work deals mainly with the thermodynamic and physical properties of the hydrides of the lanthanides and actinides. In addition, statistical models have been developed and applied to metal-hydrogen systems. A kinetic study of the uranium-hydrogen system was performed. The thermodynamic properties of the hydrides of neptunium, thorium, praseodymium, neodymium, samarium and europium were determined. In addition the samarium-europium-hydrogen ternary system was investigated. Moessbauer effect measurements of cubic neptunium hydrides were interpreted according to a model presented. A comparison. (author)

Thermodynamic modeling of the Na-X (X = Si, Ag, Cu, Cr systems

Directory of Open Access Journals (Sweden)

Hao D.

2012-01-01

Full Text Available The Na-X (X = Si, Ag, Cu, Cr systems have been critically reviewed and modeled by means of the CALPHAD approach. The two compounds, NaSi and Ag2Na, are treated as stoichiometric ones. By means of first-principles calculations, the enthalpies of formation at 0 K for the LT-NaSi (low temperature form of NaSi and Ag2Na have been computed to be -5210 and -29821.8 Jmol-1, respectively, with the desire to assist thermodynamic modeling. One set of self-consistent thermodynamic parameters is obtained for each of these binary systems. Comparisons between calculated and measured phase diagrams show that most of the experimental information can be satisfactorily accounted for by the present thermodynamic descriptions.

The physical basis of thermodynamics with applications to chemistry

CERN Document Server

Richet, Pascal

2001-01-01

Given that thermodynamics books are not a rarity on the market, why would an additional one be useful? The answer is simple: at any level, thermodynamics is usually taught as a somewhat abstruse discipline where many students get lost in a maze of difficult concepts. However, thermodynamics is not as intricate a subject as most people feel. This book fills a niche between elementary textbooks and mathematically oriented treatises, and provides readers with a distinct approach to the subject. As indicated by the title, this book explains thermodynamic phenomena and concepts in physical terms before proceeding to focus on the requisite mathematical aspects. It focuses on the effects of pressure, temperature and chemical composition on thermodynamic properties and places emphasis on rapidly evolving fields such as amorphous materials, metastable phases, numerical simulations of microsystems and high-pressure thermodynamics. Topics like redox reactions are dealt with in less depth, due to the fact that there is a...

Pathway Thermodynamics Highlights Kinetic Obstacles in Central Metabolism

Science.gov (United States)

Flamholz, Avi; Reznik, Ed; Liebermeister, Wolfram; Milo, Ron

2014-01-01

In metabolism research, thermodynamics is usually used to determine the directionality of a reaction or the feasibility of a pathway. However, the relationship between thermodynamic potentials and fluxes is not limited to questions of directionality: thermodynamics also affects the kinetics of reactions through the flux-force relationship, which states that the logarithm of the ratio between the forward and reverse fluxes is directly proportional to the change in Gibbs energy due to a reaction (ΔrG′). Accordingly, if an enzyme catalyzes a reaction with a ΔrG′ of -5.7 kJ/mol then the forward flux will be roughly ten times the reverse flux. As ΔrG′ approaches equilibrium (ΔrG′ = 0 kJ/mol), exponentially more enzyme counterproductively catalyzes the reverse reaction, reducing the net rate at which the reaction proceeds. Thus, the enzyme level required to achieve a given flux increases dramatically near equilibrium. Here, we develop a framework for quantifying the degree to which pathways suffer these thermodynamic limitations on flux. For each pathway, we calculate a single thermodynamically-derived metric (the Max-min Driving Force, MDF), which enables objective ranking of pathways by the degree to which their flux is constrained by low thermodynamic driving force. Our framework accounts for the effect of pH, ionic strength and metabolite concentration ranges and allows us to quantify how alterations to the pathway structure affect the pathway's thermodynamics. Applying this methodology to pathways of central metabolism sheds light on some of their features, including metabolic bypasses (e.g., fermentation pathways bypassing substrate-level phosphorylation), substrate channeling (e.g., of oxaloacetate from malate dehydrogenase to citrate synthase), and use of alternative cofactors (e.g., quinone as an electron acceptor instead of NAD). The methods presented here place another arrow in metabolic engineers' quiver, providing a simple means of evaluating

Thermodynamics and statistical mechanics

CERN Document Server

Landsberg, Peter T

1990-01-01

Exceptionally articulate treatment combines precise mathematical style with strong physical intuition. Wide range of applications includes negative temperatures, negative heat capacities, special and general relativistic effects, black hole thermodynamics, gravitational collapse, more. Over 100 problems with worked solutions. Advanced undergraduate, graduate level. Table of applications. Useful formulas and other data.

Thermodynamics a complete undergraduate course

CERN Document Server

Steane, Andrew M

2016-01-01

This is an undergraduate textbook in thermodynamics—the science of heat, work, temperature, and entropy. The text presents thermodynamics in and of itself, as an elegant and powerful set of ideas and methods. These methods open the way to understanding a very wide range of phenomena in physics, chemistry, engineering, and biology. Starting out from an introduction of concepts at first year undergraduate level, the roles of temperature, internal energy, and entropy are explained via the laws of thermodynamics. The text employs a combination of examples, exercises, and careful discussion, with a view to conveying the feel of the subject as well as avoiding common misunderstandings. The Feynman–Smuluchowski ratchet, Szilard’s engine, and Maxwell’s daemon are used to elucidate entropy and the second law. Free energy and thermodynamic potentials are discussed at length, with applications to solids as well as fluids and flow processes. Thermal radiation is discussed, and the main ideas significant to global...

Thermodynamic assessment of the Sn–Sr system supported by first-principles calculations

International Nuclear Information System (INIS)

Zhao, Jingrui; Du, Yong; Zhang, Lijun; Wang, Aijun; Zhou, Liangcai; Zhao, Dongdong; Liang, Jianlie

2012-01-01

Highlights: ► All the literature data of Sn–Sr system is critically reviewed. ► First-principles calculation of enthalpy of formation is carried out for each compound. ► Thermodynamic parameters for Sn–Sr system are obtained by CALPHAD method. ► A hybrid approach of CALPHAD and first-principles calculations is recommended. - Abstract: A hybrid approach of CALPHAD and first-principles calculations was employed to perform a thermodynamic modeling of the Sn–Sr system. The experimental phase diagram and thermodynamic data available in the literature were critically reviewed. The enthalpies of formation for the 6 stoichiometric compounds (i.e. Sr 2 Sn, Sr 5 Sn 3 , SrSn, Sr 3 Sn 5 , SrSn 3 and SrSn 4 ) at 0 K were computed by means of first-principles calculations. These data were used as the experimental values in the optimization module PARROT in the subsequent CALPHAD assessment to provide thermodynamic parameters with sound physical meaning. A set of self-consistent thermodynamic parameters was finally obtained by considering reliable literature data and the first-principles computed results. Comprehensive comparisons between the calculated and measured quantities indicate that all the reliable experimental information can be satisfactorily accounted for by the present thermodynamic description.

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

Science.gov (United States)

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

2018-04-01

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

Thermodynamic contributions of deforestation to global climate change

International Nuclear Information System (INIS)

Bell, A.

2009-01-01

This paper examines a portion of the thermodynamics of global warming. The calculations use the endothermic photosynthesis reaction and yearly measures of CO 2 uptake to determine the amount of energy that is absorbed by forest cover each year. The energy absorption value of forest coverage determines the yearly cost of deforestation. The calculations reveal that 3.92 * 10 15 kJ less solar energy is absorbed by global forest coverage because of deforestation each year. The energy is enough to warm the atmosphere by 0.00008 °C / year. By comparison the same amount of energy represents 0.001 % of the atmospheric energy gains between 1995 and 2003. The results of this paper raise questions about the nature of global warming and the possibility that thermodynamic contributions to global climate change are significant. (author)

Thermodynamic comparison of three small-scale gas liquefaction systems

DEFF Research Database (Denmark)

Nguyen, Tuong-Van; Rothuizen, Erasmus Damgaard; Markussen, Wiebke Brix

2017-01-01

. The present work investigates three configurations suitable for small-scale applications because of their simplicity and compactness: the single-mixed refrigerant, single and dual reverse Brayton cycles. The impact of different feed compositions and refrigerant properties is analysed. A detailed assessment...... to be more efficient (1000-2000 kJ/kgLNG) than expander-based ones (2500-5000 kJ/kgLNG) over larger ranges of operating conditions, at the expense of a greater system complexity and higher thermal conductance (250-500kW/K against 80-160 kW/K). The results show that the use of different thermodynamic models...

Correct thermodynamic forces in Tsallis thermodynamics: connection with Hill nanothermodynamics

International Nuclear Information System (INIS)

Garcia-Morales, Vladimir; Cervera, Javier; Pellicer, Julio

2005-01-01

The equivalence between Tsallis thermodynamics and Hill's nanothermodynamics is established. The correct thermodynamic forces in Tsallis thermodynamics are pointed out. Through this connection we also find a general expression for the entropic index q which we illustrate with two physical examples, allowing in both cases to relate q to the underlying dynamics of the Hamiltonian systems

Thermodynamics and heat power

CERN Document Server

Granet, Irving

2014-01-01

Fundamental ConceptsIntroductionThermodynamic SystemsTemperatureForce and MassElementary Kinetic Theory of GasesPressureReviewKey TermsEquations Developed in This ChapterQuestionsProblemsWork, Energy, and HeatIntroductionWorkEnergyInternal EnergyPotential EnergyKinetic EnergyHeatFlow WorkNonflow WorkReviewKey TermsEquations Developed in This ChapterQuestionsProblemsFirst Law of ThermodynamicsIntroductionFirst Law of ThermodynamicsNonflow SystemSteady-Flow SystemApplications of First Law of ThermodynamicsReviewKey TermsEquations Developed in This ChapterQuestionsProblemsThe Second Law of ThermodynamicsIntroductionReversibility-Second Law of ThermodynamicsThe Carnot CycleEntropyReviewKey TermsEquations Developed in This ChapterQuestionsProblemsProperties of Liquids and GasesIntroductionLiquids and VaporsThermodynamic Properties of SteamComputerized PropertiesThermodynamic DiagramsProcessesReviewKey TermsEquations Developed in This ChapterQuestionsProblemsThe Ideal GasIntroductionBasic ConsiderationsSpecific Hea...

Heat and thermodynamics

CERN Document Server

Saxena, A K

2014-01-01

Heat and thermodynamics aims to serve as a textbook for Physics, Chemistry and Engineering students. The book covers basic ideas of Heat and Thermodynamics, Kinetic Theory and Transport Phenomena, Real Gases, Liquafaction and Production and Measurement of very Low Temperatures, The First Law of Thermodynamics, The Second and Third Laws of Thermodynamics and Heat Engines and Black Body Radiation. KEY FEATURES Emphasis on concepts Contains 145 illustrations (drawings), 9 Tables and 48 solved examples At the end of chapter exercises and objective questions

Non-hard sphere thermodynamic perturbation theory.

Science.gov (United States)

Zhou, Shiqi

2011-08-21

A non-hard sphere (HS) perturbation scheme, recently advanced by the present author, is elaborated for several technical matters, which are key mathematical details for implementation of the non-HS perturbation scheme in a coupling parameter expansion (CPE) thermodynamic perturbation framework. NVT-Monte Carlo simulation is carried out for a generalized Lennard-Jones (LJ) 2n-n potential to obtain routine thermodynamic quantities such as excess internal energy, pressure, excess chemical potential, excess Helmholtz free energy, and excess constant volume heat capacity. Then, these new simulation data, and available simulation data in literatures about a hard core attractive Yukawa fluid and a Sutherland fluid, are used to test the non-HS CPE 3rd-order thermodynamic perturbation theory (TPT) and give a comparison between the non-HS CPE 3rd-order TPT and other theoretical approaches. It is indicated that the non-HS CPE 3rd-order TPT is superior to other traditional TPT such as van der Waals/HS (vdW/HS), perturbation theory 2 (PT2)/HS, and vdW/Yukawa (vdW/Y) theory or analytical equation of state such as mean spherical approximation (MSA)-equation of state and is at least comparable to several currently the most accurate Ornstein-Zernike integral equation theories. It is discovered that three technical issues, i.e., opening up new bridge function approximation for the reference potential, choosing proper reference potential, and/or using proper thermodynamic route for calculation of f(ex-ref), chiefly decide the quality of the non-HS CPE TPT. Considering that the non-HS perturbation scheme applies for a wide variety of model fluids, and its implementation in the CPE thermodynamic perturbation framework is amenable to high-order truncation, the non-HS CPE 3rd-order or higher order TPT will be more promising once the above-mentioned three technological advances are established. © 2011 American Institute of Physics

Thermodynamics of Bioreactions.

Science.gov (United States)

Held, Christoph; Sadowski, Gabriele

2016-06-07

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

Thermodynamic properties of alkali borosilicate gasses and metaborates

International Nuclear Information System (INIS)

Asano, Mitsuru

1992-01-01

Borosilicate glasses are the proposed solidifying material for storing high level radioactive wastes in deep underground strata. Those have low melting point, and can contain relatively large amount of high level radioactive wastes. When borosilicate glasses are used for this purpose, they must be sufficiently stable and highly reliable in the vitrification process, engineered storage and the disposal in deep underground strata. The main vaporizing components from borosilicate glasses are alkali elements and boron. In this report, as for the vaporizing behavior of alkali borosilicate glasses, the research on thermodynamic standpoint carried out by the authors is explained, and the thermodynamic properties of alkali metaborates of monomer and dimer which are the main evaporation gases are reported. The evaporation and the activity of alkali borosilicate glasses, the thermodynamic properties of alkali borosilicate glasses, gaseous alkali metaborates and alkali metaborate system solid solution and so on are described. (K.I.)

DISTRIBUTION OF PARASTATISTICS FUNCTIONS: AN OVERVIEW OF THERMODYNAMICS PROPERTIES

Directory of Open Access Journals (Sweden)

R. Yosi Aprian Sari

2016-05-01

Full Text Available This study aims to determine the thermodynamic properties of the parastatistics system of order two. The thermodynamic properties to be searched include the Grand Canonical Partition Function (GCPF Z, and the average number of particles N. These parastatistics systems is in a more general form compared to quantum statistical distribution that has been known previously, i.e.: the Fermi-Dirac (FD and Bose-Einstein (BE. Starting from the recursion relation of grand canonical partition function for parastatistics system of order two that has been known, recuresion linkages for some simple thermodynamic functions for parastatistics system of order two are derived. The recursion linkages are then used to calculate the thermodynamic functions of the model system of identical particles with limited energy levels which is similar to the harmonic oscillator. From these results we concluded that from the Grand Canonical Partition Function (GCPF, Z, the thermodynamics properties of parastatistics system of order two (paraboson and parafermion can be derived and have similar shape with parastatistics system of order one (Boson and Fermion. The similarity of the graph shows similar thermodynamic properties.   Keywords: parastatistics, thermodynamic properties

Comparisons of kinetics, thermodynamics and regeneration of tetramethylammonium hydroxide adsorption in aqueous solution with graphene oxide, zeolite and activated carbon

Energy Technology Data Exchange (ETDEWEB)

Chang, Shenteng; Lu, Chungsying, E-mail: clu@nchu.edu.tw; Lin, Kun-Yi Andrew

2015-01-30

Graphical abstract: A comparison of TMAH adsorption capacity with GO, NaY and GAC is conducted and the result reveals that the magnitude of qe follows the order of GO > NaY > GAC. The adsorption capacity of GO is significantly higher than those of zeolite and activated carbon in this and reported studies, showing its encouraging potential. GO also exhibits good reversibility of TMAH adsorption through 10 cycles of adsorption and desorption process. This reflects that GO is a promising and efficient adsorbent for TMAH removal in wastewater treatment. - Highlights: • Adsorption kinetics and isotherms of TMAH to GO, NaY and GAC are compared. • Thermodynamics of TMAH adsorption to GO, NaY and GAC is determined. • GO exhibits the highest TMAH adsorption capacity, followed by NaY and GAC. • Recyclabilities of NaY and GO remain above 95% but that of GAC dropped to 70%. - Abstract: Graphene oxide (GO), sodium Y-type zeolite (NaY) and granular activated carbon (GAC) are selected as adsorbents to study their kinetics, thermodynamics and regeneration of tetramethylammonium hydroxide (TMAH) adsorption from water. The adsorption kinetics follows the pseudo-second-order rate law while the adsorption thermodynamics shows an exothermic reaction with GO and GAC but displays an endothermic reaction with NaY. The adsorbed TMAH can be readily desorbed from the surface of GO and NaY by 0.05 M NaCl solution. A comparative study on the cyclic TMAH adsorption with GO, NaY and GAC is also conducted and the results reveal that GO exhibits the greatest TMAH adsorption capacity as well as superior reversibility of TMAH adsorption over 10 cycles of adsorption and desorption process. These features indicate that GO is a promising and efficient adsorbent for TMAH removal in wastewater treatment.

Thermodynamic properties by Equation of state of liquid sodium under pressure

Science.gov (United States)

Li, Huaming; Sun, Yongli; Zhang, Xiaoxiao; Li, Mo

Isothermal bulk modulus, molar volume and speed of sound of molten sodium are calculated through an equation of state of a power law form within good precision as compared with the experimental data. The calculated internal energy data show the minimum along the isothermal lines as the previous result but with slightly larger values. The calculated values of isobaric heat capacity show the unexpected minimum in the isothermal compression. The temperature and pressure derivative of various thermodynamic quantities in liquid Sodium are derived. It is discussed about the contribution from entropy to the temperature and pressure derivative of isothermal bulk modulus. The expressions for acoustical parameter and nonlinearity parameter are obtained based on thermodynamic relations from the equation of state. Both parameters for liquid Sodium are calculated under high pressure along the isothermal lines by using the available thermodynamic data and numeric derivations. By comparison with the results from experimental measurements and quasi-thermodynamic theory, the calculated values are found to be very close at melting point at ambient condition. Furthermore, several other thermodynamic quantities are also presented. Scientific Research Starting Foundation from Taiyuan university of Technology, Shanxi Provincial government (``100-talents program''), China Scholarship Council and National Natural Science Foundation of China (NSFC) under Grant No. 11204200.

Modelling thermodynamic properties of lanthanide (LnL)3+ and actinide (AnL)3+ complexes with tridentate planar nitrogen ligands (L)

International Nuclear Information System (INIS)

Ionova, G.; Rabbe, C.; Charbonnel, M.C.; Hill, C.; Guillaumont, D.; Guillaumont, R.; Ionov, S.; Madic, C.

2004-01-01

We report here the results obtained from a systematic theoretical study on the thermodynamic properties of trivalent lanthanide (Ln) and actinide (An) complexes with chelating nitrogen tridentate ligands. The mechanism of chelation has been investigated and the role of cation dissolution is investigated through a comparison of the thermodynamic properties of solvated cations and complexes. The difference in thermodynamic properties of LnL and AnL complexes is analyzed. (authors)

Potential and flux field landscape theory. II. Non-equilibrium thermodynamics of spatially inhomogeneous stochastic dynamical systems

International Nuclear Information System (INIS)

Wu, Wei; Wang, Jin

2014-01-01

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

Thermodynamically consistent coarse graining of biocatalysts beyond Michaelis–Menten

Science.gov (United States)

Wachtel, Artur; Rao, Riccardo; Esposito, Massimiliano

2018-04-01

Starting from the detailed catalytic mechanism of a biocatalyst we provide a coarse-graining procedure which, by construction, is thermodynamically consistent. This procedure provides stoichiometries, reaction fluxes (rate laws), and reaction forces (Gibbs energies of reaction) for the coarse-grained level. It can treat active transporters and molecular machines, and thus extends the applicability of ideas that originated in enzyme kinetics. Our results lay the foundations for systematic studies of the thermodynamics of large-scale biochemical reaction networks. Moreover, we identify the conditions under which a relation between one-way fluxes and forces holds at the coarse-grained level as it holds at the detailed level. In doing so, we clarify the speculations and broad claims made in the literature about such a general flux–force relation. As a further consequence we show that, in contrast to common belief, the second law of thermodynamics does not require the currents and the forces of biochemical reaction networks to be always aligned.

Interphase thermodynamic bond in heterogeneous alloys: effects on alloy properties

International Nuclear Information System (INIS)

Savchenko, A.M.; Konovalov, Yu.V.; Yuferov, O.I.

2005-01-01

Inconsistency between a conventional thermodynamic description of alloys as a mechanical mixture of phases and a real alloys state as a common thermodynamic system in which there is a complicated physical-chemical phases interaction has been considered. It is supposed that in heterogeneous alloys (eutectic ones, for instance), so called interphase thermodynamic bond can become apparent due to a partial electron levels splitting under phase interaction. Thermodynamic description of phase equilibrium in alloys is proposed taking into account a thermodynamic bond for the system with phase diagram of eutectic type, and methods of the value of this bond estimation are presented. Experimental evidence (Al-Cu-Si, Al-Si-Mg-Cu, U-Mo + Al) of the effect of interphase thermodynamic bond on temperature and enthalpy of melting of alloys are produced as well as possibility of its effects on alloys electrical conduction, strength, heat and corrosion resistance is substantiated theoretically [ru

Design of thermodynamic experiments and analyses of thermodynamic relationships

International Nuclear Information System (INIS)

Oezer Arnas, A.

2009-01-01

In teaching of thermodynamics, a certain textbook is followed internationally whatever language it is written in. However, although some do a very good job, most are not correct and precise and furthermore NONE discuss at all the need for and importance of designing thermodynamic experiments although experimentation in engineering is considered to be the back bone of analyses, not pursued much these days, or numerical studies, so very predominant these days. Here some thermodynamic experiments along with physical interpretation of phenomena through simple mathematics will be discussed that are straightforward, meaningful and which can be performed by any undergraduate/graduate student. Another important topic for discussion is the fact that the thermodynamic state principle demands uniqueness of results. It has been found in literature that this fact is not well understood by those who attempt to apply it loosely and end up with questionable results. Thermodynamics is the fundamental science that clarifies all these issues if well understood, applied and interpreted. The attempt of this paper is to clarify these situations and offer alternative methods for analyses. (author)

Thermodynamic cycle calculations for a pumped gaseous core fission reactor

International Nuclear Information System (INIS)

Kuijper, J.C.; Van Dam, H.

1991-01-01

Finite and 'infinitesimal' thermodynamic cycle calculations have been performed for a 'solid piston' model of a pumped Gaseous Core Fission Reactor with dissociating reactor gas, consisting of Uranium, Carbon and Fluorine ('UCF'). In the finite cycle calculations the influence has been investigated of several parameters on the thermodynamics of the system, especially on the attainable direct (nuclear to electrical) energy conversion efficiency. In order to facilitate the investigation of the influence of dissociation, a model gas, 'Modelium', was developed, which approximates, in a simplified, analytical way, the dissociation behaviour of the 'real' reactor gas. Comparison of the finite cycle calculation results with those of a so-called infinitesimal Otto cycle calculation leads to the conclusion that the conversion efficiency of a finite cycle can be predicted, without actually performing the finite cycle calculation, with reasonable accuracy, from the so-called 'infinitesimal efficiency factor', which is determined only by the thermodynamic properties of the reactor gas used. (author)

Quantum Coherence, Time-Translation Symmetry, and Thermodynamics

Directory of Open Access Journals (Sweden)

Matteo Lostaglio

2015-04-01

Full Text Available The first law of thermodynamics imposes not just a constraint on the energy content of systems in extreme quantum regimes but also symmetry constraints related to the thermodynamic processing of quantum coherence. We show that this thermodynamic symmetry decomposes any quantum state into mode operators that quantify the coherence present in the state. We then establish general upper and lower bounds for the evolution of quantum coherence under arbitrary thermal operations, valid for any temperature. We identify primitive coherence manipulations and show that the transfer of coherence between energy levels manifests irreversibility not captured by free energy. Moreover, the recently developed thermomajorization relations on block-diagonal quantum states are observed to be special cases of this symmetry analysis.

An introduction to equilibrium thermodynamics

CERN Document Server

Morrill, Bernard; Hartnett, James P; Hughes, William F

1973-01-01

An Introduction to Equilibrium Thermodynamics discusses classical thermodynamics and irreversible thermodynamics. It introduces the laws of thermodynamics and the connection between statistical concepts and observable macroscopic properties of a thermodynamic system. Chapter 1 discusses the first law of thermodynamics while Chapters 2 through 4 deal with statistical concepts. The succeeding chapters describe the link between entropy and the reversible heat process concept of entropy; the second law of thermodynamics; Legendre transformations and Jacobian algebra. Finally, Chapter 10 provides a

Thermodynamics for scientists and engineers

International Nuclear Information System (INIS)

Lim, Gyeong Hui

2011-02-01

This book deals with thermodynamics for scientists and engineers. It consists of 11 chapters, which are concept and background of thermodynamics, the first law of thermodynamics, the second law of thermodynamics and entropy, mathematics related thermodynamics, properties of thermodynamics on pure material, equilibrium, stability of thermodynamics, the basic of compound, phase equilibrium of compound, excess gibbs energy model of compound and activity coefficient model and chemical equilibrium. It has four appendixes on properties of pure materials and thermal mass.

Methods of thermodynamics

CERN Document Server

Reiss, Howard

1997-01-01

Since there is no shortage of excellent general books on elementary thermodynamics, this book takes a different approach, focusing attention on the problem areas of understanding of concept and especially on the overwhelming but usually hidden role of ""constraints"" in thermodynamics, as well as on the lucid exposition of the significance, construction, and use (in the case of arbitrary systems) of the thermodynamic potential. It will be especially useful as an auxiliary text to be used along with any standard treatment.Unlike some texts, Methods of Thermodynamics does not use statistical m

Mathematical foundations of thermodynamics

CERN Document Server

Giles, R; Stark, M; Ulam, S

2013-01-01

Mathematical Foundations of Thermodynamics details the core concepts of the mathematical principles employed in thermodynamics. The book discusses the topics in a way that physical meanings are assigned to the theoretical terms. The coverage of the text includes the mechanical systems and adiabatic processes; topological considerations; and equilibrium states and potentials. The book also covers Galilean thermodynamics; symmetry in thermodynamics; and special relativistic thermodynamics. The book will be of great interest to practitioners and researchers of disciplines that deal with thermodyn

Comparison of the applicability of commercial computer programs to study the thermodynamic stability of metal oxides; Vertailu kaupallisten laskentaohjelmien soveltuvuudesta metallioksidien termodynaamiseen stabiilisuustarkasteluun

Energy Technology Data Exchange (ETDEWEB)

Koukkari, P.; Olin, M. [VTT Chemical Technology, Espoo (Finland); Laitinen, T. [VTT Manufacturing Technology, Espoo (Finland); Sippola, H. [GEM Systems Oy (Finland)

1999-04-01

The oxide films formed on primary circuit surfaces incorporate radioactive species from the coolant and influence different corrosion phenomena in nuclear power plants. One approach to improve the understanding on the formation and properties of these oxide films is to evaluate their thermodynamic stability. The aim of this work was to compare and demonstrate the applicability of different commercial thermodynamic computer programs to model the deposition of oxides containing iron, chromium and/or nickel in various nuclear power plant environments. The programs considered in this evaluation comprised the EQ3/6 program and a product group including such products as ChemSage, HSC (including SOLGASMIX and GIBBS), H+PLUS and ChemSheet. In the group the transfer of data between different products is relatively easy. The goal was to find out which programs can be applied to evaluate the stability of oxide films, but not to assess the absolute accuracy of the calculations. The evaluation was done by means of applying the programs to calculate the stability of pure and mixed oxides of iron, nickel and chromium on stainless steel both in WWER and BWR conditions at different temperatures and coolant compositions. The comparison showed that EQ3/6 is suitable for most thermodynamic calculations. EQ3/6 can be characterised as a professional tool, for which no commercial training is available. ChemSage is a versatile and reliable program, which can be well used together with HSC and H+PLUS. ChemSage is mainly a professional tool, while HSC is easier to operate by an occasional user. Commercial training and support is available for both ChemSage and HSC. ChemSheet has been designed to utilise the properties of ChemSage in a user-friendly spreadsheet environment. All the products tested calculate thermodynamic equilibrium. Thus they are suitable to characterise such conditions in which the formation of a certain phase is or becomes possible. On the other hand, the modelling of the

A New Perspective on Thermodynamics

CERN Document Server

Lavenda, Bernard H

2010-01-01

Dr. Bernard H. Lavenda has written A New Perspective on Thermodynamics to combine an old look at thermodynamics with a new foundation. The book presents a historical perspective, which unravels the current presentation of thermodynamics found in standard texts, and which emphasizes the fundamental role that Carnot played in the development of thermodynamics. A New Perspective on Thermodynamics will: Chronologically unravel the development of the principles of thermodynamics and how they were conceived by their discoverers Bring the theory of thermodynamics up to the present time and indicate areas of further development with the union of information theory and the theory of means and their inequalities. New areas include nonextensive thermodynamics, the thermodynamics of coding theory, multifractals, and strange attractors. Reintroduce important, yet nearly forgotten, teachings of N.L. Sardi Carnot Highlight conceptual flaws in timely topics such as endoreversible engines, finite-time thermodynamics, geometri...

Contact symmetries and Hamiltonian thermodynamics

International Nuclear Information System (INIS)

Bravetti, A.; Lopez-Monsalvo, C.S.; Nettel, F.

2015-01-01

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

Some aeroacoustic and aerodynamic applications of the theory of nonequilibrium thermodynamics

Science.gov (United States)

Horne, W. Clifton; Smith, Charles A.; Karamcheti, Krishnamurty

1990-01-01

An exact equation is derived for the dissipation function of a homogeneous, isotropic, Newtonian fluid, with terms associated with irreversible compression or expansion, wave radiation, and the square of the vorticity. This and other forms of the dissipation function are used to identify simple flows, such as incompressible channel flow, the potential vortex with rotational core, and incompressible, irrotational flow as minimally dissipative distributions. A comparison of the hydrodynamic and thermodynamic stability characteristics of a parallel shear flow suggests that an association exists between flow stability and the variation of net dissipation with disturbance amplitude, and that nonlinear effects, such as bounded disturbance amplitude, may be examined from a thermodynamic basis.

Introduction to applied thermodynamics

CERN Document Server

Helsdon, R M; Walker, G E

1965-01-01

Introduction to Applied Thermodynamics is an introductory text on applied thermodynamics and covers topics ranging from energy and temperature to reversibility and entropy, the first and second laws of thermodynamics, and the properties of ideal gases. Standard air cycles and the thermodynamic properties of pure substances are also discussed, together with gas compressors, combustion, and psychrometry. This volume is comprised of 16 chapters and begins with an overview of the concept of energy as well as the macroscopic and molecular approaches to thermodynamics. The following chapters focus o

Twenty lectures on thermodynamics

CERN Document Server

Buchdahl, H A

2013-01-01

Twenty Lectures on Thermodynamics is a course of lectures, parts of which the author has given various times over the last few years. The book gives the readers a bird's eye view of phenomenological and statistical thermodynamics. The book covers many areas in thermodynamics such as states and transition; adiabatic isolation; irreversibility; the first, second, third and Zeroth laws of thermodynamics; entropy and entropy law; the idea of the application of thermodynamics; pseudo-states; the quantum-static al canonical and grand canonical ensembles; and semi-classical gaseous systems. The text

Thermodynamic performance comparison between ORC and Kalina cycles for multi-stream waste heat recovery

International Nuclear Information System (INIS)

Wang, Yufei; Tang, Qikui; Wang, Mengying; Feng, Xiao

2017-01-01

Highlights: • Comparison between ORC and Kalina cycles (KC) for multi-stream waste heat recovery. • Divide waste heat into straight, convex and concave based on its composite curve. • Use heat ratio and temperature of the most point to show the feature of waste heat. • KC is suitable for straight and most concave heat, while ORC for convex one. - Abstract: Organic Rankine cycle (ORC) and Kalina cycle are the main technologies to recover waste heat for power generation. Up to now, many works dealing with the thermodynamic performance comparison between ORC and Kalina cycles are available, but these studies considered for heat recovery from a single heat source or stream. In the process industry, there are multiple waste heat streams, forming a complex heat source profile. In this paper, based on the simulation model developed in the Aspen Hysys software, the two cycles are calculated and compared. According to the waste heat composite curve, the multi-stream waste heat is divided into three kinds, straight, convex, and concave waste heat. Two parameters, the ratio of the heat above and below the most salient/concave point (R) and the temperature of the most point, are used to roughly express the feature of waste heat. With the efficiency from waste heat (exergy) to power as energy performance indicator, the calculation results for waste heat with maximum supply temperature 180 °C show that for straight and concave waste heat with R not less than 0.2, Kalina cycle is better than ORC, while for convex waste heat, ORC is preferable. The work can provide a reference to choose a suitable technology to recover low temperature waste heat for power generation in the process industry.

Thermodynamic holography

Science.gov (United States)

Wei, Bo-Bo; Jiang, Zhan-Feng; Liu, Ren-Bao

2015-01-01

The holographic principle states that the information about a volume of a system is encoded on the boundary surface of the volume. Holography appears in many branches of physics, such as optics, electromagnetism, many-body physics, quantum gravity, and string theory. Here we show that holography is also an underlying principle in thermodynamics, a most important foundation of physics. The thermodynamics of a system is fully determined by its partition function. We prove that the partition function of a finite but arbitrarily large system is an analytic function on the complex plane of physical parameters, and therefore the partition function in a region on the complex plane is uniquely determined by its values along the boundary. The thermodynamic holography has applications in studying thermodynamics of nano-scale systems (such as molecule engines, nano-generators and macromolecules) and provides a new approach to many-body physics. PMID:26478214

Advanced classical thermodynamics

International Nuclear Information System (INIS)

Emanuel, G.

1987-01-01

The theoretical and mathematical foundations of thermodynamics are presented in an advanced text intended for graduate engineering students. Chapters are devoted to definitions and postulates, the fundamental equation, equilibrium, the application of Jacobian theory to thermodynamics, the Maxwell equations, stability, the theory of real gases, critical-point theory, and chemical thermodynamics. Diagrams, graphs, tables, and sample problems are provided. 38 references

Fluctuating Thermodynamics for Biological Processes

Science.gov (United States)

Ham, Sihyun

Because biomolecular processes are largely under thermodynamic control, dynamic extension of thermodynamics is necessary to uncover the mechanisms and driving factors of fluctuating processes. The fluctuating thermodynamics technology presented in this talk offers a practical means for the thermodynamic characterization of conformational dynamics in biomolecules. The use of fluctuating thermodynamics has the potential to provide a comprehensive picture of fluctuating phenomena in diverse biological processes. Through the application of fluctuating thermodynamics, we provide a thermodynamic perspective on the misfolding and aggregation of the various proteins associated with human diseases. In this talk, I will present the detailed concepts and applications of the fluctuating thermodynamics technology for elucidating biological processes. This work was supported by Samsung Science and Technology Foundation under Project Number SSTF-BA1401-13.

The development of flux-split algorithms for flows with non-equilibrium thermodynamics and chemical reactions

Science.gov (United States)

Grossman, B.; Cinella, P.

1988-01-01

A finite-volume method for the numerical computation of flows with nonequilibrium thermodynamics and chemistry is presented. A thermodynamic model is described which simplifies the coupling between the chemistry and thermodynamics and also results in the retention of the homogeneity property of the Euler equations (including all the species continuity and vibrational energy conservation equations). Flux-splitting procedures are developed for the fully coupled equations involving fluid dynamics, chemical production and thermodynamic relaxation processes. New forms of flux-vector split and flux-difference split algorithms are embodied in a fully coupled, implicit, large-block structure, including all the species conservation and energy production equations. Several numerical examples are presented, including high-temperature shock tube and nozzle flows. The methodology is compared to other existing techniques, including spectral and central-differenced procedures, and favorable comparisons are shown regarding accuracy, shock-capturing and convergence rates.

Is neoclassical microeconomics formally valid? An approach based on an analogy with equilibrium thermodynamics

Energy Technology Data Exchange (ETDEWEB)

Sousa, Tania; Domingos, Tiago [Environment and Energy Section, DEM, Instituto Superior Tecnico, Avenida Rovisco Pais, 1, 1049-001 Lisboa (Portugal)

2006-06-10

The relation between Thermodynamics and Economics is a paramount issue in Ecological Economics. Two different levels can be distinguished when discussing it: formal and substantive. At the formal level, a mathematical framework is used to describe both thermodynamic and economic systems. At the substantive level, thermodynamic laws are applied to economic processes. In Ecological Economics, there is a widespread claim that neoclassical economics has the same mathematical formulation as classical mechanics and is therefore fundamentally flawed because: (1) utility does not obey a conservation law as energy does; (2) an equilibrium theory cannot be used to study irreversible processes. Here, we show that neoclassical economics is based on a wrong formulation of classical mechanics, being in fact formally analogous to equilibrium thermodynamics. The similarity between both formalisms, namely that they are both cases of constrained optimisation, is easily perceived when thermodynamics is looked upon using the Tisza-Callen axiomatisation. In this paper, we take the formal analogy between equilibrium thermodynamics and economic systems far enough to answer the formal criticisms, proving that the formalism of neoclassical economics has irreversibility embedded in it. However, the formal similarity between equilibrium thermodynamics and neoclassical microeconomics does not mean that economic models are in accordance with mass, energy and entropy balance equations. In fact, neoclassical theory suffers from flaws in the substantive integration with thermodynamic laws as has already been fully demonstrated by valuable work done by ecological economists in this field. (author)

Thermodynamics of nuclear materials

International Nuclear Information System (INIS)

1979-01-01

Full text: The science of chemical thermodynamics has substantially contributed to the understanding of the many problems encountered in nuclear and reactor technology. These problems include reaction of materials with their surroundings and chemical and physical changes of fuels. Modern reactor technology, by its very nature, has offered new fields of investigations for the scientists and engineers concerned with the design of nuclear fuel elements. Moreover, thermodynamics has been vital in predicting the behaviour of new materials for fission as well as fusion reactors. In this regard, the Symposium was organized to provide a mechanism for review and discussion of recent thermodynamic investigations of nuclear materials. The Symposium was held in the Juelich Nuclear Research Centre, at the invitation of the Government of the Federal Republic of Germany. The International Atomic Energy Agency has given much attention to the thermodynamics of nuclear materials, as is evidenced by its sponsorship of four international symposia in 1962, 1965, 1967, and 1974. The first three meetings were primarily concerned with the fundamental thermodynamics of nuclear materials; as with the 1974 meeting, this last Symposium was primarily aimed at the thermodynamic behaviour of nuclear materials in actual practice, i.e., applied thermodynamics. Many advances have been made since the 1974 meeting, both in fundamental and applied thermodynamics of nuclear materials, and this meeting provided opportunities for an exchange of new information on this topic. The Symposium dealt in part with the thermodynamic analysis of nuclear materials under conditions of high temperatures and a severe radiation environment. Several sessions were devoted to the thermodynamic studies of nuclear fuels and fission and fusion reactor materials under adverse conditions. These papers and ensuing discussions provided a better understanding of the chemical behaviour of fuels and materials under these

Reduction of tungstates and molybdates by hydrogen and thermodynamic properties of these salts

International Nuclear Information System (INIS)

Gerasimov, Ya.I.; Rezukhina, T.N.; Simanov, Yu.P.; Vasil'eva, I.A.; Kurshakova, R.D.

1988-01-01

Study of thermodynamic properties of a series of tungstates of bivalent metals (Mg, Ca, Sr, Ba, Mn, Co, Fe, Ni, Cu, Zn, Cd and Pb) as well as of some molybdates- of Mg, Ca, Sr, Ba is carried out. The obtained values are compared with magnetic characteristics of compounds and parameters of their crystal lattices. Thermodynamic properties were studied by measuring constants of their reduction with hydrogen in the 500-1350 deg C temperature range. It is concluded that dependence of thermodynamic values on geometric parameters of the lattice is not definitive. Comparison of salt formation atomic entropies with deviations of salt magnetic moments from theoretical ionic moments points to the fact of existence of some accordance between these two series of values. 25 refs.; 10 figs.; 6 tabs

The role of comparison motives in the relationship between personality and comparison level choice

NARCIS (Netherlands)

Eggens, L.; Hendriks, A. A. J.; Bosker, R. J.; van der Werf, M. P. C.

2011-01-01

This article studied whether the motives for comparison of grades with those of others play a mediating role in the relationship between the Big Five personality traits and the choice of the level of comparison of students. The study was conducted among about 1,500 students in higher education. Of

Development of thermodynamic databases for geochemical calculations

Energy Technology Data Exchange (ETDEWEB)

Arthur, R.C. [Monitor Scientific, L.L.C., Denver, Colorado (United States); Sasamoto, Hiroshi; Shibata, Masahiro; Yui, Mikazu [Japan Nuclear Cycle Development Inst., Tokai, Ibaraki (Japan); Neyama, Atsushi [Computer Software Development Corp., Tokyo (Japan)

1999-09-01

Two thermodynamic databases for geochemical calculations supporting research and development on geological disposal concepts for high level radioactive waste are described in this report. One, SPRONS.JNC, is compatible with thermodynamic relations comprising the SUPCRT model and software, which permits calculation of the standard molal and partial molal thermodynamic properties of minerals, gases, aqueous species and reactions from 1 to 5000 bars and 0 to 1000degC. This database includes standard molal Gibbs free energies and enthalpies of formation, standard molal entropies and volumes, and Maier-Kelly heat capacity coefficients at the reference pressure (1 bar) and temperature (25degC) for 195 minerals and 16 gases. It also includes standard partial molal Gibbs free energies and enthalpies of formation, standard partial molal entropies, and Helgeson, Kirkham and Flowers (HKF) equation-of-state coefficients at the reference pressure and temperature for 1147 inorganic and organic aqueous ions and complexes. SPRONS.JNC extends similar databases described elsewhere by incorporating new and revised data published in the peer-reviewed literature since 1991. The other database, PHREEQE.JNC, is compatible with the PHREEQE series of geochemical modeling codes. It includes equilibrium constants at 25degC and l bar for mineral-dissolution, gas-solubility, aqueous-association and oxidation-reduction reactions. Reaction enthalpies, or coefficients in an empirical log K(T) function, are also included in this database, which permits calculation of equilibrium constants between 0 and 100degC at 1 bar. All equilibrium constants, reaction enthalpies, and log K(T) coefficients in PHREEQE.JNC are calculated using SUPCRT and SPRONS.JNC, which ensures that these two databases are mutually consistent. They are also internally consistent insofar as all the data are compatible with basic thermodynamic definitions and functional relations in the SUPCRT model, and because primary

Development of thermodynamic databases for geochemical calculations

International Nuclear Information System (INIS)

Arthur, R.C.; Sasamoto, Hiroshi; Shibata, Masahiro; Yui, Mikazu; Neyama, Atsushi

1999-09-01

Two thermodynamic databases for geochemical calculations supporting research and development on geological disposal concepts for high level radioactive waste are described in this report. One, SPRONS.JNC, is compatible with thermodynamic relations comprising the SUPCRT model and software, which permits calculation of the standard molal and partial molal thermodynamic properties of minerals, gases, aqueous species and reactions from 1 to 5000 bars and 0 to 1000degC. This database includes standard molal Gibbs free energies and enthalpies of formation, standard molal entropies and volumes, and Maier-Kelly heat capacity coefficients at the reference pressure (1 bar) and temperature (25degC) for 195 minerals and 16 gases. It also includes standard partial molal Gibbs free energies and enthalpies of formation, standard partial molal entropies, and Helgeson, Kirkham and Flowers (HKF) equation-of-state coefficients at the reference pressure and temperature for 1147 inorganic and organic aqueous ions and complexes. SPRONS.JNC extends similar databases described elsewhere by incorporating new and revised data published in the peer-reviewed literature since 1991. The other database, PHREEQE.JNC, is compatible with the PHREEQE series of geochemical modeling codes. It includes equilibrium constants at 25degC and l bar for mineral-dissolution, gas-solubility, aqueous-association and oxidation-reduction reactions. Reaction enthalpies, or coefficients in an empirical log K(T) function, are also included in this database, which permits calculation of equilibrium constants between 0 and 100degC at 1 bar. All equilibrium constants, reaction enthalpies, and log K(T) coefficients in PHREEQE.JNC are calculated using SUPCRT and SPRONS.JNC, which ensures that these two databases are mutually consistent. They are also internally consistent insofar as all the data are compatible with basic thermodynamic definitions and functional relations in the SUPCRT model, and because primary

Atmospheric thermodynamics

CERN Document Server

Iribarne, J V

1973-01-01

The thermodynamics of the atmosphere is the subject of several chapters in most textbooks on dynamic meteorology, but there is no work in English to give the subject a specific and more extensive treatment. In writing the present textbook, we have tried to fill this rather remarkable gap in the literature related to atmospheric sciences. Our aim has been to provide students of meteorology with a book that can playa role similar to the textbooks on chemical thermodynamics for the chemists. This implies a previous knowledge of general thermodynamics, such as students acquire in general physics courses; therefore, although the basic principles are reviewed (in the first four chapters), they are only briefly discussed, and emphasis is laid on those topics that will be useful in later chapters, through their application to atmospheric problems. No attempt has been made to introduce the thermodynamics of irreversible processes; on the other hand, consideration of heterogeneous and open homogeneous systems permits a...

Thermodynamic laws in isolated systems.

Science.gov (United States)

Hilbert, Stefan; Hänggi, Peter; Dunkel, Jörn

2014-12-01

The recent experimental realization of exotic matter states in isolated quantum systems and the ensuing controversy about the existence of negative absolute temperatures demand a careful analysis of the conceptual foundations underlying microcanonical thermostatistics. Here we provide a detailed comparison of the most commonly considered microcanonical entropy definitions, focusing specifically on whether they satisfy or violate the zeroth, first, and second laws of thermodynamics. Our analysis shows that, for a broad class of systems that includes all standard classical Hamiltonian systems, only the Gibbs volume entropy fulfills all three laws simultaneously. To avoid ambiguities, the discussion is restricted to exact results and analytically tractable examples.

Stochastic Thermodynamics: A Dynamical Systems Approach

Directory of Open Access Journals (Sweden)

Tanmay Rajpurohit

2017-12-01

Full Text Available In this paper, we develop an energy-based, large-scale dynamical system model driven by Markov diffusion processes to present a unified framework for statistical thermodynamics predicated on a stochastic dynamical systems formalism. Specifically, using a stochastic state space formulation, we develop a nonlinear stochastic compartmental dynamical system model characterized by energy conservation laws that is consistent with statistical thermodynamic principles. In particular, we show that the difference between the average supplied system energy and the average stored system energy for our stochastic thermodynamic model is a martingale with respect to the system filtration. In addition, we show that the average stored system energy is equal to the mean energy that can be extracted from the system and the mean energy that can be delivered to the system in order to transfer it from a zero energy level to an arbitrary nonempty subset in the state space over a finite stopping time.

Evaluated and estimated solubility of some elements for performance assessment of geological disposal of high-level radioactive waste using updated version of thermodynamic database

International Nuclear Information System (INIS)

Kitamura, Akira; Doi, Reisuke; Yoshida, Yasushi

2011-01-01

Japan Atomic Energy Agency (JAEA) established the thermodynamic database (JAEA-TDB) for performance assessment of geological disposal of high-level radioactive waste (HLW) and TRU waste. Twenty-five elements which were important for the performance assessment of geological disposal were selected for the database. JAEA-TDB enhanced reliability of evaluation and estimation of their solubility through selecting the latest and the most reliable thermodynamic data at present. We evaluated and estimated solubility of the 25 elements in the simulated porewaters established in the 'Second Progress Report for Safety Assessment of Geological Disposal of HLW in Japan' using the JAEA-TDB and compared with those using the previous thermodynamic database (JNC-TDB). It was found that most of the evaluated and estimated solubility values were not changed drastically, but the solubility and speciation of dominant aqueous species for some elements using the JAEA-TDB were different from those using the JNC-TDB. We discussed about how to provide reliable solubility values for the performance assessment. (author)

Thermodynamic Model of Spatial Memory

Science.gov (United States)

Kaufman, Miron; Allen, P.

1998-03-01

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

[On the principle of substance stability and thermodynamic feedback in hierarchic systems of the bio-world].

Science.gov (United States)

Gladyshev, G P

2002-01-01

The creation of structural hierarchies in open natural biosystems within the framework of quasi-closed systems is investigated by the methods of hierarchic thermodynamics (thermostatics). During the evolution of natural open systems, every higher hierarchic level j appears as a consequence of thermodynamic self-organization (self-assembly) of the structures of the lower (j-1)-th level. Such a self-assembly proceeds as a result of stabilization of the j-th level. This is related to the Gibbs' (Helmholtz') specific function of formation of the structure of the j-th level tending to a minimum. As a result of action of the principle of substance (matter) stability, the structures of the j-th level are enriched with less stable structures of the (j-1)-th level in the course of evolution. This provides a thermodynamic feedback between the structures of the higher j-th level and lower (j-1)-th level, thus preventing full structural stabilization of the j-th level and causing "thermodynamic rejuvenation" of biosystems. The latter enhances "thermodynamic" deceleration of evolution and practically unlimited maintenance of life. Examples of quantitative correlations are provided that call for further application of the substance stability principle to living and nonliving hierarchic structures.

Gravity as a thermodynamic phenomenon

OpenAIRE

Moustos, Dimitris

2017-01-01

The analogy between the laws of black hole mechanics and the laws of thermodynamics led Bekenstein and Hawking to argue that black holes should be considered as real thermodynamic systems that are characterised by entropy and temperature. Black hole thermodynamics indicates a deeper connection between thermodynamics and gravity. We review and examine in detail the arguments that suggest an interpretation of gravity itself as a thermodynamic theory.

Chemical kinetics, thermodynamics and the interpretation of in vivo processes - Part I

International Nuclear Information System (INIS)

Ferreira, R.

1976-01-01

A brief review of thermodynamic and kinetic concepts, the relationships between thermodynamic and kinetic information and the limitations of these concepts when confronted with the problems of biochemical processes and biological evaluation at the molecular level are presented [pt

Thermodynamic estimation: Ionic materials

International Nuclear Information System (INIS)

Glasser, Leslie

2013-01-01

Thermodynamics establishes equilibrium relations among thermodynamic parameters (“properties”) and delineates the effects of variation of the thermodynamic functions (typically temperature and pressure) on those parameters. However, classical thermodynamics does not provide values for the necessary thermodynamic properties, which must be established by extra-thermodynamic means such as experiment, theoretical calculation, or empirical estimation. While many values may be found in the numerous collected tables in the literature, these are necessarily incomplete because either the experimental measurements have not been made or the materials may be hypothetical. The current paper presents a number of simple and relible estimation methods for thermodynamic properties, principally for ionic materials. The results may also be used as a check for obvious errors in published values. The estimation methods described are typically based on addition of properties of individual ions, or sums of properties of neutral ion groups (such as “double” salts, in the Simple Salt Approximation), or based upon correlations such as with formula unit volumes (Volume-Based Thermodynamics). - Graphical abstract: Thermodynamic properties of ionic materials may be readily estimated by summation of the properties of individual ions, by summation of the properties of ‘double salts’, and by correlation with formula volume. Such estimates may fill gaps in the literature, and may also be used as checks of published values. This simplicity arises from exploitation of the fact that repulsive energy terms are of short range and very similar across materials, while coulombic interactions provide a very large component of the attractive energy in ionic systems. Display Omitted - Highlights: • Estimation methods for thermodynamic properties of ionic materials are introduced. • Methods are based on summation of single ions, multiple salts, and correlations. • Heat capacity, entropy

Determining Cloud Thermodynamic Phase from Micropulse Lidar Network Data

Science.gov (United States)

Lewis, Jasper R.; Campbell, James; Lolli, Simone; Tan, Ivy; Welton, Ellsworth J.

2017-01-01

Determining cloud thermodynamic phase is a critical factor in studies of Earth's radiation budget. Here we use observations from the NASA Micro Pulse Lidar Network (MPLNET) and thermodynamic profiles from the Goddard Earth Observing System, version 5 (GEOS-5) to distinguish liquid water, mixed-phase, and ice water clouds. The MPLNET provides sparse global, autonomous, and continuous measurements of clouds and aerosols which have been used in a number of scientific investigations to date. The use of a standardized instrument and a common suite of data processing algorithms with thorough uncertainty characterization allows for straightforward comparisons between sites. Lidars with polarization capabilities have recently been incorporated into the MPLNET project which allows, for the first time, the ability to infer a cloud thermodynamic phase. This presentation will look specifically at the occurrence of ice and mixed phase clouds in the temperature region of -10 C to -40 C for different climatological regions and seasons. We compare MPLNET occurrences of mixed-phase clouds to an historical climatology based on observations from the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) instrument aboard the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) spacecraft.

Establishment of data base files of thermodynamic data developed by OECD/NEA. Part 4. Addition of thermodynamic data for iron, tin and thorium

International Nuclear Information System (INIS)

Yoshida, Yasushi; Kitamura, Akira

2014-12-01

Thermodynamic data for compounds and complexes of elements with auxiliary species specialized in modeling requirements for safety assessments of radioactive waste disposal systems have been developed by the Thermochemical Data Base (TDB) project of the Nuclear Energy Agency in the Organization for Economic Co-operation and Development (OECD/NEA). Recently, thermodynamic data for aqueous complexes, solids and gases of thorium, tin and iron (Part 1) have been published in 2008, 2012 and 2013, respectively. These thermodynamic data have been selected on the basis of NEA’s guidelines which describe peer review and data selection, extrapolation to zero ionic strength, assignment of uncertainty, and temperature correction; therefore the selected data are considered to be reliable. The reliability of selected thermodynamic data of TDB developed by Japan Atomic Energy Agency (JAEA-TDB) has been confirmed by comparing with selected data by the NEA. For this comparison, text files of the selected data on some geochemical calculation programs are required. In the present report, the database files for the NEA’s TDB with addition of selected data for iron, tin and thorium to the previous files have been established for use of PHREEQC, Geochemist’s Workbench and EQ3/6. In addition, as an example of confirmation of quality, dominant species in iron TDB were compared in Eh-pH diagram and differences between JAEA-TDB and NEA-TDB were shown. Data base files established in the present study will be at the Website of thermodynamic, sorption and diffusion database in JAEA (http://migrationdb.jaea.go.jp/). A CD-ROM is attached as an appendix. (J.P.N.)

Comparison of the thermodynamic properties and high temperature chemical behavior of lanthanide and actinide oxides

International Nuclear Information System (INIS)

Ackermann, R.J.; Rauh, E.G.

1977-01-01

The thermodynamic properties of the lanthanide and actinide oxides are examined, compared, and associated with a variety of high temperature chemical behavior. Trends are cited resulting from a number of thermodynamic and spectroscopic correlations involving solid phases, species in aqueous solution, and molecules and ions in the vapor phase. Inadequacies in the data and alternative approaches are discussed. The characterization of nonstoichiometric phases stable only at high temperatures is related to a network of heterogeneous and homogeneous equilibria. A broad perspective of similarity and dissimilarity between the lanthanides and actinides emerges and forms the basis of the projected needs for further study

A Hamiltonian approach to Thermodynamics

Energy Technology Data Exchange (ETDEWEB)

Baldiotti, M.C., E-mail: baldiotti@uel.br [Departamento de Física, Universidade Estadual de Londrina, 86051-990, Londrina-PR (Brazil); Fresneda, R., E-mail: rodrigo.fresneda@ufabc.edu.br [Universidade Federal do ABC, Av. dos Estados 5001, 09210-580, Santo André-SP (Brazil); Molina, C., E-mail: cmolina@usp.br [Escola de Artes, Ciências e Humanidades, Universidade de São Paulo, Av. Arlindo Bettio 1000, CEP 03828-000, São Paulo-SP (Brazil)

2016-10-15

In the present work we develop a strictly Hamiltonian approach to Thermodynamics. A thermodynamic description based on symplectic geometry is introduced, where all thermodynamic processes can be described within the framework of Analytic Mechanics. Our proposal is constructed on top of a usual symplectic manifold, where phase space is even dimensional and one has well-defined Poisson brackets. The main idea is the introduction of an extended phase space where thermodynamic equations of state are realized as constraints. We are then able to apply the canonical transformation toolkit to thermodynamic problems. Throughout this development, Dirac’s theory of constrained systems is extensively used. To illustrate the formalism, we consider paradigmatic examples, namely, the ideal, van der Waals and Clausius gases. - Highlights: • A strictly Hamiltonian approach to Thermodynamics is proposed. • Dirac’s theory of constrained systems is extensively used. • Thermodynamic equations of state are realized as constraints. • Thermodynamic potentials are related by canonical transformations.

A Hamiltonian approach to Thermodynamics

International Nuclear Information System (INIS)

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

2016-01-01

In the present work we develop a strictly Hamiltonian approach to Thermodynamics. A thermodynamic description based on symplectic geometry is introduced, where all thermodynamic processes can be described within the framework of Analytic Mechanics. Our proposal is constructed on top of a usual symplectic manifold, where phase space is even dimensional and one has well-defined Poisson brackets. The main idea is the introduction of an extended phase space where thermodynamic equations of state are realized as constraints. We are then able to apply the canonical transformation toolkit to thermodynamic problems. Throughout this development, Dirac’s theory of constrained systems is extensively used. To illustrate the formalism, we consider paradigmatic examples, namely, the ideal, van der Waals and Clausius gases. - Highlights: • A strictly Hamiltonian approach to Thermodynamics is proposed. • Dirac’s theory of constrained systems is extensively used. • Thermodynamic equations of state are realized as constraints. • Thermodynamic potentials are related by canonical transformations.

Treatise on irreversible and statistical thermodynamics an introduction to nonclassical thermodynamics

CERN Document Server

Yourgrau, Wolfgang; Raw, Gough

2002-01-01

Extensively revised edition of a much-respected work examines thermodynamics of irreversible processes, general principles of statistical thermodynamics, assemblies of noninteracting structureless particles, and statistical theory. 1966 edition.

Chemical Thermodynamics Vol. 12 - Chemical Thermodynamics of tin

International Nuclear Information System (INIS)

Gamsjaeger, Heinz; GAJDA, Tamas; Sangster, James; Saxena, Surendra K.; Voigt, Wolfgang; Perrone, Jane

2012-01-01

This is the 12th volume of a series of expert reviews of the chemical thermodynamics of key chemical elements in nuclear technology and waste management. This volume is devoted to the inorganic species and compounds of tin. The tables contained in Chapters III and IV list the currently selected thermodynamic values within the NEA TDB Project. The database system developed at the NEA Data Bank, see Section II.6, assures consistency among all the selected and auxiliary data sets. The recommended thermodynamic data are the result of a critical assessment of published information. The values in the auxiliary data set, see Tables IV-1 and IV-2, have been adopted from CODATA key values or have been critically reviewed in this or earlier volumes of the series

Thermodynamic Data to 20,000 K For Monatomic Gases

Science.gov (United States)

Gordon, Sanford; McBride, Bonnie J.

1999-01-01

This report contains standard-state thermodynamic functions for 50 gaseous atomic elements plus deuterium and electron gas, 51 singly ionized positive ions, and 36 singly ionized negative ions. The data were generated by the NASA Lewis computer program PAC97, a modified version of PAC91 reported in McBride and Gordon. This report is being published primarily to document part of the data currently being used in several NASA Lewis computer programs. The data are presented in tabular and graphical format and are also represented in the form of least-squares coefficients. The tables give the following data as functions of temperature : heat capacity, enthalpy, entropy Gibbs energy, enthalpy of formation, and equilibrium constant. A brief discussion and a comparison of calculated results are given for several models for calculating ideal thermodynamic data for monatomic gases.

Nonequilibrium thermodynamics and energy efficiency in weight loss diets

Directory of Open Access Journals (Sweden)

Fine Eugene J

2007-07-01

Full Text Available Abstract 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

Applied chemical engineering thermodynamics

CERN Document Server

Tassios, Dimitrios P

1993-01-01

Applied Chemical Engineering Thermodynamics provides the undergraduate and graduate student of chemical engineering with the basic knowledge, the methodology and the references he needs to apply it in industrial practice. Thus, in addition to the classical topics of the laws of thermodynamics,pure component and mixture thermodynamic properties as well as phase and chemical equilibria the reader will find: - history of thermodynamics - energy conservation - internmolecular forces and molecular thermodynamics - cubic equations of state - statistical mechanics. A great number of calculated problems with solutions and an appendix with numerous tables of numbers of practical importance are extremely helpful for applied calculations. The computer programs on the included disk help the student to become familiar with the typical methods used in industry for volumetric and vapor-liquid equilibria calculations.

Thermodynamics of nuclear materials

International Nuclear Information System (INIS)

Rand, M.H.

1975-01-01

A report is presented of the Fourth International Symposium on Thermodynamics of Nuclear Materials held in Vienna, 21-25 October 1974. The technological theme of the Symposium was the application of thermodynamics to the understanding of the chemistry of irradiated nuclear fuels and to safety assessments for hypothetical accident conditions in reactors. The first four sessions were devoted to these topics and they were followed by four more sessions on the more basic thermodynamics, phase diagrams and the thermodynamic properties of a wide range of nuclear materials. Sixty-seven papers were presented

Statistical thermodynamics of long straight rigid rods on triangular lattices: nematic order and adsorption thermodynamic functions.

Science.gov (United States)

Matoz-Fernandez, D A; Linares, D H; Ramirez-Pastor, A J

2012-09-04

The statistical thermodynamics of straight rigid rods of length k on triangular lattices was developed on a generalization in the spirit of the lattice-gas model and the classical Guggenheim-DiMarzio approximation. In this scheme, the Helmholtz free energy and its derivatives were written in terms of the order parameter, δ, which characterizes the nematic phase occurring in the system at intermediate densities. Then, using the principle of minimum free energy with δ as a parameter, the main adsorption properties were calculated. Comparisons with Monte Carlo simulations and experimental data were performed in order to evaluate the outcome and limitations of the theoretical model.

Thermodynamics and mechanisms of sintering

International Nuclear Information System (INIS)

Pask, J.A.

1978-10-01

A phenomenological overview and exploration of the thermodynamic and geometric factors play a role in the process of densification of model compact systems consisting of crystalline spheres of uniform size in regular and irregular packing that form grain boundaries at every contact point. A further assumption is the presence of isotropic surface and grain boundary energies. Although such systems are unrealistic in comparison with normal powder compacts, their potential sintering behavior can be analyzed and provided with a limiting set of behavior conditions which can be looked upon as one boundary condition. This approach is logically realistic since it is easier to understand and provide a basis for understanding the more complex real powder systems

Thermodynamic Properties and Thermodynamic Geometries of Black p-Branes

International Nuclear Information System (INIS)

Yi-Huan Wei; Xiao Cui; Jia-Xin Zhao

2016-01-01

The heat capacity and the electric capacitance of the black p-branes (BPB) are generally defined, then they are calculated for some special processes. It is found that the Ruppeiner thermodynamic geometry of BPB is flat. Finally, we give some discussions for the flatness of the Ruppeiner thermodynamic geometry of BPB and some black holes. (paper)

General thermodynamics

CERN Document Server

Olander, Donald

2007-01-01

The book’s methodology is unified, concise, and multidisciplinary, allowing students to understand how the principles of thermodynamics apply to all technical fields that touch upon this most fundamental of scientific theories. It also offers a rigorous approach to the quantitative aspects of thermodynamics, accompanied by clear explanations to help students transition smoothly from the physical concepts to their mathematical representations

Calorimetry and thermodynamics of living systems

International Nuclear Information System (INIS)

Lamprecht, Ingolf

2003-01-01

Calorimetry of living systems and classical thermodynamics developed in parallel, from Lavoisier's early ice calorimeter experiments on guinea pigs, followed by Dubrunfaut's macrocalorimetric research of fermentation processes and Atwater-Rosa's whole-body calorimetry on humans and domestic animals, to the introduction of the famous Tian-Calvet instrument that found entrance into so many different fields of biology. In this work, six examples of living-system calorimetry and thermodynamics are presented. These are: (i) glycolytic oscillations far off the thermodynamic equilibrium; (ii) growth and energy balances in fermenting and respiring yeast cultures; (iii) direct and indirect calorimetric monitoring of electrically stimulated reptile metabolism; (iv) biologic and climatic factors influencing the temperature constancy and distribution in the mound of a wood ant colony as an example of a complex ecological system; (v) energetic considerations on the clustering of European honeybees in winter as a means to save energy and stored food as well as for their Japanese counterparts in defending against hornet predators; and (vi) energetic and evolutionary aspects of the mass specific entropy production rate, the so-called bound dissipation or psiu-function. The examples presented here are just a very personal selection of living systems from a broad spectrum at all levels of complexity. Common for all of them is that they were investigated calorimetrically on the background of classical and irreversible thermodynamics

Non-equilibrium thermodynamics

CERN Document Server

De Groot, Sybren Ruurds

1984-01-01

The study of thermodynamics is especially timely today, as its concepts are being applied to problems in biology, biochemistry, electrochemistry, and engineering. This book treats irreversible processes and phenomena - non-equilibrium thermodynamics.S. R. de Groot and P. Mazur, Professors of Theoretical Physics, present a comprehensive and insightful survey of the foundations of the field, providing the only complete discussion of the fluctuating linear theory of irreversible thermodynamics. The application covers a wide range of topics: the theory of diffusion and heat conduction, fluid dyn

Advanced thermodynamics engineering

CERN Document Server

Annamalai, Kalyan; Jog, Milind A

2011-01-01

Thermolab Excel-Based Software for Thermodynamic Properties and Flame Temperatures of Fuels IntroductionImportance, Significance and LimitationsReview of ThermodynamicsMathematical BackgroundOverview of Microscopic/NanothermodynamicsSummaryAppendix: Stokes and Gauss Theorems First Law of ThermodynamicsZeroth LawFirst Law for a Closed SystemQuasi Equilibrium (QE) and Nonquasi-equilibrium (NQE) ProcessesEnthalpy and First LawAdiabatic Reversible Process for Ideal Gas with Constant Specific HeatsFirst Law for an Open SystemApplications of First Law for an Open SystemIntegral and Differential Form

Modern engineering thermodynamics

CERN Document Server

Balmer, Robert T

2010-01-01

Designed for use in a standard two-semester engineering thermodynamics course sequence. The first half of the text contains material suitable for a basic Thermodynamics course taken by engineers from all majors. The second half of the text is suitable for an Applied Thermodynamics course in mechanical engineering programs. The text has numerous features that are unique among engineering textbooks, including historical vignettes, critical thinking boxes, and case studies. All are designed to bring real engineering applications into a subject that can be somewhat abstract and mathematica

GGDC Productivity Level Database : International Comparisons of Output, Inputs and Productivity at the Industry Level

NARCIS (Netherlands)

Inklaar, Robert; Timmer, Marcel P.

2008-01-01

In this paper we introduce the GGDC Productivity Level database. This database provides comparisons of output, inputs and productivity at a detailed industry level for a set of thirty OECD countries. It complements the EU KLEMS growth and productivity accounts by providing comparative levels and

A thermodynamic study of waste heat recovery from GT-MHR using organic Rankine cycles

International Nuclear Information System (INIS)

Yari, Mortaza; Mahmoudi, S.M.S.

2011-01-01

This paper presents an investigation on the utilization of waste heat from a gas turbine-modular helium reactor (GT-MHR) using different arrangements of organic Rankine cycles (ORCs) for power production. The considered organic Rankine cycles were: simple organic Rankine cycle (SORC), ORC with internal heat exchanger (HORC) and regenerative organic Rankine cycle (RORC). The performances of the combined cycles were studied from the point of view of first and second-laws of thermodynamics. Individual models were developed for each component and the effects of some important parameters such as compressor pressure ratio, turbine inlet temperature, and evaporator and environment temperatures on the efficiencies and on the exergy destruction rate were studied. Finally the combined cycles were optimized thermodynamically using the EES (Engineering Equation Solver) software. Based on the identical operating conditions for the GT-MHR cycle, a comparison between the three combined cycles and a simple GT-MHR cycle is also were made. This comparison was also carried out from the point of view of economics. The GT-MHR/SORC combined cycle proved to be the best among all the cycles from the point of view of both thermodynamics and economics. The efficiency of this cycle was about 10% higher than that of GT-MHR alone. (orig.)

Thermodynamic assessment of liquid composition change during solidification and its effect on freckle formation in superalloys

International Nuclear Information System (INIS)

Long Zhengdong; Liu Xingbo; Yang Wanhong; Chang, K.-M.; Barbero, Ever

2004-01-01

The solidification macrosegregation, i.e. freckle, becomes more and more concerned with ever increasing demand for the large ingot size of superalloys. The evaluation of freckle formation is very difficult because of the less understanding of freckle formation mechanism and complex solidification behaviors of multi-component superalloys. The macrostructure of typical Nb-bearing and Ti-bearing superalloys in horizontally directional solidification and vacuum arc remelting (VAR) ingots were investigated to clarify the freckle formation mechanism. The thermodynamic approach was proposed to simulate the solidification behaviors. The relative Ra numbers, a reliable criterion, of freckle formation for some alloys were obtained based on the results of thermodynamic calculations. This thermodynamic approach was evaluated through comparison of the calculations from semi-experimental results. The Ra numbers obtained by thermodynamic approach are in good agreement with the ingot size capability of the industry melting shops, which is limited mainly by freckle defects

Thermodynamics I essentials

CERN Document Server

REA, The Editors of

2012-01-01

REA's Essentials provide quick and easy access to critical information in a variety of different fields, ranging from the most basic to the most advanced. As its name implies, these concise, comprehensive study guides summarize the essentials of the field covered. Essentials are helpful when preparing for exams, doing homework and will remain a lasting reference source for students, teachers, and professionals. Thermodynamics I includes review of properties and states of a pure substance, work and heat, energy and the first law of thermodynamics, entropy and the second law of thermodynamics

Thermodynamics of spinning branes and their dual field theories

DEFF Research Database (Denmark)

Harmark, Troels; Obers, N. A.

2000-01-01

We discuss general spinning p-branes of string and M-theory and use their thermodynamics along with the correspondence between near-horizon brane solutions and field theories with 16 supercharges to describe the thermodynamic behavior of these theories in the presence of voltages under the R......-symmetry. The thermodynamics is used to provide two pieces of evidence in favor of a smooth interpolation function between the free energy at weak and strong coupling of the field theory. (i) A computation of the boundaries of stability shows that for the D2, D3, D4, M2 and M5-branes the critical values of Omega/T in the two...... limits are remarkably close and (ii) The tree-level R^4 corrections to the spinning D3-brane generate a decrease in the free energy at strong coupling towards the weak coupling result. We also comment on the generalization to spinning brane bound states and their thermodynamics, which are relevant...

Statistical Thermodynamics and Microscale Thermophysics

Science.gov (United States)

Carey, Van P.

1999-08-01

Many exciting new developments in microscale engineering are based on the application of traditional principles of statistical thermodynamics. In this text Van Carey offers a modern view of thermodynamics, interweaving classical and statistical thermodynamic principles and applying them to current engineering systems. He begins with coverage of microscale energy storage mechanisms from a quantum mechanics perspective and then develops the fundamental elements of classical and statistical thermodynamics. Subsequent chapters discuss applications of equilibrium statistical thermodynamics to solid, liquid, and gas phase systems. The remainder of the book is devoted to nonequilibrium thermodynamics of transport phenomena and to nonequilibrium effects and noncontinuum behavior at the microscale. Although the text emphasizes mathematical development, Carey includes many examples and exercises to illustrate how the theoretical concepts are applied to systems of scientific and engineering interest. In the process he offers a fresh view of statistical thermodynamics for advanced undergraduate and graduate students, as well as practitioners, in mechanical, chemical, and materials engineering.

Thermodynamic analysis of Mg-doped p-type GaN semiconductor

International Nuclear Information System (INIS)

Li Jingbo; Liang Jingkui; Rao Guanghui; Zhang Yi; Liu Guangyao; Chen Jingran; Liu Quanlin; Zhang Weijing

2006-01-01

A thermodynamic modeling of Mg-doped p-type GaN was carried out to describe the thermodynamic behaviors of native defects, dopants (Mg and H) and carriers in GaN. The formation energies of charged component compounds in a four-sublattice model were defined as functions of the Fermi-level based on the results of the first-principles calculations and adjusted to fit experimental data. The effect of the solubility of Mg on the low doping efficiency of Mg in GaN and the role of H in the Mg-doping MOCVD process were discussed. The modeling provides a thermodynamic approach to understand the doping process of GaN semiconductors

Thermodynamical analysis of an ADAM/EVA-process for electricity generation

International Nuclear Information System (INIS)

Knoche, K.F.; Tsatsaronis, G.; Loehrer, F.

1982-01-01

In this article, the so-called ADAM/EVA-process for long-range heat transport is presented as an alternative method of electricity generation, as being interesting from the purely thermodynamic point of view. For various variants of this process, extensive mass and energy balances are calculated. With the help of exact energy balances, the irreversibilities of the individual parts of the plant are determined and evaluated by comparison. (orig.) [de

Thermodynamic analysis and evaluation of the nitrogen solubility in liquid Nb and Fe-Nb alloys

International Nuclear Information System (INIS)

Qiu Caian

1994-01-01

Experimental information on the nitrogen solubility in liquid Nb and Fe-Nb alloys has been critically analysed and then utilized to evaluate the thermodynamic properties of the Nb-N and Fe-Nb-N liquid phases on the basis of thermodynamic models of Gibbs energy. A thermodynamic description of the Fe-Nb-N liquid phase was obtained, which has been used to calculate the N solubility in comparison with experimental results. The effect of an addition of Nb on the temperature dependence of the N solubility in liquid Fe has been examined by comparing with the effect of the Cr and V additions. It has been shown that the N solubility in liquid Nb and Fe-Nb alloys under various conditions is well described by the present calculation. (orig.)

Thermodynamics an engineering approach

CERN Document Server

Cengel, Yunus A

2014-01-01

Thermodynamics, An Engineering Approach, eighth edition, covers the basic principles of thermodynamics while presenting a wealth of real-world engineering examples so students get a feel for how thermodynamics is applied in engineering practice. This text helps students develop an intuitive understanding by emphasizing the physics and physical arguments. Cengel and Boles explore the various facets of thermodynamics through careful explanations of concepts and use of numerous practical examples and figures, having students develop necessary skills to bridge the gap between knowledge and the confidence to properly apply their knowledge. McGraw-Hill is proud to offer Connect with the eighth edition of Cengel/Boles, Thermodynamics, An Engineering Approach. This innovative and powerful new system helps your students learn more efficiently and gives you the ability to assign homework problems simply and easily. Problems are graded automatically, and the results are recorded immediately. Track individual stude...

Mechanical breakdown in the nuclear multifragmentation phenomena. Thermodynamic analysis

International Nuclear Information System (INIS)

Bulavin, L.A.; Cherevko, K.V.; Sysoev, V.M.

2012-01-01

Based on a similarity of the Van der Waals and nucleon-nucleon interaction the known thermodynamic relations for ordinary liquids are used to analyze the possible decay channels in the proton induced nuclear multifragmentation phenomena. The main features of the different phase trajectories in the P-V plane are compared with the experimental data on multifragmentation. It allowed choosing the phase trajectories with the correct qualitative picture of the phenomena. Based on the thermodynamic analysis of the proton-induced multifragmentation phenomena the most appropriate decay channel corresponding to the realistic phase trajectory is chosen. Macroscopic analysis of the suggested decay channel is done in order to check the possibility of the mechanical breakdown of the heated system. Based on a simple thermodynamic model preliminary quantitative calculations of corresponding macroscopic parameters (energy, pressure) are done and therefore the model verification on macroscopic level is held. It is shown that on macroscopic level the chosen decay channel through the mechanical breakdown meets the necessary conditions for describing the proton-induced multifragmentation phenomena

Thermodynamic modeling of the Ge-Ti system supported by key experiment

International Nuclear Information System (INIS)

Liu, Dandan; Yan, Huanli; Yuan, Xiaoming; Chung, Yoonsung; Du, Yong; Xu, Honghui; Liu, Libin; Nash, Philip

2011-01-01

Highlights: → All of the experimental phase diagram and thermodynamic data available for the Ge-Ti system have been critically evaluated. → The general feature of the Ge-Ti system and enthalpy of formation of Ti 5 Ge 3 have been checked via experiment. The annealed samples are characterized by X-ray diffraction, scanning electron microscope and differential thermal analysis. → An optimum thermodynamic data set for the Ge-Ti system was obtained. The comprehensive comparison shows that the calculated phase diagram and thermodynamic properties are in good agreement with the experimental data. - Abstract: A complete thermodynamic investigation of the Ge-Ti system was performed in this study. Seven samples were prepared by arc-melting the pure elements in order to check the literature data on phase diagram and enthalpy of formation of Ti 5 Ge 3 . The samples were annealed at certain temperatures for extended periods of time, and then quenched. Both the as-cast and annealed samples were examined by X-ray diffraction (XRD) analysis and scanning electron microscope (SEM) technology. The phase transformation temperatures were measured by differential thermal analysis (DTA). The measurement on enthalpy of formation for Ti 5 Ge 3 was performed using the Kleppa-type HTRC with the calorimeter temperature set at 1100 ± 2 o C. Based upon the literature data and current experimental results, the Ge-Ti system was critically assessed by means of CALPHAD approach. The calculated phase diagram and thermodynamic properties agree well with the literature data and the present experimental results.

Thermodynamics of adaptive molecular resolution.

Science.gov (United States)

Delgado-Buscalioni, R

2016-11-13

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

Equilibrium thermodynamics - Callen's postulational approach

NARCIS (Netherlands)

Jongschaap, R.J.J.; Öttinger, Hans Christian

2001-01-01

In order to provide the background for nonequilibrium thermodynamics, we outline the fundamentals of equilibrium thermodynamics. Equilibrium thermodynamics must not only be obtained as a special case of any acceptable nonequilibrium generalization but, through its shining example, it also elucidates

An introduction to statistical thermodynamics

CERN Document Server

Hill, Terrell L

1987-01-01

""A large number of exercises of a broad range of difficulty make this book even more useful…a good addition to the literature on thermodynamics at the undergraduate level."" - Philosophical MagazineAlthough written on an introductory level, this wide-ranging text provides extensive coverage of topics of current interest in equilibrium statistical mechanics. Indeed, certain traditional topics are given somewhat condensed treatment to allow room for a survey of more recent advances.The book is divided into four major sections. Part I deals with the principles of quantum statistical mechanics a

A simulation assessment of the thermodynamics of dense ion-dipole mixtures with polarization

International Nuclear Information System (INIS)

Bastea, Sorin

2014-01-01

Molecular dynamics (MD) simulations are employed to ascertain the relative importance of various electrostatic interaction contributions, including induction interactions, to the thermodynamics of dense, hot ion-dipole mixtures. In the absence of polarization, we find that an MD-constrained free energy term accounting for the ion-dipole interactions, combined with well tested ionic and dipolar contributions, yields a simple, fairly accurate free energy form that may be a better option for describing the thermodynamics of such mixtures than the mean spherical approximation (MSA). Polarization contributions induced by the presence of permanent dipoles and ions are found to be additive to a good approximation, simplifying the thermodynamic modeling. We suggest simple free energy corrections that account for these two effects, based in part on standard perturbative treatments and partly on comparisons with MD simulation. Even though the proposed approximations likely need further study, they provide a first quantitative assessment of polarization contributions at high densities and temperatures and may serve as a guide for future modeling efforts

Thermodynamics for the practicing engineer

CERN Document Server

Theodore, Louis; Vanvliet, Timothy

2009-01-01

This book concentrates specifically on the applications of thermodynamics, rather than the theory. It addresses both technical and pragmatic problems in the field, and covers such topics as enthalpy effects, equilibrium thermodynamics, non-ideal thermodynamics and energy conversion applications. Providing the reader with a working knowledge of the principles of thermodynamics, as well as experience in their application, it stands alone as an easy-to-follow self-teaching aid to practical applications and contains worked examples.

The thermodynamics of latent fingerprint corrosion of metal elements and alloys.

Science.gov (United States)

Bond, John W

2008-11-01

Redox reactions taking place between the surface of a metal and fingerprint residue have been expressed thermodynamically in terms of both the Nernst equation for reduction potential and the complexation constant for the formation of complex metal halide ions in aqueous solution. These expressions are used to explain experimental results for the corrosion of 10 different metal elements by fingerprint residue in air at room temperature. Corrosion of noble metals, such as silver and gold, supports the proposition that the degree of metal corrosion is enhanced by the presence of chloride ions in eccrine sweat. Extending the experiments to include 10 metal alloys enabled the construction of a fingerprint corrosion series for 20 different metals. Fingerprint corrosion on metals alloyed with > approximately 40% copper was found to display third level fingerprint detail. A comparison of both conventional ink on paper and digital (Livescan) fingerprinting techniques with fingerprints deposited on 9 Karat gold alloy has shown that gold alloy depositions are least susceptible to third level detail obliteration by poor fingerprint capturing techniques.

Comparative thermodynamic analysis of the Pb-Au0.7Sn0.3 section in the Pb-Au-Sn ternary system

International Nuclear Information System (INIS)

Trumic, B.; Zivkovic, D.; Zivkovic, Z.; Manasijevic, D.

2005-01-01

The results of comparative thermodynamic analysis of Pb-Au 0.7 Sn 0.3 section in Pb-Au-Sn system are presented in this paper. Investigation was done comparatively by calorimetric measurements and thermodynamic calculation according to the general solution model. Thermodynamic parameters, such as partial and integral molar quantities, were determined at different temperatures. The comparison between experimental and calculated results showed mutual agreement. Demixing tendency of lead, presented in the positive deviation from ideal behavior, was confirmed through the study of concentration fluctuation in the long-wavelength limit. Also, chosen alloys in the investigated section were characterized using SEM-EDX analysis

Thermodynamics of Gas Turbine Cycles with Analytic Derivatives in OpenMDAO

Science.gov (United States)

Gray, Justin; Chin, Jeffrey; Hearn, Tristan; Hendricks, Eric; Lavelle, Thomas; Martins, Joaquim R. R. A.

2016-01-01

A new equilibrium thermodynamics analysis tool was built based on the CEA method using the OpenMDAO framework. The new tool provides forward and adjoint analytic derivatives for use with gradient based optimization algorithms. The new tool was validated against the original CEA code to ensure an accurate analysis and the analytic derivatives were validated against finite-difference approximations. Performance comparisons between analytic and finite difference methods showed a significant speed advantage for the analytic methods. To further test the new analysis tool, a sample optimization was performed to find the optimal air-fuel equivalence ratio, , maximizing combustion temperature for a range of different pressures. Collectively, the results demonstrate the viability of the new tool to serve as the thermodynamic backbone for future work on a full propulsion modeling tool.

Water in the physiology of plant: thermodynamics and kinetic

Directory of Open Access Journals (Sweden)

Maurizio Cocucci

2011-02-01

Full Text Available Molecular properties of water molecule determine its role in plant physiology. At molecular level the properties of water molecules determine the behaviour of other plant molecules; in particular its physic characteristics are important in the operativeness of macromolecules and in plant thermoregulation. Plant water supply primarily dependent on thermodynamics properties in particular water chemical potential and its components, more recently there are evidences that suggest an important role in the water kinetic characteristics, depending, at cell membrane level, in particular plasmalemma, on the presence of specific water channel, the aquaporines controlled in its activity by a number of physiological and biochemical factors. Thermodynamics and kinetic factors controlled by physiological, biochemical properties and molecular effectors, control water supply and level in plants to realize their survival, growth and differentiation and the consequent plant production.

The thermodynamics of direct air capture of carbon dioxide

International Nuclear Information System (INIS)

Lackner, Klaus S.

2013-01-01

An analysis of thermodynamic constraints shows that the low concentration of carbon dioxide in ambient air does not pose stringent limits on air capture economics. The thermodynamic energy requirement is small even using an irreversible sorbent-based process. A comparison to flue gas scrubbing suggests that the additional energy requirement is small and can be supplied with low-cost energy. In general, the free energy expended in the regeneration of a sorbent will exceed the free energy of mixing, as absorption is usually not reversible. The irreversibility, which grows with the depth of scrubbing, tends to affect flue gas scrubbing more than air capture which can successfully operate while extracting only a small fraction of the carbon dioxide available in air. This is reflected in a significantly lower theoretical thermodynamic efficiency for a single stage flue gas scrubber than for an air capture device, but low carbon dioxide concentration in air still results in a larger energy demand for air capture. The energy required for capturing carbon dioxide from air could be delivered in various ways. I analyze a thermal swing and also a previously described moisture swing which is driven by the evaporation of water. While the total amount of heat supplied for sorbent regeneration in a thermal swing, in accordance with Carnot's principle, exceeds the total free energy requirement, the additional free energy required as one moves from flue gas scrubbing to air capture can be paid with an amount of additional low grade heat that equals the additional free energy requirement. Carnot's principle remains satisfied because the entire heat supplied, not just the additional amount, must be delivered at a slightly higher temperature. Whether the system is driven by water evaporation or by low grade heat, the cost of the thermodynamically-required energy can be as small as $1 to $2 per metric ton of carbon dioxide. Thermodynamics does not pose a practical constraint on the

Thermodynamics: The Unique Universal Science

Directory of Open Access Journals (Sweden)

Wassim M. Haddad

2017-11-01

Full Text Available Thermodynamics is a physical branch of science that governs the thermal behavior of dynamical systems from those as simple as refrigerators to those as complex as our expanding universe. The laws of thermodynamics involving conservation of energy and nonconservation of entropy are, without a doubt, two of the most useful and general laws in all sciences. The first law of thermodynamics, according to which energy cannot be created or destroyed, merely transformed from one form to another, and the second law of thermodynamics, according to which the usable energy in an adiabatically isolated dynamical system is always diminishing in spite of the fact that energy is conserved, have had an impact far beyond science and engineering. In this paper, we trace the history of thermodynamics from its classical to its postmodern forms, and present a tutorial and didactic exposition of thermodynamics as it pertains to some of the deepest secrets of the universe.

Unifying mechanical and thermodynamic descriptions across the thioredoxin protein family.

Science.gov (United States)

Mottonen, James M; Xu, Minli; Jacobs, Donald J; Livesay, Dennis R

2009-05-15

We compare various predicted mechanical and thermodynamic properties of nine oxidized thioredoxins (TRX) using a Distance Constraint Model (DCM). The DCM is based on a nonadditive free energy decomposition scheme, where entropic contributions are determined from rigidity and flexibility of structure based on distance constraints. We perform averages over an ensemble of constraint topologies to calculate several thermodynamic and mechanical response functions that together yield quantitative stability/flexibility relationships (QSFR). Applied to the TRX protein family, QSFR metrics display a rich variety of similarities and differences. In particular, backbone flexibility is well conserved across the family, whereas cooperativity correlation describing mechanical and thermodynamic couplings between the residue pairs exhibit distinctive features that readily standout. The diversity in predicted QSFR metrics that describe cooperativity correlation between pairs of residues is largely explained by a global flexibility order parameter describing the amount of intrinsic flexibility within the protein. A free energy landscape is calculated as a function of the flexibility order parameter, and key values are determined where the native-state, transition-state, and unfolded-state are located. Another key value identifies a mechanical transition where the global nature of the protein changes from flexible to rigid. The key values of the flexibility order parameter help characterize how mechanical and thermodynamic response is linked. Variation in QSFR metrics and key characteristics of global flexibility are related to the native state X-ray crystal structure primarily through the hydrogen bond network. Furthermore, comparison of three TRX redox pairs reveals differences in thermodynamic response (i.e., relative melting point) and mechanical properties (i.e., backbone flexibility and cooperativity correlation) that are consistent with experimental data on thermal stabilities

Thermodynamic and experimental studies of the CVD of A-15 superconductors. I

International Nuclear Information System (INIS)

Madar, R.; Weiss, F.; Fruchart, R.; Bernard, C.

1978-01-01

This paper deals with the experimental and thermodynamic study of the chemical vapor deposition (CVD) synthesis of Nb 3 Ga layers on various metallic and insulating substrates using the coreduction of mixed halides by hydrogen. Thermodynamic equilibrium in the seven-component system Nb-Ga-H-Cl-Si-O-Ar has been calculated using the method of minimization of the system Gibbs free energy as a function of the variables directly available in the CVD system. The chosen variables were the chloride ratio, the reduction and dilution parameters and the temperature of the deposition zone. The equilibrium compositions were calculated for the two composition limits of the A-15 phase: NbGasub(0.15) and Nb 3 Ga. They are presented in the form of CVD phase diagrams. A CVD reactor has been set up and more than one hundred measurements have been made in order to check the validity of the equilibrium calculations. The comparisons between equilibrium and experimental results show a good agreement and lead to a better understanding of the chemistry and thermodynamics of the system. (Auth.)

Experimental approaches to membrane thermodynamics

DEFF Research Database (Denmark)

Westh, Peter

2009-01-01

Thermodynamics describes a system on the macroscopic scale, yet it is becoming an important tool for the elucidation of many specific molecular aspects of membrane properties. In this note we discuss this application of thermodynamics, and give a number of examples on how thermodynamic measurements...... have contributed to the understanding of specific membrane phenomena. We mainly focus on non-specific interactions of bilayers and small molecules (water and solutes) in the surrounding solvent, and the changes in membrane properties they bring about. Differences between thermodynamic...

Black Holes and Thermodynamics

OpenAIRE

Wald, Robert M.

1997-01-01

We review the remarkable relationship between the laws of black hole mechanics and the ordinary laws of thermodynamics. It is emphasized that - in analogy with the laws of thermodynamics - the validity the laws of black hole mechanics does not appear to depend upon the details of the underlying dynamical theory (i.e., upon the particular field equations of general relativity). It also is emphasized that a number of unresolved issues arise in ``ordinary thermodynamics'' in the context of gener...

Kinetics and Thermodynamics of Membrane Protein Folding

Directory of Open Access Journals (Sweden)

Ernesto A. Roman

2014-03-01

Full Text Available Understanding protein folding has been one of the great challenges in biochemistry and molecular biophysics. Over the past 50 years, many thermodynamic and kinetic studies have been performed addressing the stability of globular proteins. In comparison, advances in the membrane protein folding field lag far behind. Although membrane proteins constitute about a third of the proteins encoded in known genomes, stability studies on membrane proteins have been impaired due to experimental limitations. Furthermore, no systematic experimental strategies are available for folding these biomolecules in vitro. Common denaturing agents such as chaotropes usually do not work on helical membrane proteins, and ionic detergents have been successful denaturants only in few cases. Refolding a membrane protein seems to be a craftsman work, which is relatively straightforward for transmembrane β-barrel proteins but challenging for α-helical membrane proteins. Additional complexities emerge in multidomain membrane proteins, data interpretation being one of the most critical. In this review, we will describe some recent efforts in understanding the folding mechanism of membrane proteins that have been reversibly refolded allowing both thermodynamic and kinetic analysis. This information will be discussed in the context of current paradigms in the protein folding field.

Thermodynamics and statistical physics. 2. rev. ed.

International Nuclear Information System (INIS)

Schnakenberg, J.

2002-01-01

This textbook covers tthe following topics: Thermodynamic systems and equilibrium, irreversible thermodynamics, thermodynamic potentials, stability, thermodynamic processes, ideal systems, real gases and phase transformations, magnetic systems and Landau model, low temperature thermodynamics, canonical ensembles, statistical theory, quantum statistics, fermions and bosons, kinetic theory, Bose-Einstein condensation, photon gas

EquilTheTA: Thermodynamic and transport properties of complex equilibrium plasmas

International Nuclear Information System (INIS)

Colonna, G.; D'Angola, A.

2012-01-01

EquilTheTA (EQUILibrium for plasma THErmodynamics and Transport Applications) is a web-based software which calculates chemical equilibrium product concentrations from any set of reactants and determines thermodynamic and transport properties for the product mixture in wide temperature and pressure ranges. The program calculates chemical equilibrium by using a hierarchical approach, thermodynamic properties and transport coefficients starting from recent and accurate databases of atomic and molecular energy levels and collision integrals. In the calculations, Debye length and cut-off are consistently updated and virial corrections (up to third order) can be considered. Transport coefficients are calculated by using high order approximations of the Chapman-Enskog method.

Thermodynamics of novel charged dilatonic BTZ black holes

Science.gov (United States)

Dehghani, M.

2017-10-01

In this paper, the three-dimensional Einstein-Maxwell theory in the presence of a dilatonic scalar field has been studied. It has been shown that the dilatonic potential must be considered as the linear combination of two Liouville-type potentials. Two new classes of charged dilatonic BTZ black holes, as the exact solutions to the coupled scalar, vector and tensor field equations, have been obtained and their properties have been studied. The conserved charge and mass of the new black holes have been calculated, making use of the Gauss's law and Abbott-Deser proposal, respectively. Through comparison of the thermodynamical extensive quantities (i.e. temperature and entropy) obtained from both, the geometrical and the thermodynamical methods, the validity of the first law of black hole thermodynamics has been confirmed for both of the new black holes we just obtained. A black hole thermal stability or phase transition analysis has been performed, making use of the canonical ensemble method. Regarding the black hole heat capacity, it has been found that for either of the new black hole solutions there are some specific ranges in such a way that the black holes with the horizon radius in these ranges are locally stable. The points of type one and type two phase transitions have been determined. The black holes, with the horizon radius equal to the transition points are unstable. They undergo type one or type two phase transitions to be stabilized.

Molecular thermodynamics of nonideal fluids

CERN Document Server

Lee, Lloyd L

2013-01-01

Molecular Thermodynamics of Nonideal Fluids serves as an introductory presentation for engineers to the concepts and principles behind and the advances in molecular thermodynamics of nonideal fluids. The book covers related topics such as the laws of thermodynamics; entropy; its ensembles; the different properties of the ideal gas; and the structure of liquids. Also covered in the book are topics such as integral equation theories; theories for polar fluids; solution thermodynamics; and molecular dynamics. The text is recommended for engineers who would like to be familiarized with the concept

Coherence and measurement in quantum thermodynamics.

Science.gov (United States)

Kammerlander, P; Anders, J

2016-02-26

Thermodynamics is a highly successful macroscopic theory widely used across the natural sciences and for the construction of everyday devices, from car engines to solar cells. With thermodynamics predating quantum theory, research now aims to uncover the thermodynamic laws that govern finite size systems which may in addition host quantum effects. Recent theoretical breakthroughs include the characterisation of the efficiency of quantum thermal engines, the extension of classical non-equilibrium fluctuation theorems to the quantum regime and a new thermodynamic resource theory has led to the discovery of a set of second laws for finite size systems. These results have substantially advanced our understanding of nanoscale thermodynamics, however putting a finger on what is genuinely quantum in quantum thermodynamics has remained a challenge. Here we identify information processing tasks, the so-called projections, that can only be formulated within the framework of quantum mechanics. We show that the physical realisation of such projections can come with a non-trivial thermodynamic work only for quantum states with coherences. This contrasts with information erasure, first investigated by Landauer, for which a thermodynamic work cost applies for classical and quantum erasure alike. Repercussions on quantum work fluctuation relations and thermodynamic single-shot approaches are also discussed.

Solvation thermodynamics

CERN Document Server

Ben-Naim, Arieh

1987-01-01

This book deals with a subject that has been studied since the beginning of physical chemistry. Despite the thousands of articles and scores of books devoted to solvation thermodynamics, I feel that some fundamen­ tal and well-established concepts underlying the traditional approach to this subject are not satisfactory and need revision. The main reason for this need is that solvation thermodynamics has traditionally been treated in the context of classical (macroscopic) ther­ modynamics alone. However, solvation is inherently a molecular pro­ cess, dependent upon local rather than macroscopic properties of the system. Therefore, the starting point should be based on statistical mechanical methods. For many years it has been believed that certain thermodynamic quantities, such as the standard free energy (or enthalpy or entropy) of solution, may be used as measures of the corresponding functions of solvation of a given solute in a given solvent. I first challenged this notion in a paper published in 1978 b...

Modern thermodynamics

CERN Document Server

Ben-Naim, Arieh

2017-01-01

This textbook introduces thermodynamics with a modern approach, starting from four fundamental physical facts (the atomic nature of matter, the indistinguishability of atoms and molecules of the same species, the uncertainty principle, and the existence of equilibrium states) and analyzing the behavior of complex systems with the tools of information theory, in particular with Shannon's measure of information (or SMI), which can be defined on any probability distribution. SMI is defined and its properties and time evolution are illustrated, and it is shown that the entropy is a particular type of SMI, i.e. the SMI related to the phase-space distribution for a macroscopic system at equilibrium. The connection to SMI allows the reader to understand what entropy is and why isolated systems follow the Second Law of Thermodynamics. The Second Llaw is also formulated for other systems, not thermally isolated and even open with respect to the transfer of particles. All the fundamental aspects of thermodynamics are d...

Comparison of real development levels of countries: Genesis and perspectives

Directory of Open Access Journals (Sweden)

Prekajac Zora

2007-01-01

Full Text Available Comparison of levels of development among countries is usually done by reducing values in national currencies with a common denominator, using the official exchange rate. Because of its unreality, the values calculated in this way do not illustrate real relations between compared countries. That brings about the launching of the UN International Comparison Project (latter Programme with two fold aims: developing a method for international comparison of real domestic product which could be applied to a number of very heterogeneous countries, and the comparison of growing number of very different countries. Until now six phases of comparisons are finished. Taking into consideration problems that appeared in the realization of the VI ICP phase as well as quality improvement proposals, a decision has been made to launch a new, global round for 2003-2006. Comparison will cover 150 countries (the widest coverage ever. This will give global character to the comparison, which was the end cause of the ICP.

Thermodynamically efficient solar concentrators

Science.gov (United States)

Winston, Roland

2012-10-01

Non-imaging Optics is the theory of thermodynamically efficient optics and as such depends more on thermodynamics than on optics. Hence in this paper a condition for the "best" design is proposed based on purely thermodynamic arguments, which we believe has profound consequences for design of thermal and even photovoltaic systems. This new way of looking at the problem of efficient concentration depends on probabilities, the ingredients of entropy and information theory while "optics" in the conventional sense recedes into the background.

Thermodynamics of quantum strings

CERN Document Server

Morgan, M J

1994-01-01

A statistical mechanical analysis of an ideal gas of non-relativistic quantum strings is presented, in which the thermodynamic properties of the string gas are calculated from a canonical partition function. This toy model enables students to gain insight into the thermodynamics of a simple 'quantum field' theory, and provides a useful pedagogical introduction to the more complicated relativistic string theories. A review is also given of the thermodynamics of the open bosonic string gas and the type I (open) superstring gas. (author)

Estimation model for evaporative emissions from gasoline vehicles based on thermodynamics.

Science.gov (United States)

Hata, Hiroo; Yamada, Hiroyuki; Kokuryo, Kazuo; Okada, Megumi; Funakubo, Chikage; Tonokura, Kenichi

2018-03-15

In this study, we conducted seven-day diurnal breathing loss (DBL) tests on gasoline vehicles. We propose a model based on the theory of thermodynamics that can represent the experimental results of the current and previous studies. The experiments were performed using 14 physical parameters to determine the dependence of total emissions on temperature, fuel tank fill, and fuel vapor pressure. In most cases, total emissions after an apparent breakthrough were proportional to the difference between minimum and maximum environmental temperatures during the day, fuel tank empty space, and fuel vapor pressure. Volatile organic compounds (VOCs) were measured using a Gas Chromatography Mass Spectrometer and Flame Ionization Detector (GC-MS/FID) to determine the Ozone Formation Potential (OFP) of after-breakthrough gas emitted to the atmosphere. Using the experimental results, we constructed a thermodynamic model for estimating the amount of evaporative emissions after a fully saturated canister breakthrough occurred, and a comparison between the thermodynamic model and previous models was made. Finally, the total annual evaporative emissions and OFP in Japan were determined and compared by each model. Copyright © 2017 Elsevier B.V. All rights reserved.

Electrochemical thermodynamic measurement system

Science.gov (United States)

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.

Thermodynamics in Loop Quantum Cosmology

International Nuclear Information System (INIS)

Li, L.F.; Zhu, J.Y.

2009-01-01

Loop quantum cosmology (LQC) is very powerful to deal with the behavior of early universe. Moreover, the effective loop quantum cosmology gives a successful description of the universe in the semiclassical region. We consider the apparent horizon of the Friedmann-Robertson-Walker universe as a thermodynamical system and investigate the thermodynamics of LQC in the semiclassical region. The effective density and effective pressure in the modified Friedmann equation from LQC not only determine the evolution of the universe in LQC scenario but also are actually found to be the thermodynamic quantities. This result comes from the energy definition in cosmology (the Misner-Sharp gravitational energy) and is consistent with thermodynamic laws. We prove that within the framework of loop quantum cosmology, the elementary equation of equilibrium thermodynamics is still valid.

German activities towards a thermodynamic reference data base

Energy Technology Data Exchange (ETDEWEB)

Herbert, H.J.; Hagemann, S. [Gesellschaft fuer Anlagen- und Reaktorsicherheit mbH (GRS), Braunschweig (Germany); Brendler, V. [Forschungszentrum Rossendorf, Institut fur Radiochemie, Dresden (Germany); Marquardt, Ch. [Forschungszentrum Karlsruhe, Institut fur Nukleare Entsorgung, Karlsruhe (Germany); Voigt, W. [Technische Univ. Bergakademie Freiberg, Freiberg (Germany); Wilhelm, S. [Colenco Power Engineering, Baden (Switzerland)

2006-07-01

Leading research centres in the field of radioactive waste disposal in Germany have decided to combine their efforts in order to achieve a common goal, the development of a comprehensive and consistent thermodynamic reference database. All the thermodynamic data needed for the modelling of geochemical near- and far field processes in the geological media for high level waste repositories presently under discussion in Germany (salt, clay, granite) shall be collected and qualified in a single database. The partners participating in the project are a group of experts, who are generating, collecting and evaluating thermodynamic data of all relevant radionuclides and matrix elements according to uniform previously established and internationally accepted criteria. Special attention will be given to complete documentation and traceability of all data entries in the database. Existing data from international databases such as those of NEA, NAGRA, YMP will be integrated. Ion interaction coefficients (SIT, Pitzer) needed for modelling in a high saline environment will be included also. (authors)

German activities towards a thermodynamic reference data base

International Nuclear Information System (INIS)

Herbert, H.J.; Hagemann, S.; Brendler, V.; Marquardt, Ch.; Voigt, W.; Wilhelm, S.

2006-01-01

Leading research centres in the field of radioactive waste disposal in Germany have decided to combine their efforts in order to achieve a common goal, the development of a comprehensive and consistent thermodynamic reference database. All the thermodynamic data needed for the modelling of geochemical near- and far field processes in the geological media for high level waste repositories presently under discussion in Germany (salt, clay, granite) shall be collected and qualified in a single database. The partners participating in the project are a group of experts, who are generating, collecting and evaluating thermodynamic data of all relevant radionuclides and matrix elements according to uniform previously established and internationally accepted criteria. Special attention will be given to complete documentation and traceability of all data entries in the database. Existing data from international databases such as those of NEA, NAGRA, YMP will be integrated. Ion interaction coefficients (SIT, Pitzer) needed for modelling in a high saline environment will be included also. (authors)

Choice of the thermodynamic variables

International Nuclear Information System (INIS)

Balian, R.

1985-09-01

Some basic ideas of thermodynamics and statistical mechanics, both at equilibrium and off equilibrium, are recalled. In particular, the selection of relevant variables which underlies any macroscopic description is discussed, together with the meaning of the various thermodynamic quantities, in order to set the thermodynamic approaches used in nuclear physics in a general prospect [fr

Development of a representational conceptual evaluation in the first law of thermodynamics

Science.gov (United States)

Sriyansyah, S. P.; Suhandi, A.

2016-08-01

As part of an ongoing research to investigate student consistency in understanding the first law of thermodynamics, a representational conceptual evaluation (RCET) has been developed to assess student conceptual understanding, representational consistency, and scientific consistency in the introductory physics course. Previous physics education research findings were used to develop the test. RCET items were 30 items which designed as an isomorphic multiple-choice test with three different representations concerning the concept of work, heat, first law of thermodynamics, and its application in the thermodynamic processes. Here, we present preliminary measures of the validity and reliability of the instrument, including the classical test statistics. This instrument can be used to measure the intended concept in the first law of thermodynamics and it will give the consistent results with the ability to differentiate well between high-achieving students and low-achieving students and also students at different level. As well as measuring the effectiveness of the learning process in the concept of the first law of thermodynamics.

Development of a representational conceptual evaluation in the first law of thermodynamics

International Nuclear Information System (INIS)

Sriyansyah, S P; Suhandi, A

2016-01-01

As part of an ongoing research to investigate student consistency in understanding the first law of thermodynamics, a representational conceptual evaluation (RCET) has been developed to assess student conceptual understanding, representational consistency, and scientific consistency in the introductory physics course. Previous physics education research findings were used to develop the test. RCET items were 30 items which designed as an isomorphic multiple-choice test with three different representations concerning the concept of work, heat, first law of thermodynamics, and its application in the thermodynamic processes. Here, we present preliminary measures of the validity and reliability of the instrument, including the classical test statistics. This instrument can be used to measure the intended concept in the first law of thermodynamics and it will give the consistent results with the ability to differentiate well between high-achieving students and low-achieving students and also students at different level. As well as measuring the effectiveness of the learning process in the concept of the first law of thermodynamics. (paper)

Thermodynamics in Einstein's thought

International Nuclear Information System (INIS)

Klein, M.J.

1983-01-01

The role of the thermodynamical approach in the Einstein's scientific work is analyzed. The Einstein's development of a notion about statistical fluctuations of thermodynamical systems that leads him to discovery of corpuscular-wave dualism is retraced

The OpenCalphad thermodynamic software interface

Science.gov (United States)

Sundman, Bo; Kattner, Ursula R; Sigli, Christophe; Stratmann, Matthias; Le Tellier, Romain; Palumbo, Mauro; Fries, Suzana G

2017-01-01

Thermodynamic data are needed for all kinds of simulations of materials processes. Thermodynamics determines the set of stable phases and also provides chemical potentials, compositions and driving forces for nucleation of new phases and phase transformations. Software to simulate materials properties needs accurate and consistent thermodynamic data to predict metastable states that occur during phase transformations. Due to long calculation times thermodynamic data are frequently pre-calculated into “lookup tables” to speed up calculations. This creates additional uncertainties as data must be interpolated or extrapolated and conditions may differ from those assumed for creating the lookup table. Speed and accuracy requires that thermodynamic software is fully parallelized and the Open-Calphad (OC) software is the first thermodynamic software supporting this feature. This paper gives a brief introduction to computational thermodynamics and introduces the basic features of the OC software and presents four different application examples to demonstrate its versatility. PMID:28260838

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

Science.gov (United States)

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.

Dynamics of contact line depinning during droplet evaporation based on thermodynamics.

Science.gov (United States)

Yu, Dong In; Kwak, Ho Jae; Doh, Seung Woo; Ahn, Ho Seon; Park, Hyun Sun; Kiyofumi, Moriyama; Kim, Moo Hwan

2015-02-17

For several decades, evaporation phenomena have been intensively investigated for a broad range of applications. However, the dynamics of contact line depinning during droplet evaporation has only been inductively inferred on the basis of experimental data and remains unclear. This study focuses on the dynamics of contact line depinning during droplet evaporation based on thermodynamics. Considering the decrease in the Gibbs free energy of a system with different evaporation modes, a theoretical model was developed to estimate the receding contact angle during contact line depinning as a function of surface conditions. Comparison of experimentally measured and theoretically modeled receding contact angles indicated that the dynamics of contact line depinning during droplet evaporation was caused by the most favorable thermodynamic process encountered during constant contact radius (CCR mode) and constant contact angle (CCA mode) evaporation to rapidly reach an equilibrium state during droplet evaporation.

Black hole chemistry: thermodynamics with Lambda

International Nuclear Information System (INIS)

Kubizňák, David; Mann, Robert B; Teo, Mae

2017-01-01

We review recent developments on the thermodynamics of black holes in extended phase space, where the cosmological constant is interpreted as thermodynamic pressure and treated as a thermodynamic variable in its own right. In this approach, the mass of the black hole is no longer regarded as internal energy, rather it is identified with the chemical enthalpy. This leads to an extended dictionary for black hole thermodynamic quantities; in particular a notion of thermodynamic volume emerges for a given black hole spacetime. This volume is conjectured to satisfy the reverse isoperimetric inequality—an inequality imposing a bound on the amount of entropy black hole can carry for a fixed thermodynamic volume. New thermodynamic phase transitions naturally emerge from these identifications. Namely, we show that black holes can be understood from the viewpoint of chemistry, in terms of concepts such as Van der Waals fluids, reentrant phase transitions, and triple points. We also review the recent attempts at extending the AdS/CFT dictionary in this setting, discuss the connections with horizon thermodynamics, applications to Lifshitz spacetimes, and outline possible future directions in this field. (topical review)

Thermodynamic approach to improving solubility prediction of co-crystals in comparison with individual poorly soluble components

International Nuclear Information System (INIS)

Perlovich, German L.

2014-01-01

Highlights: • Thermodynamic approach for solubility improvement of co-crystal was developed. • The graphical technique for estimation of co-crystal solubility was elaborated. • Hydration enthalpies of some drugs and amino acids were calculated. • Applicability/operability of the approach was exemplified by some drugs and amino acids. - Abstract: A novel thermodynamic approach to compare poorly soluble components (active pharmaceutical ingredient (API)) both in co-crystals and individual compounds was developed. An algorithm of choosing potential co-crystals with improved solubility characteristics on the basis of the known solvation/hydration API and co-former enthalpies is described. The applicability and operability of the algorithm were tested exemplified by some drugs and amino acids

Thermodynamics of Accelerating Black Holes.

Science.gov (United States)

Appels, Michael; Gregory, Ruth; Kubizňák, David

2016-09-23

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

Thermodynamics of complexity

DEFF Research Database (Denmark)

Westerhoff, Hans V.; Jensen, Peter Ruhdal; Snoep, Jacky L.

1998-01-01

-called emergent properties. Tendency towards increased entropy is an essential determinant for the behaviour of ideal gas mixtures, showing that even in the simplest physical/chemical systems, (dys)organisation of components is crucial for the behaviour of systems. This presentation aims at illustrating...... that the behaviour of two functionally interacting biological components (molecules, protein domains, pathways, organelles) differs from the behaviour these components would exhibit in isolation from one another, where the difference should be essential for the maintenance and growth of the living state, For a true...... understanding of this BioComplexity, modem thermodynamic concepts and methods (nonequilibrium thermodynamics, metabolic and hierarchical control analysis) will be needed. We shall propose to redefine nonequilibrium thermodynamics as: The science that aims at understanding the behaviour of nonequilibrium systems...

Thermodynamics Far from the Thermodynamic Limit.

Science.gov (United States)

de Miguel, Rodrigo; Rubí, J Miguel

2017-11-16

Understanding how small systems exchange energy with a heat bath is important to describe how their unique properties can be affected by the environment. In this contribution, we apply Landsberg's theory of temperature-dependent energy levels to describe the progressive thermalization of small systems as their spectrum is perturbed by a heat bath. We propose a mechanism whereby the small system undergoes a discrete series of excitations and isentropic spectrum adjustments leading to a final state of thermal equilibrium. This produces standard thermodynamic results without invoking system size. The thermal relaxation of a single harmonic oscillator is analyzed as a model example of a system with a quantized spectrum than can be embedded in a thermal environment. A description of how the thermal environment affects the spectrum of a small system can be the first step in using environmental factors, such as temperature, as parameters in the design and operation of nanosystem properties.

Generalization of Gibbs Entropy and Thermodynamic Relation

OpenAIRE

Park, Jun Chul

2010-01-01

In this paper, we extend Gibbs's approach of quasi-equilibrium thermodynamic processes, and calculate the microscopic expression of entropy for general non-equilibrium thermodynamic processes. Also, we analyze the formal structure of thermodynamic relation in non-equilibrium thermodynamic processes.

Applying the Coupled-Cluster Ansatz to Solids and Surfaces in the Thermodynamic Limit

Science.gov (United States)

Gruber, Thomas; Liao, Ke; Tsatsoulis, Theodoros; Hummel, Felix; Grüneis, Andreas

2018-04-01

Modern electronic structure theories can predict and simulate a wealth of phenomena in surface science and solid-state physics. In order to allow for a direct comparison with experiment, such ab initio predictions have to be made in the thermodynamic limit, substantially increasing the computational cost of many-electron wave-function theories. Here, we present a method that achieves thermodynamic limit results for solids and surfaces using the "gold standard" coupled cluster ansatz of quantum chemistry with unprecedented efficiency. We study the energy difference between carbon diamond and graphite crystals, adsorption energies of water on h -BN, as well as the cohesive energy of the Ne solid, demonstrating the increased efficiency and accuracy of coupled cluster theory for solids and surfaces.

Perform Thermodynamics Measurements on Fuel Cycle Case Study Systems

Energy Technology Data Exchange (ETDEWEB)

Martin, Leigh R. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

2014-09-01

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 extraction 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.

Entropy and black-hole thermodynamics

International Nuclear Information System (INIS)

Wald, R.M.

1979-01-01

The concept of entropy is examined with an eye toward gaining insight into the nature of black-hole thermodynamics. Definitions of entropy are given for ordinary classical and quantum-mechanical systems which lead to plausibility arguments for the ordinary laws of thermodynamics. The treatment of entropy for a classical system is in the spirit of the information-theory viewpoint, but by explicitly incorporating the coarse-grained observable into the definition of entropy, we eliminate any nonobjective features. The definition of entropy for a quantum-mechanical system is new, but directly parallels the classical treatment. We then apply these ideas to a self-gravitating quantum system which contains a black hole. Under some assumptions: which, although nontrivial, are by no means exotic: about the nature of such a system, it is seen that the same plausibility arguments which lead to the ordinary laws of thermodynamics for ordinary systems now lead to the laws of black-hole mechanics, including the generalized second law of thermodynamics. Thus, it appears perfectly plausible that black-hole thermodynamics is nothing more than ordinary thermodynamics applied to a self-gravitating quantum system

An N+3 Technology Level Reference Propulsion System

Science.gov (United States)

Jones, Scott M.; Haller, William J.; Tong, Michael To-Hing

2017-01-01

An N+3 technology level engine, suitable as a propulsion system for an advanced single-aisle transport, was developed as a reference cycle for use in technology assessment and decision-making efforts. This reference engine serves three main purposes: it provides thermodynamic quantities at each major engine station, it provides overall propulsion system performance data for vehicle designers to use in their analyses, and it can be used for comparison against other proposed N+3 technology-level propulsion systems on an equal basis. This reference cycle is meant to represent the expected capability of gas turbine engines in the N+3 timeframe given reasonable extrapolations of technology improvements and the ability to take full advantage of those improvements.

Thermodynamic properties of cryogenic fluids

CERN Document Server

Leachman, Jacob; Lemmon, Eric; Penoncello, Steven

2017-01-01

This update to a classic reference text provides practising engineers and scientists with accurate thermophysical property data for cryogenic fluids. The equations for fifteen important cryogenic fluids are presented in a basic format, accompanied by pressure-enthalpy and temperature-entropy charts and tables of thermodynamic properties. It begins with a chapter introducing the thermodynamic relations and functional forms for equations of state, and goes on to describe the requirements for thermodynamic property formulations, needed for the complete definition of the thermodynamic properties of a fluid. The core of the book comprises extensive data tables and charts for the most commonly-encountered cryogenic fluids. This new edition sees significant updates to the data presented for air, argon, carbon monoxide, deuterium, ethane, helium, hydrogen, krypton, nitrogen and xenon. The book supports and complements NIST’s REFPROP - an interactive database and tool for the calculation of thermodynamic propertie...

Comparison between regenerative organic Rankine cycle (RORC) and basic organic Rankine cycle (BORC) based on thermoeconomic multi-objective optimization considering exergy efficiency and levelized energy cost (LEC)

International Nuclear Information System (INIS)

Feng, Yongqiang; Zhang, Yaning; Li, Bingxi; Yang, Jinfu; Shi, Yang

2015-01-01

Highlights: • The thermoeconomic comparison of regenerative RORC and BORC is investigated. • The Pareto frontier solution with bi-objective compares with the corresponding single-objective solutions. • The three-objective optimization of the RORC and BORC is studied. • The RORC owns 8.1% higher exergy efficiency and 21.1% more LEC than the BORC under the Pareto-optimal solution. - Abstract: Based on the thermoeconomic multi-objective optimization by using non-dominated sorting genetic algorithm (NSGA-II), considering both thermodynamic performance and economic factors, the thermoeconomic comparison of regenerative organic Rankine cycles (RORC) and basic organic Rankine cycles (BORC) are investigated. The effects of five key parameters including evaporator outlet temperature, condenser temperature, degree of superheat, pinch point temperature difference and degree of supercooling on the exergy efficiency and levelized energy cost (LEC) are examined. Meanwhile, the Pareto frontier solution with bi-objective for maximizing exergy efficiency and minimizing LEC is obtained and compared with the corresponding single-objective solutions. Research demonstrates that there is a significant negative correlation between thermodynamic performance and economic factors. And the optimum exergy efficiency and LEC for the Pareto-optimal solution of the RORC are 55.97% and 0.142 $/kW h, respectively, which are 8.1% higher exergy efficiency and 21.1% more LEC than that of the BORC under considered condition. Highest exergy and thermal efficiencies are accompanied with lowest net power output and worst economic performance. Furthermore, taking the net power output into account, detailed investigation on the three-objective optimization for maximizing exergy efficiency, maximizing net power output and minimizing LEC is discussed

Thermodynamics and statistical mechanics. [thermodynamic properties of gases

Science.gov (United States)

1976-01-01

The basic thermodynamic properties of gases are reviewed and the relations between them are derived from the first and second laws. The elements of statistical mechanics are then formulated and the partition function is derived. The classical form of the partition function is used to obtain the Maxwell-Boltzmann distribution of kinetic energies in the gas phase and the equipartition of energy theorem is given in its most general form. The thermodynamic properties are all derived as functions of the partition function. Quantum statistics are reviewed briefly and the differences between the Boltzmann distribution function for classical particles and the Fermi-Dirac and Bose-Einstein distributions for quantum particles are discussed.

Thermodynamic assessment of EuBr2 unary and LiBr-EuBr2 and NaBr-EuBr2 binary systems

International Nuclear Information System (INIS)

Gong, Weiping; Gaune-Escard, Marcelle

2009-01-01

As a basis for the design and development of molten salt mixtures, thermodynamic calculations of the phase diagrams and thermodynamic properties were carried out on the EuBr 2 unary and LiBr-EuBr 2 and NaBr-EuBr 2 binary systems over a wide temperature and composition range, respectively. The Gibbs energy of EuBr 2 was evaluated using an independent polynomial to fit the experimental heat capacity, the thermodynamic parameters for each phase in the LiBr-EuBr 2 and NaBr-EuBr 2 systems were optimized by using available experimental information on phase diagrams. A regular substitutional solution model for the liquid phase and Neumann-Kopp rule for the stoichiometric compound LiEu 2 Br 5 were adopted to reproduce the experimental data with reasonable excess Gibbs energy. Comparisons between the calculated phase diagrams and thermodynamic quantities show that all reliable experimental information is satisfactorily accounted for by the present thermodynamic description. Some thermodynamic properties were predicted to check the suitability of the present calculation.

Theoretical physics 5 thermodynamics

CERN Document Server

Nolting, Wolfgang

2017-01-01

This concise textbook offers a clear and comprehensive introduction to thermodynamics, one of the core components of undergraduate physics courses. It follows on naturally from the previous volumes in this series, defining macroscopic variables, such as internal energy, entropy and pressure,together with thermodynamic principles. The first part of the book introduces the laws of thermodynamics and thermodynamic potentials. More complex themes are covered in the second part of the book, which describes phases and phase transitions in depth. Ideally suited to undergraduate students with some grounding in classical mechanics, the book is enhanced throughout with learning features such as boxed inserts and chapter summaries, with key mathematical derivations highlighted to aid understanding. The text is supported by numerous worked examples and end of chapter problem sets. About the Theoretical Physics series Translated from the renowned and highly successful German editions, the eight volumes of this series cove...

A numerical simulation of thermodynamic processes for cryogenic metal forming of aluminum sheets and comparison with experimental results

International Nuclear Information System (INIS)

Reichl, Ch.; Schneider, R.; Hohenauer, W.; Grabner, F.; Grant, R.J.

2017-01-01

Highlights: • Thermodynamic processes for cryogenic sheet metal forming tools were examined. • Static and transient temperature field simulations are evaluated on a Nakajima tool. • Differently arranged cooling loops lead to homogeneous temperature distribution. • Scaling of the geometry leads to significantly increased heat transfer times. • The temperature management of complex forming tools can be developed numerically. - Abstract: Forming at cryogenic temperatures provides a significant improvement in formability of aluminum sheets. This offers the potential for light, complex and highly integrated one-piece components to be produced out of aluminum alloys at sub-zero temperatures. This would allow weight reduction, environmental conservation and cost reduction of a car body to give one example in the automotive industry. For temperature supported processes special forming tools and cooling strategies are required to be able to reach and maintain process stability. Time dependent numerical simulations of the thermodynamic processes of cryogenic sheet metal forming covering all aspects of heat transfer through conduction, convection and radiation play a vital role in the design and development of future tools and are presented for several geometries. Cooling (and heating) strategies (including selection of the number of cooling loops and their relative positioning) in a Nakajima testing tool were evaluated using computational fluid dynamics. These simulations were performed with static and transient solvers to demonstrate the extraction of tool surface temperature distributions on different forming tool geometries. Comparisons of predicted temperature characteristics of an aluminum sheet and experimentally determined temperature distributions were made. The temperature distribution of the surface of an aluminum sheet could be predicted with high accuracy. Further, the influence of the tool size on the parameters temperature transfer times and

Thermodynamic optimization of the Cu-Nd system

International Nuclear Information System (INIS)

Wang Peisheng; Zhou Liangcai; Du Yong; Xu Honghui; Liu Shuhong; Chen Li; Ouyang Yifang

2011-01-01

Research highlights: → The enthalpies of formation of the compounds Cu 6 Nd, Cu 5 Nd, Cu 2 Nd and αCuNd were calculated using DFT. → The thermodynamic constraints to eliminate the artificial phase relations were imposed during the thermodynamic optimization procedure. → The Cu-Nd system was optimized under the thermodynamic constraints. - Abstract: The thermodynamic constraints to eliminate artificial phase relations were introduced with the Cu-Nd system as an example. The enthalpies of formation of the compounds Cu 6 Nd, Cu 5 Nd, Cu 2 Nd and αCuNd are calculated using density functional theory. Taking into account all the experimental data and the first-principles calculated enthalpies of formation of these compounds, the thermodynamic optimization of the Cu-Nd system was performed under the proposed thermodynamic constraints. It is demonstrated that the thermodynamic constraints are critical to obtain a set of thermodynamic parameters for the Cu-Nd system, which can avoid the appearance of all the artificial phase relations.

Possible extended forms of thermodynamic entropy

International Nuclear Information System (INIS)

Sasa, Shin-ichi

2014-01-01

Thermodynamic entropy is determined by a heat measurement through the Clausius equality. The entropy then formalizes a fundamental limitation of operations by the second law of thermodynamics. The entropy is also expressed as the Shannon entropy of the microscopic degrees of freedom. Whenever an extension of thermodynamic entropy is attempted, we must pay special attention to how its three different aspects just mentioned are altered. In this paper, we discuss possible extensions of the thermodynamic entropy. (paper)

Thermodynamics of statistical inference by cells.

Science.gov (United States)

Lang, Alex H; Fisher, Charles K; Mora, Thierry; Mehta, Pankaj

2014-10-03

The deep connection between thermodynamics, computation, and information is now well established both theoretically and experimentally. Here, we extend these ideas to show that thermodynamics also places fundamental constraints on statistical estimation and learning. To do so, we investigate the constraints placed by (nonequilibrium) thermodynamics on the ability of biochemical signaling networks to estimate the concentration of an external signal. We show that accuracy is limited by energy consumption, suggesting that there are fundamental thermodynamic constraints on statistical inference.

Microbial diversity arising from thermodynamic constraints

Science.gov (United States)

Großkopf, Tobias; Soyer, Orkun S

2016-01-01

The microbial world displays an immense taxonomic diversity. This diversity is manifested also in a multitude of metabolic pathways that can utilise different substrates and produce different products. Here, we propose that these observations directly link to thermodynamic constraints that inherently arise from the metabolic basis of microbial growth. We show that thermodynamic constraints can enable coexistence of microbes that utilise the same substrate but produce different end products. We find that this thermodynamics-driven emergence of diversity is most relevant for metabolic conversions with low free energy as seen for example under anaerobic conditions, where population dynamics is governed by thermodynamic effects rather than kinetic factors such as substrate uptake rates. These findings provide a general understanding of the microbial diversity based on the first principles of thermodynamics. As such they provide a thermodynamics-based framework for explaining the observed microbial diversity in different natural and synthetic environments. PMID:27035705

Microbial diversity arising from thermodynamic constraints.

Science.gov (United States)

Großkopf, Tobias; Soyer, Orkun S

2016-11-01

The microbial world displays an immense taxonomic diversity. This diversity is manifested also in a multitude of metabolic pathways that can utilise different substrates and produce different products. Here, we propose that these observations directly link to thermodynamic constraints that inherently arise from the metabolic basis of microbial growth. We show that thermodynamic constraints can enable coexistence of microbes that utilise the same substrate but produce different end products. We find that this thermodynamics-driven emergence of diversity is most relevant for metabolic conversions with low free energy as seen for example under anaerobic conditions, where population dynamics is governed by thermodynamic effects rather than kinetic factors such as substrate uptake rates. These findings provide a general understanding of the microbial diversity based on the first principles of thermodynamics. As such they provide a thermodynamics-based framework for explaining the observed microbial diversity in different natural and synthetic environments.

Thermodynamics for Chemists, Physicists and Engineers

CERN Document Server

Hołyst, Robert

2012-01-01

Thermodynamics is an essential part of chemical physics and is of fundamental importance in physics, chemistry and engineering courses. This textbook takes an interdisciplinary approach to the subject and is therefore suitable for undergraduates in all those courses. The book is an introduction to phenomenological thermodynamics and its applications to phase transitions and chemical reactions, with some references to statistical mechanics. It strikes the balance between the rigorousness of the Callen text and phenomenological approach of the Atkins text. The book is divided in three parts. The first introduces the postulates and laws of thermodynamics and complements these initial explanations with practical examples. The second part is devoted to applications of thermodynamics to phase transitions in pure substances and mixtures. The third part covers thermodynamic systems in which chemical reactions take place. There are some sections on more advanced topics such as thermodynamic potentials, natural variabl...

Thermodynamic study of selected monoterpenes III

International Nuclear Information System (INIS)

Štejfa, Vojtěch; Fulem, Michal; Růžička, Květoslav; Červinka, Ctirad

2014-01-01

Highlights: • (−)-trans-Pinane, (+)-Δ-carene, eucalyptol, and limonene were studied. • New thermodynamic data were measured and calculated. • Many of thermodynamic data are reported for the first time. - Abstract: A thermodynamic study of selected monoterpenes, (−)-trans-pinane, (+)-Δ-carene, eucalyptol, (+)-limonene, and (−)-limonene, is presented in this work. The vapor pressure measurements were performed using the static method over the environmentally important temperature range (238 to 308) K. Liquid heat capacities were measured by Tian–Calvet calorimetry in the temperature interval (258 to 355) K. The phase behavior was investigated by differential scanning calorimetry (DSC) from T = 183 K. The thermodynamic properties in the ideal-gas state were calculated by combining statistical thermodynamic and density functional theory (DFT) calculations. Calculated ideal-gas heat capacities and experimental data for vapor pressures and condensed phase heat capacities were treated simultaneously to obtain a consistent thermodynamic description

On thermodynamic and microscopic reversibility

International Nuclear Information System (INIS)

Crooks, Gavin E

2011-01-01

The word 'reversible' has two (apparently) distinct applications in statistical thermodynamics. A thermodynamically reversible process indicates an experimental protocol for which the entropy change is zero, whereas the principle of microscopic reversibility asserts that the probability of any trajectory of a system through phase space equals that of the time reversed trajectory. However, these two terms are actually synonymous: a thermodynamically reversible process is microscopically reversible, and vice versa

Thermodynamics of an accelerated expanding universe

International Nuclear Information System (INIS)

Wang Bin; Gong Yungui; Abdalla, Elcio

2006-01-01

We investigate the laws of thermodynamics in an accelerating universe driven by dark energy with a time-dependent equation of state. In the case we consider that the physically relevant part of the Universe is that enveloped by the dynamical apparent horizon, we have shown that both the first law and second law of thermodynamics are satisfied. On the other hand, if the boundary of the Universe is considered to be the cosmological event horizon the thermodynamical description based on the definitions of boundary entropy and temperature breaks down. No parameter redefinition can rescue the thermodynamics laws from such a fate, rendering the cosmological event horizon unphysical from the point of view of the laws of thermodynamics

Application of Statistical Thermodynamics in Refrigeration

International Nuclear Information System (INIS)

Avsec, J.; Marcic, M.

1999-01-01

The paper presents the mathematical model for computing the thermodynamical properties in the liquid, gas and two-phase domain by means of statistical thermodynamics. The paper features all important components (translation, rotation, internal rotation, vibration, intermolecular potential energy and influence of electron and nuclei excitation). To calculate the thermodynamic properties of real gases, we have developed the cluster theory, which yields better results than the virial equation. In case of real liquids, the Johnson-Zollweg-Gubbins model based on the modified Benedict-Webb-Rubin (BWR) equation was applied. The Lennard-Jones intermolecular potential was used. The analytical results are compared with the thermodynamical data and models obtained from classical thermodynamics, and they show relatively good agreement. (author)

Thermodynamic study of selected monoterpenes II

International Nuclear Information System (INIS)

Štejfa, Vojtěch; Fulem, Michal; Růžička, Květoslav; Červinka, Ctirad

2014-01-01

Highlights: • (−)-Borneol, (−)-camphor, (±)-camphene, and (+)-fenchone were studied. • New thermodynamic data were measured and calculated. • Most of thermodynamic data are reported for the first time. - Abstract: A thermodynamic study of selected monoterpenes, (−)-borneol, (−)-camphor, (±)-camphene, and (+)-fenchone is presented in this work. The vapor pressure measurements were performed using the static method over the environmentally important temperature range from (238 to 308) K. Heat capacities of condensed phases were measured by Tian–Calvet calorimetry in the temperature interval from (258 to 355) K. The phase behavior was investigated by differential scanning calorimetry (DSC) from subambient temperatures up to the fusion temperatures. The thermodynamic properties in the ideal-gas state were calculated by combining statistical thermodynamic and density functional theory (DFT) calculations. Calculated ideal-gas heat capacities and experimental data for vapor pressures and condensed phase heat capacities were treated simultaneously to obtain a consistent thermodynamic description

Local thermodynamics and the generalized Gibbs-Duhem equation in systems with long-range interactions.

Science.gov (United States)

Latella, Ivan; Pérez-Madrid, Agustín

2013-10-01

The local thermodynamics of a system with long-range interactions in d dimensions is studied using the mean-field approximation. Long-range interactions are introduced through pair interaction potentials that decay as a power law in the interparticle distance. We compute the local entropy, Helmholtz free energy, and grand potential per particle in the microcanonical, canonical, and grand canonical ensembles, respectively. From the local entropy per particle we obtain the local equation of state of the system by using the condition of local thermodynamic equilibrium. This local equation of state has the form of the ideal gas equation of state, but with the density depending on the potential characterizing long-range interactions. By volume integration of the relation between the different thermodynamic potentials at the local level, we find the corresponding equation satisfied by the potentials at the global level. It is shown that the potential energy enters as a thermodynamic variable that modifies the global thermodynamic potentials. As a result, we find a generalized Gibbs-Duhem equation that relates the potential energy to the temperature, pressure, and chemical potential. For the marginal case where the power of the decaying interaction potential is equal to the dimension of the space, the usual Gibbs-Duhem equation is recovered. As examples of the application of this equation, we consider spatially uniform interaction potentials and the self-gravitating gas. We also point out a close relationship with the thermodynamics of small systems.

The thermodynamics of protein folding: a critique of widely used quasi-thermodynamic interpretations and a restatement based on the Gibbs-Duhem relation and consistent with the Phase Rule.

Science.gov (United States)

Pethica, Brian A

2010-07-21

Interpretations of data in the extensive literature on the unfolding of proteins in aqueous solution follow a variety of methods involving assumptions leading to estimates of thermodynamic quantities associated with the unfolding transition. Inconsistencies and thermodynamic errors in these methods are identified. Estimates of standard molar free energies and enthalpies of unfolding using incompletely defined equilibrium constants and the van't Hoff relation are unsound, and typically contradict model-free interpretation of the data. A widely used routine for estimating the change in heat capacity associated with unfolding based on changes in the unfolding temperature and enthalpy co-induced by addition of denaturant or protective additives is thermodynamically incorrect by neglect of the Phase Rule. Many models and simulations predicting thermodynamic measures of unfolding are presently making comparisons with insecure quantities derived by incorrect thermodynamic analyses of experimental data. Analysis of unfolding via the Gibbs-Duhem equation with the correct Phase Rule constraints avoids the assumptions associated with incomplete equilibrium constants and misuse of the van't Hoff relation, and applies equally to positive, negative, sitewise or diffuse solute binding to the protein. The method gives the necessary relations between the thermodynamic parameters for thermal and isothermal unfolding and is developed for the case of two-state unfolding. The differences in binding of denaturants or stabilizers to the folded and unfolded forms of the protein are identified as major determinants of the unfolding process. The Phase Rule requires the temperature and enthalpy of unfolding to depend generally on the protein concentration. The available evidence bears out this expectation for thermal unfolding, indicating that protein-protein interactions influence folding. A parallel dependence of the denaturant concentrations for isothermal unfolding on the protein

Thermodynamic description of the Al-Cu-Mg-Mn-Si quinary system and its application to solidification simulation

International Nuclear Information System (INIS)

Chang, Keke; Liu, Shuhong; Zhao, Dongdong; Du, Yong; Zhou, Liangcai; Chen, Li

2011-01-01

By means of the first-principles calculations, the enthalpy of formation for the quaternary phase in the Al-Cu-Mg-Si system was computed. A set of self-consistent thermodynamic parameters for the Al-Cu-Mg-Si and Al-Cu-Mn-Si systems was then obtained using CALPHAD approach taking into account the reliable experimental data and the first-principles calculations. The thermodynamic database for the Al-Cu-Mg-Mn-Si system was developed based on the constituent binary, ternary, and quaternary systems. Comprehensive comparisons between the calculated and measured phase diagrams and invariant reactions showed that the experimental information was satisfactorily accounted for by the present thermodynamic description. The obtained database was used to describe the solidification behavior of Al alloys B319.1 (90.2Al-6Si-3.5Cu-0.3Mg, in wt.%) and B319.1 + xMn (x = 0.5-2, in wt.%) under Gulliver-Scheil non-equilibrium condition. The reliability of the present thermodynamic database was also verified by the good agreement between calculation and experiment for Gulliver-Scheil non-equilibrium solidification.

Thermodynamically consistent model calibration in chemical kinetics

Directory of Open Access Journals (Sweden)

Goutsias John

2011-05-01

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

Level comparison theorems and supersymmetric quantum mechanics

International Nuclear Information System (INIS)

Baumgartner, B.; Grosse, H.

1986-01-01

The sign of the Laplacian of the spherical symmetric potential determines the order of energy levels with the same principal Coulomb quantum number. This recently derived theorem has been generalized, extended and applied to various situations in particle, nuclear and atomic physics. Besides a comparison theorem the essential step was the use of supersymmetric quantum mechanics. Recently worked out applications of supersymmetric quantum mechanics to index problems of Dirac operators are mentioned. (Author)

Geometric description of BTZ black hole thermodynamics

International Nuclear Information System (INIS)

Quevedo, Hernando; Sanchez, Alberto

2009-01-01

We study the properties of the space of thermodynamic equilibrium states of the Banados-Teitelboim-Zanelli (BTZ) black hole in (2+1) gravity. We use the formalism of geometrothermodynamics to introduce in the space of equilibrium states a two-dimensional thermodynamic metric whose curvature is nonvanishing, indicating the presence of thermodynamic interaction, and free of singularities, indicating the absence of phase transitions. Similar results are obtained for generalizations of the BTZ black hole which include a Chern-Simons term and a dilatonic field. Small logarithmic corrections of the entropy turn out to be represented by small corrections of the thermodynamic curvature, reinforcing the idea that thermodynamic curvature is a measure of thermodynamic interaction.

Braun-Le Chatelier principle in dissipative thermodynamics

OpenAIRE

Pavelka, Michal; Grmela, Miroslav

2016-01-01

Braun-Le Chatelier principle is a fundamental result of equilibrium thermodynamics, showing how stable equilibrium states shift when external conditions are varied. The principle follows from convexity of thermodynamic potential. Analogously, from convexity of dissipation potential it follows how steady non-equilibrium states shift when thermodynamic forces are varied, which is the extension of the principle to dissipative thermodynamics.

Thermodynamic approach to biomass gasification

International Nuclear Information System (INIS)

Boissonnet, G.; Seiler, J.M.

2003-01-01

The document presents an approach of biomass transformation in presence of steam, hydrogen or oxygen. Calculation results based on thermodynamic equilibrium are discussed. The objective of gasification techniques is to increase the gas content in CO and H 2 . The maximum content in these gases is obtained when thermodynamic equilibrium is approached. Any optimisation action of a process. will, thus, tend to approach thermodynamic equilibrium conditions. On the other hand, such calculations can be used to determine the conditions which lead to an increase in the production of CO and H 2 . An objective is also to determine transformation enthalpies that are an important input for process calculations. Various existing processes are assessed, and associated thermodynamic limitations are evidenced. (author)

Gravitation, Thermodynamics, and Quantum Theory

OpenAIRE

Wald, Robert M.

1999-01-01

During the past 30 years, research in general relativity has brought to light strong hints of a very deep and fundamental relationship between gravitation, thermodynamics, and quantum theory. The most striking indication of such a relationship comes from black hole thermodynamics, where it appears that certain laws of black hole mechanics are, in fact, simply the ordinary laws of thermodynamics applied to a system containing a black hole. This article will review the present status of black h...

Thermodynamic Studies for Drug Design and Screening

Science.gov (United States)

Garbett, Nichola C.; Chaires, Jonathan B.

2012-01-01

Introduction A key part of drug design and development is the optimization of molecular interactions between an engineered drug candidate and its binding target. Thermodynamic characterization provides information about the balance of energetic forces driving binding interactions and is essential for understanding and optimizing molecular interactions. Areas covered This review discusses the information that can be obtained from thermodynamic measurements and how this can be applied to the drug development process. Current approaches for the measurement and optimization of thermodynamic parameters are presented, specifically higher throughput and calorimetric methods. Relevant literature for this review was identified in part by bibliographic searches for the period 2004 – 2011 using the Science Citation Index and PUBMED and the keywords listed below. Expert opinion The most effective drug design and development platform comes from an integrated process utilizing all available information from structural, thermodynamic and biological studies. Continuing evolution in our understanding of the energetic basis of molecular interactions and advances in thermodynamic methods for widespread application are essential to realize the goal of thermodynamically-driven drug design. Comprehensive thermodynamic evaluation is vital early in the drug development process to speed drug development towards an optimal energetic interaction profile while retaining good pharmacological properties. Practical thermodynamic approaches, such as enthalpic optimization, thermodynamic optimization plots and the enthalpic efficiency index, have now matured to provide proven utility in design process. Improved throughput in calorimetric methods remains essential for even greater integration of thermodynamics into drug design. PMID:22458502

Thermodynamic studies for drug design and screening.

Science.gov (United States)

Garbett, Nichola C; Chaires, Jonathan B

2012-04-01

A key part of drug design and development is the optimization of molecular interactions between an engineered drug candidate and its binding target. Thermodynamic characterization provides information about the balance of energetic forces driving binding interactions and is essential for understanding and optimizing molecular interactions. This review discusses the information that can be obtained from thermodynamic measurements and how this can be applied to the drug development process. Current approaches for the measurement and optimization of thermodynamic parameters are presented, specifically higher throughput and calorimetric methods. Relevant literature for this review was identified in part by bibliographic searches for the period 2004 - 2011 using the Science Citation Index and PUBMED and the keywords listed below. The most effective drug design and development platform comes from an integrated process utilizing all available information from structural, thermodynamic and biological studies. Continuing evolution in our understanding of the energetic basis of molecular interactions and advances in thermodynamic methods for widespread application are essential to realize the goal of thermodynamically driven drug design. Comprehensive thermodynamic evaluation is vital early in the drug development process to speed drug development toward an optimal energetic interaction profile while retaining good pharmacological properties. Practical thermodynamic approaches, such as enthalpic optimization, thermodynamic optimization plots and the enthalpic efficiency index, have now matured to provide proven utility in the design process. Improved throughput in calorimetric methods remains essential for even greater integration of thermodynamics into drug design. © 2012 Informa UK, Ltd.

Thermodynamic evolution far from equilibrium

Science.gov (United States)

Khantuleva, Tatiana A.

2018-05-01

The presented model of thermodynamic evolution of an open system far from equilibrium is based on the modern results of nonequilibrium statistical mechanics, the nonlocal theory of nonequilibrium transport developed by the author and the Speed Gradient principle introduced in the theory of adaptive control. Transition to a description of the system internal structure evolution at the mesoscopic level allows a new insight at the stability problem of non-equilibrium processes. The new model is used in a number of specific tasks.

Thermodynamics of quasi-topological cosmology

International Nuclear Information System (INIS)

Dehghani, M.H.; Sheykhi, A.; Dehghani, R.

2013-01-01

In this Letter, we study thermodynamical properties of the apparent horizon in a universe governed by quasi-topological gravity. Our aim is twofold. First, by using the variational method we derive the general form of Friedmann equation in quasi-topological gravity. Then, by applying the first law of thermodynamics on the apparent horizon, after using the entropy expression associated with the black hole horizon in quasi-topological gravity, and replacing the horizon radius, r + , with the apparent horizon radius, r -tilde A , we derive the corresponding Friedmann equation in quasi-topological gravity. We find that these two different approaches yield the same result which shows the profound connection between the first law of thermodynamics and the gravitational field equations of quasi-topological gravity. We also study the validity of the generalized second law of thermodynamics in quasi-topological cosmology. We find that, with the assumption of the local equilibrium hypothesis, the generalized second law of thermodynamics is fulfilled for the universe enveloped by the apparent horizon for the late time cosmology

Thermodynamic Study of Tl6SBr4 Compound and Some Regularities in Thermodynamic Properties of Thallium Chalcohalides

Directory of Open Access Journals (Sweden)

Dunya Mahammad Babanly

2017-01-01

Full Text Available The solid-phase diagram of the Tl-TlBr-S system was clarified and the fundamental thermodynamic properties of Tl6SBr4 compound were studied on the basis of electromotive force (EMF measurements of concentration cells relative to a thallium electrode. The EMF results were used to calculate the relative partial thermodynamic functions of thallium in alloys and the standard integral thermodynamic functions (-ΔfG0, -ΔfH0, and S0298 of Tl6SBr4 compound. All data regarding thermodynamic properties of thallium chalcogen-halides are generalized and comparatively analyzed. Consequently, certain regularities between thermodynamic functions of thallium chalcogen-halides and their binary constituents as well as degree of ionization (DI of chemical bonding were revealed.

Extended Irreversible Thermodynamics

CERN Document Server

Jou, David

2010-01-01

This is the 4th edition of the highly acclaimed monograph on Extended Irreversible Thermodynamics, a theory that goes beyond the classical theory of irreversible processes. In contrast to the classical approach, the basic variables describing the system are complemented by non-equilibrium quantities. The claims made for extended thermodynamics are confirmed by the kinetic theory of gases and statistical mechanics. The book covers a wide spectrum of applications, and also contains a thorough discussion of the foundations and the scope of the current theories on non-equilibrium thermodynamics. For this new edition, the authors critically revised existing material while taking into account the most recent developments in fast moving fields such as heat transport in micro- and nanosystems or fast solidification fronts in materials sciences. Several fundamental chapters have been revisited emphasizing physics and applications over mathematical derivations. Also, fundamental questions on the definition of non-equil...

Thermodynamic properties of the amorphous and crystalline modifications of carbon and the metastable synthesis of diamond

Energy Technology Data Exchange (ETDEWEB)

Guencheva, V.; Grantscharova, E.; Gutzow, I. [Bulgarian Academy of Sciences, Sofia (Bulgaria). Inst. of Physical Chemistry

2001-07-01

The temperature dependencies of the thermodynamic properties of the little known (or even hypothetical) undercooled carbon melt and of the glasses that could be obtained from it at appropriate cooling rates are constructed. This is done using both a general thermodynamic formalism to estimate equilibrium properties of undercooled glass-forming melts and the expected analogy in properties of Fourth Group Elements. A comparison of the hypothetical carbon glasses with amorphous materials, obtained by the pyrolisis of organic resins, usually called vitreous (or glassy) carbon, is made. It turns out that from a thermodynamic point of view existing vitreous carbon materials, although characterized by an amorphous, frozen-in structure, differ significantly from the carbon glasses, which could be obtained by a splat-cool-quench of the carbon melt. It is shown also that the hypothetical carbon glasses should have at any temperature a thermodynamic potential, significantly higher than that of diamond. Thus they could be used as a source of constant supersaturation in metastable diamond synthesis. Existing amorphous carbon materials, although showing considerably lower thermodynamic potentials than the hypothetical carbon glasses, could also be used as sources of constant supersaturation in a process of isothermal diamond synthesis if their thermodynamic potential is additionally increased (e.g. by mechano-chemical treatment or by dispersion into nano-size scale). Theoretical estimates made in terms of Ostwald's Rule of Stages indicate that in processes of metastable isothermal diamond synthesis additional kinetic factors (e.g. influencing the formation of sp{sup 3} - carbon structures in the ambient phase) and the introduction of active substrates (e.g. diamond powder) are to be of significance in the realization of this thermodynamic possibility. (orig.)

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

Science.gov (United States)

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.

Development of a thermodynamic data base for selected heavy metals

International Nuclear Information System (INIS)

Hageman, Sven; Scharge, Tina; Willms, Thomas

2015-07-01

The report on the development of a thermodynamic data base for selected heavy metals covers the description of experimental methods, the thermodynamic model for chromate, the thermodynamic model for dichromate, the thermodynamic model for manganese (II), the thermodynamic model for cobalt, the thermodynamic model for nickel, the thermodynamic model for copper (I), the thermodynamic model for copper(II), the thermodynamic model for mercury (0) and mercury (I), the thermodynamic model for mercury (III), the thermodynamic model for arsenate.

On the thermodynamics of multilevel evolution.

Science.gov (United States)

Tessera, Marc; Hoelzer, Guy A

2013-09-01

Biodiversity is hierarchically structured both phylogenetically and functionally. Phylogenetic hierarchy is understood as a product of branching organic evolution as described by Darwin. Ecosystem biologists understand some aspects of functional hierarchy, such as food web architecture, as a product of evolutionary ecology; but functional hierarchy extends to much lower scales of organization than those studied by ecologists. We argue that the more general use of the term "evolution" employed by physicists and applied to non-living systems connects directly to the narrow biological meaning. Physical evolution is best understood as a thermodynamic phenomenon, and this perspective comfortably includes all of biological evolution. We suggest four dynamical factors that build on each other in a hierarchical fashion and set the stage for the Darwinian evolution of biological systems: (1) the entropic erosion of structure; (2) the construction of dissipative systems; (3) the reproduction of growing systems and (4) the historical memory accrued to populations of reproductive agents by the acquisition of hereditary mechanisms. A particular level of evolution can underpin the emergence of higher levels, but evolutionary processes persist at each level in the hierarchy. We also argue that particular evolutionary processes can occur at any level of the hierarchy where they are not obstructed by material constraints. This theoretical framework provides an extensive basis for understanding natural selection as a multilevel process. The extensive literature on thermodynamics in turn provides an important advantage to this perspective on the evolution of higher levels of organization, such as the evolution of altruism that can accompany the emergence of social organization. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Solute induced relaxation in glassy polymers: Experimental measurements and nonequilibrium thermodynamic model

International Nuclear Information System (INIS)

Minelli, Matteo; Doghieri, Ferruccio

2014-01-01

Data for kinetics of mass uptake from vapor sorption experiments in thin glassy polymer samples are here interpreted in terms of relaxation times for volume dilation. To this result, both models from non-equilibrium thermodynamics and from mechanics of volume relaxation contribute. Different kind of sorption experiments have been considered in order to facilitate the direct comparison between kinetics of solute induced volume dilation and corresponding data from process driven by pressure or temperature jumps

RNA Thermodynamic Structural Entropy.

Directory of Open Access Journals (Sweden)

Juan Antonio Garcia-Martin

Full Text Available Conformational entropy for atomic-level, three dimensional biomolecules is known experimentally to play an important role in protein-ligand discrimination, yet reliable computation of entropy remains a difficult problem. Here we describe the first two accurate and efficient algorithms to compute the conformational entropy for RNA secondary structures, with respect to the Turner energy model, where free energy parameters are determined from UV absorption experiments. An algorithm to compute the derivational entropy for RNA secondary structures had previously been introduced, using stochastic context free grammars (SCFGs. However, the numerical value of derivational entropy depends heavily on the chosen context free grammar and on the training set used to estimate rule probabilities. Using data from the Rfam database, we determine that both of our thermodynamic methods, which agree in numerical value, are substantially faster than the SCFG method. Thermodynamic structural entropy is much smaller than derivational entropy, and the correlation between length-normalized thermodynamic entropy and derivational entropy is moderately weak to poor. In applications, we plot the structural entropy as a function of temperature for known thermoswitches, such as the repression of heat shock gene expression (ROSE element, we determine that the correlation between hammerhead ribozyme cleavage activity and total free energy is improved by including an additional free energy term arising from conformational entropy, and we plot the structural entropy of windows of the HIV-1 genome. Our software RNAentropy can compute structural entropy for any user-specified temperature, and supports both the Turner'99 and Turner'04 energy parameters. It follows that RNAentropy is state-of-the-art software to compute RNA secondary structure conformational entropy. Source code is available at https://github.com/clotelab/RNAentropy/; a full web server is available at http

RNA Thermodynamic Structural Entropy.

Science.gov (United States)

Garcia-Martin, Juan Antonio; Clote, Peter

2015-01-01

Conformational entropy for atomic-level, three dimensional biomolecules is known experimentally to play an important role in protein-ligand discrimination, yet reliable computation of entropy remains a difficult problem. Here we describe the first two accurate and efficient algorithms to compute the conformational entropy for RNA secondary structures, with respect to the Turner energy model, where free energy parameters are determined from UV absorption experiments. An algorithm to compute the derivational entropy for RNA secondary structures had previously been introduced, using stochastic context free grammars (SCFGs). However, the numerical value of derivational entropy depends heavily on the chosen context free grammar and on the training set used to estimate rule probabilities. Using data from the Rfam database, we determine that both of our thermodynamic methods, which agree in numerical value, are substantially faster than the SCFG method. Thermodynamic structural entropy is much smaller than derivational entropy, and the correlation between length-normalized thermodynamic entropy and derivational entropy is moderately weak to poor. In applications, we plot the structural entropy as a function of temperature for known thermoswitches, such as the repression of heat shock gene expression (ROSE) element, we determine that the correlation between hammerhead ribozyme cleavage activity and total free energy is improved by including an additional free energy term arising from conformational entropy, and we plot the structural entropy of windows of the HIV-1 genome. Our software RNAentropy can compute structural entropy for any user-specified temperature, and supports both the Turner'99 and Turner'04 energy parameters. It follows that RNAentropy is state-of-the-art software to compute RNA secondary structure conformational entropy. Source code is available at https://github.com/clotelab/RNAentropy/; a full web server is available at http

Thermodynamics of a stochastic twin elevator.

Science.gov (United States)

Kumar, Niraj; Van den Broeck, Christian; Esposito, Massimiliano; Lindenberg, Katja

2011-11-01

We study the nonequilibrium thermodynamics of a single particle with two available energy levels, in contact with a classical (Maxwell-Boltzmann) or quantum (Bose-Einstein) heat bath. The particle can undergo transitions between the levels via thermal activation or deactivation. The energy levels are alternately raised at a given rate regardless of occupation by the particle, maintaining a fixed energy gap equal to ε between them. We explicitly calculate the work, heat, and entropy production rates. The efficiency in both the classical and the quantum case goes to a limit between 100 and 50% that depends on the relative rates of particle transitions and level elevation. In the classical problem we explicitly find the large deviation functions for heat, work, and internal energy.

Thermodynamic origin of nonimaging optics

Science.gov (United States)

Jiang, Lun; Winston, Roland

2016-10-01

Nonimaging optics is the theory of thermodynamically efficient optics and as such depends more on thermodynamics than on optics. Hence, in this paper, a condition for the "best" design is proposed based on purely thermodynamic arguments, which we believe has profound consequences for the designs of thermal and even photovoltaic systems. This way of looking at the problem of efficient concentration depends on probabilities, the ingredients of entropy and information theory, while "optics" in the conventional sense recedes into the background. Much of the paper is pedagogical and retrospective. Some of the development of flowline designs will be introduced at the end and the connection between the thermodynamics and flowline design will be graphically presented. We will conclude with some speculative directions of where the ideas might lead.

Thermodynamic efficiency of solar concentrators.

Science.gov (United States)

Shatz, Narkis; Bortz, John; Winston, Roland

2010-04-26

The optical thermodynamic efficiency is a comprehensive metric that takes into account all loss mechanisms associated with transferring flux from the source to the target phase space, which may include losses due to inadequate design, non-ideal materials, fabrication errors, and less than maximal concentration. We discuss consequences of Fermat's principle of geometrical optics and review étendue dilution and optical loss mechanisms associated with nonimaging concentrators. We develop an expression for the optical thermodynamic efficiency which combines the first and second laws of thermodynamics. As such, this metric is a gold standard for evaluating the performance of nonimaging concentrators. We provide examples illustrating the use of this new metric for concentrating photovoltaic systems for solar power applications, and in particular show how skewness mismatch limits the attainable optical thermodynamic efficiency.

Thermodynamic properties of tert-butylbenzene and 1,4-di-tert-butylbenzene

International Nuclear Information System (INIS)

Chirico, Robert D.; Steele, William V.

2009-01-01

Heat capacities, enthalpies of phase transitions, and derived thermodynamic properties over the temperature range 5 < (T/K) < 442 were determined with adiabatic calorimetry for tert-butylbenzene (TBB) {Chemical Abstracts Service registry number (CASRN) [98-06-6]} and 1,4-di-tert-butylbenzene (DTBB) {CASRN [1012-72-2]}. A crystal to plastic crystal transition very near the triple-point temperature of DTBB was observed. New vapor pressures near the triple-point temperature are also reported for DTBB for the liquid and crystal states. These new measurements, when combined with published results, allow calculation of the thermodynamic properties for the ideal gas state for both compounds. The contribution of the tert-butyl group to the entropy of the ideal gas is determined quantitatively here for the first time based on the calorimetric results over the temperature range 298.15 < (T/K) < 600. Comparisons with literature values are shown for all measured and derived properties, including entropies for the ideal gas derived from quantum chemical calculations

Thermodynamic performance evaluation of combustion gas turbine cogeneration system with reheat

International Nuclear Information System (INIS)

Khaliq, A.; Kaushik, S.C.

2004-01-01

This communication presents thermodynamic methodology for the performance evaluation of combustion gas turbine cogeneration system with reheat. The energetic and exergetic efficiencies have been defined. The effects of process steam pressure and pinch point temperature used in the design of heat recovery steam generator, and reheat on energetic and exergetic efficiencies have been investigated. From the results obtained in graphs it is observed that the power to heat ratio increases with an increase in pinch point, but the first-law efficiency and second-law efficiency decreases with an increase in pinch point. The power to heat ratio and second-law efficiency increases significantly with increase in process steam pressure, but the first-law efficiency decreases with the same. Results also show that inclusion of reheat, provide significant improvement in electrical power output, process heat production, fuel-utilization (energetic) efficiency and second-law (exergetic) efficiency. This methodology may be quite useful in the selection and comparison of combined energy production systems from thermodynamic performance point of view

Secondary phases formed during nuclear waste glass-water interactions: Thermodynamic and derived properties

International Nuclear Information System (INIS)

McKenzie, W.F.

1992-08-01

The thermodynamic properties of secondary phases observed to form during nuclear waste glass-water interactions are of particular interest as it is with the application of these properties together with the thermodynamic properties of other solid phases, fluid phases, and aqueous species that one may predict the environmental consequences of introducing radionuclides contained in the glass into groundwater at a high-level nuclear waste repository. The validation of these predicted consequences can be obtained from laboratory experiments and field observations at natural analogue sites. The purpose of this report is to update and expand the previous compilation (McKenzie, 1991) of thermodynamic data retrieved from the literature and/or estimated for secondary phases observed to form (and candidate phases from observed chemical compositions) during nuclear waste glass-water interactions. In addition, this report includes provisionally recommended thermodynamic data of secondary phases

The thermodynamic solar energy

International Nuclear Information System (INIS)

Rivoire, B.

2002-04-01

The thermodynamic solar energy is the technic in the whole aiming to transform the solar radiation energy in high temperature heat and then in mechanical energy by a thermodynamic cycle. These technic are most often at an experimental scale. This paper describes and analyzes the research programs developed in the advanced countries, since 1980. (A.L.B.)

Quasiparticles and thermodynamical consistency

International Nuclear Information System (INIS)

Shanenko, A.A.; Biro, T.S.; Toneev, V.D.

2003-01-01

A brief and simple introduction into the problem of the thermodynamical consistency is given. The thermodynamical consistency relations, which should be taken into account under constructing a quasiparticle model, are found in a general manner from the finite-temperature extension of the Hellmann-Feynman theorem. Restrictions following from these relations are illustrated by simple physical examples. (author)

Chemical Equilibrium as Balance of the Thermodynamic Forces

OpenAIRE

Zilbergleyt, B.

2004-01-01

The article sets forth comprehensive basics of thermodynamics of chemical equilibrium as balance of the thermodynamic forces. Based on the linear equations of irreversible thermodynamics, De Donder definition of the thermodynamic force, and Le Chatelier's principle, new thermodynamics of chemical equilibrium offers an explicit account for multiple chemical interactions within the system. Basic relations between energetic characteristics of chemical transformations and reaction extents are bas...

Thermodynamic light on black holes

International Nuclear Information System (INIS)

Davies, P.

1977-01-01

The existence of black holes and their relevance to our understanding of the nature of space and time are considered, with especial reference to the application of thermodynamic arguments which can reveal their energy-transfer processes in a new light. The application of thermodynamics to strongly gravitating systems promises some fascinating new insights into the nature of gravity. Situations can occur during gravitational collapse in which existing physics breaks down. Under these circumstances, the application of universal thermodynamical principles might be our only guide. (U.K.)

Thermodynamics in f(G,T Gravity

Directory of Open Access Journals (Sweden)

M. Sharif

2018-01-01

Full Text Available This paper explores the nonequilibrium behavior of thermodynamics at the apparent horizon of isotropic and homogeneous universe model in f(G,T gravity (G and T represent the Gauss-Bonnet invariant and trace of the energy-momentum tensor, resp.. We construct the corresponding field equations and analyze the first as well as generalized second law of thermodynamics in this scenario. It is found that an auxiliary term corresponding to entropy production appears due to the nonequilibrium picture of thermodynamics in first law. The universal condition for the validity of generalized second law of thermodynamics is also obtained. Finally, we check the validity of generalized second law of thermodynamics for the reconstructed f(G,T models (de Sitter and power-law solutions. We conclude that this law holds for suitable choices of free parameters.

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

Science.gov (United States)

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

2014-01-01

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

Analysis of the influence of the plasma thermodynamic regime in the spectrally resolved and mean radiative opacity calculations of carbon plasmas in a wide range of density and temperature

International Nuclear Information System (INIS)

Gil, J.M.; Rodriguez, R.; Martel, P.; Florido, R.; Rubiano, J.G.; Mendoza, M.A.; Minguez, E.

2013-01-01

In this work the spectrally resolved, multigroup and mean radiative opacities of carbon plasmas are calculated for a wide range of plasma conditions which cover situations where corona, local thermodynamic and non-local thermodynamic equilibrium regimes are found. An analysis of the influence of the thermodynamic regime on these magnitudes is also carried out by means of comparisons of the results obtained from collisional-radiative, corona or Saha–Boltzmann equations. All the calculations presented in this work were performed using ABAKO/RAPCAL code. -- Highlights: ► Spectrally resolved, multigroup and mean radiative opacities of carbon plasmas are calculated. ► Corona, local thermodynamic and non-local thermodynamic equilibrium regimes are analyzed. ► Simulations performed using the computational package ABAKO/RAPCAL. ► A criterion for the establishment of the thermodynamic regime is proposed.

Comparison of RASS temperature profiles with other tropospheric soundings

International Nuclear Information System (INIS)

Bonino, G.; Lombardini, P.P.; Trivero, P.

1980-01-01

The vertical temperature profile of the lower troposphere can be measured with a radio-acoustic sounding system (RASS). A comparison of the thermal profiles measured with the RASS and with traditional methods shows a) RASS ability to produce vertical thermal profiles at an altitude range of 170 to 1000 m with temperature accuracy and height discrimination comparable with conventional soundings, b) advantages of remote sensing as offered by new sounder, c) applicability of RASS both in assessing evolution of thermodynamic conditions in PBL and in sensing conditions conducive to high concentrations of air pollutants at the ground level. (author)

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

Science.gov (United States)

Glavatskiy, K S

2015-10-28

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

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

International Nuclear Information System (INIS)

Glavatskiy, K. S.

2015-01-01

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

Stability of black holes based on horizon thermodynamics

Directory of Open Access Journals (Sweden)

Meng-Sen Ma

2015-12-01

Full Text Available On the basis of horizon thermodynamics we study the thermodynamic stability of black holes constructed in general relativity and Gauss–Bonnet gravity. In the framework of horizon thermodynamics there are only five thermodynamic variables E, P, V, T, S. It is not necessary to consider concrete matter fields, which may contribute to the pressure of black hole thermodynamic system. In non-vacuum cases, we can derive the equation of state, P=P(V,T. According to the requirements of stable equilibrium in conventional thermodynamics, we start from these thermodynamic variables to calculate the heat capacity at constant pressure and Gibbs free energy and analyze the local and global thermodynamic stability of black holes. It is shown that P>0 is the necessary condition for black holes in general relativity to be thermodynamically stable, however this condition cannot be satisfied by many black holes in general relativity. For black hole in Gauss–Bonnet gravity negative pressure can be feasible, but only local stable black hole exists in this case.

Thermodynamic study of selected monoterpenes

Czech Academy of Sciences Publication Activity Database

Štejfa, V.; Fulem, Michal; Růžička, K.; Červinka, C.; Rocha, M.A.A.; Santos, L.M.N.B.F.; Schröder, B.

2013-01-01

Roč. 60, MAY (2013), 117-125 ISSN 0021-9614 Institutional support: RVO:68378271 Keywords : monoterpenes * pinene * vapor pressure * heat capacity * vaporization and sublimation enthalpy * ideal - gas thermodynamic Subject RIV: BJ - Thermodynamics Impact factor: 2.423, year: 2013

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

Science.gov (United States)

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

2013-09-01

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

Thermodynamic Calculations for Systems Biocatalysis

DEFF Research Database (Denmark)

Abu, Rohana; Gundersen, Maria T.; Woodley, John M.

2015-01-01

the transamination of a pro-chiral ketone into a chiral amine (interesting in many pharmaceutical applications). Here, the products are often less energetically stable than the reactants, meaning that the reaction may be thermodynamically unfavourable. As in nature, such thermodynamically-challenged reactions can...... on the basis of kinetics. However, many of the most interesting non-natural chemical reactions which could potentially be catalysed by enzymes, are thermodynamically unfavourable and are thus limited by the equilibrium position of the reaction. A good example is the enzyme ω-transaminase, which catalyses...... be altered by coupling with other reactions. For instance, in the case of ω-transaminase, such a coupling could be with alanine dehydrogenase. Herein, the aim of this work is to identify thermodynamic bottlenecks within a multi-enzyme process, using group contribution method to calculate the Gibbs free...

Thermodynamics II essentials

CERN Document Server

REA, The Editors of

2013-01-01

REA's Essentials provide quick and easy access to critical information in a variety of different fields, ranging from the most basic to the most advanced. As its name implies, these concise, comprehensive study guides summarize the essentials of the field covered. Essentials are helpful when preparing for exams, doing homework and will remain a lasting reference source for students, teachers, and professionals. Thermodynamics II includes review of thermodynamic relations, power and refrigeration cycles, mixtures and solutions, chemical reactions, chemical equilibrium, and flow through nozzl

Concise chemical thermodynamics

CERN Document Server

Peters, APH

2010-01-01

EnergyThe Realm of ThermodynamicsEnergy BookkeepingNature's Driving ForcesSetting the Scene: Basic IdeasSystem and SurroundingsFunctions of StateMechanical Work and Expanding GasesThe Absolute Temperature Scale Forms of Energy and Their Interconversion Forms of Renewable Energy Solar Energy Wind Energy Hydroelectric Power Geothermal Energy Biomass Energy References ProblemsThe First Law of Thermodynamics Statement of the First Law Reversible Expansion of an Ideal GasConstant-Volume ProcessesConstant-Pressure ProcessesA New Function: EnthalpyRelationship between ?H and ?UUses and Conventions of

Microcanonical ensemble extensive thermodynamics of Tsallis statistics

International Nuclear Information System (INIS)

Parvan, A.S.

2005-01-01

The microscopic foundation of the generalized equilibrium statistical mechanics based on the Tsallis entropy is given by using the Gibbs idea of statistical ensembles of the classical and quantum mechanics.The equilibrium distribution functions are derived by the thermodynamic method based upon the use of the fundamental equation of thermodynamics and the statistical definition of the functions of the state of the system. It is shown that if the entropic index ξ = 1/q - 1 in the microcanonical ensemble is an extensive variable of the state of the system, then in the thermodynamic limit z bar = 1/(q - 1)N = const the principle of additivity and the zero law of thermodynamics are satisfied. In particular, the Tsallis entropy of the system is extensive and the temperature is intensive. Thus, the Tsallis statistics completely satisfies all the postulates of the equilibrium thermodynamics. Moreover, evaluation of the thermodynamic identities in the microcanonical ensemble is provided by the Euler theorem. The principle of additivity and the Euler theorem are explicitly proved by using the illustration of the classical microcanonical ideal gas in the thermodynamic limit

Microcanonical ensemble extensive thermodynamics of Tsallis statistics

International Nuclear Information System (INIS)

Parvan, A.S.

2006-01-01

The microscopic foundation of the generalized equilibrium statistical mechanics based on the Tsallis entropy is given by using the Gibbs idea of statistical ensembles of the classical and quantum mechanics. The equilibrium distribution functions are derived by the thermodynamic method based upon the use of the fundamental equation of thermodynamics and the statistical definition of the functions of the state of the system. It is shown that if the entropic index ξ=1/(q-1) in the microcanonical ensemble is an extensive variable of the state of the system, then in the thermodynamic limit z-bar =1/(q-1)N=const the principle of additivity and the zero law of thermodynamics are satisfied. In particular, the Tsallis entropy of the system is extensive and the temperature is intensive. Thus, the Tsallis statistics completely satisfies all the postulates of the equilibrium thermodynamics. Moreover, evaluation of the thermodynamic identities in the microcanonical ensemble is provided by the Euler theorem. The principle of additivity and the Euler theorem are explicitly proved by using the illustration of the classical microcanonical ideal gas in the thermodynamic limit

Thermodynamic metrics and optimal paths.

Science.gov (United States)

Sivak, David A; Crooks, Gavin E

2012-05-11

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

Statistical Thermodynamics of Disperse Systems

DEFF Research Database (Denmark)

Shapiro, Alexander

1996-01-01

Principles of statistical physics are applied for the description of thermodynamic equilibrium in disperse systems. The cells of disperse systems are shown to possess a number of non-standard thermodynamic parameters. A random distribution of these parameters in the system is determined....... On the basis of this distribution, it is established that the disperse system has an additional degree of freedom called the macro-entropy. A large set of bounded ideal disperse systems allows exact evaluation of thermodynamic characteristics. The theory developed is applied to the description of equilibrium...

Practical chemical thermodynamics for geoscientists

CERN Document Server

Fegley, Bruce, Jr

2012-01-01

Practical Chemical Thermodynamics for Geoscientists covers classical chemical thermodynamics and focuses on applications to practical problems in the geosciences, environmental sciences, and planetary sciences. This book will provide a strong theoretical foundation for students, while also proving beneficial for earth and planetary scientists seeking a review of thermodynamic principles and their application to a specific problem. Strong theoretical foundation and emphasis on applications Numerous worked examples in each chapter Brief historical summaries and biographies of key thermodynamicists-including their fundamental research and discoveries Extensive references to relevant literature.

Contact Geometry of Mesoscopic Thermodynamics and Dynamics

Directory of Open Access Journals (Sweden)

Miroslav Grmela

2014-03-01

Full Text Available The time evolution during which macroscopic systems reach thermodynamic equilibrium states proceeds as a continuous sequence of contact structure preserving transformations maximizing the entropy. This viewpoint of mesoscopic thermodynamics and dynamics provides a unified setting for the classical equilibrium and nonequilibrium thermodynamics, kinetic theory, and statistical mechanics. One of the illustrations presented in the paper is a new version of extended nonequilibrium thermodynamics with fluxes as extra state variables.

eQuilibrator--the biochemical thermodynamics calculator.

Science.gov (United States)

Flamholz, Avi; Noor, Elad; Bar-Even, Arren; Milo, Ron

2012-01-01

The laws of thermodynamics constrain the action of biochemical systems. However, thermodynamic data on biochemical compounds can be difficult to find and is cumbersome to perform calculations with manually. Even simple thermodynamic questions like 'how much Gibbs energy is released by ATP hydrolysis at pH 5?' are complicated excessively by the search for accurate data. To address this problem, eQuilibrator couples a comprehensive and accurate database of thermodynamic properties of biochemical compounds and reactions with a simple and powerful online search and calculation interface. The web interface to eQuilibrator (http://equilibrator.weizmann.ac.il) enables easy calculation of Gibbs energies of compounds and reactions given arbitrary pH, ionic strength and metabolite concentrations. The eQuilibrator code is open-source and all thermodynamic source data are freely downloadable in standard formats. Here we describe the database characteristics and implementation and demonstrate its use.

Horizon thermodynamics in fourth-order gravity

Directory of Open Access Journals (Sweden)

Meng-Sen Ma

2017-03-01

Full Text Available In the framework of horizon thermodynamics, the field equations of Einstein gravity and some other second-order gravities can be rewritten as the thermodynamic identity: dE=TdS−PdV. However, in order to construct the horizon thermodynamics in higher-order gravity, we have to simplify the field equations firstly. In this paper, we study the fourth-order gravity and convert it to second-order gravity via a so-called “Legendre transformation” at the cost of introducing two other fields besides the metric field. With this simplified theory, we implement the conventional procedure in the construction of the horizon thermodynamics in 3 and 4 dimensional spacetime. We find that the field equations in the fourth-order gravity can also be written as the thermodynamic identity. Moreover, we can use this approach to derive the same black hole mass as that by other methods.

eQuilibrator—the biochemical thermodynamics calculator

Science.gov (United States)

Flamholz, Avi; Noor, Elad; Bar-Even, Arren; Milo, Ron

2012-01-01

The laws of thermodynamics constrain the action of biochemical systems. However, thermodynamic data on biochemical compounds can be difficult to find and is cumbersome to perform calculations with manually. Even simple thermodynamic questions like ‘how much Gibbs energy is released by ATP hydrolysis at pH 5?’ are complicated excessively by the search for accurate data. To address this problem, eQuilibrator couples a comprehensive and accurate database of thermodynamic properties of biochemical compounds and reactions with a simple and powerful online search and calculation interface. The web interface to eQuilibrator (http://equilibrator.weizmann.ac.il) enables easy calculation of Gibbs energies of compounds and reactions given arbitrary pH, ionic strength and metabolite concentrations. The eQuilibrator code is open-source and all thermodynamic source data are freely downloadable in standard formats. Here we describe the database characteristics and implementation and demonstrate its use. PMID:22064852

Applied thermodynamics: A new frontier for biotechnology

DEFF Research Database (Denmark)

Mollerup, Jørgen

2006-01-01

The scientific career of one of the most outstanding scientists in molecular thermodynamics, Professor John M. Prausnitz at Berkeley, reflects the change in the agenda of molecular thermodynamics, from hydrocarbon chemistry to biotechnology. To make thermodynamics a frontier for biotechnology...

Measuring Thermodynamic Properties of Metals and Alloys With Knudsen Effusion Mass Spectrometry

Science.gov (United States)

Copland, Evan H.; Jacobson, Nathan S.

2010-01-01

This report reviews Knudsen effusion mass spectrometry (KEMS) as it relates to thermodynamic measurements of metals and alloys. First, general aspects are reviewed, with emphasis on the Knudsen-cell vapor source and molecular beam formation, and mass spectrometry issues germane to this type of instrument are discussed briefly. The relationship between the vapor pressure inside the effusion cell and the measured ion intensity is the key to KEMS and is derived in detail. Then common methods used to determine thermodynamic quantities with KEMS are discussed. Enthalpies of vaporization, the fundamental measurement, are determined from the variation of relative partial pressure with temperature using the second-law method or by calculating a free energy of formation and subtracting the entropy contribution using the third-law method. For single-cell KEMS instruments, measurements can be used to determine the partial Gibbs free energy if the sensitivity factor remains constant over multiple experiments. The ion-current ratio method and dimer-monomer method are also viable in some systems. For a multiple-cell KEMS instrument, activities are obtained by direct comparison with a suitable component reference state or a secondary standard. Internal checks for correct instrument operation and general procedural guidelines also are discussed. Finally, general comments are made about future directions in measuring alloy thermodynamics with KEMS.

Thermodynamics of (2 +1 )-dimensional black holes in Einstein-Maxwell-dilaton gravity

Science.gov (United States)

Dehghani, M.

2017-08-01

In this paper, the linearly charged three-dimensional Einstein's theory coupled to a dilatonic field has been considered. It has been shown that the dilatonic potential must be considered in a form of generalized Liouville-type potential. Two new classes of charged dilatonic black hole solutions, as the exact solutions to the Einstein-Maxwell-dilaton (EMd) gravity, have been obtained and their properties have been studied. The conserved charge and mass related to both of the new EMd black holes have been calculated. Through comparison of the thermodynamical extensive quantities (i.e., temperature and entropy) obtained from both, the geometrical and the thermodynamical methods, the validity of first law of black hole thermodynamics has been investigated for both of the new black holes we just obtained. At the final stage, making use of the canonical ensemble method and regarding the black hole heat capacity, the thermal stability or phase transition of the new black hole solutions have been analyzed. It has been shown that there is a specific range for the horizon radius in such a way that the black holes with the horizon radius in that range are locally stable. Otherwise, they are unstable and may undergo type one or type two phase transitions to be stabilized.

Thermodynamic studies on charge-coupled substituted synthetic monazite

Energy Technology Data Exchange (ETDEWEB)

Rawat, D. [Product Development Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India); Phapale, S. [Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India); Mishra, R., E-mail: mishrar@barc.gov.in [Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India); Dash, S. [Product Development Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India)

2017-04-15

Phosphate-based monazite ceramic is considered worldwide as a potential crystalline host matrix for immobilization of long-lived tri- and tetra-valent actinides present in high-level nuclear waste. Monazite is chemically stable with respect to the leaching processes and has high radiation stability. The present paper describes the influence of charged coupled (Ca{sup 2+}, Th{sup 4+}) substitution in place of La{sup 3+} on thermodynamic stability of synthetic monazite ceramics. XRD-analysis of Ca, Th substituted LaPO{sub 4} viz., La{sub 1-x}Ca{sub x/2}Th{sub x/2}PO{sub 4} (0 ≤ x ≤ 1) points to the formation of ideal solid-solution in the entire range of composition. However, thermodynamic analysis indicates deviation from ideal solid-solution with a minima at x = 0.25. The substituted La{sub 1-x}Ca{sub x/2}Th{sub x/2}PO{sub 4} system is found to be iso-entropic and stabilized mainly by enthalpy. Enthalpies of formation as a function of Ca{sup 2+}, Th{sup 4+} substitution were analysed to provide insights into the development of thermodynamically stable nuclear waste matrix.

The comparison of parents' educational level on the breastfeeding ...

African Journals Online (AJOL)

Background: Mother's milk plays an important role in infant's health, and World Health Organization (WHO) recommends infants should be breastfed for 2 years or up. Aim: The main objective of this study was to evaluate the breastfeeding status based on parents' educational level with comparison between Turkman and ...

Thermodynamics of the vehicle. 2. ed.; Thermodynamik des Kraftfahrzeugs

Energy Technology Data Exchange (ETDEWEB)

Stan, Cornel [California Univ., Berkeley, CA (United States); Paris Univ., 75 (France); Pisa Univ. (Italy); Perugia Univ. (Italy); Kronstadt Univ. (Russian Federation)

2012-07-01

The vehicle is characterized by thermodynamic processes at almost all levels: Drive systems (from internal combustion engines and hybrids to electric motors with fuel cells), charging, cooling and heating circuits, air conditioners, aerodynamics of the vehicle body, damper systems, fuel injection systems, exhaust systems, brakes, tires. However, due to an enhanced complexity and phenomenological approach the thermodynamics is a challenge for engineers. This book under considerations combines the theoretical principles and their mathematical presentation with applications in the automotive technology. Numerous specific examples facilitate the understanding and practical application of the basic knowledge. In addition to corrections and updates, the new edition under consideration contains more practical exercises and in-depth questions.

Thermodynamic analysis of chromium solubility data in liquid lithium containing nitrogen: Comparison between experimental data and computer simulation

International Nuclear Information System (INIS)

Krasin, Valery P.; Soyustova, Svetlana I.

2015-01-01

The mathematical formalism for description of solute interactions in dilute solution of chromium and nitrogen in liquid lithium have been applied for calculating of the temperature dependence of the solubility of chromium in liquid lithium with the various nitrogen contents. It is shown that the derived equations are useful to provide understanding of a relationship between thermodynamic properties and local ordering in the Li–Cr–N melt. Comparison between theory and data reported in the literature for solubility of chromium in nitrogen-contaminated liquid lithium, was allowed to explain the reasons of the deviation of the experimental semi-logarithmic plot of chromium content in liquid lithium as a function of the reciprocal temperature from a straight line. - Highlights: • The activity coefficient of chromium in ternary melt can be obtained by means of integrating the Gibbs–Duhem equation. • In lithium with the high nitrogen content, the dependence of a logarithm of chromium solubility as a function of the reciprocal temperature has essentially nonlinear character. • At temperatures below a certain threshold, the process of dissolution of chromium in lithium will be controlled by the equilibrium concentration of nitrogen required for the formation of ternary nitride Li_9CrN_5at a given temperature.

Thermodynamic Cconstraints on Coupled Carbonate-Pyrite Weathering Dynamics and Carbon Fluxes

Science.gov (United States)

Winnick, M.; Maher, K.

2017-12-01

Chemical weathering within the critical zone regulates global biogeochemical cycles, atmospheric composition, and the supply of key nutrients to terrestrial and aquatic ecosystems. Recent studies suggest that thermodynamic limits on solute production act as a first-order control on global chemical weathering rates; however, few studies have addressed the factors that set these thermodynamic limits in natural systems. In this presentation, we investigate the effects of soil CO2 concentrations and pyrite oxidation rates on carbonate dissolution and associated carbon fluxes in the East River watershed in Colorado, using concentration-discharge relationships and thermodynamic constraints. Within the shallow subsurface, soil respiration rates and moisture content determine the extent of carbonic acid-promoted carbonate dissolution through their modulation of soil pCO2 and the balance of open- v. closed-system weathering processes. At greater depths, pyrite oxidation generates sulfuric acid, which alters the approach to equilibrium of infiltrating waters. Through comparisons of concentration-discharge data and reactive transport model simulations, we explore the conditions that determine whether sulfuric acid reacts to dissolve additional carbonate mineral or instead reacts with alkalinity already in solution - the balance of which determines watershed carbon flux budgets. Our study highlights the importance of interactions between the chemical structure of the critical zone and the hydrologic regulation of flowpaths in determining concentration-discharge relationships and overall carbon fluxes.

Dual QCD thermodynamics and quark–gluon plasma

International Nuclear Information System (INIS)

Chandola, H.C.; Punetha, Garima; Dehnen, H.

2016-01-01

Using grand canonical ensemble formulation of a multi-particle statistical system, the thermodynamical description of dual QCD based on magnetic symmetry has been presented and analyzed for the quark–gluon plasma phase of hadronic matter. The dual QCD based bag construction has been shown to lead to the radial pressure on bag surface in terms of the vector glueball masses of magnetically condensed QCD vacuum. Constructing the grand canonical partition function, the energy density and plasma pressure have been derived and used to compute the critical temperatures for QGP–hadron phase transition along with its dynamics. A comparison of the values of critical temperatures for QGP–hadron phase transition with those obtained for the deconfinement-phase transition, has been shown to lead to either the relaxation of the system via a mixed phase of QGP and hot hadron gas or go through a crossover. The associated profiles of the normalized energy density and specific heat have been shown to lead to a large latent heat generation and indicate the onset of a first-order QGP phase transition which turns into a rapid crossover for the case of temperature dependent bag parameter. The squared speed of sound has been shown to act as a physical measure of large thermodynamical fluctuations near transition point. The possible implications of trace anomaly and conformal measure on QGP formation have also been discussed.

Chemical Thermodynamics and Information Theory with Applications

CERN Document Server

Graham, Daniel J

2011-01-01

Thermodynamics and information touch theory every facet of chemistry. However, the physical chemistry curriculum digested by students worldwide is still heavily skewed toward heat/work principles established more than a century ago. Rectifying this situation, Chemical Thermodynamics and Information Theory with Applications explores applications drawn from the intersection of thermodynamics and information theory--two mature and far-reaching fields. In an approach that intertwines information science and chemistry, this book covers: The informational aspects of thermodynamic state equations The

Thermodynamics of nuclear materials

International Nuclear Information System (INIS)

1962-01-01

The first session of the symposium discussed in general the thermodynamic properties of actinides, including thorium, uranium and Plutonium which provide reactor fuel. The second session was devoted to applications of thermodynamic theory to the study of nuclear materials, while the experimental techniques for the determination of thermodynamic data were examined at the next session. The thermodynamic properties of alloys were considered at a separate session, and another session was concerned with solids other than alloys. Vaporization processes, which are of special interest in the development of high-temperature reactors, were discussed at a separate session. The discussions on the methods of developing the data and ascertaining their accuracy were especially useful in highlighting the importance of determining whether any given data are reliable before they can be put to practical application. Many alloys and refractory materials (i. e. materials which evaporate only at very high temperatures) are of great importance in nuclear technology, and some of these substances are extremely complex in their chemical composition. For example, until recently the phase composition of the oxides of thorium, uranium and plutonium had been only very imperfectly understood, and the same was true of the carbides of these elements. Recent developments in experimental techniques have made it possible to investigate the phase composition of these complex materials as well as the chemical species of these materials in the gaseous phase. Recent developments in measuring techniques, such as fluorine bomb calorimetry and Knudsen effusion technique, have greatly increased the accuracy of thermodynamic data

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

Science.gov (United States)

Dong, S.

2018-05-01

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

Application of thermodynamics to silicate crystalline solutions

Science.gov (United States)

Saxena, S. K.

1972-01-01

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

An introduction to thermodynamics and statistical mechanics

CERN Document Server

Saxena, A K

2016-01-01

An Introduction to Thermodynamics and Statistical Mechanics aims to serve as a text book for undergraduate hons.and postgraduate students of physics. The book covers First Law of Thermodynamics, Entropy and Second Law ofThermodynamics, Thermodynamic Relations, The Statistical Basis of Thermodynamics, Microcanonical Ensemble,Classical Statistical and Canonical Distribution, Grand Canonical Ensemble, Quantum Statistical Mechanics, PhaseTransitions, Fluctuations, Irreversible Processes and Transport Phenomena (Diffusion).SALIENT FEATURES:iC* Offers students a conceptual development of the subjectiC* Review questions at the end of chapters.NEW TO THE SECOND EDITIONiC* PVT SurfacesiC* Real Heat EnginesiC* Van der Waals Models (Qualitative Considerations)iC* Cluster ExpansioniC* Brownian Motion (Einstein's Theory)

Nonequilibrium thermodynamics of restricted Boltzmann machines

Science.gov (United States)

Salazar, Domingos S. P.

2017-08-01

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

Introduction to the thermodynamics of solids

International Nuclear Information System (INIS)

Ericksen, J.L.

1992-01-01

This book addresses issues of thermodynamics associated with solids from a unique point of view. Professor Ericksen provides a perspective of thermodynamics which is based in material science and solid mechanics, and attempts to apply basic thermodynamics to a wide range of phenomena. The book is not written as a text-book, as it does not contain example problems or exercises, is directed primarily at researchers in solids. The author states that much of the book is controversial, and that many of his treatments of thermodynamics are not traditional. The author's assessment is accurate on both counts. However, there are several reasons to believe that many of the issues raised in the book are not so much controversial, but rather simply not well described, either by the author or by thermodynamicists, in general. The primary references for much of the thermodynamics in the book are historic in nature, and certainly worthy of consideration, but only a few current references are provided

Nonequilibrium thermodynamics of restricted Boltzmann machines.

Science.gov (United States)

Salazar, Domingos S P

2017-08-01

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

Thermodynamic optimization of power plants

NARCIS (Netherlands)

Haseli, Y.

2011-01-01

Thermodynamic Optimization of Power Plants aims to establish and illustrate comparative multi-criteria optimization of various models and configurations of power plants. It intends to show what optimization objectives one may define on the basis of the thermodynamic laws, and how they can be applied

The statistical-inference approach to generalized thermodynamics

International Nuclear Information System (INIS)

Lavenda, B.H.; Scherer, C.

1987-01-01

Limit theorems, such as the central-limit theorem and the weak law of large numbers, are applicable to statistical thermodynamics for sufficiently large sample size of indipendent and identically distributed observations performed on extensive thermodynamic (chance) variables. The estimation of the intensive thermodynamic quantities is a problem in parametric statistical estimation. The normal approximation to the Gibbs' distribution is justified by the analysis of large deviations. Statistical thermodynamics is generalized to include the statistical estimation of variance as well as mean values

From coal to biomass gasification: Comparison of thermodynamic efficiency

International Nuclear Information System (INIS)

Prins, Mark J.; Ptasinski, Krzysztof J.; Janssen, Frans J.J.G.

2007-01-01

The effect of fuel composition on the thermodynamic efficiency of gasifiers and gasification systems is studied. A chemical equilibrium model is used to describe the gasifier. It is shown that the equilibrium model presents the highest gasification efficiency that can be possibly attained for a given fuel. Gasification of fuels with varying composition of organic matter, in terms of O/C and H/C ratio as illustrated in a Van Krevelen diagram, is compared. It was found that exergy losses in gasifying wood (O/C ratio around 0.6) are larger than those for coal (O/C ratio around 0.2). At a gasification temperature of 927 deg. C, a fuel with O/C ratio below 0.4 is recommended, which corresponds to a lower heating value above 23 MJ/kg. For gasification at 1227 deg. C, a fuel with O/C ratio below 0.3 and lower heating value above 26 MJ/kg is preferred. It could thus be attractive to modify the properties of highly oxygenated biofuels prior to gasification, e.g. by separation of wood into its components and gasification of the lignin component, thermal pre-treatment, and/or mixing with coal in order to enhance the heating value of the gasifier fuel

Modelling of phase diagrams and thermodynamic properties using Calphad method – Development of thermodynamic databases

Czech Academy of Sciences Publication Activity Database

Kroupa, Aleš

2013-01-01

Roč. 66, JAN (2013), s. 3-13 ISSN 0927-0256 R&D Projects: GA MŠk(CZ) OC08053 Institutional support: RVO:68081723 Keywords : Calphad method * phase diagram modelling * thermodynamic database development Subject RIV: BJ - Thermodynamics Impact factor: 1.879, year: 2013

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

Science.gov (United States)

Jenkins, H Donald Brooke; Glasser, Leslie

2004-12-08

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

Toward thermodynamic consistency of quasiparticle picture

International Nuclear Information System (INIS)

Biro, T.S.; Toneev, V.D.; Shanenko, A.A.

2003-01-01

The purpose of the present article is to call attention to some realistic quasiparticle-based description of quark/gluon matter and its consistent implementation in thermodynamics. A simple and transparent representation of the thermodynamic consistency conditions is given. This representation allows one to review critically and systemize available phenomenological approaches to the deconfinement problem with respect to their thermodynamic consistency. Particular attention is paid to the development of a method for treating the string screening in the dense matter of unbound color charges. The proposed method yields an integrable effective pair potential that can be incorporated into the mean-field picture. The results of its application are in reasonable agreement with lattice data on the QCD thermodynamics

Making thermodynamic functions of nanosystems intensive

International Nuclear Information System (INIS)

Nassimi, A M; Parsafar, G A

2007-01-01

The potential energy of interaction among particles in many systems is proportional to r -α . In systems for which α< d, we encounter nonextensive (nonintensive) thermodynamic functions, where d is the space dimension. A scaling parameter, N-tilde, has been introduced to make the nonextensive (nonintensive) thermodynamic functions of such systems extensive (intensive). Our simulation results show that this parameter is not capable of making the thermodynamic functions of a nanosystem extensive (intensive). Here we have presented a theoretical justification for N-tilde. Then we have generalized this scaling parameter to be capable of making the nonextensive (nonintensive) thermodynamic functions of nanosystems extensive (intensive). This generalized parameter is proportional to the potential energy per particle at zero temperature

Structure and thermodynamics of molten salts

International Nuclear Information System (INIS)

Papatheodorou, G.N.

1983-01-01

This chapter investigates single-component molten salts and multicomponent salt mixtures. Molten salts provide an important testing ground for theories of liquids, solutions, and plasmas. Topics considered include molten salts as liquids (the pair potential, the radial distribution function, methods of characterization), single salts (structure, thermodynamic correlations), and salt mixtures (the thermodynamics of mixing; spectroscopy and structure). Neutron and X-ray scattering techniques are used to determine the structure of molten metal halide salts. The corresponding-states theory is used to obtain thermodynamic correlations on single salts. Structural information on salt mixtures is obtained by using vibrational (Raman) and electronic absorption spectroscopy. Charge-symmetrical systems and charge-unsymmetrical systems are used to examine the thermodynamics of salt mixtures

Black hole thermodynamics with conical defects

Energy Technology Data Exchange (ETDEWEB)

Appels, Michael [Centre for Particle Theory, Durham University,South Road, Durham, DH1 3LE (United Kingdom); Gregory, Ruth [Centre for Particle Theory, Durham University,South Road, Durham, DH1 3LE (United Kingdom); Perimeter Institute,31 Caroline Street North, Waterloo, ON, N2L 2Y5 (Canada); Kubiznák, David [Perimeter Institute,31 Caroline Street North, Waterloo, ON, N2L 2Y5 (Canada)

2017-05-22

Recently we have shown https://www.doi.org/10.1103/PhysRevLett.117.131303 how to formulate a thermodynamic first law for a single (charged) accelerated black hole in AdS space by fixing the conical deficit angles present in the spacetime. Here we show how to generalise this result, formulating thermodynamics for black holes with varying conical deficits. We derive a new potential for the varying tension defects: the thermodynamic length, both for accelerating and static black holes. We discuss possible physical processes in which the tension of a string ending on a black hole might vary, and also map out the thermodynamic phase space of accelerating black holes and explore their critical phenomena.

Friedel's salt profiles from thermogravimetric analysis and thermodynamic modelling of Portland cement-based mortars exposed to sodium chloride solution

DEFF Research Database (Denmark)

Shi, Zhenguo; Geiker, Mette Rica; Lothenbach, Barbara

2017-01-01

Thermogravimetric analysis (TGA), powder X-ray diffraction (XRD) and thermodynamic modelling have been used to obtain Friedel's salt profiles for saturated mortar cylinders exposed to a 2.8 M NaCl solution. Comparison of the measured Friedel's salt profiles with the total chloride profiles...

The thermodynamic basis of entransy and entransy dissipation

International Nuclear Information System (INIS)

Xu, Mingtian

2011-01-01

In the present work, the entransy and entransy dissipation are defined from the thermodynamic point of view. It is shown that the entransy is a state variable and can be employed to describe the second law of thermodynamics. For heat conduction, a principle of minimum entransy dissipation is established based on the second law of thermodynamics in terms of entransy dissipation, which leads to the governing equation of the steady Fourier heat conduction without heat source. Furthermore, we derive the expressions of the entransy dissipation in duct flows and heat exchangers from the second law of thermodynamics, which paves the way for applications of the entransy dissipation theory in heat exchanger design. -- Highlights: → The concepts of entransy and entransy dissipation are defined from the thermodynamic point of view. → We find that the entransy is a new thermodynamic property. → The second law of thermodynamics can be described by the entransy and entransy dissipation. → The expressions of entransy dissipation in duct flows and heat exchangers are derived from the second law of thermodynamics.

[Thermodynamics of the origin of life, evolution and aging].

Science.gov (United States)

Gladyshev, G P

2014-01-01

Briefly discusses the history of the search of thermodynamic approach to explain the origin of life, evolution and aging of living beings. The origin of life is the result of requirement by the quasi-equilibrium hierarchical thermodynamics, in particular, the supramolecular thermodynamics. The evolution and aging of living beings is accompanied with changes of chemical and supramolecular compositions of living bodies, as well as with changes in the composition and structure of all hierarchies of the living world. The thermodynamic principle of substance stability predicts the existence of a single genetic code in our universe. The thermodynamic theory optimizes physiology and medicine and recommends antiaging diets and medicines. Hierarchical thermodynamics forms the design diversity of culture and art. The thermodynamic theory of origin of life, evolution and aging is the development of Clausius-Gibbs thermodynamics. Hierarchical thermodynamics is the mirror of Darwin-Wallace's-theory.

Life’s a Gas: A Thermodynamic Theory of Biological Evolution

Directory of Open Access Journals (Sweden)

Keith R. Skene

2015-07-01

Full Text Available This paper outlines a thermodynamic theory of biological evolution. Beginning with a brief summary of the parallel histories of the modern evolutionary synthesis and thermodynamics, we use four physical laws and processes (the first and second laws of thermodynamics, diffusion and the maximum entropy production principle to frame the theory. Given that open systems such as ecosystems will move towards maximizing dispersal of energy, we expect biological diversity to increase towards a level, Dmax, representing maximum entropic production (Smax. Based on this theory, we develop a mathematical model to predict diversity over the last 500 million years. This model combines diversification, post-extinction recovery and likelihood of discovery of the fossil record. We compare the output of this model with that of the observed fossil record. The model predicts that life diffuses into available energetic space (ecospace towards a dynamic equilibrium, driven by increasing entropy within the genetic material. This dynamic equilibrium is punctured by extinction events, which are followed by restoration of Dmax through diffusion into available ecospace. Finally we compare and contrast our thermodynamic theory with the MES in relation to a number of important characteristics of evolution (progress, evolutionary tempo, form versus function, biosphere architecture, competition and fitness.

Thermodynamic data for predicting concentrations of Pu(III), Am(III), and Cm(III) in geologic environments

Energy Technology Data Exchange (ETDEWEB)

Rai, Dhanpat; Rao, Linfeng; Weger, H.T.; Felmy, A.R. [Pacific Northwest National Laboratory, WA (United States); Choppin, G.R. [Florida State University, Florida (United States); Yui, Mikazu [Japan Nuclear Cycle Development Inst., Tokai Works, Tokai, Ibaraki (Japan)

1999-01-01

This report provides thermodynamic data for predicting concentrations of Pu(III), Am(III), and Cm(III) in geologic environments, and contributes to an integration of the JNC chemical thermodynamic database, JNC-TDB (previously PNC-TDB), for the performance analysis of geological isolation system for high-level radioactive wastes. Thermodynamic data for the formation of complexes or compounds with hydroxide, chloride, fluoride, carbonate, nitrate, sulfate and phosphate are discussed in this report. Where data for specific actinide(III) species are lacking, the data were selected based on chemical analogy to other trivalent actinides. In this study, the Pitzer ion-interaction model is mainly used to extrapolate thermodynamic constants to zero ionic strength at 25degC. (author)

Thermodynamics of negative absolute pressures

International Nuclear Information System (INIS)

Lukacs, B.; Martinas, K.

1984-03-01

The authors show that the possibility of negative absolute pressure can be incorporated into the axiomatic thermodynamics, analogously to the negative absolute temperature. There are examples for such systems (GUT, QCD) processing negative absolute pressure in such domains where it can be expected from thermodynamical considerations. (author)

Thermodynamic efficiency of nonimaging concentrators

Science.gov (United States)

Shatz, Narkis; Bortz, John; Winston, Roland

2009-08-01

The purpose of a nonimaging concentrator is to transfer maximal flux from the phase space of a source to that of a target. A concentrator's performance can be expressed relative to a thermodynamic reference. We discuss consequences of Fermat's principle of geometrical optics. We review étendue dilution and optical loss mechanisms associated with nonimaging concentrators, especially for the photovoltaic (PV) role. We introduce the concept of optical thermodynamic efficiency which is a performance metric combining the first and second laws of thermodynamics. The optical thermodynamic efficiency is a comprehensive metric that takes into account all loss mechanisms associated with transferring flux from the source to the target phase space, which may include losses due to inadequate design, non-ideal materials, fabrication errors, and less than maximal concentration. As such, this metric is a gold standard for evaluating the performance of nonimaging concentrators. Examples are provided to illustrate the use of this new metric. In particular we discuss concentrating PV systems for solar power applications.

One Antimatter— Two Possible Thermodynamics

Directory of Open Access Journals (Sweden)

Alexander Y. Klimenko

2014-02-01

Full Text Available Conventional thermodynamics, which is formulated for our world populated by radiation and matter, can be extended to describe physical properties of antimatter in two mutually exclusive ways: CP-invariant or CPT-invariant. Here we refer to invariance of physical laws under charge (C, parity (P and time reversal (T transformations. While in quantum field theory CPT invariance is a theorem confirmed by experiments, the symmetry principles applied to macroscopic phenomena or to the whole of the Universe represent only hypotheses. Since both versions of thermodynamics are different only in their treatment of antimatter, but are the same in describing our world dominated by matter, making a clear experimentally justified choice between CP invariance and CPT invariance in context of thermodynamics is not possible at present. This work investigates the comparative properties of the CP- and CPT-invariant extensions of thermodynamics (focusing on the latter, which is less conventional than the former and examines conditions under which these extensions can be experimentally tested.

Fundamentals of classical statistical thermodynamics dissipation, relaxation, and fluctuation theorems

CERN Document Server

Evans, Denis James; Williams, Stephen Rodney

2016-01-01

Both a comprehensive overview and a treatment at the appropriate level of detail, this textbook explains thermodynamics and generalizes the subject so it can be applied to small nano- or biosystems, arbitrarily far from or close to equilibrium. In addition, nonequilibrium free energy theorems are covered with a rigorous exposition of each one. Throughout, the authors stress the physical concepts along with the mathematical derivations. For researchers and students in physics, chemistry, materials science and molecular biology, this is a useful text for postgraduate courses in statistical mechanics, thermodynamics and molecular simulations, while equally serving as a reference for university teachers and researchers in these fields.

Thermodynamics of Growth, Non-Equilibrium Thermodynamics of Bacterial Growth : The Phenomenological and the Mosaic Approach

NARCIS (Netherlands)

Westerhoff, Hans V.; Lolkema, Juke S.; Otto, Roel; Hellingwerf, K

1982-01-01

Microbial growth is analyzed in terms of mosaic and phenomenological non-equilibrium thermodynamics. It turns out that already existing parameters devised to measure bacterial growth, such as YATP, µ, and Qsubstrate, have as thermodynamic equivalents flow ratio, output flow and input flow. With this

Thermodynamic and kinetic simulation of transient liquid-phase bonding

Science.gov (United States)

Lindner, Brad

The use of numeric computational methods for the simulation of materials systems is becoming more prevalent and an understanding of these tools may soon be a necessity for Materials Engineers and Scientists. The applicability of numerical simulation methods to transient liquid-phase (TLP) bonding is evaluated using a type 316L/MBF-51 material system. The comparisons involve the calculation of bulk diffusivities, tracking of interface positions during dissolution, widening, and isothermal solidification stages, as well as comparison of elemental composition profiles. The simulations were performed with Thermo-Calc and DICTRA software packages and the experiments with differential scanning calorimetry (DSC), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and optical microscopic methods. Analytical methods are also discussed to enhance understanding. The results of the investigation show that while general agreement between simulations and experiments can be obtained, assumptions made with the simulation programs may cause difficulty in interpretation of the results unless the user has sufficient, mathematical, thermodynamic, kinetic, and simulation background.

Deconstructing thermodynamic parameters of a coupled system from site-specific observables.

Science.gov (United States)

Chowdhury, Sandipan; Chanda, Baron

2010-11-02

Cooperative interactions mediate information transfer between structural domains of a protein molecule and are major determinants of protein function and modulation. The prevalent theories to understand the thermodynamic origins of cooperativity have been developed to reproduce the complex behavior of a global thermodynamic observable such as ligand binding or enzyme activity. However, in most cases the measurement of a single global observable cannot uniquely define all the terms that fully describe the energetics of the system. Here we establish a theoretical groundwork for analyzing protein thermodynamics using site-specific information. Our treatment involves extracting a site-specific parameter (defined as χ value) associated with a structural unit. We demonstrate that, under limiting conditions, the χ value is related to the direct interaction terms associated with the structural unit under observation and its intrinsic activation energy. We also introduce a site-specific interaction energy term (χ(diff)) that is a function of the direct interaction energy of that site with every other site in the system. When combined with site-directed mutagenesis and other molecular level perturbations, analyses of χ values of site-specific observables may provide valuable insights into protein thermodynamics and structure.

Thermodynamic assessment of the rhodium-ruthenium-oxygen (Rh-Ru-O) system

Science.gov (United States)

Gossé, S.; Bordier, S.; Guéneau, C.; Brackx, E.; Domenger, R.; Rogez, J.

2018-03-01

Ruthenium (Ru) and rhodium (Rh) are abundant platinum-group metals formed during burn-up of nuclear fuels. Under normal operating conditions, Rh and Ru accumulate and predominantly form metallic precipitates with other fission products like Mo, Pd and Tc. In the framework of vitrification of high-level nuclear waste, these fission products are poorly soluble in molten glasses. They precipitate as metallic particles and oxide phases. Moreover, these Ru and Rh rich phases strongly depend on temperature and the oxygen fugacity of the glass melt. In case of severe accidental conditions with air ingress, oxidation of the Ru and Rh is possible. At low temperatures (T 1422 K for rhodium sesquioxide and T > 1815 K for ruthenium dioxide), they may decompose into (Rh)-FCC or (Ru)-HCP metallic phases and radiotoxic volatile gaseous species. A thermodynamic assessment of the Rh-Ru-O system will enable the prediction of: (1) the metallic and oxide phases that form during the vitrification of high-level nuclear wastes and (2) the release of volatile gaseous species during a severe accident. The Calphad method developed herein employs a thermodynamic approach in the investigation of the thermochemistry of rhodium and ruthenium at high temperatures. Current literature on the thermodynamic properties and phase diagram data enables preliminary thermodynamic assessments of the Rh-O and Ru-O systems. Additionally, select compositions in the ternary Rh-Ru-O system underwent experimental tests to complement data found in literature and to establish the phase equilibria in the ternary system.

Numerical investigations on cavitating flows with thermodynamic effects in a diffuser-type centrifugal pump

International Nuclear Information System (INIS)

Xuelin, Tang Xue; Liyuan, Bian; Fujun, Wang; Xiaoqin, Lin; Man, Hao

2013-01-01

A cavitation model with thermodynamic effects for cavitating flows in a diffuser-type centrifugal pump is developed based on the bubble two-phase flow model. The proposed cavitation model includes mass, momentum, and energy transportations according to the thermodynamic mechanism of cavitation. Numerical simulations are conducted inside the entire passage of the centrifugal pump by using the proposed cavitation model and the renormalization group-based k - ε turbulent model coupled with the energy transportation equation. By using the commercial computational fluid dynamics software FLUENT 6.3, we have shown that the predicted performance characteristics of the pump, as well as the pressure, vapor, and density distributions in the impeller, agree well with that calculated by the full cavitation model. Simulation results show that cavitation initially occurs slightly behind the inlet of the blade suction surface, i.e., the area with maximum vapor concentration and minimum pressure. The predicted temperature field shows that the reduction in temperature restrains the growth of cavitating bubbles. Therefore, the thermodynamic effect should be treated as a necessary factor in cavitation models. Comparison results validate the efficiency and accuracy of the numerical technique in simulating cavitation flows in centrifugal pumps.

Comparison of the thermodynamic databases for radioactive elements in application to the calculation of the solubilities in the porewater

International Nuclear Information System (INIS)

Doi, Reisuke; Shibata, Masahiro

2006-07-01

To calculate the solubility of radioactive elements which is the important parameter for performance assessment of geological disposal system, the thermodynamic database must be reliable and based on the latest information. In this research, it has been compared in the calculation of the solubilities of the representative radioactive elements in the porewater compositions of the compacted bentonite which were set up in the second progress report (H12) that the thermodynamic database of JNC, OECD/NEA, Nagra/PSI. And the causes of the differences among the results from application of different databases were investigated and discussed. (author)

Stochastic thermodynamics, fluctuation theorems and molecular machines

International Nuclear Information System (INIS)

Seifert, Udo

2012-01-01

Stochastic thermodynamics as reviewed here systematically provides a framework for extending the notions of classical thermodynamics such as work, heat and entropy production to the level of individual trajectories of well-defined non-equilibrium ensembles. It applies whenever a non-equilibrium process is still coupled to one (or several) heat bath(s) of constant temperature. Paradigmatic systems are single colloidal particles in time-dependent laser traps, polymers in external flow, enzymes and molecular motors in single molecule assays, small biochemical networks and thermoelectric devices involving single electron transport. For such systems, a first-law like energy balance can be identified along fluctuating trajectories. For a basic Markovian dynamics implemented either on the continuum level with Langevin equations or on a discrete set of states as a master equation, thermodynamic consistency imposes a local-detailed balance constraint on noise and rates, respectively. Various integral and detailed fluctuation theorems, which are derived here in a unifying approach from one master theorem, constrain the probability distributions for work, heat and entropy production depending on the nature of the system and the choice of non-equilibrium conditions. For non-equilibrium steady states, particularly strong results hold like a generalized fluctuation–dissipation theorem involving entropy production. Ramifications and applications of these concepts include optimal driving between specified states in finite time, the role of measurement-based feedback processes and the relation between dissipation and irreversibility. Efficiency and, in particular, efficiency at maximum power can be discussed systematically beyond the linear response regime for two classes of molecular machines, isothermal ones such as molecular motors, and heat engines such as thermoelectric devices, using a common framework based on a cycle decomposition of entropy production. (review article)

THERMODYNAMIC STUDIES ON THE CHARGE-TRANSFER ...

African Journals Online (AJOL)

... technique was employed to investigate thermodynamic parameters associated with the interaction ... KEY WORDS: Amitriptyline , chloranilic acid, thermodynamic parameters. Global Jnl Pure & Applied Sciences Vol.10(1) 2004: 147-153 ...

Thermodynamics for engineers

CERN Document Server

Wong, Kaufui Vincent

2011-01-01

Praise for the First Edition from Students: "It is a great thermodynamics text…I loved it!-Mathew Walters "The book is comprehensive and easy to understand. I love the real world examples and problems, they make you feel like you are learning something very practical."-Craig Paxton"I would recommend the book to friends."-Faure J. Malo-Molina"The clear diction, as well as informative illustrations and diagrams, help convey the material clearly to the reader."-Paul C. Start"An inspiring and effective tool for any aspiring scientist or engineer. Definitely the best book on Classical Thermodynamics out."-Seth Marini.

Chemical thermodynamics. An introduction

Energy Technology Data Exchange (ETDEWEB)

Keszei, Ernoe [Budapest Univ. (Hungary). Dept. of Physical Chemistry

2012-07-01

Eminently suitable as a required textbook comprising complete material for or an undergraduate chemistry major course in chemical thermodynamics. Clearly explains details of formal derivations that students can easily follow and so master applied mathematical operations. Offers problems and solutions at the end of each chapter for self-test and self- or group study. This course-derived undergraduate textbook provides a concise explanation of the key concepts and calculations of chemical thermodynamics. Instead of the usual 'classical' introduction, this text adopts a straightforward postulatory approach that introduces thermodynamic potentials such as entropy and energy more directly and transparently. Structured around several features to assist students' understanding, Chemical Thermodynamics: - Develops applications and methods for the ready treatment of equilibria on a sound quantitative basis. - Requires minimal background in calculus to understand the text and presents formal derivations to the student in a detailed but understandable way. - Offers end-of-chapter problems (and answers) for self-testing and review and reinforcement, of use for self- or group study. This book is suitable as essential reading for courses in a bachelor and master chemistry program and is also valuable as a reference or textbook for students of physics, biochemistry and materials science.

M4FT-16LL080302052-Update to Thermodynamic Database Development and Sorption Database Integration

Energy Technology Data Exchange (ETDEWEB)

Zavarin, Mavrik [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Glenn T. Seaborg Inst.. Physical and Life Sciences; Wolery, T. J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Akima Infrastructure Services, LLC; Atkins-Duffin, C. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Global Security

2016-08-16

This progress report (Level 4 Milestone Number M4FT-16LL080302052) summarizes research conducted at Lawrence Livermore National Laboratory (LLNL) within the Argillite Disposal R&D Work Package Number FT-16LL08030205. The focus of this research is the thermodynamic modeling of Engineered Barrier System (EBS) materials and properties and development of thermodynamic databases and models to evaluate the stability of EBS materials and their interactions with fluids at various physico-chemical conditions relevant to subsurface repository environments. The development and implementation of equilibrium thermodynamic models are intended to describe chemical and physical processes such as solubility, sorption, and diffusion.

Towards thermodynamical consistency of quasiparticle picture

International Nuclear Information System (INIS)

Biro, T.S.; Shanenko, A.A.; Toneev, V.D.; Research Inst. for Particle and Nuclear Physics, Hungarian Academy of Sciences, Budapest

2003-01-01

The purpose of the present article is to call attention to some realistic quasi-particle-based description of the quark/gluon matter and its consistent implementation in thermodynamics. A simple and transparent representation of the thermodynamical consistency conditions is given. This representation allows one to review critically and systemize available phenomenological approaches to the deconfinement problem with respect to their thermodynamical consistency. A particular attention is paid to the development of a method for treating the string screening in the dense matter of unbound color charges. The proposed method yields an integrable effective pair potential, which can be incorporated into the mean-field picture. The results of its application are in reasonable agreement with lattice data on the QCD thermodynamics [ru

Thermodynamics and Chemistry by Howard DeVoe

Science.gov (United States)

Gislason, Eric A.

2001-09-01

Prentice Hall: Upper Saddle River, NJ, 2001. 439 pp. ISBN 0-02-328741-1. $90.00. Thermodynamics is a deceptively difficult subject that few people master in their first exposure (typically in the junior-level physical chemistry course). Because of this, a clear, well-written textbook is always welcome to help students and teachers master this material. Such a book is Thermodynamics and Chemistry, by Howard DeVoe of the University of Maryland. This book is written as a one-semester textbook for senior undergraduates and graduate students who have had a previous course on the topic. This is a long book (400 pages of text, 25 pages of appendices), and it is unlikely that an instructor can cover everything in one semester. On the other hand this length does allow the author to cover topics such as a "liquid solution in a centrifugal field" that shorter books would omit. All important topics in chemical thermodynamics are covered. After two introductory chapters, the three laws of thermodynamics are taken up in Chapters 3 and 4. Pure substances, including phase transitions, are treated in Chapters 5 and 6. Chapter 7, "Mixtures," is a long chapter that covers, among other topics, partial molar quantities, activities, and activity coefficients. Chemical reactions are treated in Chapter 8 and there is a detailed discussion of equilibrium in various multicomponent systems in Chapter 9. The book is completed with a discussion of the phase rule (Chapter 10) and a brief chapter on galvanic cells. There are a number of things I like about this book. First, DeVoe takes great care in defining important thermodynamic words such as the thermodynamic state of a system. Similarly, he makes the distinction between process and path understandable, and this allows him to clearly define a reversible process as well as spontaneous and impossible processes. Section 4.1 then contains the sentence "An irreversible process is a spontaneous process whose reverse is an impossible process." This

A new thermodynamic model of energetic molten fuel-coolant interactions

International Nuclear Information System (INIS)

Hall, A.N.

1987-01-01

A new thermodynamic model of energetic molten fuel-coolant interactions is presented, in which the response of fluid around the interaction zone is treated explicitly. By assuming that this fluid is compressed reversibly and adiabatically, a qualified lower limit to the efficiency of conversion of thermal energy to mechanical work is obtained. A detailed comparison of the model predictions with the results of the SUW series of experiments at AEE Winfrith is made. The predicted efficiencies are found to be in close agreement with those determined experimentally. Model predictions for a system of infinite volume are also presented. (author)

Thermodynamics of Enzyme-Catalyzed Reactions Database

Science.gov (United States)

SRD 74 Thermodynamics of Enzyme-Catalyzed Reactions Database (Web, free access)   The Thermodynamics of Enzyme-Catalyzed Reactions Database contains thermodynamic data on enzyme-catalyzed reactions that have been recently published in the Journal of Physical and Chemical Reference Data (JPCRD). For each reaction the following information is provided: the reference for the data, the reaction studied, the name of the enzyme used and its Enzyme Commission number, the method of measurement, the data and an evaluation thereof.

Thermal physics kinetic theory and thermodynamics

CERN Document Server

Singh, Devraj; Yadav, Raja Ram

2016-01-01

THERMAL PHYSICS: Kinetic Theory and Thermodynamics is designed for undergraduate course in Thermal Physics and Thermodynamics. The book provides thorough understanding of the fundamental principles of the concepts in Thermal Physics. The book begins with kinetic theory, then moves on liquefaction, transport phenomena, the zeroth, first, second and third laws, thermodynamics relations and thermal conduction. The book concluded with radiation phenomenon. KEY FEATURES: * Include exercises * Short Answer Type Questions * Long Answer Type Questions * Numerical Problems * Multiple Choice Questions

On thermodynamic limits of entropy densities

NARCIS (Netherlands)

Moriya, H; Van Enter, A

We give some sufficient conditions which guarantee that the entropy density in the thermodynamic limit is equal to the thermodynamic limit of the entropy densities of finite-volume (local) Gibbs states.

Limits of predictions in thermodynamic systems: a review

Science.gov (United States)

Marsland, Robert, III; England, Jeremy

2018-01-01

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

Non-equilibrium thermodynamics in cells.

Science.gov (United States)

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

2018-03-15

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

Some aspects of plasma thermodynamics

International Nuclear Information System (INIS)

Gorgoraki, V.I.

1986-01-01

The objective reasons which have inhibited the development of a plasma-thermodynamics theory are discussed and the authors formulate the fundamental principles which can be the basis of a common plasma-thermodynamics theory. Two kinds of thermodynamic equilibrium plasmas are discussed, an isothermal plasma and a nonisothermal plasma. An isothermal plasma is a high-temperature plasma; the Saha-Eggert equation describes its behavior. A nonisothermal plasma is a low-temperature plasma, and the reactions taking place therein are purely plasma-chemical. The ionization equilibrium and the composition of such a plasma can be found with the aid of the equations presented in this paper

Fundamental functions in equilibrium thermodynamics

NARCIS (Netherlands)

Horst, H.J. ter

In the standard presentations of the principles of Gibbsian equilibrium thermodynamics one can find several gaps in the logic. For a subject that is as widely used as equilibrium thermodynamics, it is of interest to clear up such questions of mathematical rigor. In this paper it is shown that using

Thermodynamic data-base for metal fluorides

Energy Technology Data Exchange (ETDEWEB)

Yoo, Jae Hyung; Lee, Byung Gik; Kang, Young Ho and others

2001-05-01

This study is aimed at collecting useful data of thermodynamic properties of various metal fluorides. Many thermodynamic data for metal fluorides are needed for the effective development, but no report of data-base was published. Accordingly, the objective of this report is to rearrange systematically the existing thermodynamic data based on metal fluorides and is to use it as basic data for the development of pyrochemical process. The physicochemical properties of various metal fluorides and metals were collected from literature and such existing data base as HSC code, TAPP code, FACT code, JANAF table, NEA data-base, CRC handbook. As major contents of the thermodynamic data-base, the physicochemical properties such as formation energy, viscosity, density, vapor pressure, etc. were collected. Especially, some phase diagrams of eutectic molten fluorides are plotted and thermodynamic data of liquid metals are also compiled. In the future, the technical report is to be used as basic data for the development of the pyrochemical process which is being carried out as a long-term nuclear R and D project.

Thermodynamics of Inozemtsev's elliptic spin chain

International Nuclear Information System (INIS)

Klabbers, Rob

2016-01-01

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

Thermodynamic data-base for metal fluorides

International Nuclear Information System (INIS)

Yoo, Jae Hyung; Lee, Byung Gik; Kang, Young Ho and others

2001-05-01

This study is aimed at collecting useful data of thermodynamic properties of various metal fluorides. Many thermodynamic data for metal fluorides are needed for the effective development, but no report of data-base was published. Accordingly, the objective of this report is to rearrange systematically the existing thermodynamic data based on metal fluorides and is to use it as basic data for the development of pyrochemical process. The physicochemical properties of various metal fluorides and metals were collected from literature and such existing data base as HSC code, TAPP code, FACT code, JANAF table, NEA data-base, CRC handbook. As major contents of the thermodynamic data-base, the physicochemical properties such as formation energy, viscosity, density, vapor pressure, etc. were collected. Especially, some phase diagrams of eutectic molten fluorides are plotted and thermodynamic data of liquid metals are also compiled. In the future, the technical report is to be used as basic data for the development of the pyrochemical process which is being carried out as a long-term nuclear R and D project

Quantum thermodynamics. Emergence of thermodynamic behavior within composite quantum systems. 2. ed.

International Nuclear Information System (INIS)

Gemmer, Jochen; Michel, M.; Mahler, Guenter

2009-01-01

This introductory text treats thermodynamics as an incomplete description of quantum systems with many degrees of freedom. Its main goal is to show that the approach to equilibrium -with equilibrium characterized by maximum ignorance about the open system of interest- neither requires that many particles nor is the precise way of partitioning, relevant for the salient features of equilibrium and equilibration. Furthermore, the text depicts that it is indeed quantum effects that are at work in bringing about thermodynamic behavior of modest-sized open systems, thus making Von Neumann's concept of entropy appear much more widely useful than sometimes feared, far beyond truly macroscopic systems in equilibrium. This significantly revised and expanded second edition pays more attention to the growing number of applications, especially non-equilibrium phenomena and thermodynamic processes of the nano-domain. In addition, to improve readability and reduce unneeded technical details, a large portion of this book has been thoroughly rewritten. (orig.)

Casimir effect and thermodynamics of horizon instabilities

International Nuclear Information System (INIS)

Hartnoll, Sean A.

2004-01-01

We propose a dual thermodynamic description of a classical instability of generalized black hole spacetimes. From a thermodynamic perspective, the instability is due to negative compressibility in regions where the Casimir pressure is large. The argument indicates how the correspondence between thermodynamic and classical instability for horizons may be extended to cases without translational invariance

Thermodynamic analysis of direct expansion configurations for electricity production by LNG cold energy recovery

International Nuclear Information System (INIS)

Franco, Alessandro; Casarosa, Claudio

2015-01-01

In the present paper, after a brief review of the perspectives of the various schemes proposed for electricity generation from the regasification of Liquefied Natural Gas (LNG), a detailed analysis of two particular direct expansion solutions is proposed. The purpose is to identify the upper level of the energy that can be recovered with the aim of electricity production, using configurations with direct expansion. The analysis developed resorting to a simplified thermodynamic model, shows that using a direct expansion configurations with multistage turbine, values of power production typical of optimized ORC plant configurations (120 kJ for each kg of natural gas that flows through the plant) can be obtained. The development of a direct expansion plant with multistage turbine and internal heat recovery systems could permit to approach the production of more than 160 kJ for each kg of flowing liquefied natural gas. Considering values of the mass flow rate typical of LNG gas stations (e.g. 70 kg/s); this corresponds to an output power ranging between 8.3 MW and 11.4 MW. - Highlights: • Recovery of the cold energy contained in Liquefied Natural Gas. • Thermodynamic analysis of systems for electricity generation in regasification. • Direct expansion solutions with multistage expansion. • Comparison of direct expansion solutions with conventional ORC systems. • Power output in conditions typical of existing LNG regasification terminals

Quantum thermodynamics of general quantum processes.

Science.gov (United States)

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

2015-03-01

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

Surface dependency in thermodynamics of ideal gases

International Nuclear Information System (INIS)

Sisman, Altug

2004-01-01

The Casimir-like size effect rises in ideal gases confined in a finite domain due to the wave character of atoms. By considering this effect, thermodynamic properties of an ideal gas confined in spherical and cylindrical geometries are derived and compared with those in rectangular geometry. It is seen that an ideal gas exhibits an unavoidable quantum surface free energy and surface over volume ratio becomes a control variable on thermodynamic state functions in microscale. Thermodynamics turns into non-extensive thermodynamics and geometry difference becomes a driving force since the surface over volume ratio depends on the geometry

Mass transport thermodynamics in nonisothermal molecular liquid mixtures

Energy Technology Data Exchange (ETDEWEB)

Semenov, Semen N [Institute for Biochemical Physics, Russian Academy of Sciences, Moscow (Russian Federation); Schimpf, M E [Department of Chemistry and Biochemistry, Boise State University, Boise, ID (United States)

2009-10-31

Mass transport in a nonisothermal binary molecular mixture is systematically discussed in terms of nonequilibrium thermodynamics, which for the first time allows a consistent and unambiguous description of the process. The thermodynamic and hydrodynamic approaches are compared, revealing that nonequilibrium thermodynamics and physicochemical hydrodynamics yield essentially the same results for molecular systems. The applicability limits for the proposed version of the thermodynamic approach are determined for large particles. (methodological notes)

Thermodynamics from Car to Kitchen

Science.gov (United States)

Auty, Geoff

2014-01-01

The historical background to the laws of thermodynamics is explained using examples we can all observe in the world around us, focusing on motorised transport, refrigeration and solar heating. This is not to be considered as an academic article. The purpose is to improve understanding of thermodynamics rather than impart new knowledge, and for…

Thermodynamics of Crystalline States

CERN Document Server

Fujimoto, Minoru

2010-01-01

Thermodynamics is a well-established discipline of physics for properties of matter in thermal equilibrium surroundings. Applying to crystals, however, the laws encounter undefined properties of crystal lattices, which therefore need to be determined for a clear and well-defined description of crystalline states. Thermodynamics of Crystalline States explores the roles played by order variables and dynamic lattices in crystals in a wholly new way. This book is divided into three parts. The book begins by clarifying basic concepts for stable crystals. Next, binary phase transitions are discussed to study collective motion of order variables, as described mostly as classical phenomena. In the third part, the multi-electron system is discussed theoretically, as a quantum-mechanical example, for the superconducting state in metallic crystals. Throughout the book, the role played by the lattice is emphasized and examined in-depth. Thermodynamics of Crystalline States is an introductory treatise and textbook on meso...

Thermodynamic theory of black holes

Energy Technology Data Exchange (ETDEWEB)

Davies, P C.W. [King' s Coll., London (UK). Dept. of Mathematics

1977-04-21

The thermodynamic theory underlying black hole processes is developed in detail and applied to model systems. It is found that Kerr-Newman black holes undergo a phase transition at a = 0.68M or Q = 0.86M, where the heat capacity has an infinite discontinuity. Above the transition values the specific heat is positive, permitting isothermal equilibrium with a surrounding heat bath. Simple processes and stability criteria for various black hole situations are investigated. The limits for entropically favoured black hole formation are found. The Nernst conditions for the third law of thermodynamics are not satisfied fully for black holes. There is no obvious thermodynamic reason why a black hole may not be cooled down below absolute zero and converted into a naked singularity. Quantum energy-momentum tensor calculations for uncharged black holes are extended to the Reissner-Nordstrom case, and found to be fully consistent with the thermodynamic picture for Q < M. For Q < M the model predicts that 'naked' collapse also produces radiation, with such intensity that the collapsing matter is entirely evaporated away before a naked singularity can form.

Thermodynamic and mechanical properties of TiC from ab initio calculation

International Nuclear Information System (INIS)

Dang, D. Y.; Fan, J. L.; Gong, H. R.

2014-01-01

The temperature-dependent thermodynamic and mechanical properties of TiC are systematically investigated by means of a combination of density-functional theory, quasi-harmonic approximation, and thermal electronic excitation. It is found that the quasi-harmonic Debye model should be pertinent to reflect thermodynamic properties of TiC, and the elastic properties of TiC decease almost linearly with the increase of temperature. Calculations also reveal that TiC possesses a pronounced directional pseudogap across the Fermi level, mainly due to the strong hybridization of Ti 3d and C 2p states. Moreover, the strong covalent bonding of TiC would be enhanced (reduced) with the decrease (increase) of temperature, while the change of volume (temperature) should have negligible effect on density of states at the Fermi level. The calculated results agree well with experimental observations in the literature.

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

International Nuclear Information System (INIS)

Noh, Seunghyo; Kwak, Dohyun; Lee, Juseung; Kang, Joonhee; Han, Byungchan

2014-01-01

We utilized first-principles density-functional-theory (DFT) calculations to evaluate the thermodynamic feasibility of a pyroprocessing methodology for reducing the volume of high-level radioactive materials and recycling spent nuclear fuels. The thermodynamic properties of transuranium elements (Pu, Np and Cm) were obtained in electrochemical equilibrium with a LiCl-KCl molten salt as ionic phases and as adsorbates on a W(110) surface. To accomplish the goal, we rigorously calculated the double layer interface structures on an atomic resolution, on the thermodynamically most stable configurations on W(110) surfaces and the chemical activities of the transuranium elements for various coverages of those elements. Our results indicated that the electrodeposition process was very sensitive to the atomic level structures of Cl ions at the double-layer interface. Our studies are easily expandable to general electrochemical applications involving strong redox reactions of transition metals in non-aqueous solutions.

Multi-pressure boiler thermodynamics analysis code

International Nuclear Information System (INIS)

Lorenzoni, G.

1992-01-01

A new method and the relative FORTRAN program for the thermodynamics design analysis of a multipressure boiler are reported. This method permits the thermodynamics design optimization with regard to total exergy production and a preliminary costs

Comparison of trace element contamination levels (Cu, Zn, Fe, Cd ...

African Journals Online (AJOL)

Comparison of trace element contamination levels (Cu, Zn, Fe, Cd and Pb) in the soft tissues of the gastropods Tympanotonus fuscatus fuscatus and Tf radula collected in the Ebrié Lagoon (Côte d'Ivoire): Evidence of the risks linked to linked to lead and.

Canonical operator formulation of nonequilibrium thermodynamics

International Nuclear Information System (INIS)

Mehrafarin, M.

1992-09-01

A novel formulation of nonequilibrium thermodynamics is proposed which emphasises the fundamental role played by the Boltzmann constant k in fluctuations. The equivalence of this and the stochastic formulation is demonstrated. The k → 0 limit of this theory yields the classical deterministic description of nonequilibrium thermodynamics. The new formulation possesses unique features which bear two important results namely the thermodynamic uncertainty principle and the quantisation of entropy production rate. Such a theory becomes indispensable whenever fluctuations play a significant role. (author). 7 refs

Thermodynamic analysis of elastic-plastic deformation

International Nuclear Information System (INIS)

Lubarda, V.

1981-01-01

The complete set of constitutive equations which fully describes the behaviour of material in elastic-plastic deformation is derived on the basis of thermodynamic analysis of the deformation process. The analysis is done after the matrix decomposition of the deformation gradient is introduced into the structure of thermodynamics with internal state variables. The free energy function, is decomposed. Derive the expressions for the stress response, entropy and heat flux, and establish the evolution equation. Finally, we establish the thermodynamic restrictions of the deformation process. (Author) [pt

Thermodynamic laws apply to brain function.

Science.gov (United States)

Salerian, Alen J

2010-02-01

Thermodynamic laws and complex system dynamics govern brain function. Thus, any change in brain homeostasis by an alteration in brain temperature, neurotransmission or content may cause region-specific brain dysfunction. This is the premise for the Salerian Theory of Brain built upon a new paradigm for neuropsychiatric disorders: the governing influence of neuroanatomy, neurophysiology, thermodynamic laws. The principles of region-specific brain function thermodynamics are reviewed. The clinical and supporting evidence including the paradoxical effects of various agents that alter brain homeostasis is demonstrated.

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

Science.gov (United States)

Shnip, A. I.

2018-01-01

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

Ch. 33 Modeling: Computational Thermodynamics

International Nuclear Information System (INIS)

Besmann, Theodore M.

2012-01-01

This chapter considers methods and techniques for computational modeling for nuclear materials with a focus on fuels. The basic concepts for chemical thermodynamics are described and various current models for complex crystalline and liquid phases are illustrated. Also included are descriptions of available databases for use in chemical thermodynamic studies and commercial codes for performing complex equilibrium calculations.

Thermodynamics of urban population flows.

Science.gov (United States)

Hernando, A; Plastino, A

2012-12-01

Orderliness, reflected via mathematical laws, is encountered in different frameworks involving social groups. Here we show that a thermodynamics can be constructed that macroscopically describes urban population flows. Microscopic dynamic equations and simulations with random walkers underlie the macroscopic approach. Our results might be regarded, via suitable analogies, as a step towards building an explicit social thermodynamics.

Black hole thermodynamical entropy

International Nuclear Information System (INIS)

Tsallis, Constantino; Cirto, Leonardo J.L.

2013-01-01

As early as 1902, Gibbs pointed out that systems whose partition function diverges, e.g. gravitation, lie outside the validity of the Boltzmann-Gibbs (BG) theory. Consistently, since the pioneering Bekenstein-Hawking results, physically meaningful evidence (e.g., the holographic principle) has accumulated that the BG entropy S BG of a (3+1) black hole is proportional to its area L 2 (L being a characteristic linear length), and not to its volume L 3 . Similarly it exists the area law, so named because, for a wide class of strongly quantum-entangled d-dimensional systems, S BG is proportional to lnL if d=1, and to L d-1 if d>1, instead of being proportional to L d (d ≥ 1). These results violate the extensivity of the thermodynamical entropy of a d-dimensional system. This thermodynamical inconsistency disappears if we realize that the thermodynamical entropy of such nonstandard systems is not to be identified with the BG additive entropy but with appropriately generalized nonadditive entropies. Indeed, the celebrated usefulness of the BG entropy is founded on hypothesis such as relatively weak probabilistic correlations (and their connections to ergodicity, which by no means can be assumed as a general rule of nature). Here we introduce a generalized entropy which, for the Schwarzschild black hole and the area law, can solve the thermodynamic puzzle. (orig.)

Thermodynamics of Weakly Measured Quantum Systems.

Science.gov (United States)

Alonso, Jose Joaquin; Lutz, Eric; Romito, Alessandro

2016-02-26

We consider continuously monitored quantum systems and introduce definitions of work and heat along individual quantum trajectories that are valid for coherent superposition of energy eigenstates. We use these quantities to extend the first and second laws of stochastic thermodynamics to the quantum domain. We illustrate our results with the case of a weakly measured driven two-level system and show how to distinguish between quantum work and heat contributions. We finally employ quantum feedback control to suppress detector backaction and determine the work statistics.

Does social comparison make a difference? Optimism as a moderator of the relation between comparison level and academic performance

NARCIS (Netherlands)

Gibbons, FX; Blanton, H; Gerrard, M; Buunk, B; Eggleston, T

Previous research has demonstrated that poor academic performance is associated with a downward shift in preferred level of academic comparison level (ACL). The current study assessed the long-term impact of this downward shift on the academic performance of college students and also examined the

Uniqueness of thermodynamic projector and kinetic basis of molecular individualism

Science.gov (United States)

Gorban, Alexander N.; Karlin, Iliya V.

2004-05-01

Three results are presented: First, we solve the problem of persistence of dissipation for reduction of kinetic models. Kinetic equations with thermodynamic Lyapunov functions are studied. Uniqueness of the thermodynamic projector is proven: There exists only one projector which transforms any vector field equipped with the given Lyapunov function into a vector field with the same Lyapunov function for a given anzatz manifold which is not tangent to the Lyapunov function levels. Second, we use the thermodynamic projector for developing the short memory approximation and coarse-graining for general nonlinear dynamic systems. We prove that in this approximation the entropy production increases. ( The theorem about entropy overproduction.) In example, we apply the thermodynamic projector to derive the equations of reduced kinetics for the Fokker-Planck equation. A new class of closures is developed, the kinetic multipeak polyhedra. Distributions of this type are expected in kinetic models with multidimensional instability as universally as the Gaussian distribution appears for stable systems. The number of possible relatively stable states of a nonequilibrium system grows as 2 m, and the number of macroscopic parameters is in order mn, where n is the dimension of configuration space, and m is the number of independent unstable directions in this space. The elaborated class of closures and equations pretends to describe the effects of “molecular individualism”. This is the third result.

Thermodynamic DFT analysis of natural gas.

Science.gov (United States)

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

2017-08-01

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

Thermodynamic Database for Zirconium Alloys

International Nuclear Information System (INIS)

Jerlerud Perez, Rosa

2003-05-01

For many decades zirconium alloys have been commonly used in the nuclear power industry as fuel cladding material. Besides their good corrosion resistance and acceptable mechanical properties the main reason of using these alloys is the low neutron absorption. Zirconium alloys are exposed to a very severe environment during the nuclear fission process and there is a demand for better design of this material. To meet this requirement a thermodynamic database is developed to support material designers. In this thesis some aspects about the development of a thermodynamic database for zirconium alloys are presented. A thermodynamic database represents an important facility in applying thermodynamic equilibrium calculations for a given material providing: 1) relevant information about the thermodynamic properties of the alloys e.g. enthalpies, activities, heat capacity, and 2) significant information for the manufacturing process e.g. heat treatment temperature. The basic information in the database is first the unary data, i.e. pure elements; those are taken from the compilation of the Scientific Group Thermodata Europe (SGTE) and then the binary and ternary systems. All phases present in those binary and ternary systems are described by means of the Gibbs energy dependence on composition and temperature. Many of those binary systems have been taken from published or unpublished works and others have been assessed in the present work. All the calculations have been made using Thermo C alc software and the representation of the Gibbs energy obtained by applying Calphad technique

Thermodynamic measurement and analysis of dual-temperature thermoacoustic oscillations for energy harvesting application

International Nuclear Information System (INIS)

Zhao, Dan; Ji, Chenzhen; Li, Shihuai; Li, Junwei

2014-01-01

The present work considers energy harvesting by implementing both thermo- and piezo-electric power generation modules on a bifurcating tube, which produces dual-temperature thermoacoustic oscillations. The present system distinguished from the conventional standing-wave one does not involve heat exchangers and uses two different energy conversion processes to produce electricity. To measure and analyze the sound waves generated, an infrared thermal imaging camera, hot wire anemometry, and two arrays of K-type thermocouples and microphones are employed. It is found that the total electric power is approximately 5.71 mW, of which the piezo module produces about 0.21 mW. It is about 61% more than that generated by a similar conduction-driven thermo-acoustic-piezo harvester. In order to gain insight on the heat-driven acoustic oscillations and to simulate the experiment, thermodynamic laws are used to develop a nonlinear thermoacoustic model. Comparison is then made between the numerical and experimental results. Good agreement is obtained in terms of frequency and sound pressure level. Finally, Rayleigh index is examined to characterize the conversion between thermal and sound energy. In addition, energy redistribution between different thermoacoustic modes is estimated. It is found that lower frequency thermoacoustic oscillations are easier to trigger. - Highlights: • Energy harvesting from thermo- and piezo-electric diaphragms is obtained. • Total electrical power is approximately 5.71 mW. • Thermodynamic analysis of heat-driven oscillations is performed. • Rayleigh index characterizing heat-to-sound conversion is estimated. • Energy redistribution between various eigenmodes is calculated

The thermodynamic characteristics of high efficiency, internal-combustion engines

International Nuclear Information System (INIS)

Caton, Jerald A.

2012-01-01

Highlights: ► The thermodynamics of an automotive engine are determined using a cycle simulation. ► The net indicated thermal efficiency increased from 37.0% to 53.9%. ► High compression ratio, lean mixtures and high EGR were the important features. ► Efficiency increased due to lower heat losses, and increased work conversion. ► The nitric oxides were essentially zero due to the low combustion temperatures. - Abstract: Recent advancements have demonstrated new combustion modes for internal combustion engines that exhibit low nitric oxide emissions and high thermal efficiencies. These new combustion modes involve various combinations of stratification, lean mixtures, high levels of EGR, multiple injections, variable valve timings, two fuels, and other such features. Although the exact combination of these features that provides the best design is not yet clear, the results (low emissions with high efficiencies) are of major interest. The current work is directed at determining some of the fundamental thermodynamic reasons for the relatively high efficiencies and to quantify these factors. Both the first and second laws are used in this assessment. An automotive engine (5.7 l) which included some of the features mentioned above (e.g., high compression ratios, lean mixtures, and high EGR) was evaluated using a thermodynamic cycle simulation. These features were examined for a moderate load (bmep = 900 kPa), moderate speed (2000 rpm) condition. By the use of lean operation, high EGR levels, high compression ratio and other features, the net indicated thermal efficiency increased from 37.0% to 53.9%. These increases are explained in a step-by-step fashion. The major reasons for these improvements include the higher compression ratio and the dilute charge (lean mixture, high EGR). The dilute charge resulted in lower temperatures which in turn resulted in lower heat loss. In addition, the lower temperatures resulted in higher ratios of the specific heats which

Statistical thermodynamics of alloys

International Nuclear Information System (INIS)

Gokcen, N.A.

1986-01-01

This book presents information on the following topics: consequences of laws of thermodynamics; Helmholtz and Gibbs energies; analytical forms of excess partial molar properties; single-component and multicomponent equilibria; phase rules and diagrams; lever rule; fermions, bosons, and Boltzons; approximate equations; enthalpy and heat capacity; Pd-H system; hydrogen-metal systems; limitations of Wagner model; energy of electrons and hols; dopants in semiconductors; derived thermodynamic properties; simple equivalent circuit; calculation procedure; multicompoent diagrams re; Engel-Brewer theories; p-n junctions; and solar cells

On thermodynamics of methane+carbonaceous materials adsorption

KAUST Repository

Rahman, Kazi Afzalur

2012-01-01

This study presents the theoretical frameworks for the thermodynamic quantities namely the heat of adsorption, specific heat capacity, entropy, and enthalpy for the adsorption of methane onto various carbonaceous materials. The proposed theoretical frameworks are developed from the rigor of thermodynamic property surfaces of a single component adsorbate-adsorbent system and by incorporating the micropore filling theory approach, where the effect of adsorbed phase volume is considered. The abovementioned thermodynamic properties are quantitatively evaluated from the experimental uptake data for methane adsorption onto activated carbons such as Maxsorb III at temperatures ranging from 120 to 350 K and pressures up to 25 bar. Employing the proposed thermodynamic approaches, this paper shows the thermodynamic maps of the charge and discharge processes of adsorbed natural gas (ANG) storage system for understanding the behaviors of natural gas in ANG vessel. © 2011 Elsevier Ltd. All rights reserved.

Introduction to physics mechanics, hydrodynamics thermodynamics

CERN Document Server

Frauenfelder, P

2013-01-01

Introduction of Physics: Mechanics , Hydrodynamics, Thermodynamics covers the principles of matter and its motion through space and time, as well as the related concepts of energy and force. This book is composed of eleven chapters, and begins with an introduction to the basic principles of mechanics, hydrodynamics, and thermodynamics. The subsequent chapters deal with the statics of rigid bodies and the dynamics of particles and rigid bodies. These topics are followed by discussions on elasticity, mechanics of fluids, the basic concept of thermodynamic, kinetic theory, and crystal structure o

Stochastic deformation of a thermodynamic symplectic structure

OpenAIRE

Kazinski, P. O.

2008-01-01

A stochastic deformation of a thermodynamic symplectic structure is studied. The stochastic deformation procedure is analogous to the deformation of an algebra of observables like deformation quantization, but for an imaginary deformation parameter (the Planck constant). Gauge symmetries of thermodynamics and corresponding stochastic mechanics, which describes fluctuations of a thermodynamic system, are revealed and gauge fields are introduced. A physical interpretation to the gauge transform...

Pyroelectric Energy Harvesting: With Thermodynamic-Based Cycles

OpenAIRE

Saber Mohammadi; Akram Khodayari

2012-01-01

This work deals with energy harvesting from temperature variations using ferroelectric materials as a microgenerator. The previous researches show that direct pyroelectric energy harvesting is not effective, whereas thermodynamic-based cycles give higher energy. Also, at different temperatures some thermodynamic cycles exhibit different behaviours. In this paper pyroelectric energy harvesting using Lenoir and Ericsson thermodynamic cycles has been studied numerically and the two cycles were c...

The discovery of thermodynamics

Science.gov (United States)

Weinberger, Peter

2013-07-01

Based on the idea that a scientific journal is also an "agora" (Greek: market place) for the exchange of ideas and scientific concepts, the history of thermodynamics between 1800 and 1910 as documented in the Philosophical Magazine Archives is uncovered. Famous scientists such as Joule, Thomson (Lord Kelvin), Clausius, Maxwell or Boltzmann shared this forum. Not always in the most friendly manner. It is interesting to find out, how difficult it was to describe in a scientific (mathematical) language a phenomenon like "heat", to see, how long it took to arrive at one of the fundamental principles in physics: entropy. Scientific progress started from the simple rule of Boyle and Mariotte dating from the late eighteenth century and arrived in the twentieth century with the concept of probabilities. Thermodynamics was the driving intellectual force behind the industrial revolution, behind the enormous social changes caused by this revolution. The history of thermodynamics is a fascinating story, which also gives insights into the mechanism that seem to govern science.

Statistical thermodynamics of alloys

CERN Document Server

Gokcen, N A

1986-01-01

This book is intended for scientists, researchers, and graduate students interested in solutions in general, and solutions of metals in particular. Readers are assumed to have a good background in thermodynamics, presented in such books as those cited at the end of Chapter 1, "Thermo­ dynamic Background." The contents of the book are limited to the solutions of metals + metals, and metals + metalloids, but the results are also appli­ cable to numerous other types of solutions encountered by metallurgists, materials scientists, geologists, ceramists, and chemists. Attempts have been made to cover each topic in depth with numerical examples whenever necessary. Chapter 2 presents phase equilibria and phase diagrams as related to the thermodynamics of solutions. The emphasis is on the binary diagrams since the ternary diagrams can be understood in terms of the binary diagrams coupled with the phase rule, and the Gibbs energies of mixing. The cal­ culation of thermodynamic properties from the phase diagrams is ...

Differential Scanning Calorimetry and Thermodynamic Predictions—A Comparative Study of Al-Zn-Mg-Cu Alloys

Directory of Open Access Journals (Sweden)

Gernot K.-H. Kolb

2016-08-01

Full Text Available Al-Zn-Mg-Cu alloys are widely used in aircraft applications because of their superior mechanical properties and strength/weight ratios. Commercial Al-Zn-Mg-Cu alloys have been intensively studied over the last few decades. However, well-considered thermodynamic calculations, via the CALPHAD approach, on a variation of alloying elements can guide the fine-tuning of known alloy systems and the development of optimized heat treatments. In this study, a comparison was made of the solidus temperatures of different Al-Zn-Mg-Cu alloys determined from thermodynamic predictions and differential scanning calorimetry (DSC measurements. A variation of the main alloying elements Zn, Mg, and Cu generated 38 experimentally produced alloys. An experimental determination of the solidus temperature via DSC was carried out according to a user-defined method, because the broad melting interval present in Al-Zn-Mg-Cu alloys does not allow the use of the classical onset method for pure substances. The software algorithms implemented in FactSage®, Pandat™, and MatCalc with corresponding commercially available databases were deployed for thermodynamic predictions. Based on these investigations, the predictive power of the commercially available CALPHAD databases and software packages was critically reviewed.

Thermodynamic simulation of biomass gas steam reforming for a solid oxide fuel cell (SOFC system

Directory of Open Access Journals (Sweden)

A. Sordi

2009-12-01

Full Text Available This paper presents a methodology to simulate a small-scale fuel cell system for power generation using biomass gas as fuel. The methodology encompasses the thermodynamic and electrochemical aspects of a solid oxide fuel cell (SOFC, as well as solves the problem of chemical equilibrium in complex systems. In this case the complex system is the internal reforming of biomass gas to produce hydrogen. The fuel cell input variables are: operational voltage, cell power output, composition of the biomass gas reforming, thermodynamic efficiency, electrochemical efficiency, practical efficiency, the First and Second law efficiencies for the whole system. The chemical compositions, molar flows and temperatures are presented to each point of the system as well as the exergetic efficiency. For a molar water/carbon ratio of 2, the thermodynamic simulation of the biomass gas reforming indicates the maximum hydrogen production at a temperature of 1070 K, which can vary as a function of the biomass gas composition. The comparison with the efficiency of simple gas turbine cycle and regenerative gas turbine cycle shows the superiority of SOFC for the considered electrical power range.

First-principles calculations of bulk and interfacial thermodynamic properties for fcc-based Al-Sc alloys

International Nuclear Information System (INIS)

Asta, M.; Foiles, S.M.; Quong, A.A.

1998-01-01

The configurational thermodynamic properties of fcc-based Al-Sc alloys and coherent Al/Al 3 Sc interphase-boundary interfaces have been calculated from first principles. The computational approach used in this study combines the results of pseudopotential total-energy calculations with a cluster-expansion description of the alloy energetics. Bulk and interface configurational-thermodynamic properties are computed using a low-temperature-expansion technique. Calculated values of the {100} and {111} Al/Al 3 Sc interfacial energies at zero temperature are, respectively, 192 and 226mJ/m 2 . The temperature dependence of the calculated interfacial free energies is found to be very weak for {100} and more appreciable for {111} orientations; the primary effect of configurational disordering at finite temperature is to reduce the degree of crystallographic anisotropy associated with calculated interfacial free energies. The first-principles-computed solid-solubility limits for Sc in bulk fcc Al are found to be underestimated significantly in comparison with experimental measurements. It is argued that this discrepancy can be largely attributed to nonconfigurational contributions to the entropy which have been neglected in the present thermodynamic calculations. copyright 1998 The American Physical Society

Thermodynamics-based models of transcriptional regulation with gene sequence.

Science.gov (United States)

Wang, Shuqiang; Shen, Yanyan; Hu, Jinxing

2015-12-01

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

International thermodynamic tables of the fluid state propylene (propene)

CERN Document Server

Angus, S; De Reuck, K M

2013-01-01

International Thermodynamic Tables of the Fluid State - 7 Propylene (Propene) is a compilation of internationally agreed values of the equilibrium thermodynamic properties of propylene. This book is composed of three chapters, and begins with the presentation of experimental result of thermodynamic studies compared with the equations used to generate the tables. The succeeding chapter deals with correlating equations for thermodynamic property determination of propylene. The last chapter provides the tabulations of the propylene's thermodynamic properties and constants. This book will prove

New methods of thermodynamics; Nouvelles methodes en thermodynamique

Energy Technology Data Exchange (ETDEWEB)

NONE

2001-07-01

This day, organized by the SFT French Society of Thermology, took stock on the new methods in the domain of the thermodynamics. Eight papers have been presented during this day: new developments of the thermodynamics in finite time; the optimal efficiency of energy converters; a version of non-equilibrium thermodynamics with entropy and information as positive and negative thermal change; the role of thermodynamics in process integration; application of the thermodynamics to critical nuclear accidents; the entropic analysis help in the case of charge and discharge state of an energy storage process; fluid flow threw a stable state in the urban hydraulic; a computer code for phase diagram prediction. (A.L.B.)

Modern Thermodynamics Based on the Extended Carnot Theorem

CERN Document Server

Wang, Jitao

2012-01-01

"Modern Thermodynamics- Based on the Extended Carnot Theorem" provides comprehensive definitions and mathematical expressions of both classical and modern thermodynamics. The goal is to develop the fundamental theory on an extended Carnot theorem without incorporating any extraneous assumptions. In particular, it offers a fundamental thermodynamic and calculational methodology for the synthesis of low-pressure diamonds. It also discusses many "abnormal phenomena", such as spiral reactions, cyclic reactions, chemical oscillations, low-pressure carat-size diamond growth, biological systems, and more. The book is intended for chemists and physicists working in thermodynamics, chemical thermodynamics, phase diagrams, biochemistry and complex systems, as well as graduate students in these fields. Jitao Wang is a professor emeritus at Fudan University, Shanghai, China.

A thermodynamic evaluation of the Fe-Nb system

International Nuclear Information System (INIS)

Srikanth, S.; Petric, A.

1994-01-01

An optimised set of thermodynamic functions consistent with the phase diagram was derived for the Fe-Nb system from information on phase equilibria and thermodynamic data available in the literature. The thermodynamic properties of the intermediate ε (Fe 2 Nb) phase were described using the sublattice model. A Redlich-Kister equation was used to describe the excess thermodynamic functions of the liquid, bcc and fcc phases. For the μ phase, the enthalpy of formation was estimated from Miedema's model. The interaction coefficients were evaluated using an optimisation procedure employing a conjugate gradient method. The phase diagram and the thermodynamic functions calculated from the evaluated parameters are in good agreement with experimental data. (orig.)

Thermodynamic analysis of a refrigeration cycle using regenerative heat exchanger - suction/liquid line

Energy Technology Data Exchange (ETDEWEB)

Tebchirani, Tarik Linhares; Matos, Rudmar Serafim [Pos graduate Programme in Mechanical Engineering (PGMEC), Universidade Federal do Parana, Curitiba, PR (Brazil)], e-mails: tarik@utfpr.edu.br, rudmar@demec.ufpr.br

2010-07-01

This paper presents results from thermodynamic comparison of a conventional compression cycle and a steam cycle that uses a heat exchanger countercurrent (liquid line/suction line) in an air conditioning system split. The main objective is to study the relationship between the COP and the mass variation of refrigerant to the effectiveness of the heat exchanger. The papers presented in the literature discuss the matter in a theoretical way, are summarized in tables of rare loss statements without specification of methods. The methodology of work is based on testing of an air conditioner operating conventionally and also with the heat exchanger for the determination of values and parameters of interest. The tests were performed in a thermal chamber with temperature controlled and equipped with a data acquisition system for reading and storage results. The refrigerant was R22. Besides making possible an assessment of the feasibility of cost-benefit thermodynamics, it is suggested a different method for installing the equipment type split. (author)

Thermodynamics and kinetics of RNA tertiary structure formation in the junctionless hairpin ribozyme.

Science.gov (United States)

White, Neil A; Hoogstraten, Charles G

2017-09-01

The hairpin ribozyme consists of two RNA internal loops that interact to form the catalytically active structure. This docking transition is a rare example of intermolecular formation of RNA tertiary structure without coupling to helix annealing. We have used temperature-dependent surface plasmon resonance (SPR) to characterize the thermodynamics and kinetics of RNA tertiary structure formation for the junctionless form of the ribozyme, in which loops A and B reside on separate molecules. We find docking to be strongly enthalpy-driven and to be accompanied by substantial activation barriers for association and dissociation, consistent with the structural reorganization of both internal loops upon complex formation. Comparisons with the parallel analysis of a ribozyme variant carrying a 2'-O-methyl modification at the self-cleavage site and with published data in other systems reveal a surprising diversity of thermodynamic signatures, emphasizing the delicate balance of contributions to the free energy of formation of RNA tertiary structure. Copyright © 2017 Elsevier B.V. All rights reserved.

Thermodynamics for the Formation of Double-Stranded DNA-Single-Walled Carbon Nanotube Hybrids.

Science.gov (United States)

Shiraki, Tomohiro; Tsuzuki, Akiko; Toshimitsu, Fumiyuki; Nakashima, Naotoshi

2016-03-24

For the first time, the thermodynamics are described for the formation of double-stranded DNA (ds-DNA)-single-walled carbon nanotube (SWNT) hybrids. This treatment is applied to the exchange reaction of sodium cholate (SC) molecules on SWNTs and the ds-DNAs d(A)20 -d(T)20 and nuclear factor (NF)-κB decoy. UV/Vis/near-IR spectroscopy with temperature variations was used for analyzing the exchange reaction on the SWNTs with four different chiralities: (n,m)=(8,3), (6,5), (7,5), and (8,6). Single-stranded DNAs (ss-DNAs), including d(A)20 and d(T)20, are also used for comparison. The d(A)20-d(T)20 shows a drastic change in its thermodynamic parameters around the melting temperature (Tm ) of the DNA oligomer. No such Tm dependency was measured, owing to high Tm in the NF-κB decoy DNA and no Tm in the ss-DNA. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Use of thermodynamic calculation to predict the effect of Si on the ageing behavior of Al-Mg-Si-Cu alloys

International Nuclear Information System (INIS)

Ji, Yanli; Zhong, Hao; Hu, Ping; Guo, Fuan

2011-01-01

Research highlights: → Thermodynamic calculation can predict the ageing behavior of 6xxx alloys. → The hardness level of the alloys depends on the Si content in as-quenched matrix. → The precipitation strengthening effect depends on the Mg 2 Si level of the alloys. -- Abstract: Thermodynamic calculation was employed to predict the influence of Si content on the ageing behavior of Al-Mg-Si-Cu alloys. In addition, experiments were carried out to verify the predictions. The results show that thermodynamic calculation can predict the effect of Si content on the ageing behavior of the studied alloys. This study further proposes that the hardness level of alloys during ageing is directly related to the Si content in the as-quenched supersaturated solution, while the precipitation strengthening effect is directly related to the Mg 2 Si level of the alloys.

Thermodynamic properties of gaseous ruthenium species.

Science.gov (United States)

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

2015-05-21

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

Development of Thermodynamic Conceptual Evaluation

Science.gov (United States)

Talaeb, P.; Wattanakasiwich, P.

2010-07-01

This research aims to develop a test for assessing student understanding of fundamental principles in thermodynamics. Misconceptions found from previous physics education research were used to develop the test. Its topics include heat and temperature, the zeroth and the first law of thermodynamics, and the thermodynamics processes. The content validity was analyzed by three physics experts. Then the test was administered to freshmen, sophomores and juniors majored in physics in order to determine item difficulties and item discrimination of the test. A few items were eliminated from the test. Finally, the test will be administered to students taking Physics I course in order to evaluate the effectiveness of Interactive Lecture Demonstrations that will be used for the first time at Chiang Mai University.

Statistical thermodynamics of clustered populations.

Science.gov (United States)

Matsoukas, Themis

2014-08-01

We present a thermodynamic theory for a generic population of M individuals distributed into N groups (clusters). We construct the ensemble of all distributions with fixed M and N, introduce a selection functional that embodies the physics that governs the population, and obtain the distribution that emerges in the scaling limit as the most probable among all distributions consistent with the given physics. We develop the thermodynamics of the ensemble and establish a rigorous mapping to regular thermodynamics. We treat the emergence of a so-called giant component as a formal phase transition and show that the criteria for its emergence are entirely analogous to the equilibrium conditions in molecular systems. We demonstrate the theory by an analytic model and confirm the predictions by Monte Carlo simulation.

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

International Nuclear Information System (INIS)

Hamm, L.L.; Van Brunt, V.

1982-08-01

A comparison of implicit Runge-Kutta and orthogonal collocation methods is made for the numerical solution to the ordinary differential equation which describes the high-pressure vapor-liquid equilibria of a binary system. The systems of interest are limited to binary solubility systems where one of the components is supercritical and exists as a noncondensable gas in the pure state. Of the two methods - implicit Runge-Kuta and orthogonal collocation - this paper attempts to present some preliminary but not necessarily conclusive results that the implicit Runge-Kutta method is superior for the solution to the ordinary differential equation utilized in the thermodynamic consistency testing of binary solubility systems. Due to the extreme nonlinearity of thermodynamic properties in the region near the critical locus, an extended cubic spline fitting technique is devised for correlating the P-x data. The least-squares criterion is employed in smoothing the experimental data. Even though the derivation is presented specifically for the correlation of P-x 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

Size- and shape-dependent surface thermodynamic properties of nanocrystals

Science.gov (United States)

Fu, Qingshan; Xue, Yongqiang; Cui, Zixiang

2018-05-01

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

Modern thermodynamics from heat engines to dissipative structures

CERN Document Server

Kondepudi, Dilip

2014-01-01

Modern Thermodynamics: From Heat Engines to Dissipative Structures, Second Edition presents a comprehensive introduction to 20th century thermodynamics that can be applied to both equilibrium and non-equilibrium systems, unifying what was traditionally divided into 'thermodynamics' and 'kinetics' into one theory of irreversible processes. This comprehensive text, suitable for introductory as well as advanced courses on thermodynamics, has been widely used by chemists, physicists, engineers and geologists.  Fully revised and expanded, this new edition includes the following updates and featur

Concepts of the First Law of Thermodynamic and of Energy. As analysis methods of energetic system operation

International Nuclear Information System (INIS)

Hernandez, L.F.

1998-01-01

The technologies developed from 1973 on rational use, conservation and efficiency in the use of energy updated in a framework of sustain ability energetic and environment protection, it has not taken into account the concepts of quality of energy within of any energetic system (Source - Technology - Final Use), neither the favorable economic and technical implications of adopting the concepts of the Exergy and of exegetic efficiency, derivatives from the Second Law of the Thermodynamic, those which should be included as methods in the environmental and economic technical evaluations of an energetic system. This article presents the basic development of the concepts referenced from the Zero Law of the Thermodynamic, illustrating with examples the advantages to incorporate them as valuation and comparison parameters

Mechanics, Waves and Thermodynamics

Science.gov (United States)

Ranjan Jain, Sudhir

2016-05-01

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

Thermodynamics of Fluids Under Flow Second Edition

CERN Document Server

Jou, David; Criado-Sancho, Manuel

2011-01-01

This is the second edition of the book “Thermodynamics of Fluids under Flow,” which was published in 2000 and has now been corrected, expanded and updated. This is a companion book to our other title Extended irreversible thermodynamics (D. Jou, J. Casas-Vázquez and G. Lebon, Springer, 4th edition 2010), and of the textbook Understanding non-equilibrium thermodynamics (G. Lebon, D. Jou and J. Casas-Vázquez, Springer, 2008. The present book is more specialized than its counterpart, as it focuses its attention on the non-equilibrium thermodynamics of flowing fluids, incorporating non-trivial thermodynamic contributions of the flow, going beyond local equilibrium theories, i.e., including the effects of internal variables and of external forcing due to the flow. Whereas the book's first edition was much more focused on polymer solutions, with brief glimpses into ideal and real gases, the present edition covers a much wider variety of systems, such as: diluted and concentrated polymer solutions, polymer ble...

Thermodynamics of micellization from heat-capacity measurements.

Science.gov (United States)

Šarac, Bojan; Bešter-Rogač, Marija; Lah, Jurij

2014-06-23

Differential scanning calorimetry (DSC), the most important technique for studying the thermodynamics of structural transitions of biological macromolecules, is seldom used in quantitative thermodynamic studies of surfactant micellization/demicellization. The reason for this could be ascribed to an insufficient understanding of the temperature dependence of the heat capacity of surfactant solutions (DSC data) in terms of thermodynamics, which leads to problems with the design of experiments and interpretation of the output signals. We address these issues by careful design of DSC experiments performed with solutions of ionic and nonionic surfactants at various surfactant concentrations, and individual and global mass-action model analysis of the obtained DSC data. Our approach leads to reliable thermodynamic parameters of micellization for all types of surfactants, comparable with those obtained by using isothermal titration calorimetry (ITC). In summary, we demonstrate that DSC can be successfully used as an independent method to obtain temperature-dependent thermodynamic parameters for micellization. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An Experimental Determination of Thermodynamic Values

Science.gov (United States)

Antony, Erling; Muccianti, Christine; Vogel, Tracy

2012-01-01

Measurements have been added to an old demonstration of chemical equilibria allowing the determination of thermodynamic constants. The experiment allows the students an opportunity to merge qualitative observations associated with Le Chatelier's principle and thermodynamic calculations using graphical techniques. (Contains 4 figures.)

International thermodynamic tables of the fluid state helium-4

CERN Document Server

de Reuck, K M; McCarty, R D

2013-01-01

International Thermodynamic Tables of the Fluid State Helium-4 presents the IUPAC Thermodynamic Tables for the thermodynamic properties of helium. The IUPAC Thermodynamic Tables Project has therefore encouraged the critical analysis of the available thermodynamic measurements for helium and their synthesis into tables. This book is divided into three chapters. The first chapter discusses the experimental results and compares with the equations used to generate the tables. These equations are supplemented by a vapor pressure equation, which represents the 1958 He-4 scale of temperature that is

Irreversible thermodynamics of Poisson processes with reaction.

Science.gov (United States)

Méndez, V; Fort, J

1999-11-01

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

From thermodynamics to the solutions in gravity theory

International Nuclear Information System (INIS)

Zhang, Hongsheng; Li, Xin-Zhou

2014-01-01

In a recent work, we present a new point of view to the relation of gravity and thermodynamics, in which we derive the Schwarzschild solution through thermodynamic considerations by the aid of the Misner–Sharp mass in an adiabatic system. In this Letter we continue to investigate the relation between gravity and thermodynamics for obtaining solutions via thermodynamics. We generalize our studies on gravi-thermodynamics in Einstein gravity to modified gravity theories. By using the first law with the assumption that the Misner–Sharp mass is the mass for an adiabatic system, we reproduce the Boulware–Deser–Cai solution in Gauss–Bonnet gravity. Using this gravi-thermodynamic thought, we obtain a NEW class of solution in F(R) gravity in an n-dimensional (n≥3) spacetime which permits three-type (n−2)-dimensional maximally symmetric subspace, as an extension of our recent three-dimensional black hole solution, and four-dimensional Clifton–Barrow solution in F(R) gravity

From thermodynamics to the solutions in gravity theory

Directory of Open Access Journals (Sweden)

Hongsheng Zhang

2014-10-01

Full Text Available In a recent work, we present a new point of view to the relation of gravity and thermodynamics, in which we derive the Schwarzschild solution through thermodynamic considerations by the aid of the Misner–Sharp mass in an adiabatic system. In this Letter we continue to investigate the relation between gravity and thermodynamics for obtaining solutions via thermodynamics. We generalize our studies on gravi-thermodynamics in Einstein gravity to modified gravity theories. By using the first law with the assumption that the Misner–Sharp mass is the mass for an adiabatic system, we reproduce the Boulware–Deser–Cai solution in Gauss–Bonnet gravity. Using this gravi-thermodynamic thought, we obtain a NEW class of solution in F(R gravity in an n-dimensional (n≥3 spacetime which permits three-type (n−2-dimensional maximally symmetric subspace, as an extension of our recent three-dimensional black hole solution, and four-dimensional Clifton–Barrow solution in F(R gravity.

Quantum private comparison with d-level single-particle states

International Nuclear Information System (INIS)

Yu, Chao-Hua; Guo, Gong-De; Lin, Song

2013-01-01

In this paper, a quantum private comparison protocol with d-level single-particle states is proposed. In the protocol, a semi-honest third party is introduced to help two participants compare the size relationship of their secrets without revealing them to any other people. It is shown that the protocol is secure in theory. Moreover, the security of the protocol in real circumstance is also discussed. (paper)

Thermodynamic modeling of the stacking fault energy of austenitic steels

International Nuclear Information System (INIS)

Curtze, S.; Kuokkala, V.-T.; Oikari, A.; Talonen, J.; Haenninen, H.

2011-01-01

The stacking fault energies (SFE) of 10 austenitic steels were determined in the temperature range 50 ≤ T ≤ 600 K by thermodynamic modeling of the Fe-Cr-Ni-Mn-Al-Si-Cu-C-N system using a modified Olson and Cohen modeling approach (Olson GB, Cohen M. Metall Trans 1976;7A:1897 ). The applied model accounts for each element's contribution to the Gibbs energy, the first-order excess free energies, magnetic contributions and the effect of interstitial nitrogen. Experimental SFE values from X-ray diffraction measurements were used for comparison. The effect of SFE on deformation mechanisms was also studied by electron backscatter diffraction.

Thermodynamic behaviour of ruthenium at high temperatures

International Nuclear Information System (INIS)

Garisto, F.

1988-01-01

Thermodynamic equilibrium calculations are used to determine the chemical speciation of ruthenium under postulated reactor accident conditions. The speciation of ruthenium is determined for various values of temperature, pressure, oxygen partial pressure and ruthenium concentration. The importance of these variables, in particular the oxygen partial pressure, in determining the volatility of ruthenium is clearly demonstrated in this report. Reliable thermodynamic data are required to determine the behaviour of ruthenium using equilibrium calculations. Therefore, it was necessary to compile a thermodynamic database for the ruthenium species that can be formed under reactor accident conditions. The origin of the thermodynamic data for the ruthenium species included in our calculations is discussed in detail in Appendix A. 23 refs

The Dynamics of Heat A Unified Approach to Thermodynamics and Heat Transfer

CERN Document Server

Fuchs, Hans U

2010-01-01

Based on courses for students of science, engineering, and systems science at the Zurich University of Applied Sciences at Winterthur, this text approaches the fundamentals of thermodynamics from the point of view of continuum physics. By describing physical processes in terms of the flow and balance of physical quantities, the author achieves a unified approach to hydraulics, electricity, mechanics and thermodynamics. In this way, it becomes clear that entropy is the fundamental property that is transported in thermal processes (i.e., heat), and that temperature is the corresponding potential. The resulting theory of the creation, flow, and balance of entropy provides the foundation of a dynamical theory of heat. This extensively revised and updated second edition includes new material on dynamical chemical processes, thermoelectricity, and explicit dynamical modeling of thermal and chemical processes. To make the book more useful for courses on thermodynamics and physical chemistry at different levels, cove...

Binding thermodynamics discriminates fragments from druglike compounds: a thermodynamic description of fragment-based drug discovery.

Science.gov (United States)

Williams, Glyn; Ferenczy, György G; Ulander, Johan; Keserű, György M

2017-04-01

Small is beautiful - reducing the size and complexity of chemical starting points for drug design allows better sampling of chemical space, reveals the most energetically important interactions within protein-binding sites and can lead to improvements in the physicochemical properties of the final drug. The impact of fragment-based drug discovery (FBDD) on recent drug discovery projects and our improved knowledge of the structural and thermodynamic details of ligand binding has prompted us to explore the relationships between ligand-binding thermodynamics and FBDD. Information on binding thermodynamics can give insights into the contributions to protein-ligand interactions and could therefore be used to prioritise compounds with a high degree of specificity in forming key interactions. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

Science.gov (United States)

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.

Modern thermodynamics. Based on the extended Carnot theorem

Energy Technology Data Exchange (ETDEWEB)

Wang, Jitao [Fudan Univ., Shanghai (China). Microelectronics Dept.

2011-07-01

''Modern Thermodynamics- Based on the Extended Carnot Theorem'' provides comprehensive definitions and mathematical expressions of both classical and modern thermodynamics. The goal is to develop the fundamental theory on an extended Carnot theorem without incorporating any extraneous assumptions. In particular, it offers a fundamental thermodynamic and calculational methodology for the synthesis of low-pressure diamonds. It also discusses many ''abnormal phenomena'', such as spiral reactions, cyclic reactions, chemical oscillations, low-pressure carat-size diamond growth, biological systems, and more. The book is intended for chemists and physicists working in thermodynamics, chemical thermodynamics, phase diagrams, biochemistry and complex systems, as well as graduate students in these fields. Jitao Wang is a professor emeritus at Fudan University, Shanghai, China. (orig.)

Comparison of norovirus RNA levels in outbreak-related oysters with background environmental levels.

Science.gov (United States)

Lowther, James A; Gustar, Nicole E; Hartnell, Rachel E; Lees, David N

2012-02-01

Norovirus is the principal agent of bivalve shellfish-associated gastroenteric illness worldwide. Numerous studies using PCR have demonstrated norovirus contamination in a significant proportion of both oyster and other bivalve shellfish production areas and ready-to-eat products. By comparison, the number of epidemiologically confirmed shellfish-associated outbreaks is relatively low. This suggests that factors other than the simple presence or absence of virus RNA are important contributors to the amount of illness reported. This study compares norovirus RNA levels in oyster samples strongly linked to norovirus or norovirus-type illness with the levels typically found in commercial production areas (non-outbreak-related samples). A statistically significant difference between norovirus levels in the two sets of samples was observed. The geometric mean of the levels in outbreak samples (1,048 copies per g) was almost one order of magnitude higher than for positive non-outbreak-related samples (121 copies per g). Further, while none of the outbreak-related samples contained fewer than 152 copies per g, the majority of positive results for non-outbreak-related samples was below this level. These observations support the concept of a dose-response for norovirus RNA levels in shellfish and could help inform the establishment of threshold criteria for risk management.

Lactation yield: Interval level comparison of milk records for genetic ...

African Journals Online (AJOL)

1220 records ... Lactation yield: Interval level comparison of milk records for genetic improvement in Friesian vs Arsi crossbred cows in the highlands of south eastern. Ethiopia. Dumar Wabe1 and Kassahun Asmare2. 1Allage Agricultural Technical, Vocational Education Training College, P.O. Box 077. 2School of Veterinary ...

Thermodynamic properties of uranium--mercury system

International Nuclear Information System (INIS)

Lee, T.S.

1979-01-01

The EMF values in the fused salt cells of the type U(α)/KCl--LiCl--BaCl 2 eutectic, UCl 3 /U--Hg alloy, for the different two-phase alloys in the uranium--mercury system have been measured and the thermodynamic properties of this system have been calculated. These calculated values are in good agreement with values based on mercury vapor pressure measurements made by previous investigators. The inconsistency of the thermodynamic properties with the phase diagram determined by Frost are also confirmed. A tentative phase diagram based on the thermodynamic properties measured in this work was constructed

Using Rubber-Elastic Material-Ideal Gas Analogies To Teach Introductory Thermodynamics. Part II: The Laws of Thermodynamics.

Science.gov (United States)

Smith, Brent

2002-01-01

Describes the laws of thermodynamics as a supplement to an introductory thermodynamics undergraduate course. Uses rubber-elastic materials (REM) which have strong analogies to the concept of ideal gas. Provides examples of the analogies between ideal gas and REM and mathematical analogies. (YDS)

Thermodynamic stability of biomolecules and evolution.

Science.gov (United States)

Chakravarty, Ashim K

2017-08-01

The thermodynamic stability of biomolecules in the perspective of evolution is a complex issue and needs discussion. Intra molecular bonds maintain the structure and the state of internal energy (E) of a biomolecule at "local minima". In this communication, possibility of loss in internal energy level of a biomolecule through the changes in the bonds has been discussed, that might earn more thermodynamic stability for the molecule. In the process variations in structure and functions of the molecule could occur. Thus, E of a biomolecule is likely to have energy stature for minimization. Such change in energy status is an intrinsic factor for evolving biomolecules buying more stability and generating variations in the structure and function of DNA molecules undergoing natural selection. Thus, the variations might very well contribute towards the process of evolution. A brief discussion on conserved sequence in the light of proposition in this communication has been made at the end. Extension of the idea may resolve certain standing problems in evolution, such as maintenance of conserved sequences in genome of diverse species, pre- versus post adaptive mutations, 'orthogenesis', etc. Copyright © 2017 Elsevier Ltd. All rights reserved.

Assessment of thermodynamic models for the design, analysis and optimisation of gas liquefaction systems

International Nuclear Information System (INIS)

Nguyen, Tuong-Van; Elmegaard, Brian

2016-01-01

Highlights: • Six thermodynamic models used for evaluating gas liquefaction systems are compared. • Three gas liquefaction systems are modelled, assessed and optimised for each equation of state. • The predictions of thermophysical properties and energy flows are significantly different. • The GERG-2008 model is the only consistent one, while cubic, virial and statistical equations are unsatisfying. - Abstract: Natural gas liquefaction systems are based on refrigeration cycles – they consist of the same operations such as heat exchange, compression and expansion, but they have different layouts, components and working fluids. The design of these systems requires a preliminary simulation and evaluation of their performance. However, the thermodynamic models used for this purpose are characterised by different mathematical formulations, ranges of application and levels of accuracy. This may lead to inconsistent results when estimating hydrocarbon properties and assessing the efficiency of a given process. This paper presents a thorough comparison of six equations of state widely used in the academia and industry, including the GERG-2008 model, which has recently been adopted as an ISO standard for natural gases. These models are used to (i) estimate the thermophysical properties of a Danish natural gas, (ii) simulate, and (iii) optimise liquefaction systems. Three case studies are considered: a cascade layout with three pure refrigerants, a single mixed-refrigerant unit, and an expander-based configuration. Significant deviations are found between all property models, and in all case studies. The main discrepancies are related to the prediction of the energy flows (up to 7%) and to the heat exchanger conductances (up to 11%), and they are not systematic errors. The results illustrate the superiority of using the GERG-2008 model for designing gas processes in real applications, with the aim of reducing their energy use. They demonstrate as well that

Thermodynamic data for predicting concentrations of Th(IV), U(IV), Np(IV), and Pu(IV) in geologic environments

Energy Technology Data Exchange (ETDEWEB)

Rai, Dhanpat; Roa, Linfeng; Weger, H.T.; Felmy, A.R. [Battelle, Pacific Northwest National Laboratory (PNNL) (United States); Choppin, G.R. [Florida State University (United States); Yui, Mikazu [Waste Isolation Research Division, Tokai Works, Japan Nuclear Cycle Development Inst., Tokai, Ibaraki (Japan)

1999-01-01

This report provides thermodynamic data for predicting concentrations of Th(IV), U(IV), Np(IV), and Pu(IV) in geologic environments, and contributes to an integration of the JNC chemical thermodynamic database, JNC-TDB (previously PNC-TDB), for the performance analysis of geological isolation system for high-level radioactive wastes. Thermodynamic data for the formation of complexes or compounds with hydroxide, chloride, fluoride, carbonate, nitrate, sulfate and phosphate are discussed in this report. Where data for specific actinide(IV) species was lacking, the data were selected based on chemical analogy to other tetravalent actinides. In this study, the Pitzer ion-interaction model is used to extrapolate thermodynamic constants to zero ionic strength at 25degC. (author)

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

Science.gov (United States)

Dron, Julien; Dodi, Alain

2011-03-15

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

Complexation thermodynamics of modified cyclodextrins

DEFF Research Database (Denmark)

Schönbeck, Jens Christian Sidney; Westh, Peter; Holm, Rene

2014-01-01

Inclusion complexes between two bile salts and a range of differently methylated β-cyclodextrins were studied in an attempt to rationalize the complexation thermodynamics of modified cyclodextrins. Calorimetric titrations at a range of temperatures provided precise values of the enthalpies (ΔH......°), entropies (ΔS°), and heat capacities (ΔCp) of complexation, while molecular dynamics simulations assisted the interpretation of the obtained thermodynamic parameters. As previously observed for several types of modified cyclodextrins, the substituents at the rims of the cyclodextrin induced large changes......° and then a strong decrease when the degree of substitution exceeded some threshold. Exactly the same trend was observed for ΔCp. The dehydration of nonpolar surface, as quantified by the simulations, can to a large extent explain the variation in the thermodynamic parameters. The methyl substituents form additional...

Warming to ecocide a thermodynamic diagnosis

CERN Document Server

Sangster, Alan J

2011-01-01

Suggests a route to avoiding runaway climate change by reinstating the greenhouse thermostat to its full operational capacity Addresses mankind's contribution to climate change from a thermodynamic perspective Describes and illustrates the power of thermodynamics to furnish insights into the thermal behaviour of complex physical systems

Thermodynamic modeling of the Co-Fe-O system

DEFF Research Database (Denmark)

Zhang, Weiwei; Chen, Ming

2013-01-01

As a part of the research project aimed at developing a thermodynamic database of the La-Sr-Co-Fe-O system for applications in Solid Oxide Fuel Cells (SOFCs), the Co-Fe-O subsystem was thermodynamically re-modeled in the present work using the CALPHAD methodology. The solid phases were described...... using the Compound Energy Formalism (CEF) and the ionized liquid was modeled with the ionic two-sublattice model based on CEF. A set of self-consistent thermodynamic parameters was obtained eventually. Calculated phase diagrams and thermodynamic properties are presented and compared with experimental...

Thermodynamic Modeling of Savannah River Evaporators

Energy Technology Data Exchange (ETDEWEB)

Weber, C.F.

2001-08-02

A thermodynamic model based on the code SOLGASMIX is developed to calculate phase equilibrium in evaporators and related tank wastes at the Savannah River Site (SRS). This model uses the Pitzer method to calculate activity coefficients, and many of the required Pitzer parameters have been determined in the course of this work. Principal chemical species in standard SRS simulant solutions are included, and the temperature range for most parameters has been extended above 100 C. The SOLGASMIX model and calculations using the code Geochemists Workbench are compared to actual solubility data including silicate, aluminate, and aluminosilicate solutions. In addition, SOLGASMIX model calculations are also compared to transient solubility data involving SRS simulant solutions. These comparisons indicate that the SOLGASMIX predictions closely match reliable data over the range of temperature and solution composition expected in the SRS evaporator and related tanks. Predictions using the Geochemists Workbench may be unreliable, due primarily to the use of an inaccurate activity coefficient model.

Non-Equilibrium Thermodynamics in Multiphase Flows

CERN Document Server

Mauri, Roberto

2013-01-01

Non-equilibrium thermodynamics is a general framework that allows the macroscopic description of irreversible processes. This book introduces non-equilibrium thermodynamics and its applications to the rheology of multiphase flows. The subject is relevant to graduate students in chemical and mechanical engineering, physics and material science. This book is divided into two parts. The first part presents the theory of non-equilibrium thermodynamics, reviewing its essential features and showing, when possible, some applications. The second part of this book deals with how the general theory can be applied to model multiphase flows and, in particular, how to determine their constitutive relations. Each chapter contains problems at the end, the solutions of which are given at the end of the book. No prior knowledge of statistical mechanics is required; the necessary prerequisites are elements of transport phenomena and on thermodynamics. “The style of the book is mathematical, but nonetheless it remains very re...

Simulated pressure denaturation thermodynamics of ubiquitin.

Science.gov (United States)

Ploetz, Elizabeth A; Smith, Paul E

2017-12-01

Simulations of protein thermodynamics are generally difficult to perform and provide limited information. It is desirable to increase the degree of detail provided by simulation and thereby the potential insight into the thermodynamic properties of proteins. In this study, we outline how to analyze simulation trajectories to decompose conformation-specific, parameter free, thermodynamically defined protein volumes into residue-based contributions. The total volumes are obtained using established methods from Fluctuation Solution Theory, while the volume decomposition is new and is performed using a simple proximity method. Native and fully extended ubiquitin are used as the test conformations. Changes in the protein volumes are then followed as a function of pressure, allowing for conformation-specific protein compressibility values to also be obtained. Residue volume and compressibility values indicate significant contributions to protein denaturation thermodynamics from nonpolar and coil residues, together with a general negative compressibility exhibited by acidic residues. Copyright © 2017 Elsevier B.V. All rights reserved.

How to make thermodynamic perturbation theory to be suitable for low temperature?

Science.gov (United States)

Zhou, Shiqi

2009-02-07

Low temperature unsuitability is a problem plaguing thermodynamic perturbation theory (TPT) for years. Present investigation indicates that the low temperature predicament can be overcome by employing as reference system a nonhard sphere potential which incorporates one part of the attractive ingredient in a potential function of interest. In combination with a recently proposed TPT [S. Zhou, J. Chem. Phys. 125, 144518 (2006)] based on a lambda expansion (lambda being coupling parameter), the new perturbation strategy is employed to predict for several model potentials. It is shown that the new perturbation strategy can very accurately predict various thermodynamic properties even if the potential range is extremely short and hence the temperature of interest is very low and current theoretical formalisms seriously deteriorate or critically fail to predict even the existence of the critical point. Extensive comparison with existing liquid state theories and available computer simulation data discloses a superiority of the present TPT to two Ornstein-Zernike-type integral equation theories, i.e., hierarchical reference theory and self-consistent Ornstein-Zernike approximation.

Speeds of Propagation in Classical and Relativistic Extended Thermodynamics

Directory of Open Access Journals (Sweden)

Müller Ingo

1999-01-01

Full Text Available The Navier-Stokes-Fourier theory of viscous, heat-conducting fluids provides parabolic equations and thus predicts infinite pulse speeds. Naturally this feature has disqualified the theory for relativistic thermodynamics which must insist on finite speeds and, moreover, on speeds smaller than $c$. The attempts at a remedy have proved heuristically important for a new systematic type of thermodynamics: Extended thermodynamics. That new theory has symmetric hyperbolic field equations and thus it provides finite pulse speeds. Extended thermodynamics is a whole hierarchy of theories with an increasing number of fields when gradients and rates of thermodynamic processes become steeper and faster. The first stage in this hierarchy is the 14-field theory which may already be a useful tool for the relativist in many applications. The 14 fields -- and further fields -- are conveniently chosen from the moments of the kinetic theory of gases. The hierarchy is complete only when the number of fields tends to infinity. In that case the pulse speed of non-relativistic extended thermodynamics tends to infinity while the pulse speed of relativistic extended thermodynamics tends to $c$, the speed of light. In extended thermodynamics symmetric hyperbolicity -- and finite speeds -- are implied by the concavity of the entropy density. This is still true in relativistic thermodynamics for a privileged entropy density which is the entropy density of the rest frame for non-degenerate gases.

Phase equilibria and thermodynamics of the Fe–Al–C system: Critical evaluation, experiment and thermodynamic optimization

International Nuclear Information System (INIS)

Phan, Anh Thu; Paek, Min-Kyu; Kang, Youn-Bae

2014-01-01

In order to provide an efficient tool to design alloy chemistry and processing conditions for high-strength, lightweight steel, an investigation of the Fe–Al–C ternary system was carried out by experimental phase diagram measurement and a CALPHAD thermodynamic analysis. Discrepancies between previously available experimental results and thermodynamic calculations were identified. The Fe–Al sub-binary system was re-optimized in order to obtain an accurate description of the liquid phase, while Gibbs energies of solid phases were mainly taken from a previous thermodynamic modeling. Phase equilibria among face-centered cubic (fcc)/body-centered cubic (bcc)/graphite/κ-carbide/liquid phases in the Fe–Al–C system in the temperature range from 1000 to 1400 °C were obtained by chemical equilibration followed by quenching, and subsequent composition analysis using electron probe microanalysis/inductively coupled plasma spectroscopy. By merging the revised Fe–Al binary description with existing Fe–C and Al–C binary descriptions, a complete thermodynamic description of the Fe–Al–C system was obtained in the present study. The modified quasi-chemical model in the pair approximation was used to model the liquid phase, while solid solutions were modeled using compound energy formalism. A2/B2 order/disorder transition in the bcc phase was taken into account. Compared with previously known experiments/thermodynamic modeling, a better agreement was obtained in the present study, regarding the stable region of fcc and the solidification thermal peak of a ternary alloy near the liquidus temperature. The obtained thermodynamic description also reproduced various types of experimental data in the Fe–Al–C system such as isothermal sections, vertical sections, liquidus projection, etc. The solidification of various steel grades was predicted and discussed

Thermodynamic analysis and experimental investigation of a Solo V161 Stirling cogeneration unit

International Nuclear Information System (INIS)

Rogdakis, E.D.; Antonakos, G.D.; Koronaki, I.P.

2012-01-01

In order to investigate the Stirling engine implementation technology, a Solo Stirling Engine V161 cogeneration module has been installed at the Laboratory of Applied Thermodynamics of National Technical University of Athens. A special thermodynamic analysis of the engine's performance has been conducted introducing and utilizing specially designed computing codes along with the thermal balance study of the unit. Measurements were conducted under different operational conditions concerning various heat load stages of the engine, working pressure, as well as electric power production. Analysis of the experimental results has shown that the overall performance of the Stirling unit proved very promising and quite adequate for various areal applications, equally competing with other CHP systems. The performance of the unit experienced significant stability all over the operating range. The power stand ratio 0.35 differentiates Stirling cogeneration units from others that use diverging technologies significantly. The energy savings using a Stirling CHP unit, in respect to the concurrent use of a thermal and an electrical system at the same equivalent power has revealed 36.8%. -- Highlights: ► Thermodynamic analysis of an a-type Stirling engine. ► Development of generated electrical and thermal power of the m-CHP Solo Stirling Unit to engine's load comparison. ► Stirling m-CHP until heat balance analysis. ► Evaluation of the Solo Stirling V161 unit efficiency.

Statistical thermodynamics

CERN Document Server

Schrödinger, Erwin

1952-01-01

Nobel Laureate's brilliant attempt to develop a simple, unified standard method of dealing with all cases of statistical thermodynamics - classical, quantum, Bose-Einstein, Fermi-Dirac, and more.The work also includes discussions of Nernst theorem, Planck's oscillator, fluctuations, the n-particle problem, problem of radiation, much more.

Some consideration on the thermodynamics of the universe

International Nuclear Information System (INIS)

Hoenl, H.

1977-01-01

It is shown that the thermodynamics of the universe display certain features that are foreign to classical thermodynamics, the discrepancy having its origin in the cosmic expansion of the universe. This is apparent, for example, in the outstanding fact that in the early stages of the universe (some 10 5 or 10 6 years after the Big Bang) the distribution of matter was essentially homogeneous and, owing to the extremely high density and temperature, was in thermodynamic equilibrium. However, in its present state, after the formation of the celestial bodies, (the inhomogeneous phase of the universe), it has moved far away from thermodynamic equilibrium. It is stated that to prove entropy conservation during the homogeneous phase of the universe, one only needs the most general thermodynamical-statistical principles. (U,K)

Unified geometric description of black hole thermodynamics

International Nuclear Information System (INIS)

Alvarez, Jose L.; Quevedo, Hernando; Sanchez, Alberto

2008-01-01

In the space of thermodynamic equilibrium states we introduce a Legendre invariant metric which contains all the information about the thermodynamics of black holes. The curvature of this thermodynamic metric becomes singular at those points where, according to the analysis of the heat capacities, phase transitions occur. This result is valid for the Kerr-Newman black hole and all its special cases and, therefore, provides a unified description of black hole phase transitions in terms of curvature singularities.

Quantum thermodynamics: a nonequilibrium Green's function approach.

Science.gov (United States)

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

2015-02-27

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

Stochastic and Macroscopic Thermodynamics of Strongly Coupled Systems

Directory of Open Access Journals (Sweden)

Christopher Jarzynski

2017-01-01

Full Text Available We develop a thermodynamic framework that describes a classical system of interest S that is strongly coupled to its thermal environment E. Within this framework, seven key thermodynamic quantities—internal energy, entropy, volume, enthalpy, Gibbs free energy, heat, and work—are defined microscopically. These quantities obey thermodynamic relations including both the first and second law, and they satisfy nonequilibrium fluctuation theorems. We additionally impose a macroscopic consistency condition: When S is large, the quantities defined within our framework scale up to their macroscopic counterparts. By satisfying this condition, we demonstrate that a unifying framework can be developed, which encompasses both stochastic thermodynamics at one end, and macroscopic thermodynamics at the other. A central element in our approach is a thermodynamic definition of the volume of the system of interest, which converges to the usual geometric definition when S is large. We also sketch an alternative framework that satisfies the same consistency conditions. The dynamics of the system and environment are modeled using Hamilton’s equations in the full phase space.

UARS Solar-Stellar Irradiance Comparison Experiment (SOLSTICE) Level 3BS V001

Data.gov (United States)

National Aeronautics and Space Administration — The Solar-Stellar Irradiance Comparison Experiment (SOLSTICE) Level 3BS data product consists of daily, 1 nm resolution, solar spectral irradiances and selected...

Thermodynamics

International Nuclear Information System (INIS)

Zanchini, E.

1988-01-01

The definition of energy, in thermodynamics, is dependent by starting operative definitions of the basic concepts of physics on which it rests, such as those of isolated systems, ambient of a system, separable system and set of separable states. Then the definition of energy is rigorously extended to open systems. The extension gives a clear physical meaning to the concept of energy difference between two states with arbitrary different compositions

Thermodynamic extremal principles for irreversible processes in materials science

Czech Academy of Sciences Publication Activity Database

Fischer, F. D.; Svoboda, Jiří; Petryk, H.

2014-01-01

Roč. 67, APR (2014), s. 1-20 ISSN 1359-6454 Institutional support: RVO:68081723 Keywords : Non- equilibrium * Thermodynamics * Entropy * Onsager's principle * Thermodynamic extremal principles Subject RIV: BJ - Thermodynamics Impact factor: 4.465, year: 2014

Geometro-thermodynamics of tidal charged black holes

International Nuclear Information System (INIS)

Gergely, Laszlo Arpad; Pidokrajt, Narit; Winitzki, Sergei

2011-01-01

Tidal charged spherically symmetric vacuum brane black holes are characterized by their mass m and tidal charge q, an imprint of the five-dimensional Weyl curvature. For q>0 they are formally identical to the Reissner-Nordstroem black hole of general relativity. We study the thermodynamics and thermodynamic geometries of tidal charged black holes and discuss similarities and differences as compared to the Reissner-Nordstroe m black hole. As a similarity, we show that (for q>0) the heat capacity of the tidal charged black hole diverges on a set of measure zero of the parameter space, nevertheless both the regularity of the Ruppeiner metric and a Poincare stability analysis show no phase transition at those points. The thermodynamic state spaces being different indicates that the underlying statistical models could be different. We find that the q<0 parameter range, which enhances the localization of gravity on the brane, is thermodynamically preferred. Finally we constrain for the first time the possible range of the tidal charge from the thermodynamic limit on gravitational radiation efficiency at black hole mergers. (orig.)

Advanced thermodynamic (exergetic) analysis

International Nuclear Information System (INIS)

Tsatsaronis, G; Morosuk, T

2012-01-01

Exergy analysis is a powerful tool for developing, evaluating and improving an energy conversion system. However, the lack of a formal procedure in using the results obtained by an exergy analysis is one of the reasons for exergy analysis not being very popular among energy practitioners. Such a formal procedure cannot be developed as long as the interactions among components of the overall system are not being taken properly into account. Splitting the exergy destruction into unavoidable and avoidable parts in a component provides a realistic measure of the potential for improving the thermodynamic efficiency of this component. Alternatively splitting the exergy destruction into endogenous and exogenous parts provides information on the interactions among system components. Distinctions between avoidable and unavoidable exergy destruction on one side and endogenous and exogenous exergy destruction on the other side allow the engineer to focus on the thermodynamic inefficiencies that can be avoided and to consider the interactions among system components. The avoidable endogenous and the avoidable exogenous exergy destruction provide the best guidance for improving the thermodynamic performance of energy conversion systems.

Thermodynamic and dynamical properties of dense ICF plasma

Directory of Open Access Journals (Sweden)

Gabdullin Maratbek T.

2016-06-01

Full Text Available In present work, thermodynamic expressions were obtained through potentials that took into consideration long-range many-particle screening effects as well as short-range quantum-mechanical effects and radial distribution functions (RDFs. Stopping power of the projectile ions in dense, non-isothermal plasma was considered. One of the important values that describe the stopping power of the ions in plasma is the Coulomb logarithm. We investigated the stopping power of ions in inertial confinement fusion (ICF plasma and other energetic characteristics of fuel. Calculations of ions energy losses in the plasma for different values of the temperature and plasma density were carried out. A comparison of the calculated data of ion stopping power and energy deposition with experimental and theoretical results of other authors was also performed.

Understanding the edge effect in wetting: a thermodynamic approach.

Science.gov (United States)

Fang, Guoping; Amirfazli, A

2012-06-26

Edge effect is known to hinder spreading of a sessile drop. However, the underlying thermodynamic mechanisms responsible for the edge effect still is not well-understood. In this study, a free energy model has been developed to investigate the energetic state of drops on a single pillar (from upright frustum to inverted frustum geometries). An analysis of drop free energy levels before and after crossing the edge allows us to understand the thermodynamic origin of the edge effect. In particular, four wetting cases for a drop on a single pillar with different edge angles have been determined by understanding the characteristics of FE plots. A wetting map describing the four wetting cases is given in terms of edge angle and intrinsic contact angle. The results show that the free energy barrier observed near the edge plays an important role in determining the drop states, i.e., (1) stable or metastable drop states at the pillar's edge, and (2) drop collapse by liquid spilling over the edge completely or staying at an intermediate sidewall position of the pillar. This thermodynamic model presents an energetic framework to describe the functioning of the so-called "re-entrant" structures. Results show good consistency with the literature and expand the current understanding of Gibbs' inequality condition.

Statistical substantiation of introduction of the distributions containing lifetime as thermodynamic parameter

OpenAIRE

Ryazanov, V. V.

2007-01-01

By means of an inequality of the information and parametrization of family of distributions of the probabilities, supposing an effective estimation, introduction of the distributions containing time of the first achievement of a level as internal thermodynamic parameter ground.

An empirical method for calculating thermodynamic parameters for U(6) phases, applications to performance assessment calculations

International Nuclear Information System (INIS)

Ewing, R.C.; Chen, F.; Clark, S.B.

2002-01-01

Uranyl minerals form by oxidation and alteration of uraninite, UO 2+x , and the UO 2 in used nuclear fuels. The thermodynamic database for these phases is extremely limited. However, the Gibbs free energies and enthalpies for uranyl phases may be estimated based on a method that sums polyhedral contributions. The molar contributions of the structural components to Δ f G m 0 and Δ f H m 0 are derived by multiple regression using the thermodynamic data of phases for which the crystal structures are known. In comparison with experimentally determined values, the average residuals associated with the predicted Δ f G m 0 and Δ f H m 0 for the uranyl phases used in the model are 0.08 and 0.10%, respectively. There is also good agreement between the predicted mineral stability relations and field occurrences, thus providing confidence in this method for the estimation of Δ f G m 0 and Δ f H m 0 of the U(VI) phases. This approach provides a means of generating estimated thermodynamic data for performance assessment calcination and a basic for making bounding calcination of phase stabilities and solubilities. (author)

A Vector Representation for Thermodynamic Relationships

Science.gov (United States)

Pogliani, Lionello

2006-01-01

The existing vector formalism method for thermodynamic relationship maintains tractability and uses accessible mathematics, which can be seen as a diverting and entertaining step into the mathematical formalism of thermodynamics and as an elementary application of matrix algebra. The method is based on ideas and operations apt to improve the…

CTserver: A Computational Thermodynamics Server for the Geoscience Community

Science.gov (United States)

Kress, V. C.; Ghiorso, M. S.

2006-12-01

The CTserver platform is an Internet-based computational resource that provides on-demand services in Computational Thermodynamics (CT) to a diverse geoscience user base. This NSF-supported resource can be accessed at ctserver.ofm-research.org. The CTserver infrastructure leverages a high-quality and rigorously tested software library of routines for computing equilibrium phase assemblages and for evaluating internally consistent thermodynamic properties of materials, e.g. mineral solid solutions and a variety of geological fluids, including magmas. Thermodynamic models are currently available for 167 phases. Recent additions include Duan, Møller and Weare's model for supercritical C-O-H-S, extended to include SO2 and S2 species, and an entirely new associated solution model for O-S-Fe-Ni sulfide liquids. This software library is accessed via the CORBA Internet protocol for client-server communication. CORBA provides a standardized, object-oriented, language and platform independent, fast, low-bandwidth interface to phase property modules running on the server cluster. Network transport, language translation and resource allocation are handled by the CORBA interface. Users access server functionality in two principal ways. Clients written as browser- based Java applets may be downloaded which provide specific functionality such as retrieval of thermodynamic properties of phases, computation of phase equilibria for systems of specified composition, or modeling the evolution of these systems along some particular reaction path. This level of user interaction requires minimal programming effort and is ideal for classroom use. A more universal and flexible mode of CTserver access involves making remote procedure calls from user programs directly to the server public interface. The CTserver infrastructure relieves the user of the burden of implementing and testing the often complex thermodynamic models of real liquids and solids. A pilot application of this distributed

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

Science.gov (United States)

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

2015-07-01

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

Statistical mechanics and the foundations of thermodynamics

International Nuclear Information System (INIS)

Martin-Loef, A.

1979-01-01

These lectures are designed as an introduction to classical statistical mechanics and its relation to thermodynamics. They are intended to bridge the gap between the treatment of the subject in physics text books and the modern presentations of mathematically rigorous results. We shall first introduce the probability distributions, ensembles, appropriate for describing systems in equilibrium and consider some of their basic physical applications. We also discuss the problem of approach to equilibrium and how irreversibility comes into the dynamics. We then give a detailed description of how the law of large numbers for macrovariables in equilibrium is derived from the fact that entropy is an extensive quantity in the thermodynamic limit. We show in a natural way how to split the energy changes in an thermodynamical process into work and heat leading to a derivation of the first and second laws of thermodynamics from the rules of thermodynamical equilibrium. We have elaborated this part in detail because we feel it is quite satisfactory, that the establishment of the limit of thermodynamic functions as achieved in the modern development of the mathematical aspects of statistical mechanics allows a more general and logically clearer presentation of the bases of thermodynamics. We close these lectures by presenting the basic facts about fluctuation theory. The treatment aims to be reasonably self-contained both concerning the physics and mathematics needed. No knowledge of quantum mechanics is presupposed. Since we spent a large part on mathematical proofs and give many technical facts these lectures are probably most digestive for the mathematically inclined reader who wants to understand the physics of the subject. (HJ)

Hidden Symmetries for Thermodynamics and Emergence of Relativity

International Nuclear Information System (INIS)

Zhao Liu

2010-01-01

Erik Verlinde recently proposed an idea about the thermodynamic origin of gravity. Though this is a beautiful idea, which may resolve many long standing problems in the theories of gravity, it also raises many other problems. In this article I will comment on some of the problems of Verlinde's proposal with special emphasis on the thermodynamical origin of the principle of relativity. It is found that there is a large group of hidden symmetries of thermodynamics, which contains the Poincare group of the spacetime for which space is emergent. This explains the thermodynamic origin of the principle of relativity. (general)

Thermodynamic assessment of the Pd−Rh−Ru system using calphad and first-principles methods

Energy Technology Data Exchange (ETDEWEB)

Gossé, S., E-mail: stephane.gosse@cea.fr [DEN-Service de la Corrosion et du Comportement des Matériaux dans leur Environnement (SCCME), CEA, Université Paris-Saclay, F-91191, Gif-sur-Yvette (France); Dupin, N. [Calcul Thermodynamique, Rue de l' avenir, 63670, Orcet (France); Guéneau, C. [DEN-Service de la Corrosion et du Comportement des Matériaux dans leur Environnement (SCCME), CEA, Université Paris-Saclay, F-91191, Gif-sur-Yvette (France); Crivello, J.-C.; Joubert, J.-M. [Chimie Métallurgique des Terres Rares, Université Paris Est, ICMPE (UMR 7182), CNRS, UPEC, F-94320, Thiais (France)

2016-06-15

Palladium, rhodium and ruthenium are abundant fission products that form in oxide fuels in nuclear reactors. Under operating conditions, these Platinum-Group Metal (PGM) fission products accumulate in high concentration at the rim of the oxide fuel and mainly precipitate into metallic solid solutions. Their thermochemistry is of significant interest to predict the high temperature chemical interactions between the fuel and the cladding or the possible precipitation of PGM phases in high level nuclear waste glasses. To predict the thermodynamic properties of these PGM fission products, a thermodynamic modeling is being developed on the ternary Pd−Rh−Ru system using the Calphad method. Because experimental thermodynamic data are scarce, Special Quasirandom Structures coupled with Density Functional Theory methods were used to calculate mixing enthalpy data in the solid solutions. The resulting thermodynamic description based on only binary interaction parameters is in good agreement with the few data on the ternary system. - Highlights: • The mixing enthalpy of solid solutions in the Pd−Rh−Ru system was calculated using the DFT and SQS methods. • A thermodynamic assessment of the Pd−Rh−Ru ternary system was performed using the Calphad method. • The extrapolation based on only binary interaction parameters leads to a good agreement with the data on the ternary.

Thermodynamics of charged Lovelock: AdS black holes

International Nuclear Information System (INIS)

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

2016-01-01

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

Thermodynamics in f(R,T) theory of gravity

International Nuclear Information System (INIS)

Sharif, M.; Zubair, M.

2012-01-01

A non-equilibrium picture of thermodynamics is discussed at the apparent horizon of FRW universe in f(R,T) gravity, where R is the Ricci scalar and T is the trace of the energy-momentum tensor. We take two forms of the energy-momentum tensor of dark components and demonstrate that equilibrium description of thermodynamics is not achievable in both cases. We check the validity of the first and second law of thermodynamics in this scenario. It is shown that the Friedmann equations can be expressed in the form of first law of thermodynamics T h dS' h +T h d jmath S' = −dE'+W'dV, where d jmath S' is the entropy production term. Finally, we conclude that the second law of thermodynamics holds both in phantom and non-phantom phases

Thermodynamics of perfect fluids from scalar field theory

CERN Document Server

Ballesteros, Guillermo; Pilo, Luigi

2016-01-01

The low-energy dynamics of relativistic continuous media is given by a shift-symmetric effective theory of four scalar fields. These scalars describe the embedding in spacetime of the medium and play the role of Stuckelberg fields for spontaneously broken spatial and time translations. Perfect fluids are selected imposing a stronger symmetry group or reducing the field content to a single scalar. We explore the relation between the field theory description of perfect fluids to thermodynamics. By drawing the correspondence between the allowed operators at leading order in derivatives and the thermodynamic variables, we find that a complete thermodynamic picture requires the four Stuckelberg fields. We show that thermodynamic stability plus the null energy condition imply dynamical stability. We also argue that a consistent thermodynamic interpretation is not possible if any of the shift symmetries is explicitly broken.

Thermodynamics of hairy black holes in Lovelock gravity

Science.gov (United States)

Hennigar, Robie A.; Tjoa, Erickson; Mann, Robert B.

2017-02-01

We perform a thorough study of the thermodynamic properties of a class of Lovelock black holes with conformal scalar hair arising from coupling of a real scalar field to the dimensionally extended Euler densities. We study the linearized equations of motion of the theory and describe constraints under which the theory is free from ghosts/tachyons. We then consider, within the context of black hole chemistry, the thermodynamics of the hairy black holes in the Gauss-Bonnet and cubic Lovelock theories. We clarify the connection between isolated critical points and thermodynamic singularities, finding a one parameter family of these critical points which occur for well-defined thermodynamic parameters. We also report on a number of novel results, including `virtual triple points' and the first example of a `λ-line' — a line of second order phase transitions — in black hole thermodynamics.

Thermodynamics of charged Lovelock: AdS black holes

Science.gov (United States)

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

2016-04-01

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

A comparative thermodynamic analysis of ORC and Kalina cycles for waste heat recovery: A case study for CGAM cogeneration system

Directory of Open Access Journals (Sweden)

Arash Nemati

2017-03-01

Full Text Available A thermodynamic modeling and optimization is carried out to compare the advantages and disadvantages of organic Rankine cycle (ORC and Kalina cycle (KC as a bottoming cycle for waste heat recovery from CGAM cogeneration system. Thermodynamic models for combined CGAM/ORC and CGAM/KC systems are performed and the effects of some decision variables on the energy and exergy efficiency and turbine size parameter of the combined systems are investigated. Solving simulation equations and optimization process have been done using direct search method by EES software. It is observed that at the optimum pressure ratio of air compressor, produced power of bottoming cycles has minimum values. Also, evaporator pressure optimizes the performance of cycle, but this optimum pressure level in ORC (11 bar is much lower than that of Kalina (46 bar. In addition, ORC's simpler configuration, higher net produced power and superheated turbine outlet flow, which leads to a reliable performance for turbine, are other advantages of ORC. Kalina turbine size parameter is lower than that of the ORC which is a positive aspect of Kalina cycle. However, by a comprehensive comparison between Kalina and ORC, it is concluded that the ORC has significant privileges for waste heat recovery in this case.

Extrinsic and intrinsic curvatures in thermodynamic geometry

Energy Technology Data Exchange (ETDEWEB)

Hosseini Mansoori, Seyed Ali, E-mail: shossein@bu.edu [Department of Physics, Boston University, 590 Commonwealth Ave., Boston, MA 02215 (United States); Department of Physics, Isfahan University of Technology, Isfahan 84156-83111 (Iran, Islamic Republic of); Mirza, Behrouz, E-mail: b.mirza@cc.iut.ac.ir [Department of Physics, Isfahan University of Technology, Isfahan 84156-83111 (Iran, Islamic Republic of); Sharifian, Elham, E-mail: e.sharifian@ph.iut.ac.ir [Department of Physics, Isfahan University of Technology, Isfahan 84156-83111 (Iran, Islamic Republic of)

2016-08-10

We investigate the intrinsic and extrinsic curvatures of a certain hypersurface in thermodynamic geometry of a physical system and show that they contain useful thermodynamic information. For an anti-Reissner–Nordström-(A)de Sitter black hole (Phantom), the extrinsic curvature of a constant Q hypersurface has the same sign as the heat capacity around the phase transition points. The intrinsic curvature of the hypersurface can also be divergent at the critical points but has no information about the sign of the heat capacity. Our study explains the consistent relationship holding between the thermodynamic geometry of the KN-AdS black holes and those of the RN (J-zero hypersurface) and Kerr black holes (Q-zero hypersurface) ones [1]. This approach can easily be generalized to an arbitrary thermodynamic system.

Extrinsic and intrinsic curvatures in thermodynamic geometry

International Nuclear Information System (INIS)

Hosseini Mansoori, Seyed Ali; Mirza, Behrouz; Sharifian, Elham

2016-01-01

We investigate the intrinsic and extrinsic curvatures of a certain hypersurface in thermodynamic geometry of a physical system and show that they contain useful thermodynamic information. For an anti-Reissner–Nordström-(A)de Sitter black hole (Phantom), the extrinsic curvature of a constant Q hypersurface has the same sign as the heat capacity around the phase transition points. The intrinsic curvature of the hypersurface can also be divergent at the critical points but has no information about the sign of the heat capacity. Our study explains the consistent relationship holding between the thermodynamic geometry of the KN-AdS black holes and those of the RN (J-zero hypersurface) and Kerr black holes (Q-zero hypersurface) ones [1]. This approach can easily be generalized to an arbitrary thermodynamic system.

Non-Equilibrium Thermodynamics of Self-Replicating Protocells

DEFF Research Database (Denmark)

Fellermann, Harold; Corominas-Murtra, Bernat; Hansen, Per Lyngs

2018-01-01

We provide a non-equilibrium thermodynamic description of the life-cycle of a droplet based, chemically feasible, system of protocells. By coupling the protocells metabolic kinetics with its thermodynamics, we demonstrate how the system can be driven out of equilibrium to ensure protocell growth...... and replication. This coupling allows us to derive the equations of evolution and to rigorously demonstrate how growth and replication life-cycle can be understood as a non-equilibrium thermodynamic cycle. The process does not appeal to genetic information or inheritance, and is based only on non......-equilibrium physics considerations. Our non-equilibrium thermodynamic description of simple, yet realistic, processes of protocell growth and replication, represents an advance in our physical understanding of a central biological phenomenon both in connection to the origin of life and for modern biology....

pycalphad: CALPHAD-based Computational Thermodynamics in Python

Directory of Open Access Journals (Sweden)

Richard Otis

2017-01-01

Full Text Available The pycalphad software package is a free and open-source Python library for designing thermodynamic models, calculating phase diagrams and investigating phase equilibria using the CALPHAD method. It provides routines for reading thermodynamic databases and solving the multi-component, multi-phase Gibbs energy minimization problem. The pycalphad software project advances the state of thermodynamic modeling by providing a flexible yet powerful interface for manipulating CALPHAD data and models. The key feature of the software is that the thermodynamic models of individual phases and their associated databases can be programmatically manipulated and overridden at run-time without modifying any internal solver or calculation code. Because the models are internally decoupled from the equilibrium solver and the models themselves are represented symbolically, pycalphad is an ideal tool for CALPHAD database development and model prototyping.

Stochastic approach to equilibrium and nonequilibrium thermodynamics.

Science.gov (United States)

Tomé, Tânia; de Oliveira, Mário J

2015-04-01

We develop the stochastic approach to thermodynamics based on stochastic dynamics, which can be discrete (master equation) and continuous (Fokker-Planck equation), and on two assumptions concerning entropy. The first is the definition of entropy itself and the second the definition of entropy production rate, which is non-negative and vanishes in thermodynamic equilibrium. Based on these assumptions, we study interacting systems with many degrees of freedom in equilibrium or out of thermodynamic equilibrium and how the macroscopic laws are derived from the stochastic dynamics. These studies include the quasiequilibrium processes; the convexity of the equilibrium surface; the monotonic time behavior of thermodynamic potentials, including entropy; the bilinear form of the entropy production rate; the Onsager coefficients and reciprocal relations; and the nonequilibrium steady states of chemical reactions.