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Indian Academy of Sciences (India)

First page Back Continue Last page Overview Graphics. Limitations of existing web services. Uploading or downloading large data. Serving too many user from single source. Difficult to provide computer intensive job. Depend on internet and its bandwidth. Security of data in transition. Maintain confidentiality of data ...

Singular limits in thermodynamics of viscous fluids

CERN Document Server

Feireisl, Eduard

2017-01-01

This book is about singular limits of systems of partial differential equations governing the motion of thermally conducting compressible viscous fluids. "The main aim is to provide mathematically rigorous arguments how to get from the compressible Navier-Stokes-Fourier system several less complex systems of partial differential equations used e.g. in meteorology or astrophysics. However, the book contains also a detailed introduction to the modelling in mechanics and thermodynamics of fluids from the viewpoint of continuum physics. The book is very interesting and important. It can be recommended not only to specialists in the field, but it can also be used for doctoral students and young researches who want to start to work in the mathematical theory of compressible fluids and their asymptotic limits." Milan Pokorný (zbMATH) "This book is of the highest quality from every point of view. It presents, in a unified way, recent research material of fundament al importance. It is self-contained, thanks to Chapt...

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.

Introduction to thermodynamics of spin models in the Hamiltonian limit

Energy Technology Data Exchange (ETDEWEB)

Berche, Bertrand [Groupe M, Laboratoire de Physique des Materiaux, UMR CNRS No 7556, Universite Henri Poincare, Nancy 1, BP 239, F-54506 Vandoeuvre les Nancy, (France); Lopez, Alexander [Instituto Venezolano de Investigaciones CientIficas, Centro de Fisica, Carr. Panamericana, km 11, Altos de Pipe, Aptdo 21827, 1020-A Caracas, (Venezuela)

2006-01-01

A didactic description of the thermodynamic properties of classical spin systems is given in terms of their quantum counterpart in the Hamiltonian limit. Emphasis is on the construction of the relevant Hamiltonian and the calculation of thermal averages is explicitly done in the case of small systems described, in Hamiltonian field theory, by small matrices. The targeted students are those of a graduate statistical physics course.

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.

Momentum distribution critical exponents for one dimensional large U hubbard model in thermodynamic limit

International Nuclear Information System (INIS)

Qin Shaojin; Yu Lu.

1996-03-01

The critical exponent of the momentum distribution near k F , 3k F and 5k F are studied numerically for one-dimensional U → ∞ Hubbard model, using finite size systems and extrapolating them to the thermodynamic limit. Results at k F agree with earlier calculations, while at 3k F exponents less than 1 are obtained for finite size systems with extrapolation to 1 (regular behaviour) in the thermodynamic limit, in contrast to earlier analytic prediction 9/8. The distribution is regular at 5k F even for finite systems. The singularity near 3k F is interpreted as due to low energy excitations near 3k F in finite systems. (author). 18 refs, 4 figs, 1 tab

Kac limit and thermodynamic characterization of stochastic dynamics driven by Poisson-Kac fluctuations

Science.gov (United States)

Giona, Massimiliano; Brasiello, Antonio; Crescitelli, Silvestro

2017-07-01

We analyze the thermodynamic properties of stochastic differential equations driven by smooth Poisson-Kac fluctuations, and their convergence, in the Kac limit, towards Wiener-driven Langevin equations. Using a Markovian embedding of the stochastic work variable, it is proved that the Kac-limit convergence implies a Stratonovich formulation of the limit Langevin equations, in accordance with the Wong-Zakai theorem. Exact moment analysis applied to the case of a purely frictional system shows the occurrence of different regimes and crossover phenomena in the parameter space.

The Lanczos algorithm for extensive many-body systems in the thermodynamic limit

International Nuclear Information System (INIS)

Witte, N.S.; Bessis, D.

1999-01-01

We establish rigorously the scaling properties of the Lanczos process applied to an arbitrary extensive Many-Body System which is carried to convergence n → ∞ and the thermodynamic limit N → ∞ taken. In this limit the solution for the limiting Lanczos coefficients are found exactly and generally through two equivalent sets of equations, given initial knowledge of the exact cumulant generating function. The measure and the Orthogonal Polynomial System associated with the Lanczos process in this regime are also given explicitly. Some important representations of these Lanczos functions are provided, including Taylor series expansions, and the theorems controlling their general properties are proven. (authors)

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.

Exact solution for the inhomogeneous Dicke model in the canonical ensemble: Thermodynamical limit and finite-size corrections

Energy Technology Data Exchange (ETDEWEB)

Pogosov, W.V., E-mail: walter.pogosov@gmail.com [N.L. Dukhov All-Russia Research Institute of Automatics, Moscow (Russian Federation); Institute for Theoretical and Applied Electrodynamics, Russian Academy of Sciences, Moscow (Russian Federation); Moscow Institute of Physics and Technology, Dolgoprudny (Russian Federation); Shapiro, D.S. [N.L. Dukhov All-Russia Research Institute of Automatics, Moscow (Russian Federation); Moscow Institute of Physics and Technology, Dolgoprudny (Russian Federation); V.A. Kotel' nikov Institute of Radio Engineering and Electronics, Russian Academy of Sciences, Moscow (Russian Federation); National University of Science and Technology MISIS, Moscow (Russian Federation); Bork, L.V. [N.L. Dukhov All-Russia Research Institute of Automatics, Moscow (Russian Federation); Institute for Theoretical and Experimental Physics, Moscow (Russian Federation); Onishchenko, A.I. [Bogoliubov Laboratory of Theoretical Physics, Joint Institute for Nuclear Research, Dubna (Russian Federation); Moscow Institute of Physics and Technology, Dolgoprudny (Russian Federation); Skobeltsyn Institute of Nuclear Physics, Moscow State University, Moscow (Russian Federation)

2017-06-15

We consider an exactly solvable inhomogeneous Dicke model which describes an interaction between a disordered ensemble of two-level systems with single mode boson field. The existing method for evaluation of Richardson–Gaudin equations in the thermodynamical limit is extended to the case of Bethe equations in Dicke model. Using this extension, we present expressions both for the ground state and lowest excited states energies as well as leading-order finite-size corrections to these quantities for an arbitrary distribution of individual spin energies. We then evaluate these quantities for an equally-spaced distribution (constant density of states). In particular, we study evolution of the spectral gap and other related quantities. We also reveal regions on the phase diagram, where finite-size corrections are of particular importance.

Description of quantum coherence in thermodynamic processes requires constraints beyond free energy

Science.gov (United States)

Lostaglio, Matteo; Jennings, David; Rudolph, Terry

2015-03-01

Recent studies have developed fundamental limitations on nanoscale thermodynamics, in terms of a set of independent free energy relations. Here we show that free energy relations cannot properly describe quantum coherence in thermodynamic processes. By casting time-asymmetry as a quantifiable, fundamental resource of a quantum state, we arrive at an additional, independent set of thermodynamic constraints that naturally extend the existing ones. These asymmetry relations reveal that the traditional Szilárd engine argument does not extend automatically to quantum coherences, but instead only relational coherences in a multipartite scenario can contribute to thermodynamic work. We find that coherence transformations are always irreversible. Our results also reveal additional structural parallels between thermodynamics and the theory of entanglement.

Non-existence of limit cycles for planar vector fields

Directory of Open Access Journals (Sweden)

Jaume Gine

2014-03-01

Full Text Available This article presents sufficient conditions for the non-existence of limit cycles for planar vector fields. Classical methods for the nonexistence of limit cycles are connected with the theory developed here.

Capillary adhesion in the limit of saturation: Thermodynamics, self-consistent field modeling and experiment

NARCIS (Netherlands)

Sprakel, J.H.B.; Besseling, N.A.M.; Cohen Stuart, M.A.; Leermakers, F.A.M.

2008-01-01

We introduce a simple thermodynamic argument for capillary adhesion forces, for various geometries, in the limit of saturation of the bulk phase. For one specific geometry (i.e., the sphere¿plate geometry such as that found in the colloidal probe AFM technique), we provide evidence of the validity

Description of quantum coherence in thermodynamic processes requires constraints beyond free energy

Science.gov (United States)

Lostaglio, Matteo; Jennings, David; Rudolph, Terry

2015-01-01

Recent studies have developed fundamental limitations on nanoscale thermodynamics, in terms of a set of independent free energy relations. Here we show that free energy relations cannot properly describe quantum coherence in thermodynamic processes. By casting time-asymmetry as a quantifiable, fundamental resource of a quantum state, we arrive at an additional, independent set of thermodynamic constraints that naturally extend the existing ones. These asymmetry relations reveal that the traditional Szilárd engine argument does not extend automatically to quantum coherences, but instead only relational coherences in a multipartite scenario can contribute to thermodynamic work. We find that coherence transformations are always irreversible. Our results also reveal additional structural parallels between thermodynamics and the theory of entanglement. PMID:25754774

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.)

Approach to the thermodynamic limit in lattice QCD at μ≠0

International Nuclear Information System (INIS)

Splittorff, K.; Verbaarschot, J. J. M.

2008-01-01

The expectation value of the complex phase factor of the fermion determinant is computed to leading order in the p expansion of the chiral Lagrangian. The computation is valid for μ π /2 and determines the dependence of the sign problem on the volume and on the geometric shape of the volume. In the thermodynamic limit with L i →∞ at fixed temperature 1/L 0 , the average phase factor vanishes. In the low temperature limit where L i /L 0 is fixed as L i becomes large, the average phase factor approaches 1 for μ π /2. The results for a finite volume compare well with lattice results obtained by Allton et al. After taking appropriate limits, we reproduce previously derived results for the ε regime and for one-dimensional QCD. The distribution of the phase itself is also computed

Thermodynamic approach to biomass gasification; Approche thermodynamique des transformations de la biomasse

Energy Technology Data Exchange (ETDEWEB)

Boissonnet, G.; Seiler, J.M.

2003-07-01

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{sub 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{sub 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)

Fluctuations, Finite-Size Effects and the Thermodynamic Limit in Computer Simulations: Revisiting the Spatial Block Analysis Method

Directory of Open Access Journals (Sweden)

Maziar Heidari

2018-03-01

Full Text Available The spatial block analysis (SBA method has been introduced to efficiently extrapolate thermodynamic quantities from finite-size computer simulations of a large variety of physical systems. In the particular case of simple liquids and liquid mixtures, by subdividing the simulation box into blocks of increasing size and calculating volume-dependent fluctuations of the number of particles, it is possible to extrapolate the bulk isothermal compressibility and Kirkwood–Buff integrals in the thermodynamic limit. Only by explicitly including finite-size effects, ubiquitous in computer simulations, into the SBA method, the extrapolation to the thermodynamic limit can be achieved. In this review, we discuss two of these finite-size effects in the context of the SBA method due to (i the statistical ensemble and (ii the finite integration domains used in computer simulations. To illustrate the method, we consider prototypical liquids and liquid mixtures described by truncated and shifted Lennard–Jones (TSLJ potentials. Furthermore, we show some of the most recent developments of the SBA method, in particular its use to calculate chemical potentials of liquids in a wide range of density/concentration conditions.

Self-synchronization of populations of nonlinear oscillators in the thermodynamic limit

International Nuclear Information System (INIS)

Bonilla, L.L.; Casado, J.M.; Morillo, M.

1987-01-01

A population of identical nonlinear oscillators, subject to random forces and coupled via a mean-field interaction, is studied in the thermodynamic limit. The model presents a nonequilibrium phase transition from a stationary to a time-periodic probability density. Below the transition line, the population of oscillators is in a quiescent state with order parameter equal to zero. Above the transition line, there is a state of collective rhythmicity characterized by a time-periodic behavior of the order parameter and all moments of the probability distribution. The information entropy of the ensemble is a constant both below and above the critical line. Analytical and numerical analyses of the model are provided

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.

Had We But World Enough, and Time... But We Don't!: Justifying the Thermodynamic and Infinite-Time Limits in Statistical Mechanics

Science.gov (United States)

Palacios, Patricia

2018-05-01

In this paper, I compare the use of the thermodynamic limit in the theory of phase transitions with the infinite-time limit in the explanation of equilibrium statistical mechanics. In the case of phase transitions, I will argue that the thermodynamic limit can be justified pragmatically since the limit behavior (i) also arises before we get to the limit and (ii) for values of N that are physically significant. However, I will contend that the justification of the infinite-time limit is less straightforward. In fact, I will point out that even in cases where one can recover the limit behavior for finite t, i.e. before we get to the limit, one cannot recover this behavior for realistic time scales. I will claim that this leads us to reconsider the role that the rate of convergence plays in the justification of infinite limits and calls for a revision of the so-called Butterfield's principle.

Had We But World Enough, and Time... But We Don't!: Justifying the Thermodynamic and Infinite-Time Limits in Statistical Mechanics

Science.gov (United States)

Palacios, Patricia

2018-04-01

In this paper, I compare the use of the thermodynamic limit in the theory of phase transitions with the infinite-time limit in the explanation of equilibrium statistical mechanics. In the case of phase transitions, I will argue that the thermodynamic limit can be justified pragmatically since the limit behavior (i) also arises before we get to the limit and (ii) for values of N that are physically significant. However, I will contend that the justification of the infinite-time limit is less straightforward. In fact, I will point out that even in cases where one can recover the limit behavior for finite t, i.e. before we get to the limit, one cannot recover this behavior for realistic time scales. I will claim that this leads us to reconsider the role that the rate of convergence plays in the justification of infinite limits and calls for a revision of the so-called Butterfield's principle.

Thermodynamics and entanglements of walks under stress

International Nuclear Information System (INIS)

Janse van Rensburg, E J; Orlandini, E; Tesi, M C; Whittington, S G

2009-01-01

We use rigorous arguments and Monte Carlo simulations to study the thermodynamics and the topological properties of self-avoiding walks on the cubic lattice subjected to an external force f. The walks are anchored at one or both endpoints to an impenetrable plane at Z = 0 and the force is applied in the Z-direction. If a force is applied to the free endpoint of an anchored walk, then a model of pulled walks is obtained. If the walk is confined to a slab and a force is applied to the top bounding plane, then a model of stretched walks is obtained. For both models we prove the existence of the limiting free energy for any value of the force and we show that, for compressive forces, the thermodynamic properties of the two models differ substantially. For pulled walks we prove the existence of a phase transition that, by numerical simulation, we estimate to be second order and located at f = 0. By using a pattern theorem for large positive forces we show that almost all sufficiently long stretched walks are knotted. We examine the entanglement complexity of stretched and pulled walks; our numerical results show a sharp reduction with increasing pulling and stretching forces. Finally, we also examine models of pulled and stretched loops. We prove the existence of limiting free energies in these models and consider the knot probability numerically as a function of the applied pulling or stretching force

Breaking the Carnot limit without violating the second law: A thermodynamic analysis of off-resonant quantum light generation

Science.gov (United States)

Boukobza, E.; Ritsch, H.

2013-06-01

The Carnot limit, formulated in 1824, represents the maximal efficiency of a classical heat engine. In this work we present a thermodynamical analysis of a light amplifier based on a three-level atom coupled off-resonantly to a single quantized cavity mode and to two heat reservoirs with positive temperatures. Based on standard work and heat flow equilibrium, we show that for a cavity blue-detuned with respect to the atomic resonance, the system can surpass the Carnot limit. Nevertheless, the second law of thermodynamics is still obeyed, as the total entropy always increases. By analyzing a semiclassical version of the model, we derive a formula for the critical frequency for which the Carnot limit is broken and a formula for the amplifier efficiency which agrees with its quantum counterpart. In the semiclassical regime, however, the second law is not satisfied and hence it does not offer a physically acceptable description of the system. Finally, we show that breaking the Carnot limit occurs also in a blue-detuned quantum amplifier with output coupling, which represents a realistic model of a laser or maser.

Application of Enzyme Coupling Reactions to Shift Thermodynamically Limited Biocatalytic Reactions

DEFF Research Database (Denmark)

Abu, Rohana; Woodley, John M.

2015-01-01

, it can be challenging to combine several engineered enzymes in vitro for the conversion of non-natural substrates. In this mini-review we focus on enzyme coupling reactions as a tool to alleviate thermodynamic constraints in synthetically useful biocatalytic reactions. The implications of thermodynamic...... shift the equilibrium of otherwise thermodynamically unfavourable reactions to give a higher conversion of the target product. By coupling an energetically unfavourable reaction with a more favourable one, the multi-enzyme cascade mimics the approach taken in nature in metabolic pathways. Nevertheless...

31 CFR 370.26 - What limitations exist on liability?

Science.gov (United States)

2010-07-01

... TRANSFERS RELATING TO UNITED STATES SECURITIES Debit Entries § 370.26 What limitations exist on liability? If we sustain a loss because a financial institution fails to handle an entry in accordance with this...

Absence of zero-temperature transmission rate of a double-chain tight-binding model for DNA with random sequence of nucleotides in thermodynamic limit

International Nuclear Information System (INIS)

Xiong Gang; Wang, X.R.

2005-01-01

The zero-temperature transmission rate spectrum of a double-chain tight-binding model for real DNA is calculated. It is shown that a band of extended-like states exists only for finite chain length with strong inter-chain coupling. While the whole spectrum tends to zero in thermodynamic limit, regardless of the strength of inter-chain coupling. It is also shown that a more faithful model for real DNA with periodic sugar-phosphate chains in backbone structures can be mapped into the above simple double-chain tight-binding model. Combined with above results, the transmission rate of real DNA with long random sequence of nucleotides is expected to be poor

Thermodynamics at work - on the limits and potentials of biogeochemical processes

Science.gov (United States)

Peiffer, Stefan

2017-04-01

The preferential use of high potential electron acceptors by microorganisms has lead to the classical concept of a redox sequence with a sequential use of O2 nitrate, Fe(III), sulfate, and finally CO2 as electron acceptors for respiration (Stumm & Morgan, 1996). Christian Blodau has rigourously applied this concept to constrain the thermodynamical limits at which specific aquatic systems operate. In sediments from acidic mining lakes his analysis revealed that sulfate reducers are not competitive as long as low-crystallinity ferric oxides are available for organic matter decomposition (Blodau et al, 1998). This analysis opened up the possibility to generalize the linkage between the iron and sulphur cycle in such systems and to constrain the biogeochemical limits for remediation (e. g. Peine et al, 2000). In a similar approach, Beer & Blodau (2007) were able to demonstrate that constraints on the removal of products from acetoclastic methanogenesis in deeper peat layers are inhibiting organic matter decomposition and provide a thermodynamic argument for peat accumulation. In this contribution I will review such ideas and further refine the limits and potentials of biogeochemical reactions in terms of redox-active metastable phases (RAMPS) that are typically mixed-valent carbon-, iron-, and sulfur-containing compounds and which allow for the occurrence of a number of enigmatic reactions, e. g. limited greenhouse gas emission (CH4) under dynamic redox conditions. It is proposed that redox equivalents are generated, stored and recycled during oxidation and reduction cycles thus suppressing methanogenesis (Blodau, 2002). Such RAMPS will preferentially occur at dynamic interfaces being exposed to frequent redox cycles. The concept of RAMPS will be illustrated along the interaction between ferric (hydr)oxides and dissolved sulphide. Recent studies using modern analytical tools revealed the formation of a number of amorphous products within a short time scale (days) both

Conditional solvation thermodynamics of isoleucine in model peptides and the limitations of the group-transfer model.

Science.gov (United States)

Tomar, Dheeraj S; Weber, Valéry; Pettitt, B Montgomery; Asthagiri, D

2014-04-17

The hydration thermodynamics of the amino acid X relative to the reference G (glycine) or the hydration thermodynamics of a small-molecule analog of the side chain of X is often used to model the contribution of X to protein stability and solution thermodynamics. We consider the reasons for successes and limitations of this approach by calculating and comparing the conditional excess free energy, enthalpy, and entropy of hydration of the isoleucine side chain in zwitterionic isoleucine, in extended penta-peptides, and in helical deca-peptides. Butane in gauche conformation serves as a small-molecule analog for the isoleucine side chain. Parsing the hydrophobic and hydrophilic contributions to hydration for the side chain shows that both of these aspects of hydration are context-sensitive. Furthermore, analyzing the solute-solvent interaction contribution to the conditional excess enthalpy of the side chain shows that what is nominally considered a property of the side chain includes entirely nonobvious contributions of the background. The context-sensitivity of hydrophobic and hydrophilic hydration and the conflation of background contributions with energetics attributed to the side chain limit the ability of a single scaling factor, such as the fractional solvent exposure of the group in the protein, to map the component energetic contributions of the model-compound data to their value in the protein. But ignoring the origin of cancellations in the underlying components the group-transfer model may appear to provide a reasonable estimate of the free energy for a given error tolerance.

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

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

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

Update of a thermodynamic database for radionuclides to assist solubility limits calculation for performance assessment

Energy Technology Data Exchange (ETDEWEB)

Duro, L.; Grive, M.; Cera, E.; Domenech, C.; Bruno, J. (Enviros Spain S.L., Barcelona (ES))

2006-12-15

This report presents and documents the thermodynamic database used in the assessment of the radionuclide solubility limits within the SR-Can Exercise. It is a supporting report to the solubility assessment. Thermodynamic data are reviewed for 20 radioelements from Groups A and B, lanthanides and actinides. The development of this database is partially based on the one prepared by PSI and NAGRA. Several changes, updates and checks for internal consistency and completeness to the reference NAGRA-PSI 01/01 database have been conducted when needed. These modifications are mainly related to the information from the various experimental programmes and scientific literature available until the end of 2003. Some of the discussions also refer to a previous database selection conducted by Enviros Spain on behalf of ANDRA, where the reader can find additional information. When possible, in order to optimize the robustness of the database, the description of the solubility of the different radionuclides calculated by using the reported thermodynamic database is tested in front of experimental data available in the open scientific literature. When necessary, different procedures to estimate gaps in the database have been followed, especially accounting for temperature corrections. All the methodologies followed are discussed in the main text

Update of a thermodynamic database for radionuclides to assist solubility limits calculation for performance assessment

International Nuclear Information System (INIS)

Duro, L.; Grive, M.; Cera, E.; Domenech, C.; Bruno, J.

2006-12-01

This report presents and documents the thermodynamic database used in the assessment of the radionuclide solubility limits within the SR-Can Exercise. It is a supporting report to the solubility assessment. Thermodynamic data are reviewed for 20 radioelements from Groups A and B, lanthanides and actinides. The development of this database is partially based on the one prepared by PSI and NAGRA. Several changes, updates and checks for internal consistency and completeness to the reference NAGRA-PSI 01/01 database have been conducted when needed. These modifications are mainly related to the information from the various experimental programmes and scientific literature available until the end of 2003. Some of the discussions also refer to a previous database selection conducted by Enviros Spain on behalf of ANDRA, where the reader can find additional information. When possible, in order to optimize the robustness of the database, the description of the solubility of the different radionuclides calculated by using the reported thermodynamic database is tested in front of experimental data available in the open scientific literature. When necessary, different procedures to estimate gaps in the database have been followed, especially accounting for temperature corrections. All the methodologies followed are discussed in the main text

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.

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

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

Thermodynamics of Inozemtsev's elliptic spin chain

Energy Technology Data Exchange (ETDEWEB)

Klabbers, Rob, E-mail: rob.klabbers@desy.de

2016-06-15

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 optimization of geometry in engineering flow systems

Energy Technology Data Exchange (ETDEWEB)

Bejan, A.; Jones, J.A. [Duke Univ., Durham, NC (United States)

2000-07-01

This review draws attention to an emerging body of work that relies on global thermodynamic optimization in the pursuit of flow system architecture. Exergy analysis establishes the theoretical performance limit. Thermodynamic optimization (or entropy generation minimization) brings the design as closely as permissible to the theoretical limit. The design is destined to remain imperfect because of constraints (finite sizes, times, and costs). Improvements are registered by spreading the imperfection (e.g., flow resistances) through the system. Resistances compete against each other and must be optimized together. Optimal spreading means spatial distribution, geometric form, topology, and geography. System architecture springs out of constrained global optimization. The principle is illustrated by simple examples: the optimization of dimensions, spacings, and the distribution (allocation) of heat transfer surface to the two heat exchangers of a power plant. Similar opportunities for deducing flow architecture exist in more complex systems for power and refrigeration. Examples show that the complete structure of heat exchangers for environmental control systems of aircraft can be derived based on this principle. (authors)

Thermodynamic limits to information harvesting by sensory systems

International Nuclear Information System (INIS)

Bo, Stefano; Giudice, Marco Del; Celani, Antonio

2015-01-01

In view of the relation between information and thermodynamics we investigate how much information about an external protocol can be stored in the memory of a stochastic measurement device given an energy budget. We consider a layered device with a memory component storing information about the external environment by monitoring the history of a sensory part coupled to the environment. We derive an integral fluctuation theorem for the entropy production and a measure of the information accumulated in the memory device. Its most immediate consequence is that the amount of information is bounded by the average thermodynamic entropy produced by the process. At equilibrium no entropy is produced and therefore the memory device does not add any information about the environment to the sensory component. Consequently, if the system operates at equilibrium the addition of a memory component is superfluous. Such a device can be used to model the sensing process of a cell measuring the external concentration of a chemical compound and encoding the measurement in the amount of phosphorylated cytoplasmic proteins. (paper)

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.

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.

Numerical investigation into the existence of limit cycles in two-dimensional predator�prey systems

Directory of Open Access Journals (Sweden)

Quay van der Hoff

2013-05-01

Full Text Available There has been a surge of interest in developing and analysing models of interacting species in ecosystems, with specific interest in investigating the existence of limit cycles in systems describing the dynamics of these species. The original Lotka–Volterra model does not possess any limit cycles. In recent years this model has been modified to take disturbances into consideration and allow populations to return to their original numbers. By introducing logistic growth and a Holling Type II functional response to the traditional Lotka–Volterra-type models, it has been proven analytically that a unique, stable limit cycle exists. These proofs make use of Dulac functions, Liénard equations and invariant regions, relying on theory developed by Poincaré, Poincaré-Bendixson, Dulac and Liénard, and are generally perceived as difficult. Computer algebra systems are ideally suited to apply numerical methods to confirm or refute the analytical findings with respect to the existence of limit cycles in non-linear systems. In this paper a class of predator–prey models of a Gause type is used as the vehicle to illustrate the use of a simple, yet novel numerical algorithm. This algorithm confirms graphically the existence of at least one limit cycle that has analytically been proven to exist. Furthermore, adapted versions of the proposed algorithm may be applied to dynamic systems where it is difficult, if not impossible, to prove analytically the existence of limit cycles.

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.

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…

Unlocking Ft: Modeling thermodynamic controls and isotope fractionation factors in nutrient limited environments

Science.gov (United States)

Druhan, J. L.; Giannetta, M.; Sanford, R. A.

2017-12-01

In recent years, reactive transport principles have expanded from early applications, largely based in contaminant hydrology, to a wide range of biologically mediated redox environments including marine sedimentary diagenesis, terrestrial metal ore deposits, soils, and critical zone weathering profiles. A common observation across this diversity of systems is that they often function under energetically limited conditions in comparison to those typical of contaminated aquifers subject to engineered remediation techniques. As a result, the kinetic rate expressions traditionally employed within reactive transport frameworks to simulate microbially mediated redox transformations have required modification. This was recognized in a series of seminal papers by Jin and Bethke (2005, 2007) in which the authors expanded upon a Monod rate law to include a thermodynamic potential factor `Ft' which exerts a limitation on the overall rate based on the thermodynamic driving force of the electron transfer reaction. This new rate expression is now commonly implemented within many of the major reactive transport software packages, though appropriate application has yet to be thoroughly demonstrated. Notably, the characteristically large partitioning of stable isotopes during microbially mediated reactions, which is extensively utilized to identify and quantify these redox transformations, has yet to be simulated under conditions in which the Ft term may be expected to exert a significant mass dependent influence. Here, we develop a series of simplified simulations for the microbially mediated reduction of sulfate based on the datasets reported by Jin and Bethke, and apply appropriate mass-bias within the Ft term to consider the extent to which the resulting isotopic fractionation is consistent with that observed in energetically limited systems. We show that the Ft term can exert a significant influence on the observed fractionation factor under common environmental conditions

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...

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

Coherence-limited solar power conversion: the fundamental thermodynamic bounds and the consequences for solar rectennas

Science.gov (United States)

Mashaal, Heylal; Gordon, Jeffrey M.

2014-10-01

Solar rectifying antennas constitute a distinct solar power conversion paradigm where sunlight's spatial coherence is a basic constraining factor. In this presentation, we derive the fundamental thermodynamic limit for coherence-limited blackbody (principally solar) power conversion. Our results represent a natural extension of the eponymous Landsberg limit, originally derived for converters that are not constrained by the radiation's coherence, and are irradiated at maximum concentration (i.e., with a view factor of unity to the solar disk). We proceed by first expanding Landsberg's results to arbitrary solar view factor (i.e., arbitrary concentration and/or angular confinement), and then demonstrate how the results are modified when the converter can only process coherent radiation. The results are independent of the specific power conversion mechanism, and hence are valid for diffraction-limited as well as quantum converters (and not just classical heat engines or in the geometric optics regime). The derived upper bounds bode favorably for the potential of rectifying antennas as potentially high-efficiency solar converters.

Thermodynamics of Fluid Polyamorphism

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Mikhail A. Anisimov

2018-01-01

Full Text Available Fluid polyamorphism is the existence of different condensed amorphous states in a single-component fluid. It is either found or predicted, usually at extreme conditions, for a broad group of very different substances, including helium, carbon, silicon, phosphorous, sulfur, tellurium, cerium, hydrogen, and tin tetraiodide. This phenomenon is also hypothesized for metastable and deeply supercooled water, presumably located a few degrees below the experimental limit of homogeneous ice formation. We present a generic phenomenological approach to describe polyamorphism in a single-component fluid, which is completely independent of the molecular origin of the phenomenon. We show that fluid polyamorphism may occur either in the presence or in the absence of fluid phase separation depending on the symmetry of the order parameter. In the latter case, it is associated with a second-order transition, such as in liquid helium or liquid sulfur. To specify the phenomenology, we consider a fluid with thermodynamic equilibrium between two distinct interconvertible states or molecular structures. A fundamental signature of this concept is the identification of the equilibrium fraction of molecules involved in each of these alternative states. However, the existence of the alternative structures may result in polyamorphic fluid phase separation only if mixing of these structures is not ideal. The two-state thermodynamics unifies all the debated scenarios of fluid polyamorphism in different areas of condensed-matter physics, with or without phase separation, and even goes beyond the phenomenon of polyamorphism by generically describing the anomalous properties of fluids exhibiting interconversion of alternative molecular states.

Thermodynamical inequivalence of quantum stress-energy and spin tensors

International Nuclear Information System (INIS)

Becattini, F.; Tinti, L.

2011-01-01

It is shown that different couples of stress-energy and spin tensors of quantum-relativistic fields, which would be otherwise equivalent, are in fact inequivalent if the second law of thermodynamics is taken into account. The proof of the inequivalence is based on the analysis of a macroscopic system at full thermodynamical equilibrium with a macroscopic total angular momentum and a specific instance is given for the free Dirac field, for which we show that the canonical and Belinfante stress-energy tensors are not equivalent. For this particular case, we show that the difference between the predicted angular momentum densities for a rotating system at full thermodynamical equilibrium is a quantum effect, persisting in the nonrelativistic limit, corresponding to a polarization of particles of the order of (ℎ/2π)ω/KT (ω being the angular velocity) and could in principle be measured experimentally. This result implies that specific stress-energy and spin tensors are physically meaningful even in the absence of gravitational coupling and raises the issue of finding the thermodynamically right (or the right class of) tensors. We argue that the maximization of the thermodynamic potential theoretically allows us to discriminate between two different couples, yet for the present we are unable to provide a theoretical method to single out the best couple of tensors in a given quantum field theory. The existence of a nonvanishing spin tensor would have major consequences in hydrodynamics, gravity and cosmology.

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...

Black hole thermodynamics under the microscope

Science.gov (United States)

Falls, Kevin; Litim, Daniel F.

2014-04-01

A coarse-grained version of the effective action is used to study the thermodynamics of black holes, interpolating from largest to smallest masses. The physical parameters of the black hole are linked to the running couplings by thermodynamics, and the corresponding equation of state includes quantum corrections for temperature, specific heat, and entropy. If quantum gravity becomes asymptotically safe, the state function predicts conformal scaling in the limit of small horizon area and bounds on black hole mass and temperature. A metric-based derivation for the equation of state and quantum corrections to the thermodynamical, statistical, and phenomenological definition of entropy are also given. Further implications and limitations of our study are discussed.

40 CFR 401.12 - Law authorizing establishment of effluent limitations guidelines for existing sources, standards...

Science.gov (United States)

2010-07-01

... effluent limitations guidelines for existing sources, standards of performance for new sources and... ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS GENERAL PROVISIONS § 401.12 Law authorizing establishment of effluent limitations guidelines for existing sources, standards of performance...

40 CFR Table 2 to Subpart Jjj of... - Class I Emission Limits for Existing Small Municipal Waste Combustion Limits

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2010-07-01

... Small Municipal Waste Combustion Limits 2 Table 2 to Subpart JJJ of Part 62 Protection of Environment... Combustion Units Constructed on or Before August 30, 1999 Pt. 62, Subpt. JJJ, Table 2 Table 2 to Subpart JJJ of Part 62—Class I Emission Limits for Existing Small Municipal Waste Combustion Limits ER31JA03.006...

Thermodynamic properties of some gallium-based binary alloys

International Nuclear Information System (INIS)

Awe, O.E.; Odusote, Y.A.; Akinlade, O.; Hussain, L.A.

2008-01-01

We have studied the concentration dependence of the free energy of mixing, concentration-concentration fluctuations in the long-wavelength limit, the chemical short-range order parameter, the enthalpy and entropy of mixing of Ga-Zn, Ga-Mg and Al-Ga binary alloys at different temperatures using a quasi-chemical approximation for compound forming binary alloys and that for simple regular alloys. From the study of the thermodynamic quantities, we observed that thermodynamic properties of Ga-Zn and Al-Ga exhibit positive deviations from Raoultian behaviour, while Ga-Mg exhibits negative deviation. Hence, this study reveals that both Ga-Zn and Al-Ga are segregating systems, while chemical order exists in Ga-Mg alloy in the whole concentration range. Furthermore, our investigation indicate that Al-Ga binary alloy have a tendency to exhibit ideal mixture behaviour in the concentration range 0≤c Al ≤0.30 and 0.7≤c Al ≤1

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)

Riemannian geometry of thermodynamics and systems with repulsive power-law interactions.

Science.gov (United States)

Ruppeiner, George

2005-07-01

A Riemannian geometric theory of thermodynamics based on the postulate that the curvature scalar R is proportional to the inverse free energy density is used to investigate three-dimensional fluid systems of identical classical point particles interacting with each other via a power-law potential energy gamma r(-alpha) . Such systems are useful in modeling melting transitions. The limit alpha-->infinity corresponds to the hard sphere gas. A thermodynamic limit exists only for short-range (alpha>3) and repulsive (gamma>0) interactions. The geometric theory solutions for given alpha>3 , gamma>0 , and any constant temperature T have the following properties: (1) the thermodynamics follows from a single function b (rho T(-3/alpha) ) , where rho is the density; (2) all solutions are equivalent up to a single scaling constant for rho T(-3/alpha) , related to gamma via the virial theorem; (3) at low density, solutions correspond to the ideal gas; (4) at high density there are solutions with pressure and energy depending on density as expected from solid state physics, though not with a Dulong-Petit heat capacity limit; (5) for 33.7913 a phase transition is required to go between these regimes; (7) for any alpha>3 we may include a first-order phase transition, which is expected from computer simulations; and (8) if alpha-->infinity, the density approaches a finite value as the pressure increases to infinity, with the pressure diverging logarithmically in the density difference.

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.

Thermodynamic limit of particle-hole form factors in the massless XXZ Heisenberg chain

Energy Technology Data Exchange (ETDEWEB)

Kitanine, N. [Univ. de Bourgogne (France). IMB, UMR 5584 du CNRS; Kozlowski, K.K. [Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); Maillet, J.M.; Terras, V. [ENS Lyon (France). UMR 5672 du CNRS, Lab. de Physique; Slavnov, N.A. [Steklov Mathematical Inst., Moscow (Russian Federation)

2011-03-15

We study the thermodynamic limit of the particle-hole form factors of the XXZ Heisenberg chain in the massless regime. We show that, in this limit, such form factors decrease as an explicitly computed power-law in the system size. Moreover, the corresponding amplitudes can be obtained as a product of a ''smooth'' and a ''discrete'' part: the former depends continuously on the rapidities of the particles and holes, whereas the latter has an additional explicit dependence on the set of integer numbers that label each excited state in the associated logarithmic Bethe equations. We also show that special form factors corresponding to zero-energy excitations lying on the Fermi surface decrease as a power-law in the system size with the same critical exponents as in the longdistance asymptotic behavior of the related two-point correlation functions. The methods we develop in this article are rather general and can be applied to other massless integrable models associated to the six-vertex R-matrix and having determinant representations for their form factors. (orig.)

Thermodynamics, Entropy, Information and the Efficiency of Solar Cells

Science.gov (United States)

Abrams, Zeev R.

For well over 50 years, the limits to photovoltaic energy conversion have been known and codified, and have played a vital role in the push for technological breakthroughs to reach—and even attempt to surpass—those limits. This limit, known as the Shockley-Queisser detailed-balance limit, was found by using only the most basic of thermodynamic assumptions, and therefore provides an upper bound that is difficult to contest without violating the laws of thermodynamics. Many different schemes have been devised to improve a solar cell's efficiency beyond this limit, with various benefits and drawbacks for each method. Since the field of solar cell research has been analyzed and dissected for so long by a large variety of researchers, it is quite hard to say or discover anything new without repeating the work of the past. The approach taken in this work is to analyze solar cells from the joint perspective of thermodynamics and information theory. These two subjects have recently been appreciated to be highly interrelated, and using the formalism of Missing Information, we can differentiate between different novel technologies, as well as devise new limits for new and existing methodologies. In this dissertation, the fundamentals of photovoltaic conversion are analyzed from the most basic of principles, emphasizing the thermodynamic parameters of the photovoltaic process. In particular, an emphasis is made on the voltage of the device, as opposed to the current. This emphasis is made since there is a direct relation between the open-circuit voltage of a solar cell and the fundamental equations of thermodynamics and the Free Energy of the system. Moreover, this relation extends to the entropy of the system, which subsequently relates to the field of Information Theory. By focusing on the voltage instead of the current, realizations are made that are not obvious to the majority or researchers in the field, and in particular to efforts of surpassing the Shockley

Thermodynamic analysis of the tetragonal to monoclinic transformation in a constrained zirconia microcrystal

International Nuclear Information System (INIS)

Garvie, R.C.

1985-01-01

A thermodynamic analysis was made of a simple model comprising a transforming t-ZrO 2 microcrystal of size d constrained in a matrix subjected to a hydrostatic tensile stress field. The field generated a critical size range such that a t-particle transformed if dsub(cl) < d < dsub(cu). The lower limit dsub(cl) exists because at this point the maximum energy (supplied by the applied stress) which can be taken up by the crystal is insufficient to drive the transformation. The upper limit dsub(cu) is a consequence of the microcrystal being so large that it transforms spontaneously when the material is cooled to room temperature. Using the thermodynamic (Griffith) approach and assuming that transformation toughening is due to the dilational strain energy, this mechanism accounted for about one-third of the total observed effective surface energy in a peak-aged Ca-PSZ alloy. (author)

Impact of Thermodynamic Principles in Systems Biology

NARCIS (Netherlands)

Heijnen, J.J.

2010-01-01

It is shown that properties of biological systems which are relevant for systems biology motivated mathematical modelling are strongly shaped by general thermodynamic principles such as osmotic limit, Gibbs energy dissipation, near equilibria and thermodynamic driving force. Each of these aspects

[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.

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.

OPTIMAL PROCESSES IN IRREVERSIBLE THERMODYNAMICS AND MICROECONOMICS

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Vladimir A. Kazakov

2004-06-01

Full Text Available This paper describes general methodology that allows one to extend Carnot efficiency of classical thermodynamic for zero rate processes onto thermodynamic systems with finite rate. We define the class of minimal dissipation processes and show that it represents generalization of reversible processes and determines the limiting possibilities of finite rate systems. The described methodology is then applied to microeconomic exchange systems yielding novel estimates of limiting efficiencies for such systems.

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.

34 CFR 99.12 - What limitations exist on the right to inspect and review records?

Science.gov (United States)

2010-07-01

... 34 Education 1 2010-07-01 2010-07-01 false What limitations exist on the right to inspect and... EDUCATIONAL RIGHTS AND PRIVACY What Are the Rights of Inspection and Review of Education Records? § 99.12 What limitations exist on the right to inspect and review records? (a) If the education records of a student...

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 properties of α-uranium

International Nuclear Information System (INIS)

Ren, Zhiyong; Wu, Jun; Ma, Rong; Hu, Guichao; Luo, Chao

2016-01-01

The lattice constants and equilibrium atomic volume of α-uranium were calculated by Density Functional Theory (DFT). The first principles calculation results of the lattice for α-uranium are in agreement with the experimental results well. The thermodynamic properties of α-uranium from 0 to 900 K and 0–100 GPa were calculated with the quasi-harmonic Debye model. Volume, bulk modulus, entropy, Debye temperature, thermal expansion coefficient and the heat capacity of α-uranium were calculated. The calculated results show that the bulk modulus and Debye temperature increase with the increasing pressure at a given temperature while decreasing with the increasing temperature at a given pressure. Volume, entropy, thermal expansion coefficient and the heat capacity decrease with the increasing pressure while increasing with the increasing temperature. The theoretical results of entropy, Debye temperature, thermal expansion coefficient and the heat capacity show good agreement with the general trends of the experimental values. The constant-volume heat capacity shows typical Debye T"3 power-law behavior at low temperature limit and approaches to the classical asymptotic Dulong-Petit limit at high temperature limit. - Highlights: • Thermodynamic properties of α-U were predicted systematically with quasi-harmonic Debye model. • Summarizations of the corresponding experimental and theoretical results have been made for the EOS and other thermodynamic parameters. • The calculated thermodynamic properties show good agreement with the experimental results in general trends.

Thermodynamic properties of α-uranium

Energy Technology Data Exchange (ETDEWEB)

Ren, Zhiyong; Wu, Jun; Ma, Rong; Hu, Guichao; Luo, Chao, E-mail: luochaoboss@sohu.com

2016-11-15

The lattice constants and equilibrium atomic volume of α-uranium were calculated by Density Functional Theory (DFT). The first principles calculation results of the lattice for α-uranium are in agreement with the experimental results well. The thermodynamic properties of α-uranium from 0 to 900 K and 0–100 GPa were calculated with the quasi-harmonic Debye model. Volume, bulk modulus, entropy, Debye temperature, thermal expansion coefficient and the heat capacity of α-uranium were calculated. The calculated results show that the bulk modulus and Debye temperature increase with the increasing pressure at a given temperature while decreasing with the increasing temperature at a given pressure. Volume, entropy, thermal expansion coefficient and the heat capacity decrease with the increasing pressure while increasing with the increasing temperature. The theoretical results of entropy, Debye temperature, thermal expansion coefficient and the heat capacity show good agreement with the general trends of the experimental values. The constant-volume heat capacity shows typical Debye T{sup 3} power-law behavior at low temperature limit and approaches to the classical asymptotic Dulong-Petit limit at high temperature limit. - Highlights: • Thermodynamic properties of α-U were predicted systematically with quasi-harmonic Debye model. • Summarizations of the corresponding experimental and theoretical results have been made for the EOS and other thermodynamic parameters. • The calculated thermodynamic properties show good agreement with the experimental results in general trends.

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

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 ...

Thermodynamics, Entropy, Information and the Efficiency of Solar Cells

OpenAIRE

Abrams, Zeev R.

2012-01-01

For well over 50 years, the limits to photovoltaic energy conversion have been known and codified, and have played a vital role in the push for technological breakthroughs to reach - and even attempt to surpass - those limits. This limit, known as the Shockley-Queisser detailed-balance limit, was found by using only the most basic of thermodynamic assumptions, and therefore provides an upper bound that is difficult to contest without violating the laws of thermodynamics. Many different scheme...

Chemical thermodynamics of uranium

International Nuclear Information System (INIS)

Grenthe, I.; Fuger, J.; Lemire, R.J.; Muller, A.B.; Nguyen-Trung Cregu, C.; Wanner, H.

1992-01-01

A comprehensive overview on the chemical thermodynamics of those elements that are of particular importance in the safety assessment of radioactive waste disposal systems is provided. This is the first volume in a series of critical reviews to be published on this subject. The book provides an extensive compilation of chemical thermodynamic data for uranium. A description of procedures for activity corrections and uncertainty estimates is given. A critical discussion of data needed for nuclear waste management assessments, including areas where significant gaps of knowledge exist is presented. A detailed inventory of chemical thermodynamic data for inorganic compounds and complexes of uranium is listed. Data and their uncertainty limits are recommended for 74 aqueous complexes and 199 solid and 31 gaseous compounds containing uranium, and on 52 aqueous and 17 solid auxiliary species containing no uranium. The data are internally consistent and compatible with the CODATA Key Values. The book contains a detailed discussion of procedures used for activity factor corrections in aqueous solution, as well as including methods for making uncertainty estimates. The recommended data have been prepared for use in environmental geochemistry. Containing contributions written by experts the chapters cover various subject areas such a s: oxide and hydroxide compounds and complexes, the uranium nitrides, the solid uranium nitrates and the arsenic-containing uranium compounds, uranates, procedures for consistent estimation of entropies, gaseous and solid uranium halides, gaseous uranium oxides, solid phosphorous-containing uranium compounds, alkali metal uranates, uncertainties, standards and conventions, aqueous complexes, uranium minerals dealing with solubility products and ionic strength corrections. The book is intended for nuclear research establishments and consulting firms dealing with uranium mining and nuclear waste disposal, as well as academic and research institutes

A New Thermodynamics from Nuclei to Stars

Directory of Open Access Journals (Sweden)

Dieter H.E. Gross

2004-03-01

Full Text Available Abstract: Equilibrium statistics of Hamiltonian systems is correctly described by the microcanonical ensemble. Classically this is the manifold of all points in the N-body phase space with the given total energy. Due to Boltzmann's principle, eS=tr(δ(E-H, its geometrical size is related to the entropy S(E,N,.... This definition does not invoke any information theory, no thermodynamic limit, no extensivity, and no homogeneity assumption, as are needed in conventional (canonical thermo-statistics. Therefore, it describes the equilibrium statistics of extensive as well of non-extensive systems. Due to this fact it is the fundamental definition of any classical equilibrium statistics. It can address nuclei and astrophysical objects as well. All kind of phase transitions can be distinguished sharply and uniquely for even small systems. It is further shown that the second law is a natural consequence of the statistical nature of thermodynamics which describes all systems with the same -- redundant -- set of few control parameters simultaneously. It has nothing to do with the thermodynamic limit. It even works in systems which are by far than any thermodynamic "limit".

Central limit theorem and deformed exponentials

International Nuclear Information System (INIS)

Vignat, C; Plastino, A

2007-01-01

The central limit theorem (CLT) can be ranked among the most important ones in probability theory and statistics and plays an essential role in several basic and applied disciplines, notably in statistical thermodynamics. We show that there exists a natural extension of the CLT from exponentials to so-called deformed exponentials (also denoted as q-Gaussians). Our proposal applies exactly in the usual conditions in which the classical CLT is used. (fast track communication)

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 of nuclear materials

International Nuclear Information System (INIS)

1979-01-01

conditions. There was also a session on accident analysis, a very important topic in today's nuclear technology. Other topics related to fission reactor technology included thermodynamics in waste management and fuel reprocessing. One severe limitation to scientists working in applied thermodynamics has been the lack of basic or fundamental thermodynamic data. Accordingly, several sessions of the Symposium were devoted to basic data on nuclear fuels as well as fundamental data on the thermodynamic properties of nuclear materials. The Symposium was indeed a timely one. It served as a mechanism by which the participants gained a comprehensive and complete picture of the current status of international thermodynamic investigations on nuclear materials. The data presented at the Symposium is not the final answer to nuclear material problems, but it will serve as a guide for further investigations. (author)

Experimental investigation and thermodynamic calculation of the Zn–Fe–Ce system

Energy Technology Data Exchange (ETDEWEB)

Lu, Longfei; Wu, Changjun [Jiangsu Key Laboratory of Materials Surface Science and Technology, Changzhou University, Jiangsu 213164 (China); Jiangsu Collaborative Innovation Center of Photovolatic Science and Engineering, Changzhou University, Jiangsu 213164 (China); Wang, Jianhua, E-mail: wangjh@cczu.edu.cn [Jiangsu Key Laboratory of Materials Surface Science and Technology, Changzhou University, Jiangsu 213164 (China); Jiangsu Collaborative Innovation Center of Photovolatic Science and Engineering, Changzhou University, Jiangsu 213164 (China); Liu, Ya; Tu, Hao; Su, Xuping [Jiangsu Key Laboratory of Materials Surface Science and Technology, Changzhou University, Jiangsu 213164 (China); Jiangsu Collaborative Innovation Center of Photovolatic Science and Engineering, Changzhou University, Jiangsu 213164 (China)

2015-11-05

The 450 °C and 600 °C isothermal sections of the Zn–Fe–Ce system were investigated using equilibrated alloys and diffusion couples. The samples were analyzed by Scanning Electron Microscopy equipped with Energy Dispersive X-ray Spectrometer analysis and X-ray power diffraction. 15 and 13 three-phase regions were identified to exist at 450 °C and 600 °C, respectively. No ternary compound was found. Ce can not dissolve into all the Zn–Fe binary compounds and the solubilities of Fe in all the Zn–Ce binary phases were limited. All the Zn–Fe compounds can equilibrate with CeZn{sub 11} and all the Ce–Zn compounds (except CeZn) can equilibrate with α-Fe. Furthermore, thermodynamic extrapolation of the Zn–Fe–Ce system was carried out and showed good agreement well with detected phase relationships. - Highlights: • 450 °C and 600 °C sections of the Zn–Fe–Ce system were constructed. • No ternary compound exists. • Ce can not dissolve into all the Zn–Fe compounds. • All the Fe–Zn compounds can equilibrate with CeZn{sub 11}. • Thermodynamic extrapolation results agree with experimental data.

A separation-integrated cascade reaction to overcome thermodynamic limitations in rare-sugar synthesis.

Science.gov (United States)

Wagner, Nina; Bosshart, Andreas; Failmezger, Jurek; Bechtold, Matthias; Panke, Sven

2015-03-27

Enzyme cascades combining epimerization and isomerization steps offer an attractive route for the generic production of rare sugars starting from accessible bulk sugars but suffer from the unfavorable position of the thermodynamic equilibrium, thus reducing the yield and requiring complex work-up procedures to separate pure product from the reaction mixture. Presented herein is the integration of a multienzyme cascade reaction with continuous chromatography, realized as simulated moving bed chromatography, to overcome the intrinsic yield limitation. Efficient production of D-psicose from sucrose in a three-step cascade reaction using invertase, D-xylose isomerase, and D-tagatose epimerase, via the intermediates D-glucose and D-fructose, is described. This set-up allowed the production of pure psicose (99.9%) with very high yields (89%) and high enzyme efficiency (300 g of D-psicose per g of enzyme). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Computation of thermodynamic equilibria of nuclear materials in multi-physics codes

International Nuclear Information System (INIS)

Piro, M.H.; Lewis, B.J.; Thompson, W.T.; Simunovic, S.; Besmann, T.M.

2011-01-01

A new equilibrium thermodynamic solver is being developed with the primary impetus of direct integration into nuclear fuel performance and safety codes to provide improved predictions of fuel behavior. This solver is intended to provide boundary conditions and material properties for continuum transport calculations. There are several legitimate concerns with the use of existing commercial thermodynamic codes: 1) licensing entanglements associated with code distribution, 2) computational performance, and 3) limited capabilities of handling large multi-component systems of interest to the nuclear industry. The development of this solver is specifically aimed at addressing these concerns. In support of this goal, a new numerical algorithm for computing chemical equilibria is presented which is not based on the traditional steepest descent method or 'Gibbs energy minimization' technique. This new approach exploits fundamental principles of equilibrium thermodynamics, which simplifies the optimization equations. The chemical potentials of all species and phases in the system are constrained by the system chemical potentials, and the objective is to minimize the residuals of the mass balance equations. Several numerical advantages are achieved through this simplification, as described in this paper. (author)

Shared probe design and existing microarray reanalysis using PICKY

Directory of Open Access Journals (Sweden)

Chou Hui-Hsien

2010-04-01

Full Text Available Abstract Background Large genomes contain families of highly similar genes that cannot be individually identified by microarray probes. This limitation is due to thermodynamic restrictions and cannot be resolved by any computational method. Since gene annotations are updated more frequently than microarrays, another common issue facing microarray users is that existing microarrays must be routinely reanalyzed to determine probes that are still useful with respect to the updated annotations. Results PICKY 2.0 can design shared probes for sets of genes that cannot be individually identified using unique probes. PICKY 2.0 uses novel algorithms to track sharable regions among genes and to strictly distinguish them from other highly similar but nontarget regions during thermodynamic comparisons. Therefore, PICKY does not sacrifice the quality of shared probes when choosing them. The latest PICKY 2.1 includes the new capability to reanalyze existing microarray probes against updated gene sets to determine probes that are still valid to use. In addition, more precise nonlinear salt effect estimates and other improvements are added, making PICKY 2.1 more versatile to microarray users. Conclusions Shared probes allow expressed gene family members to be detected; this capability is generally more desirable than not knowing anything about these genes. Shared probes also enable the design of cross-genome microarrays, which facilitate multiple species identification in environmental samples. The new nonlinear salt effect calculation significantly increases the precision of probes at a lower buffer salt concentration, and the probe reanalysis function improves existing microarray result interpretations.

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

On black hole thermodynamics with a momentum relaxation

International Nuclear Information System (INIS)

Park, Chanyong

2016-01-01

We investigate black hole thermodynamics involving a scalar hair which is dual to a momentum relaxation of the dual field theory. This black hole geometry is able to be classified by two parameters. One is a momentum relaxation and the other is a mass density of another matter localized at the center. Even though all parameters are continuous, there exists a specific point where its thermodynamic interpretation is not continuously connected to the one defined in the other parameter regime. The similar feature also appears in a topological AdS black hole. In this work, we show why such an unusual thermodynamic feature happens and provide a unified way to understand such an exotic black hole thermodynamically in the entire parameter range. (paper)

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.

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

Energy Technology Data Exchange (ETDEWEB)

Singh, Rakesh S.; Debenedetti, Pablo G. [Department of Chemical & Biological Engineering, Princeton University, Princeton, New Jersey 08544 (United States); Biddle, John W.; Anisimov, Mikhail A., E-mail: anisimov@umd.edu [Institute of Physical Science and Technology and Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, Maryland 20742 (United States)

2016-04-14

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

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

International Nuclear Information System (INIS)

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

2016-01-01

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

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

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.

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)

Thermodynamics of spin chains of Haldane–Shastry type and one-dimensional vertex models

International Nuclear Information System (INIS)

Enciso, Alberto; Finkel, Federico; González-López, Artemio

2012-01-01

We study the thermodynamic properties of spin chains of Haldane–Shastry type associated with the A N−1 root system in the presence of a uniform external magnetic field. To this end, we exactly compute the partition function of these models for an arbitrary finite number of spins. We then show that these chains are equivalent to a suitable inhomogeneous classical Ising model in a spatially dependent magnetic field, generalizing the results of Basu-Mallick et al. for the zero magnetic field case. Using the standard transfer matrix approach, we are able to compute in closed form the free energy per site in the thermodynamic limit. We perform a detailed analysis of the chains’ thermodynamics in a unified way, with special emphasis on the zero field and zero temperature limits. Finally, we provide a novel interpretation of the thermodynamic quantities of spin chains of Haldane–Shastry type as weighted averages of the analogous quantities over an ensemble of classical Ising models. - Highlights: ► Partition function of spin chains of Haldane–Shastry type in magnetic field. ► Equivalence to classical inhomogeneous Ising models. ► Free energy per site, other thermodynamic quantities in thermodynamic limit. ► Zero field, zero temperature limits. ► Thermodynamic equivalence with ensemble of classical Ising models.

Placement by thermodynamic simulated annealing

International Nuclear Information System (INIS)

Vicente, Juan de; Lanchares, Juan; Hermida, Roman

2003-01-01

Combinatorial optimization problems arise in different fields of science and engineering. There exist some general techniques coping with these problems such as simulated annealing (SA). In spite of SA success, it usually requires costly experimental studies in fine tuning the most suitable annealing schedule. In this Letter, the classical integrated circuit placement problem is faced by Thermodynamic Simulated Annealing (TSA). TSA provides a new annealing schedule derived from thermodynamic laws. Unlike SA, temperature in TSA is free to evolve and its value is continuously updated from the variation of state functions as the internal energy and entropy. Thereby, TSA achieves the high quality results of SA while providing interesting adaptive features

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

Science.gov (United States)

Glavatskiy, K S

2015-05-28

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

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.)

THERMODYNAMIC MODELING AND FIRST-PRINCIPLES CALCULATIONS

Energy Technology Data Exchange (ETDEWEB)

Turchi, P; Abrikosov, I; Burton, B; Fries, S; Grimvall, G; Kaufman, L; Korzhavyi, P; Manga, R; Ohno, M; Pisch, A; Scott, A; Zhang, W

2005-12-15

The increased application of quantum mechanical-based methodologies to the study of alloy stability has required a re-assessment of the field. The focus is mainly on inorganic materials in the solid state. In a first part, after a brief overview of the so-called ab initio methods with their approximations, constraints, and limitations, recommendations are made for a good usage of first-principles codes with a set of qualifiers. Examples are given to illustrate the power and the limitations of ab initio codes. However, despite the ''success'' of these methodologies, thermodynamics of complex multi-component alloys, as used in engineering applications, requires a more versatile approach presently afforded within CALPHAD. Hence, in a second part, the links that presently exist between ab initio methodologies, experiments, and CALPHAD approach are examined with illustrations. Finally, the issues of dynamical instability and of the role of lattice vibrations that still constitute the subject of ample discussions within the CALPHAD community are revisited in the light of the current knowledge with a set of recommendations.

Thermodynamics of a periodically driven qubit

Science.gov (United States)

Donvil, Brecht

2018-04-01

We present a new approach to the open system dynamics of a periodically driven qubit in contact with a temperature bath. We are specifically interested in the thermodynamics of the qubit. It is well known that by combining the Markovian approximation with Floquet theory it is possible to derive a stochastic Schrödinger equation in for the state of the qubit. We follow here a different approach. We use Floquet theory to embed the time-non autonomous qubit dynamics into time-autonomous yet infinite dimensional dynamics. We refer to the resulting infinite dimensional system as the dressed-qubit. Using the Markovian approximation we derive the stochastic Schrödinger equation for the dressed-qubit. The advantage of our approach is that the jump operators are ladder operators of the Hamiltonian. This simplifies the formulation of the thermodynamics. We use the thermodynamics of the infinite dimensional system to recover the thermodynamical description for the driven qubit. We compare our results with the existing literature and recover the known results.

Finite size effects in the thermodynamics of a free neutral scalar field

Science.gov (United States)

Parvan, A. S.

2018-04-01

The exact analytical lattice results for the partition function of the free neutral scalar field in one spatial dimension in both the configuration and the momentum space were obtained in the framework of the path integral method. The symmetric square matrices of the bilinear forms on the vector space of fields in both configuration space and momentum space were found explicitly. The exact lattice results for the partition function were generalized to the three-dimensional spatial momentum space and the main thermodynamic quantities were derived both on the lattice and in the continuum limit. The thermodynamic properties and the finite volume corrections to the thermodynamic quantities of the free real scalar field were studied. We found that on the finite lattice the exact lattice results for the free massive neutral scalar field agree with the continuum limit only in the region of small values of temperature and volume. However, at these temperatures and volumes the continuum physical quantities for both massive and massless scalar field deviate essentially from their thermodynamic limit values and recover them only at high temperatures or/and large volumes in the thermodynamic limit.

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 ...

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.

Towards a thermodynamics of active matter.

Science.gov (United States)

Takatori, S C; Brady, J F

2015-03-01

Self-propulsion allows living systems to display self-organization and unusual phase behavior. Unlike passive systems in thermal equilibrium, active matter systems are not constrained by conventional thermodynamic laws. A question arises, however, as to what extent, if any, can concepts from classical thermodynamics be applied to nonequilibrium systems like active matter. Here we use the new swim pressure perspective to develop a simple theory for predicting phase separation in active matter. Using purely mechanical arguments we generate a phase diagram with a spinodal and critical point, and define a nonequilibrium chemical potential to interpret the "binodal." We provide a generalization of thermodynamic concepts like the free energy and temperature for nonequilibrium active systems. Our theory agrees with existing simulation data both qualitatively and quantitatively and may provide a framework for understanding and predicting the behavior of nonequilibrium active systems.

The Markov process admits a consistent steady-state thermodynamic formalism

Science.gov (United States)

Peng, Liangrong; Zhu, Yi; Hong, Liu

2018-01-01

The search for a unified formulation for describing various non-equilibrium processes is a central task of modern non-equilibrium thermodynamics. In this paper, a novel steady-state thermodynamic formalism was established for general Markov processes described by the Chapman-Kolmogorov equation. Furthermore, corresponding formalisms of steady-state thermodynamics for the master equation and Fokker-Planck equation could be rigorously derived in mathematics. To be concrete, we proved that (1) in the limit of continuous time, the steady-state thermodynamic formalism for the Chapman-Kolmogorov equation fully agrees with that for the master equation; (2) a similar one-to-one correspondence could be established rigorously between the master equation and Fokker-Planck equation in the limit of large system size; (3) when a Markov process is restrained to one-step jump, the steady-state thermodynamic formalism for the Fokker-Planck equation with discrete state variables also goes to that for master equations, as the discretization step gets smaller and smaller. Our analysis indicated that general Markov processes admit a unified and self-consistent non-equilibrium steady-state thermodynamic formalism, regardless of underlying detailed models.

Relationships between CO2, thermodynamic limits on silicate weathering, and the strength of the silicate weathering feedback

Science.gov (United States)

Winnick, Matthew J.; Maher, Kate

2018-03-01

Recent studies have suggested that thermodynamic limitations on chemical weathering rates exert a first-order control on riverine solute fluxes and by extension, global chemical weathering rates. As such, these limitations may play a prominent role in the regulation of carbon dioxide levels (pCO2) over geologic timescales by constraining the maximum global weathering flux. In this study, we develop a theoretical scaling relationship between equilibrium solute concentrations and pCO2 based on equilibrium constants and reaction stoichiometry relating primary mineral dissolution and secondary mineral precipitation. We test this theoretical scaling relationship against reactive transport simulations of chemical weathering profiles under open- and closed-system conditions, representing partially and fully water-saturated regolith, respectively. Under open-system conditions, equilibrium bicarbonate concentrations vary as a power-law function of pCO2 (y = kxn) where n is dependent on reaction stoichiometry and k is dependent on both reaction stoichiometry and the equilibrium constant. Under closed-system conditions, bicarbonate concentrations vary linearly with pCO2 at low values and approach open-system scaling at high pCO2. To describe the potential role of thermodynamic limitations in the global silicate weathering feedback, we develop a new mathematical framework to assess weathering feedback strength in terms of both (1) steady-state atmospheric pCO2 concentrations, and (2) susceptibility to secular changes in degassing rates and transient carbon cycle perturbations, which we term 1st and 2nd order feedback strength, respectively. Finally, we discuss the implications of these results for the effects of vascular land plant evolution on feedback strength, the potential role of vegetation in controlling modern solute fluxes, and the application of these frameworks to a more complete functional description of the silicate weathering feedback. Most notably, the dependence

Axioms for quantum mechanics: relativistic causality, retrocausality, and the existence of a classical limit

Science.gov (United States)

Rohrlich, Daniel

Y. Aharonov and A. Shimony both conjectured that two axioms - relativistic causality (``no superluminal signalling'') and nonlocality - so nearly contradict each other that only quantum mechanics reconciles them. Can we indeed derive quantum mechanics, at least in part, from these two axioms? No: ``PR-box'' correlations show that quantum correlations are not the most nonlocal correlations consistent with relativistic causality. Here we replace ``nonlocality'' with ``retrocausality'' and supplement the axioms of relativistic causality and retrocausality with a natural and minimal third axiom: the existence of a classical limit, in which macroscopic observables commute. That is, just as quantum mechanics has a classical limit, so must any generalization of quantum mechanics. In this limit, PR-box correlations violaterelativistic causality. Generalized to all stronger-than-quantum bipartite correlations, this result is a derivation of Tsirelson's bound (a theorem of quantum mechanics) from the three axioms of relativistic causality, retrocausality and the existence of a classical limit. Although the derivation does not assume quantum mechanics, it points to the Hilbert space structure that underlies quantum correlations. I thank the John Templeton Foundation (Project ID 43297) and the Israel Science Foundation (Grant No. 1190/13) for support.

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.

Molecular thermodynamics using fluctuation solution theory

DEFF Research Database (Denmark)

Ellegaard, Martin Dela

. The framework relates thermodynamic variables to molecular pair correlation functions of liquid mixtures. In this thesis, application of the framework is illustrated using two approaches: 1. Solubilities of solid solutes in mixed solvent systems are determined from fluctuation solution theory application......Properties of chemicals and their mutual phase equilibria are critical variables in process design. Reliable estimates of relevant equilibrium properties, from thermodynamic models, can form the basis of good decision making in the development phase of a process design, especially when access...... to relevant experimental data is limited. This thesis addresses the issue of generating and using simple thermodynamic models within a rigorous statistical mechanical framework, the so-called fluctuation solution theory, from which relations connecting properties and phase equilibria can be obtained...

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

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

Science.gov (United States)

Hamm, L. L.; Vanbrunt, V.

1982-08-01

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

The calculation of thermodynamic properties of molecules

DEFF Research Database (Denmark)

van Speybroeck, Veronique; Gani, Rafiqul; Meier, Robert Johan

2010-01-01

Thermodynamic data are key in the understanding and design of chemical processes. Next to the experimental evaluation of such data, computational methods are valuable and sometimes indispensable tools in obtaining heats of formation and Gibbs free energies. The major toolboxes to obtain such quan......Thermodynamic data are key in the understanding and design of chemical processes. Next to the experimental evaluation of such data, computational methods are valuable and sometimes indispensable tools in obtaining heats of formation and Gibbs free energies. The major toolboxes to obtain...... molecules the combination of group contribution methods with group additive values that are determined with the best available computational ab initio methods seems to be a viable alternative to obtain thermodynamic properties near chemical accuracy. New developments and full use of existing tools may lead...

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

Thermodynamics of Taub-NUT/bolt black holes in Einstein-Maxwell gravity

International Nuclear Information System (INIS)

Dehghani, M.H.; Khodam-Mohammadi, A.

2006-01-01

First, we construct the Taub-NUT/bolt solutions of (2k+2)-dimensional Einstein-Maxwell gravity, when all the factor spaces of 2k-dimensional base space B have positive curvature. These solutions depend on two extra parameters, other than the mass and the NUT charge. These are electric charge q and electric potential at infinity V. We investigate the existence of Taub-NUT solutions and find that in addition to the two conditions of uncharged NUT solutions, there exist two extra conditions. These two extra conditions come from the regularity of vector potential at r=N and the fact that the horizon at r=N should be the outer horizon of the NUT charged black hole. We find that the NUT solutions in 2k+2 dimensions have no curvature singularity at r=N, when the 2k-dimensional base space is chosen to be CP 2k . For bolt solutions, there exists an upper limit for the NUT parameter which decreases as the potential parameter increases. Second, we study the thermodynamics of these spacetimes. We compute temperature, entropy, charge, electric potential, action and mass of the black hole solutions, and find that these quantities satisfy the first law of thermodynamics. We perform a stability analysis by computing the heat capacity, and show that the NUT solutions are not thermally stable for even k's, while there exists a stable phase for odd k's, which becomes increasingly narrow with increasing dimensionality and wide with increasing V. We also study the phase behavior of the 4 and 6 dimensional bolt solutions in canonical ensemble and find that these solutions have a stable phase, which becomes smaller as V increases

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.)

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.

Remarks about the thermodynamics of astrophysical systems in mutual interaction and related notions

International Nuclear Information System (INIS)

Velazquez, L

2016-01-01

ensembles in this scenario. To clarify how some of conventional notions and theoretical frameworks could be extended to open astrophysical systems, an exploratory study of a paradigmatic situation is presented: a binary astrophysical system. This analysis is carried out in the framework of the quadrupole approximation, which represents the lowest coupling among internal and collective degrees of freedom. Apparently, collective motions are responsible for a non-linear energy interchange among the astrophysical systems. This mechanism introduces some modifications in stationary and stability conditions for the thermodynamic equilibrium such as a generalization of Thirring’s stability condition for systems with negative heat capacities (1970 Z. Phys. 235 339). Additionally, the stability of collective motions of this binary astrophysical system is also discussed, which is related to the low energy thermodynamic behavior of the model discussed by Votyakov and colleagues (2002 Phys. Rev. Lett. 89 031101). The thermodynamic limit for self-gravitating gas of identical non-relativistic point particles is then derived and compared with other different proposals. The astrophysical counterpart of the Gibbs–Duhem relation is obtained and compared with the recent proposal of Latella and colleagues (2015 Phys. Rev. Lett. 114 230601). Finally, the incidence of non-extensivity during the merger of two identical astrophysical systems is analyzed. Contrary to the situation considered in the Gibbs paradox, the merger is an irreversible process that crucially depends on the existence (or non-existence) of the external gravitational influence of other systems. (paper: quantum statistical physics, condensed matter, integrable systems)

Methane on Mars: Thermodynamic Equilibrium and Photochemical Calculations

Science.gov (United States)

Levine, J. S.; Summers, M. E.; Ewell, M.

2010-01-01

The detection of methane (CH4) in the atmosphere of Mars by Mars Express and Earth-based spectroscopy is very surprising, very puzzling, and very intriguing. On Earth, about 90% of atmospheric ozone is produced by living systems. A major question concerning methane on Mars is its origin - biological or geological. Thermodynamic equilibrium calculations indicated that methane cannot be produced by atmospheric chemical/photochemical reactions. Thermodynamic equilibrium calculations for three gases, methane, ammonia (NH3) and nitrous oxide (N2O) in the Earth s atmosphere are summarized in Table 1. The calculations indicate that these three gases should not exist in the Earth s atmosphere. Yet they do, with methane, ammonia and nitrous oxide enhanced 139, 50 and 12 orders of magnitude above their calculated thermodynamic equilibrium concentration due to the impact of life! Thermodynamic equilibrium calculations have been performed for the same three gases in the atmosphere of Mars based on the assumed composition of the Mars atmosphere shown in Table 2. The calculated thermodynamic equilibrium concentrations of the same three gases in the atmosphere of Mars is shown in Table 3. Clearly, based on thermodynamic equilibrium calculations, methane should not be present in the atmosphere of Mars, but it is in concentrations approaching 30 ppbv from three distinct regions on Mars.

Relativistic thermodynamics of Fluids. l

International Nuclear Information System (INIS)

Havas, P.; Swenson, R.J.

1979-01-01

In 1953, Stueckelberg and Wanders derived the basic laws of relativistic linear nonequilibrium thermodynamics for chemically reacting fluids from the relativistic local conservation laws for energy-momentum and the local laws of production of substances and of nonnegative entropy production by the requirement that the corresponding currents (assumed to depend linearly on the derivatives of the state variables) should not be independent. Generalizing their method, we determine the most general allowed form of the energy-momentum tensor T/sup alphabeta/ and of the corresponding rate of entropy production under the same restriction on the currents. The problem of expressing this rate in terms of thermodynamic forces and fluxes is discussed in detail; it is shown that the number of independent forces is not uniquely determined by the theory, and seven possibilities are explored. A number of possible new cross effects are found, all of which persist in the Newtonian (low-velocity) limit. The treatment of chemical reactions is incorporated into the formalism in a consistent manner, resulting in a derivation of the law for rate of production, and in relating this law to transport processes differently than suggested previously. The Newtonian limit is discussed in detail to establish the physical interpretation of the various terms of T/sup alphabeta/. In this limit, the interpretation hinges on that of the velocity field characterizing the fluid. If it is identified with the average matter velocity following from a consideration of the number densities, the usual local conservation laws of Newtonian nonequilibrium thermodynamics are obtained, including that of mass. However, a slightly different identification allows conversion of mass into energy even in this limit, and thus a macroscopic treatment of nuclear or elementary particle reactions. The relation of our results to previous work is discussed in some detail

On the application of thermodynamics of corrosion for service life design of concrete structures

DEFF Research Database (Denmark)

Küter, Andre; Geiker, Mette Rica; Møller, Per

2010-01-01

There are unexploited possibilities in the application of thermodynamics of corrosion for service life design (SLD) of concrete structures. Thermodynamics provides means for insightful descriptions of corrosion mechanisms and of corrosion protection mechanisms. Strategies for corrosion protection...... of the application of thermodynamics for SLD and gives examples of two applications: description of corrosion processes and design of countermeasures. Emphasis is set on chloride induced corrosion....... can be based on thermodynamically consistent corrosion mechanisms and evaluation of existing and design of new countermeasures can be performed using thermodynamics. Similarly, materials concepts for embedded electrodes can be designed using thermodynamics. The present paper provides a brief outline...

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

The Thermodynamics of Internal Combustion Engines: Examples of Insights

Directory of Open Access Journals (Sweden)

Jerald A. Caton

2018-05-01

Full Text Available A major goal of the development of internal combustion (IC engines continues to be higher performance and efficiencies. A major aspect of achieving higher performance and efficiencies is based on fundamental thermodynamics. Both the first and second laws of thermodynamics provide strategies for and limits to the thermal efficiencies of engines. The current work provides three examples of the insights that thermodynamics provides to the performance and efficiencies of an IC engine. The first example evaluates low heat rejection engine concepts, and, based on thermodynamics, demonstrates the difficulty of this concept for increasing efficiencies. The second example compares and contrasts the thermodynamics associated with external and internal exhaust gas dilution. Finally, the third example starts with a discussion of the Otto cycle analysis and explains why this is an incorrect model for the IC engine. An important thermodynamic property that is responsible for many of the observed effects is specific heat.

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

Existence of the passage to the limit of an inviscid fluid.

Science.gov (United States)

Goldobin, Denis S

2017-11-24

In the dynamics of a viscous fluid, the case of vanishing kinematic viscosity is actually equivalent to the Reynolds number tending to infinity. Hence, in the limit of vanishing viscosity the fluid flow is essentially turbulent. On the other hand, the Euler equation, which is conventionally adopted for the description of the flow of an inviscid fluid, does not possess proper turbulent behaviour. This raises the question of the existence of the passage to the limit of an inviscid fluid for real low-viscosity fluids. To address this question, one should employ the theory of turbulent boundary layer near an inflexible boundary (e.g., rigid wall). On the basis of this theory, one can see how the solutions to the Euler equation become relevant for the description of the flow of low-viscosity fluids, and obtain the small parameter quantifying accuracy of this description for real fluids.

Bridging scales with thermodynamics: from nano to macro

International Nuclear Information System (INIS)

Kjelstrup, Signe; Bedeaux, Dick; Trinh, Thuat; Schnell, Sondre K; Vlugt, Thijs J H; Simon, Jean-Marc; Bardow, Andre

2014-01-01

We have recently developed a method to calculate thermodynamic properties of macroscopic systems by extrapolating properties of systems of molecular dimensions. Appropriate scaling laws for small systems were derived using the method for small systems thermodynamics of Hill, considering surface and nook energies in small systems of varying sizes. Given certain conditions, Hill's method provides the same systematic basis for small systems as conventional thermodynamics does for large systems. We show how the method can be used to compute thermodynamic data for the macroscopic limit from knowledge of fluctuations in the small system. The rapid and precise method offers an alternative to current more difficult computations of thermodynamic factors from Kirkwood–Buff integrals. When multiplied with computed Maxwell–Stefan diffusivities, agreement is found between computed predictions and experiments of the Fick diffusion coefficients for several binary systems. Diffusion coefficients were obtained by linking the Green–Kubo formulae to the Onsager coefficients. The formulae were used to improve/disprove empirical formulae for diffusion coefficients. (review)

Thermodynamic modelling of shape memory behaviour: some examples

International Nuclear Information System (INIS)

Stalmans, R.; Humbeeck, J. van; Delaey, L.

1995-01-01

This paper gives a general view of a recently developed thermodynamic model of the thermoelastic martensitic transformation. Unlike existing empirical, mathematical or thermodynamic models, this generalised thermodynamic model can be used to understand and describe quantitatively the overall thermomechanical behaviour of polycrystalline shape memory alloys. Important points of difference between this and previous thermodynamic models are that the contributions of the stored elastic energy and of the crystal defects are also included. In addition, the mathematical approach and the assumptions in this model are selected in such a way that the calculations yield close approximations of the real behaviour and that the final mathematical equations are relatively simple. Several illustrations indicate that this model, in contrast to other models, can be used to understand the shape memory behaviour of complex cases. As an example of quantitative calculations, it is shown that this modelling can be an effective tool in the ''design'' of multifunctional materials consisting of shape memory elements embedded in matrix materials. (orig.)

Thermodynamic theory of equilibrium fluctuations

International Nuclear Information System (INIS)

Mishin, Y.

2015-01-01

The postulational basis of classical thermodynamics has been expanded to incorporate equilibrium fluctuations. The main additional elements of the proposed thermodynamic theory are the concept of quasi-equilibrium states, a definition of non-equilibrium entropy, a fundamental equation of state in the entropy representation, and a fluctuation postulate describing the probability distribution of macroscopic parameters of an isolated system. Although these elements introduce a statistical component that does not exist in classical thermodynamics, the logical structure of the theory is different from that of statistical mechanics and represents an expanded version of thermodynamics. Based on this theory, we present a regular procedure for calculations of equilibrium fluctuations of extensive parameters, intensive parameters and densities in systems with any number of fluctuating parameters. The proposed fluctuation formalism is demonstrated by four applications: (1) derivation of the complete set of fluctuation relations for a simple fluid in three different ensembles; (2) fluctuations in finite-reservoir systems interpolating between the canonical and micro-canonical ensembles; (3) derivation of fluctuation relations for excess properties of grain boundaries in binary solid solutions, and (4) derivation of the grain boundary width distribution for pre-melted grain boundaries in alloys. The last two applications offer an efficient fluctuation-based approach to calculations of interface excess properties and extraction of the disjoining potential in pre-melted grain boundaries. Possible future extensions of the theory are outlined.

Thermodynamics of black-holes in Brans-Dicke gravity

International Nuclear Information System (INIS)

Kim, H.; Kim, Y.

1997-01-01

It is recently been argued that non-trivial Brans-Dicke black-hole solutions different from the usual Schwarzschild solution could exist. The authors attempt here to 'censor' these non-trivial Brans-Dicke black-hole solutions by examining their thermodynamics properties. Quantities like Hawking temperature and entropy of the black holes are computed. The analysis of the behaviors of these thermodynamic quantities appears to show that even in Brans-Dicke gravity, the usual Schwarzschild space-time turns out to be the only physically relevant uncharged black-hole solution

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

Thermodynamic Property Needs for the Oleochemical Industry

DEFF Research Database (Denmark)

Ana Perederic, Olivia; Kalakul, Sawitree; Sarup, Bent

The oleochemical industry cover mainly the food and pharmaceutical reactions but production offuels (biodiesel) and other speciality chemical production processes also handle oleochemicals (inother words, lipids). The core of process synthesis and design depend on availability of properties data...... and/or reliable thermodynamic models for the chemicals involved. Limited availability ofconsistent physical and thermodynamic properties of lipids compounds and their mixtures lead to difficulties with the use of process simulators for process synthesis and design, since all themodels to be used...

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.

40 CFR Table 5 to Subpart Jjj of... - Carbon Monoxide Emission Limits for Existing Small Municipal Waste Combustion Units

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 8 2010-07-01 2010-07-01 false Carbon Monoxide Emission Limits for Existing Small Municipal Waste Combustion Units 5 Table 5 to Subpart JJJ of Part 62 Protection of... of Part 62—Carbon Monoxide Emission Limits for Existing Small Municipal Waste Combustion Units...

Quantum Chemical Approach to Estimating the Thermodynamics of Metabolic Reactions

OpenAIRE

Adrian Jinich; Dmitrij Rappoport; Ian Dunn; Benjamin Sanchez-Lengeling; Roberto Olivares-Amaya; Elad Noor; Arren Bar Even; Alán Aspuru-Guzik

2014-01-01

Thermodynamics plays an increasingly important role in modeling and engineering metabolism. We present the first nonempirical computational method for estimating standard Gibbs reaction energies of metabolic reactions based on quantum chemistry, which can help fill in the gaps in the existing thermodynamic data. When applied to a test set of reactions from core metabolism, the quantum chemical approach is comparable in accuracy to group contribution methods for isomerization and group transfe...

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

Thermodynamics of chaos

International Nuclear Information System (INIS)

Bonasera, A.; Latora, V.; Ploszajczak, M.

1996-07-01

The maximal Lyapunov exponents (LE) are calculated, starting from concepts of hydrodynamics. Analytical expressions for the LE can be found in ergodic limit by using results of the classical thermodynamics for a Boltzmann gas and for systems undergoing a second order phase transition. A recipe is given to measure LE in systems which might have a critical behavior, such as a Bose-Einstein condensation or a transition to a quark-gluon plasma. (author)

DISTRIBUTION OF PARASTATISTICS FUNCTIONS: AN OVERVIEW OF THERMODYNAMICS PROPERTIES

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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

Thermodynamic study of gaseous CsBO2 by Knudsen effusion mass spectrometry

Science.gov (United States)

Nakajima, K.; Takai, T.; Furukawa, T.; Osaka, M.

2017-08-01

One of the main chemical forms of cesium in the gas phase during severe light-water reactor accidents is expected to be cesium metaborate, CsBO2, according to thermodynamic equilibrium calculations considering its reaction with boron. However, the accuracy of the thermodynamic data of the gaseous metaborate, CsBO2(g), has been judged as poor. Thus, Knudsen effusion mass spectrometric measurements of CsBO2 were carried out to obtain reliable thermodynamic data. The evaluated values of the standard enthalpy of formation of CsBO2(g), obtained by the 2nd and 3rd-law treatments, are -700.7 ± 10.7 kJ/mol and -697.0 ± 10.6 kJ/mol, respectively, and agree with each other within the experimental errors, which indicates that our data are reliable. Furthermore, it was found that the existing data of the Gibbs energy function and the standard enthalpy of formation agreed well with the values evaluated in this study, which indicates that the existing thermodynamic data are also reliable.

The 4th Thermodynamic Principle?

International Nuclear Information System (INIS)

Montero Garcia, Jose de la Luz; Novoa Blanco, Jesus Francisco

2007-01-01

It should be emphasized that the 4th Principle above formulated is a thermodynamic principle and, at the same time, is mechanical-quantum and relativist, as it should inevitably be and its absence has been one of main the theoretical limitations of the physical theory until today.We show that the theoretical discovery of Dimensional Primitive Octet of Matter, the 4th Thermodynamic Principle, the Quantum Hexet of Matter, the Global Hexagonal Subsystem of Fundamental Constants of Energy and the Measurement or Connected Global Scale or Universal Existential Interval of the Matter is that it is possible to be arrived at a global formulation of the four 'forces' or fundamental interactions of nature. The Einstein's golden dream is possible

Violation of the First Law of Thermodynamics in f(R,T) Gravity

International Nuclear Information System (INIS)

Jamil, Mubasher; Momeni, D.; Myrzakulov, Ratbay

2012-01-01

We derive the first law of thermodynamics using the method proposed by Wald. Treating the entropy as Noether charge and comparing with the usual first law of thermodynamics, we obtain explicitly the expression of entropy which contains infinitely many non-local terms (i.e. the integral terms). We have proved, in general, that the first law of black hole thermodynamics is violated for f(R,T) gravity. However, there might exist some special cases in which the first law for f(R,T) gravity is recovered

Thermodynamic efficiency of learning a rule in neural networks

Science.gov (United States)

Goldt, Sebastian; Seifert, Udo

2017-11-01

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

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...

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 model of a solid with RKKY interaction and magnetoelastic coupling

Science.gov (United States)

Balcerzak, T.; Szałowski, K.; Jaščur, M.

2018-04-01

Thermodynamic description of a model system with magnetoelastic coupling is presented. The elastic, vibrational, electronic and magnetic energy contributions are taken into account. The long-range RKKY interaction is considered together with the nearest-neighbour direct exchange. The generalized Gibbs potential and the set of equations of state are derived, from which all thermodynamic functions are self-consistently obtained. Thermodynamic properties are calculated numerically for FCC structure for arbitrary external pressure, magnetic field and temperature, and widely discussed. In particular, for some parameters of interaction potential and electron concentration corresponding to antiferromagnetic phase, the existence of negative thermal expansion coefficient is predicted.

A novel constraint for thermodynamically designing DNA sequences.

Directory of Open Access Journals (Sweden)

Qiang Zhang

Full Text Available Biotechnological and biomolecular advances have introduced novel uses for DNA such as DNA computing, storage, and encryption. For these applications, DNA sequence design requires maximal desired (and minimal undesired hybridizations, which are the product of a single new DNA strand from 2 single DNA strands. Here, we propose a novel constraint to design DNA sequences based on thermodynamic properties. Existing constraints for DNA design are based on the Hamming distance, a constraint that does not address the thermodynamic properties of the DNA sequence. Using a unique, improved genetic algorithm, we designed DNA sequence sets which satisfy different distance constraints and employ a free energy gap based on a minimum free energy (MFE to gauge DNA sequences based on set thermodynamic properties. When compared to the best constraints of the Hamming distance, our method yielded better thermodynamic qualities. We then used our improved genetic algorithm to obtain lower-bound DNA sequence sets. Here, we discuss the effects of novel constraint parameters on the free energy gap.

Towards Thermodynamics with Generalized Uncertainty Principle

International Nuclear Information System (INIS)

Moussa, Mohamed; Farag Ali, Ahmed

2014-01-01

Various frameworks of quantum gravity predict a modification in the Heisenberg uncertainty principle to a so-called generalized uncertainty principle (GUP). Introducing quantum gravity effect makes a considerable change in the density of states inside the volume of the phase space which changes the statistical and thermodynamical properties of any physical system. In this paper we investigate the modification in thermodynamic properties of ideal gases and photon gas. The partition function is calculated and using it we calculated a considerable growth in the thermodynamical functions for these considered systems. The growth may happen due to an additional repulsive force between constitutes of gases which may be due to the existence of GUP, hence predicting a considerable increase in the entropy of the system. Besides, by applying GUP on an ideal gas in a trapped potential, it is found that GUP assumes a minimum measurable value of thermal wavelength of particles which agrees with discrete nature of the space that has been derived in previous studies from the GUP

The critical roles of information and nonequilibrium thermodynamics in evolution of living systems.

Science.gov (United States)

Gatenby, Robert A; Frieden, B Roy

2013-04-01

Living cells are spatially bounded, low entropy systems that, although far from thermodynamic equilibrium, have persisted for billions of years. Schrödinger, Prigogine, and others explored the physical principles of living systems primarily in terms of the thermodynamics of order, energy, and entropy. This provided valuable insights, but not a comprehensive model. We propose the first principles of living systems must include: (1) Information dynamics, which permits conversion of energy to order through synthesis of specific and reproducible, structurally-ordered components; and (2) Nonequilibrium thermodynamics, which generate Darwinian forces that optimize the system.Living systems are fundamentally unstable because they exist far from thermodynamic equilibrium, but this apparently precarious state allows critical response that includes: (1) Feedback so that loss of order due to environmental perturbations generate information that initiates a corresponding response to restore baseline state. (2) Death due to a return to thermodynamic equilibrium to rapidly eliminate systems that cannot maintain order in local conditions. (3) Mitosis that rewards very successful systems, even when they attain order that is too high to be sustainable by environmental energy, by dividing so that each daughter cell has a much smaller energy requirement. Thus, nonequilibrium thermodynamics are ultimately responsible for Darwinian forces that optimize system dynamics, conferring robustness sufficient to allow continuous existence of living systems over billions of years.

Discussion on the entransy expressions of the thermodynamic laws and their applications

International Nuclear Information System (INIS)

Cheng, XueTao; Liang, XinGang

2013-01-01

In this paper, the entransy expressions of the three thermodynamic laws are discussed. The entransy expression of the first law is that the entransy of any thermodynamic system is in balance. For the second law, the entransy expression for heat transfer is that the entransy flow will never be transported from a low temperature body to a high temperature body automatically and entransy dissipation always exists. The entransy expression for heat-work conversion is that it is impossible for any device to operate in a cycle that receives heat entransy flow from a single reservoir and results in an equivalent amount of work entransy flow. The two entransy expressions of the second law are proved to be equivalent to each other. For the third law, its entransy expression is that it is impossible to achieve the zero entransy for any body through limited processes. With these expressions, the Clausius inequality is proved, and the concept of entransy loss is defined. The application of entransy loss to heat transfer and heat-work conversion is discussed. - Highlights: • The entransy expressions of the three thermodynamic laws are discussed. • The Clausius inequality is proved with the entransy expressions of the laws. • The concept of entransy loss is defined with the entransy expressions of the laws. • Entransy loss can be used to analyze heat transfer and heat-work conversion

Quantum chemical approach to estimating the thermodynamics of metabolic reactions.

Science.gov (United States)

Jinich, Adrian; Rappoport, Dmitrij; Dunn, Ian; Sanchez-Lengeling, Benjamin; Olivares-Amaya, Roberto; Noor, Elad; Even, Arren Bar; Aspuru-Guzik, Alán

2014-11-12

Thermodynamics plays an increasingly important role in modeling and engineering metabolism. We present the first nonempirical computational method for estimating standard Gibbs reaction energies of metabolic reactions based on quantum chemistry, which can help fill in the gaps in the existing thermodynamic data. When applied to a test set of reactions from core metabolism, the quantum chemical approach is comparable in accuracy to group contribution methods for isomerization and group transfer reactions and for reactions not including multiply charged anions. The errors in standard Gibbs reaction energy estimates are correlated with the charges of the participating molecules. The quantum chemical approach is amenable to systematic improvements and holds potential for providing thermodynamic data for all of metabolism.

Determination of the solubility limiting solid of the selenium in the presence of iron under anoxic conditions

International Nuclear Information System (INIS)

Iida, Y.; Yamaguchi, T.; Tanaka, T.; Kitamura, A.; Nakayama, S.

2009-01-01

Dissolution experiments of selenium were performed from both under saturation and over saturation directions to determine the solubility limiting solid of selenium under the conditions which thermodynamically prefer the formation of ferroselite (FeSe 2 ). X-ray diffractometry (XRD) showed that FeSe 2 was formed in the over-saturation experiments. However, the ion activity products for the reaction of 0.5 FeSe 2 + H + + e - 0.5 Fe 2+ + HSe - , aFe 2+0.5 aHSe - a H+ -1 a e- -1 , obtained from both under saturation and over saturation directions were 3 to 4 orders of magnitude higher than the equilibrium constants calculated from existing thermodynamic data. The dependencies of the selenium concentration on pH, Eh and the iron concentration were better interpreted as a dissolution reaction of selenium solid (Se(s)) than the iron-selenium compounds. The equilibrium constant of: Se(s) + H + + 2e - = HSe - was determined to be logK 0 -7.46±0.11. This value agrees with the value of logK 0 = -7.62±0.06 calculated from existing thermodynamic data of crystalline selenium within errors. Because crystalline selenium was not identified in the solid phases by XRD, the solubility limiting solid would be amorphous or minor amount of crystalline selenium, even if the iron-selenium compound was formed. (authors)

Stochastic thermodynamics

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Eichhorn, Ralf; Aurell, Erik

2014-04-01

'Stochastic thermodynamics as a conceptual framework combines the stochastic energetics approach introduced a decade ago by Sekimoto [1] with the idea that entropy can consistently be assigned to a single fluctuating trajectory [2]'. This quote, taken from Udo Seifert's [3] 2008 review, nicely summarizes the basic ideas behind stochastic thermodynamics: for small systems, driven by external forces and in contact with a heat bath at a well-defined temperature, stochastic energetics [4] defines the exchanged work and heat along a single fluctuating trajectory and connects them to changes in the internal (system) energy by an energy balance analogous to the first law of thermodynamics. Additionally, providing a consistent definition of trajectory-wise entropy production gives rise to second-law-like relations and forms the basis for a 'stochastic thermodynamics' along individual fluctuating trajectories. In order to construct meaningful concepts of work, heat and entropy production for single trajectories, their definitions are based on the stochastic equations of motion modeling the physical system of interest. Because of this, they are valid even for systems that are prevented from equilibrating with the thermal environment by external driving forces (or other sources of non-equilibrium). In that way, the central notions of equilibrium thermodynamics, such as heat, work and entropy, are consistently extended to the non-equilibrium realm. In the (non-equilibrium) ensemble, the trajectory-wise quantities acquire distributions. General statements derived within stochastic thermodynamics typically refer to properties of these distributions, and are valid in the non-equilibrium regime even beyond the linear response. The extension of statistical mechanics and of exact thermodynamic statements to the non-equilibrium realm has been discussed from the early days of statistical mechanics more than 100 years ago. This debate culminated in the development of linear response

Towards a common thermodynamic database for speciation models

International Nuclear Information System (INIS)

Lee, J. van der; Lomenech, C.

2004-01-01

Bio-geochemical speciation models and reactive transport models are reaching an operational stage, allowing simulation of complex dynamic experiments and description of field observations. For decades, the main focus has been on model performance but at present, the availability and reliability of thermodynamic data is the limiting factor of the models. Thermodynamic models applied to real and complex geochemical systems require much more extended thermodynamic databases with many minerals, colloidal phases, humic and fulvic acids, cementitious phases and (dissolved) organic complexing agents. Here we propose a methodological approach to achieve, ultimately, a common, operational database including the reactions and constants of these phases. Provided they are coherent with the general thermodynamic laws, sorption reactions are included as well. We therefore focus on sorption reactions and parameter values associated with specific sorption models. The case of sorption on goethite has been used to illustrate the way the methodology handles the problem of inconsistency and data quality. (orig.)

On thermodynamics of AdS black holes in M-theory

International Nuclear Information System (INIS)

Belhaj, A.; Chabab, M.; Masmar, K.; El Moumni, H.; Sedra, M.B.

2016-01-01

Motivated by recent work on asymptotically AdS 4 black holes in M-theory, we investigate the thermodynamics and thermodynamical geometry of AdS black holes from M2- and M5-branes. Concretely, we consider AdS black holes in AdS p+2 x S 11-p-2 , where p = 2,5 by interpreting the number of M2- (and M5-branes) as a thermodynamical variable. More precisely, we study the corresponding phase transition to examine their stabilities by calculating and discussing various thermodynamical quantities including the chemical potential. Then we compute the thermodynamical curvatures from the Quevedo metric for M2- and M5-branes geometries to reconsider the stability of such black holes. The Quevedo metric singularities recover similar stability results provided by the phase-transition program. It has been shown that similar behaviors are also present in the limit of large N. (orig.)

Incomplete nonextensive statistics and the zeroth law of thermodynamics

International Nuclear Information System (INIS)

Huang Zhi-Fu; Ou Cong-Jie; Chen Jin-Can

2013-01-01

On the basis of the entropy of incomplete statistics (IS) and the joint probability factorization condition, two controversial problems existing in IS are investigated: one is what expression of the internal energy is reasonable for a composite system and the other is whether the traditional zeroth law of thermodynamics is suitable for IS. Some new equivalent expressions of the internal energy of a composite system are derived through accurate mathematical calculation. Moreover, a self-consistent calculation is used to expound that the zeroth law of thermodynamics is also suitable for IS, but it cannot be proven theoretically. Finally, it is pointed out that the generalized zeroth law of thermodynamics for incomplete nonextensive statistics is unnecessary and the nonextensive assumptions for the composite internal energy will lead to mathematical contradiction. (general)

[Exists an Obligation to be Healthy? Ethical Limits of Medical Prevention].

Science.gov (United States)

Arntz, K

2016-02-01

An obligation to be healthy in the sauce of a categorical imperative "You shall change your life!" (P. Sloterdijk) does not exist. There is however a moral responsibility to shape ones own life in such a way that the resulting potentials for development can be realized within one owns possibilities (I. Kant). The example of predictive medicine illustrates, why the right not to know can be a responsible way of self governance when dealing with the knowledge of modern biomedicine. This allows the setting of limits within prevention, which preserve the quality of life of the exposed as well as enabling the individual the "acceptance of self" (R. Guardini). © Georg Thieme Verlag KG Stuttgart · New York.

Is there a link between selectivity and binding thermodynamics profiles?

Science.gov (United States)

Tarcsay, Ákos; Keserű, György M

2015-01-01

Thermodynamics of ligand binding is influenced by the interplay between enthalpy and entropy contributions of the binding event. The impact of these binding free energy components, however, is not limited to the primary target only. Here, we investigate the relationship between binding thermodynamics and selectivity profiles by combining publicly available data from broad off-target assay profiling and the corresponding thermodynamics measurements. Our analysis indicates that compounds binding their primary targets with higher entropy contributions tend to hit more off-targets compared with those ligands that demonstrated enthalpy-driven binding. Copyright © 2014 Elsevier Ltd. All rights reserved.

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.

Thermodynamic forces in coarse-grained simulations

Science.gov (United States)

Noid, William

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

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...

Carbon Inputs From Riparian Vegetation Limit Oxidation of Physically Bound Organic Carbon Via Biochemical and Thermodynamic Processes

Science.gov (United States)

Graham, Emily B.; Tfaily, Malak M.; Crump, Alex R.; Goldman, Amy E.; Bramer, Lisa M.; Arntzen, Evan; Romero, Elvira; Resch, C. Tom; Kennedy, David W.; Stegen, James C.

2017-12-01

In light of increasing terrestrial carbon (C) transport across aquatic boundaries, the mechanisms governing organic carbon (OC) oxidation along terrestrial-aquatic interfaces are crucial to future climate predictions. Here we investigate the biochemistry, metabolic pathways, and thermodynamics corresponding to OC oxidation in the Columbia River corridor using ultrahigh-resolution C characterization. We leverage natural vegetative differences to encompass variation in terrestrial C inputs. Our results suggest that decreases in terrestrial C deposition associated with diminished riparian vegetation induce oxidation of physically bound OC. We also find that contrasting metabolic pathways oxidize OC in the presence and absence of vegetation and—in direct conflict with the "priming" concept—that inputs of water-soluble and thermodynamically favorable terrestrial OC protect bound-OC from oxidation. In both environments, the most thermodynamically favorable compounds appear to be preferentially oxidized regardless of which OC pool microbiomes metabolize. In turn, we suggest that the extent of riparian vegetation causes sediment microbiomes to locally adapt to oxidize a particular pool of OC but that common thermodynamic principles govern the oxidation of each pool (i.e., water-soluble or physically bound). Finally, we propose a mechanistic conceptualization of OC oxidation along terrestrial-aquatic interfaces that can be used to model heterogeneous patterns of OC loss under changing land cover distributions.

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 instability of dielectric elastomer (Conference Presentation)

Science.gov (United States)

Liu, Liwu; Liu, Yanju; Leng, Jinsong; Mu, Tong

2017-04-01

Dielectric elastomer is a kind of typical soft active material. It can deform obviously when subjected to an external voltage. When a dielectric elastomer with randomly oriented dipoles is subject to an electric field, the dipoles will rotate to and align with the electric field. The polarization of the dielectric elastomer may be saturated when the voltage is high enough. When subjected to a mechanical force, the end-to-end distance of each polymer chain, which has a finite contour length, will approach the finite value, reaching a limiting stretch. On approaching the limiting stretch, the elastomer stiffens steeply. Here, we develop a thermodynamic constitutive model of dielectric elastomers undergoing polarization saturation and strain-stiffening, and then investigate the stability (electromechanical stability, snap-through stability) and voltage induced deformation of dielectric elastomers. Analytical solution has been obtained and it reveals the marked influence of the extension limit and polarization saturation limit on its instability. The developed thermodynamic constitutive model and simulation results would be helpful in future to the research of dielectric elastomer based high-performance transducers.

Thermodynamics of Acoustic Black Holes in Two Dimensions

Directory of Open Access Journals (Sweden)

Baocheng Zhang

2016-01-01

Full Text Available It is well-known that the thermal Hawking-like radiation can be emitted from the acoustic horizon, but the thermodynamic-like understanding for acoustic black holes was rarely made. In this paper, we will show that the kinematic connection can lead to the dynamic connection at the horizon between the fluid and gravitational models in two dimensions, which implies that there exists the thermodynamic-like description for acoustic black holes. Then, we discuss the first law of thermodynamics for the acoustic black hole via an intriguing connection between the gravitational-like dynamics of the acoustic horizon and thermodynamics. We obtain a universal form for the entropy of acoustic black holes, which has an interpretation similar to the entropic gravity. We also discuss the specific heat and find that the derivative of the velocity of background fluid can be regarded as a novel acoustic analogue of the two-dimensional dilaton potential, which interprets why the two-dimensional fluid dynamics can be connected to the gravitational dynamics but it is difficult for four-dimensional case. In particular, when a constraint is added for the fluid, the analogue of a Schwarzschild black hole can be realized.

Thermodynamic assessment of the K-Na and Cr-V system

International Nuclear Information System (INIS)

Odusote, Y.A.

2008-01-01

The assessment of the thermodynamic properties of K-Na and Cr-V molten alloys has been theoretically examined using a simple statistical mechanical model based on pairwise interaction to obtain higher-order conditional probabilities that describe the occupation of the neighbouring atoms in molten binary alloys. The optimised values of order energy ω obtained are used to describe a number of thermodynamic quantities computed for different concentrations in the alloys at 384 and 1550 K, respectively. The study shows that there is a tendency for homocoordination (like atoms pairing as nearest neighbour) in K-Na and the existence of heterocoordination in Cr-V at all concentrations. Thus, the consistency between calculated and reported experimental thermodynamic values enforces the legitimacy of the findings

Thermodynamic Modeling of a Solid Oxide Fuel Cell to Couple with an Existing Gas Turbine Engine Model

Science.gov (United States)

Brinson, Thomas E.; Kopasakis, George

2004-01-01

The Controls and Dynamics Technology Branch at NASA Glenn Research Center are interested in combining a solid oxide fuel cell (SOFC) to operate in conjunction with a gas turbine engine. A detailed engine model currently exists in the Matlab/Simulink environment. The idea is to incorporate a SOFC model within the turbine engine simulation and observe the hybrid system's performance. The fuel cell will be heated to its appropriate operating condition by the engine s combustor. Once the fuel cell is operating at its steady-state temperature, the gas burner will back down slowly until the engine is fully operating on the hot gases exhausted from the SOFC. The SOFC code is based on a steady-state model developed by The U.S. Department of Energy (DOE). In its current form, the DOE SOFC model exists in Microsoft Excel and uses Visual Basics to create an I-V (current-voltage) profile. For the project's application, the main issue with this model is that the gas path flow and fuel flow temperatures are used as input parameters instead of outputs. The objective is to create a SOFC model based on the DOE model that inputs the fuel cells flow rates and outputs temperature of the flow streams; therefore, creating a temperature profile as a function of fuel flow rate. This will be done by applying the First Law of Thermodynamics for a flow system to the fuel cell. Validation of this model will be done in two procedures. First, for a given flow rate the exit stream temperature will be calculated and compared to DOE SOFC temperature as a point comparison. Next, an I-V curve and temperature curve will be generated where the I-V curve will be compared with the DOE SOFC I-V curve. Matching I-V curves will suggest validation of the temperature curve because voltage is a function of temperature. Once the temperature profile is created and validated, the model will then be placed into the turbine engine simulation for system analysis.

On thermodynamics of AdS black holes in M-theory

Energy Technology Data Exchange (ETDEWEB)

Belhaj, A. [Universite Sultan Moulay Slimane, Departement de Physique, LIRST, Faculte Polydisciplinaire, Beni Mellal (Morocco); Cadi Ayyad University, High Energy Physics and Astrophysics Laboratory, FSSM, Marrakesh (Morocco); Chabab, M.; Masmar, K. [Cadi Ayyad University, High Energy Physics and Astrophysics Laboratory, FSSM, Marrakesh (Morocco); El Moumni, H. [Cadi Ayyad University, High Energy Physics and Astrophysics Laboratory, FSSM, Marrakesh (Morocco); Universite Ibn Zohr, Departement de Physique, Faculte des Sciences, Agadir (Morocco); Sedra, M.B. [Universite Ibn Tofail, Departement de Physique, LASIMO, Faculte des Sciences, Kenitra (Morocco)

2016-02-15

Motivated by recent work on asymptotically AdS{sub 4} black holes in M-theory, we investigate the thermodynamics and thermodynamical geometry of AdS black holes from M2- and M5-branes. Concretely, we consider AdS black holes in AdS{sub p+2} x S{sup 11-p-2}, where p = 2,5 by interpreting the number of M2- (and M5-branes) as a thermodynamical variable. More precisely, we study the corresponding phase transition to examine their stabilities by calculating and discussing various thermodynamical quantities including the chemical potential. Then we compute the thermodynamical curvatures from the Quevedo metric for M2- and M5-branes geometries to reconsider the stability of such black holes. The Quevedo metric singularities recover similar stability results provided by the phase-transition program. It has been shown that similar behaviors are also present in the limit of large N. (orig.)

Irreversible thermodynamic analysis and application for molecular heat engines

Science.gov (United States)

Lucia, Umberto; Açıkkalp, Emin

2017-09-01

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

Stability and fluctuations in black hole thermodynamics

International Nuclear Information System (INIS)

Ruppeiner, George

2007-01-01

I examine thermodynamic fluctuations for a Kerr-Newman black hole in an extensive, infinite environment. This problem is not strictly solvable because full equilibrium with such an environment cannot be achieved by any black hole with mass M, angular momentum J, and charge Q. However, if we consider one (or two) of M, J, or Q to vary so slowly compared with the others that we can regard it as fixed, instances of stability occur, and thermodynamic fluctuation theory could plausibly apply. I examine seven cases with one, two, or three independent fluctuating variables. No knowledge about the thermodynamic behavior of the environment is needed. The thermodynamics of the black hole is sufficient. Let the fluctuation moment for a thermodynamic quantity X be √( 2 >). Fluctuations at fixed M are stable for all thermodynamic states, including that of a nonrotating and uncharged environment, corresponding to average values J=Q=0. Here, the fluctuation moments for J and Q take on maximum values. That for J is proportional to M. For the Planck mass it is 0.3990(ℎ/2π). That for Q is 3.301e, independent of M. In all cases, fluctuation moments for M, J, and Q go to zero at the limit of the physical regime, where the temperature goes to zero. With M fluctuating there are no stable cases for average J=Q=0. But, there are transitions to stability marked by infinite fluctuations. For purely M fluctuations, this coincides with a curve which Davies identified as a phase transition

Principles of Considering the Effect of the Limited Volume of a System on Its Thermodynamic State

Science.gov (United States)

Tovbin, Yu. K.

2018-01-01

The features of a system with a finite volume that affect its thermodynamic state are considered in comparison to describing small bodies in macroscopic phases. Equations for unary and pair distribution functions are obtained using difference derivatives of a discrete statistical sum. The structure of the equation for the free energy of a system consisting of an ensemble of volume-limited regions with different sizes and a full set of equations describing a macroscopic polydisperse system are discussed. It is found that the equations can be applied to molecular adsorption on small faces of microcrystals, to bound and isolated pores of a polydisperse material, and to describe the spinodal decomposition of a fluid in brief periods of time and high supersaturations of the bulk phase when each local region functions the same on average. It is shown that as the size of a system diminishes, corrections must be introduced for the finiteness of the system volume and fluctuations of the unary and pair distribution functions.

Dynamics and thermodynamics of polymer glasses.

Science.gov (United States)

Cangialosi, D

2014-04-16

The fate of matter when decreasing the temperature at constant pressure is that of passing from gas to liquid and, subsequently, from liquid to crystal. However, a class of materials can exist in an amorphous phase below the melting temperature. On cooling such materials, a glass is formed; that is, a material with the rigidity of a solid but exhibiting no long-range order. The study of the thermodynamics and dynamics of glass-forming systems is the subject of continuous research. Within the wide variety of glass formers, an important sub-class is represented by glass forming polymers. The presence of chain connectivity and, in some cases, conformational disorder are unfavourable factors from the point of view of crystallization. Furthermore, many of them, such as amorphous thermoplastics, thermosets and rubbers, are widely employed in many applications. In this review, the peculiarities of the thermodynamics and dynamics of glass-forming polymers are discussed, with particular emphasis on those topics currently the subject of debate. In particular, the following aspects will be reviewed in the present work: (i) the connection between the pronounced slowing down of glassy dynamics on cooling towards the glass transition temperature (Tg) and the thermodynamics; and, (ii) the fate of the dynamics and thermodynamics below Tg. Both aspects are reviewed in light of the possible presence of a singularity at a finite temperature with diverging relaxation time and zero configurational entropy. In this context, the specificity of glass-forming polymers is emphasized.

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.

Thermodynamic inconsistency of the modified Saha equation at high pressures

International Nuclear Information System (INIS)

Sweeney, M.A.

1978-01-01

The inclusion of a pressure ionization term in the Saha equation violates the thermodynamic Maxwell identities if corresponding changes are not made to the expressions for entropy and pressure. It is demonstrated that the usual application of the Rouse and Stewart-Pyatt modesl suffers from this limitation. Negative values of the adiabatic gradient in the degenerate dwarf models of Boehm and Straka are explained in terms of this thermodynamic inconsistency

A low pressure thermodynamic cycle for electric power generation without mechanical compressor

International Nuclear Information System (INIS)

Proto, G.; Lenti, R.

1996-01-01

According to the 2 nd thermodynamic law there is no compulsion to have an expansion from high pressure level to atmospheric pressure, the only reason relying upon the minimization of the plant volumetry which is just one of the overall cost parameters. A thermodynamic cycle without rotating machinery does exist in avionic applications like the RAMJET, in which air flowing at supersonic speed is compressed in a convergent duct before being heated in the combustion chamber and then expanded to a much higher MACH number. The concept discussed here, however, is referred to a physical principle of different nature. In fact the inlet air flow is quasi static, while the propelling kinetic energy is the residual energy following the gas combustion, expansion, cooling in Supersonic Flow and ultimately its fluidic compression in a convergent duct. The concept theoretically relies upon the so called 'Simple T 0 change' transformation, according to which, in a Supersonic Flow at constant cross section and without mechanical dissipation, a decrease in the gas stagnation temperature (T 0 ) will turn into an increase of its stagnation pressure. The paper discusses the feasibility of such a process, focusing on a specific conceptual application to a subatmospheric pressure, high temperature Brayton cycle getting to the conclusion that, even with the materials technology limitations, there is the potential for significant improvement of the actual thermodynamic cycle efficiency. (author). 6 figs.,1 tab., 2 refs

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)

Thermodynamics and phase transition of black hole in an asymptotically safe gravity

International Nuclear Information System (INIS)

Ma, Meng-Sen

2014-01-01

We study the effects of quantum gravitational correction on the thermodynamics of black holes in the asymptotic safety scenario. Owing to the quantum-corrected Schwarzschild metric, the thermodynamic quantities are also corrected and a Hawking–Page-type phase transition may exist. We also employ the concept of thermodynamic geometry to the black hole to characterize the phase transition. By introducing a cavity enclosing the black hole, we apply the spatially finite boundary conditions to further investigate the thermodynamic phase transition of the black hole. It is shown that the larger and small black holes are both locally stable according to heat capacity. According to free energy, we find that the quantum-corrected black hole has similar thermodynamic phase structure to that of RN–AdS black hole. In addition, we also discuss the possibility of the phase transition between the black hole and the hot curved space. Above a certain temperature T 0 , the black hole is more probable than the hot space

Thermodynamic properties of a quasi-harmonic model for ferroelectric transitions

International Nuclear Information System (INIS)

Mkam Tchouobiap, S E; Mashiyama, H

2011-01-01

Within a framework of a quasi-harmonic model for quantum particles in a local potential of the double Morse type and within the mean-field approximation for interactions between particles, we investigate the thermodynamic properties of ferroelectric materials. A quantum thermodynamic treatment gives analytic expressions for the internal energy, the entropy, the specific heat, and the static susceptibility. The calculated thermodynamic characteristics are studied as a function of temperature and energy barrier, where it is shown that at the proper choice of the theory parameters, particularly the energy barrier, the model system exhibits characteristic features of either second-order tricritical or first-order phase transitions. Our results indicate that the barrier energy seems to be an important criterion for the character of the structural phase transition. The influence of quantum fluctuations manifested on zero-point energy on the phase transition and thermodynamic properties is analyzed and discussed. This leads to several quantum effects, including the existence of a saturation regime at low temperatures, where the order parameter saturates giving thermodynamic saturation of the calculated thermodynamic quantities. It is found that both quantum effects and energy barrier magnitude have an important influence on the thermodynamic properties of the ferroelectric materials and on driving the phase transition at low temperatures. Also, the analytical parameters' effect on the transition temperature is discussed, which seems to give a general insight into the structural phase transition and its nature.

Dominant controls of transpiration along a hillslope transect inferred from ecohydrological measurements and thermodynamic limits

Science.gov (United States)

Renner, Maik; Hassler, Sibylle K.; Blume, Theresa; Weiler, Markus; Hildebrandt, Anke; Guderle, Marcus; Schymanski, Stanislaus J.; Kleidon, Axel

2016-05-01

We combine ecohydrological observations of sap flow and soil moisture with thermodynamically constrained estimates of atmospheric evaporative demand to infer the dominant controls of forest transpiration in complex terrain. We hypothesize that daily variations in transpiration are dominated by variations in atmospheric demand, while site-specific controls, including limiting soil moisture, act on longer timescales. We test these hypotheses with data of a measurement setup consisting of five sites along a valley cross section in Luxembourg. Both hillslopes are covered by forest dominated by European beech (Fagus sylvatica L.). Two independent measurements are used to estimate stand transpiration: (i) sap flow and (ii) diurnal variations in soil moisture, which were used to estimate the daily root water uptake. Atmospheric evaporative demand is estimated through thermodynamically constrained evaporation, which only requires absorbed solar radiation and temperature as input data without any empirical parameters. Both transpiration estimates are strongly correlated to atmospheric demand at the daily timescale. We find that neither vapor pressure deficit nor wind speed add to the explained variance, supporting the idea that they are dependent variables on land-atmosphere exchange and the surface energy budget. Estimated stand transpiration was in a similar range at the north-facing and the south-facing hillslopes despite the different aspect and the largely different stand composition. We identified an inverse relationship between sap flux density and the site-average sapwood area per tree as estimated by the site forest inventories. This suggests that tree hydraulic adaptation can compensate for heterogeneous conditions. However, during dry summer periods differences in topographic factors and stand structure can cause spatially variable transpiration rates. We conclude that absorption of solar radiation at the surface forms a dominant control for turbulent heat and

Holographic free energy and thermodynamic geometry

Science.gov (United States)

Ghorai, Debabrata; Gangopadhyay, Sunandan

2016-12-01

We obtain the free energy and thermodynamic geometry of holographic superconductors in 2+1 dimensions. The gravitational theory in the bulk dual to this 2+1-dimensional strongly coupled theory lives in the 3+1 dimensions and is that of a charged AdS black hole together with a massive charged scalar field. The matching method is applied to obtain the nature of the fields near the horizon using which the holographic free energy is computed through the gauge/gravity duality. The critical temperature is obtained for a set of values of the matching point of the near horizon and the boundary behaviour of the fields in the probe limit approximation which neglects the back reaction of the matter fields on the background spacetime geometry. The thermodynamic geometry is then computed from the free energy of the boundary theory. From the divergence of the thermodynamic scalar curvature, the critical temperature is obtained once again. We then compare this result for the critical temperature with that obtained from the matching method.

Holographic free energy and thermodynamic geometry

International Nuclear Information System (INIS)

Ghorai, Debabrata; Gangopadhyay, Sunandan

2016-01-01

We obtain the free energy and thermodynamic geometry of holographic superconductors in 2 + 1 dimensions. The gravitational theory in the bulk dual to this 2 + 1-dimensional strongly coupled theory lives in the 3 + 1 dimensions and is that of a charged AdS black hole together with a massive charged scalar field. The matching method is applied to obtain the nature of the fields near the horizon using which the holographic free energy is computed through the gauge/gravity duality. The critical temperature is obtained for a set of values of the matching point of the near horizon and the boundary behaviour of the fields in the probe limit approximation which neglects the back reaction of the matter fields on the background spacetime geometry. The thermodynamic geometry is then computed from the free energy of the boundary theory. From the divergence of the thermodynamic scalar curvature, the critical temperature is obtained once again. We then compare this result for the critical temperature with that obtained from the matching method. (orig.)

Holographic free energy and thermodynamic geometry

Energy Technology Data Exchange (ETDEWEB)

Ghorai, Debabrata [S.N. Bose National Centre for Basic Sciences, Kolkata (India); Gangopadhyay, Sunandan [Indian Institute of Science Education and Research, Kolkata, Nadia (India); West Bengal State University, Department of Physics, Barasat (India); Inter University Centre for Astronomy and Astrophysics, Pune (India)

2016-12-15

We obtain the free energy and thermodynamic geometry of holographic superconductors in 2 + 1 dimensions. The gravitational theory in the bulk dual to this 2 + 1-dimensional strongly coupled theory lives in the 3 + 1 dimensions and is that of a charged AdS black hole together with a massive charged scalar field. The matching method is applied to obtain the nature of the fields near the horizon using which the holographic free energy is computed through the gauge/gravity duality. The critical temperature is obtained for a set of values of the matching point of the near horizon and the boundary behaviour of the fields in the probe limit approximation which neglects the back reaction of the matter fields on the background spacetime geometry. The thermodynamic geometry is then computed from the free energy of the boundary theory. From the divergence of the thermodynamic scalar curvature, the critical temperature is obtained once again. We then compare this result for the critical temperature with that obtained from the matching method. (orig.)

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...

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...

Generalized second law of thermodynamic in modified teleparallel theory

Energy Technology Data Exchange (ETDEWEB)

Zubair, M. [COMSATS Institute of Information Technology, Department of Mathematics, Lahore (Pakistan); Bahamonde, Sebastian [University College London, Department of Mathematics, London (United Kingdom); Jamil, Mubasher [National University of Sciences and Technology (NUST), Department of Mathematics, School of Natural Sciences (SNS), Islamabad (Pakistan)

2017-07-15

This study is conducted to examine the validity of the generalized second law of thermodynamics (GSLT) in flat FRW for modified teleparallel gravity involving coupling between a scalar field with the torsion scalar T and the boundary term B = 2∇{sub μ}T{sup μ}. This theory is very useful, since it can reproduce other important well-known scalar field theories in suitable limits. The validity of the first and second law of thermodynamics at the apparent horizon is discussed for any coupling. As examples, we have also explored the validity of those thermodynamics laws in some new cosmological solutions under the theory. Additionally, we have also considered the logarithmic entropy corrected relation and discuss the GSLT at the apparent horizon. (orig.)

Generalized second law of thermodynamic in modified teleparallel theory

International Nuclear Information System (INIS)

Zubair, M.; Bahamonde, Sebastian; Jamil, Mubasher

2017-01-01

This study is conducted to examine the validity of the generalized second law of thermodynamics (GSLT) in flat FRW for modified teleparallel gravity involving coupling between a scalar field with the torsion scalar T and the boundary term B = 2∇ μ T μ . This theory is very useful, since it can reproduce other important well-known scalar field theories in suitable limits. The validity of the first and second law of thermodynamics at the apparent horizon is discussed for any coupling. As examples, we have also explored the validity of those thermodynamics laws in some new cosmological solutions under the theory. Additionally, we have also considered the logarithmic entropy corrected relation and discuss the GSLT at the apparent horizon. (orig.)

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

Geometry of higher-dimensional black hole thermodynamics

International Nuclear Information System (INIS)

Aaman, Jan E.; Pidokrajt, Narit

2006-01-01

We investigate thermodynamic curvatures of the Kerr and Reissner-Nordstroem (RN) black holes in spacetime dimensions higher than four. These black holes possess thermodynamic geometries similar to those in four-dimensional spacetime. The thermodynamic geometries are the Ruppeiner geometry and the conformally related Weinhold geometry. The Ruppeiner geometry for a d=5 Kerr black hole is curved and divergent in the extremal limit. For a d≥6 Kerr black hole there is no extremality but the Ruppeiner curvature diverges where one suspects that the black hole becomes unstable. The Weinhold geometry of the Kerr black hole in arbitrary dimension is a flat geometry. For the RN black hole the Ruppeiner geometry is flat in all spacetime dimensions, whereas its Weinhold geometry is curved. In d≥5 the Kerr black hole can possess more than one angular momentum. Finally we discuss the Ruppeiner geometry for the Kerr black hole in d=5 with double angular momenta

Fundamental aspects of plasma chemical physics Thermodynamics

CERN Document Server

Capitelli, Mario; D'Angola, Antonio

2012-01-01

Fundamental Aspects of Plasma Chemical Physics - Thermodynamics develops basic and advanced concepts of plasma thermodynamics from both classical and statistical points of view. After a refreshment of classical thermodynamics applied to the dissociation and ionization regimes, the book invites the reader to discover the role of electronic excitation in affecting the properties of plasmas, a topic often overlooked by the thermal plasma community. Particular attention is devoted to the problem of the divergence of the partition function of atomic species and the state-to-state approach for calculating the partition function of diatomic and polyatomic molecules. The limit of ideal gas approximation is also discussed, by introducing Debye-Huckel and virial corrections. Throughout the book, worked examples are given in order to clarify concepts and mathematical approaches. This book is a first of a series of three books to be published by the authors on fundamental aspects of plasma chemical physics.  The next bo...

Thermodynamic Upper Bound on Broadband Light Coupling with Photonic Structures

KAUST Repository

Yu, Zongfu; Raman, Aaswath; Fan, Shanhui

2012-01-01

to an upper bound dictated by the second law of thermodynamics. Such bound limits how efficient light can be coupled to any photonic structure. As one example of application, we use this upper bound to derive the limit of light absorption in broadband solar

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.

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)

Thermodynamics of Error Correction

Directory of Open Access Journals (Sweden)

Pablo Sartori

2015-12-01

Full Text Available Information processing at the molecular scale is limited by thermal fluctuations. This can cause undesired consequences in copying information since thermal noise can lead to errors that can compromise the functionality of the copy. For example, a high error rate during DNA duplication can lead to cell death. Given the importance of accurate copying at the molecular scale, it is fundamental to understand its thermodynamic features. In this paper, we derive a universal expression for the copy error as a function of entropy production and work dissipated by the system during wrong incorporations. Its derivation is based on the second law of thermodynamics; hence, its validity is independent of the details of the molecular machinery, be it any polymerase or artificial copying device. Using this expression, we find that information can be copied in three different regimes. In two of them, work is dissipated to either increase or decrease the error. In the third regime, the protocol extracts work while correcting errors, reminiscent of a Maxwell demon. As a case study, we apply our framework to study a copy protocol assisted by kinetic proofreading, and show that it can operate in any of these three regimes. We finally show that, for any effective proofreading scheme, error reduction is limited by the chemical driving of the proofreading reaction.

Thermodynamics and Kinetics of Advanced Separations Systems - FY 2010 Summary Report

International Nuclear Information System (INIS)

Martin, Leigh R.; Zalupski, Peter R.

2010-01-01

This report presents a summary of the work performed in the area of thermodynamics and kinetics of advanced separations systems under the Fuel Cycle Research and Development (FCR and D) program during FY 2010. Thermodynamic investigations into metal extraction dependencies on lactate and HDEHP have been performed. These metal distribution studies indicate a substantial deviation from the expected behavior at conditions that are typical of TALSPEAK process operational platform. These studies also identify that no thermodynamically stable mixed complexes exist in the aqueous solutions and increasing the complexity of the organic medium appears to influence the observed deviations. Following on from this, the first calorimetric measurement of the heat of extraction of americium across a liquid-liquid boundary was performed.

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

Is thermodynamic irreversibility a consequence of the expansion of the Universe?

Science.gov (United States)

Osváth, Szabolcs

2018-02-01

This paper explains thermodynamic irreversibility by applying the expansion of the Universe to thermodynamic systems. The effect of metric expansion is immeasurably small on shorter scales than intergalactic distances. Multi-particle systems, however, are chaotic, and amplify any small disturbance exponentially. Metric expansion gives rise to time-asymmetric behaviour in thermodynamic systems in a short time (few nanoseconds in air, few ten picoseconds in water). In contrast to existing publications, this paper explains without any additional assumptions the rise of thermodynamic irreversibility from the underlying reversible mechanics of particles. Calculations for the special case which assumes FLRW metric, slow motions (v ≪ c) and approximates space locally by Euclidean space show that metric expansion causes entropy increase in isolated systems. The rise of time-asymmetry, however, is not affected by these assumptions. Any influence of the expansion of the Universe on the local metric causes a coupling between local mechanics and evolution of the Universe.

Brain activity and cognition: a connection from thermodynamics and information theory.

Science.gov (United States)

Collell, Guillem; Fauquet, Jordi

2015-01-01

The connection between brain and mind is an important scientific and philosophical question that we are still far from completely understanding. A crucial point to our work is noticing that thermodynamics provides a convenient framework to model brain activity, whereas cognition can be modeled in information-theoretical terms. In fact, several models have been proposed so far from both approaches. A second critical remark is the existence of deep theoretical connections between thermodynamics and information theory. In fact, some well-known authors claim that the laws of thermodynamics are nothing but principles in information theory. Unlike in physics or chemistry, a formalization of the relationship between information and energy is currently lacking in neuroscience. In this paper we propose a framework to connect physical brain and cognitive models by means of the theoretical connections between information theory and thermodynamics. Ultimately, this article aims at providing further insight on the formal relationship between cognition and neural activity.

Brain activity and cognition: a connection from thermodynamics and information theory

Science.gov (United States)

Collell, Guillem; Fauquet, Jordi

2015-01-01

The connection between brain and mind is an important scientific and philosophical question that we are still far from completely understanding. A crucial point to our work is noticing that thermodynamics provides a convenient framework to model brain activity, whereas cognition can be modeled in information-theoretical terms. In fact, several models have been proposed so far from both approaches. A second critical remark is the existence of deep theoretical connections between thermodynamics and information theory. In fact, some well-known authors claim that the laws of thermodynamics are nothing but principles in information theory. Unlike in physics or chemistry, a formalization of the relationship between information and energy is currently lacking in neuroscience. In this paper we propose a framework to connect physical brain and cognitive models by means of the theoretical connections between information theory and thermodynamics. Ultimately, this article aims at providing further insight on the formal relationship between cognition and neural activity. PMID:26136709

Thermodynamic consideration on chlorination of uraniferous phosphorite

International Nuclear Information System (INIS)

Itagaki, Kimio; Tozawa, Kazuteru; Taki, Tomihiro; Hirono, Shuichiro.

1989-01-01

The uranium ore of low grade which has apatite as a main mineral, but is different from the phosphorite used as the raw material for phosphoric acid production, exists in large amount in South America and Africa continents, and the importance of its effective utilization as future uranium resources is recognized. The Power Reactor and Nuclear Fuel Development Corp. took up the establishment of the treatment techniques to make this ore into resources as the subject of a project, and proposed the process of volatilizing the uranium in the ore as the chloride and recovering it, and at present, it attempts the experiment on the chlorination treatment. In this paper, the thermodynamic examination on the feasibility of this process, the optimum condition for leaving calcium existing in a large amount in the ore as the phosphate without chlorination and recovering only uranium by chlorination and volatilization, the phase reaction equilibrium chart and the calculation method according to thermodynamics concerning the behavior of chlorination of accompanying elements such as iron, silicon and aluminum and the effect of moisture in the ore are reported. (K.I.)

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

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…

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...

Thermodynamics and Kinetics of Advanced Separations Systems – FY 2010 Summary Report

Energy Technology Data Exchange (ETDEWEB)

Leigh R. Martin; Peter R. Zalupski

2010-09-01

This report presents a summary of the work performed in the area of thermodynamics and kinetics of advanced separations systems under the Fuel Cycle Research and Development (FCR&D) program during FY 2010. Thermodynamic investigations into metal extraction dependencies on lactate and HDEHP have been performed. These metal distribution studies indicate a substantial deviation from the expected behavior at conditions that are typical of TALSPEAK process operational platform. These studies also identify that no thermodynamically stable mixed complexes exist in the aqueous solutions and increasing the complexity of the organic medium appears to influence the observed deviations. Following on from this, the first calorimetric measurement of the heat of extraction of americium across a liquid-liquid boundary was performed.

SNG from coal: thermodynamic and kinetic constraints; use of nuclear energy

International Nuclear Information System (INIS)

Shapira, D.

1983-01-01

Part I contains an analysis of the thermodynamic constraints of converting coal to SNG. It is shown that the thermodynamic constraints that limit the thermal efficiency are not inherent, but are the result of design decisions, based on available technology, as well as on the kinetic properties of available catalysts. The latter, limits the yield of methane to that obtainable at global equilibrium over carbon in the presence of CO, H 2 , CO 2 and H 2 O. The equilibrium composition is shown to be independent of the thermodynamic properties of the char or coal fed. These limitations give the nonisothermal two-stage processes significant thermodynamic advantages. The analysis in part I results in suggesting directions for modifying present processes in order to obtain higher thermal efficiences. It also presents two-stage process schemes which may have significant advantages over present technology. As the methodology used for the thermodynamic analysis contains some novel elements, it should be of interest to the reaction engineer in general, and should be applicable to a wide range of catalytic and noncatalytic processes. Part II focuses on the use of nuclear energy in the production of synthetic fuel. Two processes for the production of hydrogen (which is used in coal-to-SNG processes) are analyzed and compared. The two processes are: 1) hydrogen from electrolysis of water using nuclear heat. 2) Hydrogen from steam reforming of methane using nuclear heat. The method used is differential economic analysis which focuses on evaluating the inherent advantages and disadvantages of the proposed technologies. Part II shows that the use of high temperature heat in production of hydrogen from coal is less attractive than the use of the same heat to generate electricity and split water into H 2 and O 2

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

Thermodynamics of AdS black holes in Einstein-Scalar gravity

Energy Technology Data Exchange (ETDEWEB)

Lü, H. [Department of Physics, Beijing Normal University,Beijing 100875 (China); Pope, C.N. [George P. & Cynthia Woods Mitchell Institute for Fundamental Physics and Astronomy,Texas A& M University,College Station, TX 77843 (United States); DAMTP, Centre for Mathematical Sciences, Cambridge University,Wilberforce Road, Cambridge CB3 OWA (United Kingdom); Wen, Qiang [Department of Physics, Renmin University of China,Beijing 100872 (China)

2015-03-31

We study the thermodynamics of n-dimensional static asymptotically AdS black holes in Einstein gravity coupled to a scalar field with a potential admitting a stationary point with an AdS vacuum. Such black holes with non-trivial scalar hair can exist provided that the mass-squared of the scalar field is negative, and above the Breitenlohner-Freedman bound. We use the Wald procedure to derive the first law of thermodynamics for these black holes, showing how the scalar hair (or “charge”) contributes non-trivially in the expression. We show in general that a black hole mass can be deduced by isolating an integrable contribution to the (non-integrable) variation of the Hamiltonian arising in the Wald construction, and that this is consistent with the mass calculated using the renormalised holographic stress tensor and also, in those cases where it is defined, with the mass calculated using the conformal method of Ashtekar, Magnon and Das. Similar arguments can also be given for the smooth solitonic solutions in these theories. Neither the black hole nor the soliton solutions can be constructed explicitly, and we carry out a numerical analysis to demonstrate their existence and to provide approximate checks on some of our thermodynamic results.

Americium thermodynamic data for the EQ3/6 database

International Nuclear Information System (INIS)

Kerrisk, J.F.

1984-07-01

Existing thermodynamic data for aqueous and solid species of americium have been reviewed and collected in a form that can be used with the EQ3/6 database. Data that are important in solubility calculations for americium at a proposed Yucca Mountain nuclear waste repository were emphasized. Conflicting data exist for americium complexes with carbonates. Essentially no data are available for americium solids or complexes at temperatures greater than 25 0 C. 17 references, 4 figures

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

Emerging of Stochastic Dynamical Equalities and Steady State Thermodynamics from Darwinian Dynamics

International Nuclear Information System (INIS)

Ao, P.

2008-01-01

The evolutionary dynamics first conceived by Darwin and Wallace, referring to as Darwinian dynamics in the present paper, has been found to be universally valid in biology. The statistical mechanics and thermodynamics, while enormous successful in physics, have been in an awkward situation of wanting a consistent dynamical understanding. Here we present from a formal point of view an exploration of the connection between thermodynamics and Darwinian dynamics and a few related topics. We first show that the stochasticity in Darwinian dynamics implies the existence temperature, hence the canonical distribution of Boltzmann-Gibbs type. In term of relative entropy the Second Law of thermodynamics is dynamically demonstrated without detailed balance condition, and is valid regardless of size of the system. In particular, the dynamical component responsible for breaking detailed balance condition does not contribute to the change of the relative entropy. Two types of stochastic dynamical equalities of current interest are explicitly discussed in the present approach: One is based on Feynman-Kac formula and another is a generalization of Einstein relation. Both are directly accessible to experimental tests. Our demonstration indicates that Darwinian dynamics represents logically a simple and straightforward starting point for statistical mechanics and thermodynamics and is complementary to and consistent with conservative dynamics that dominates the physical sciences. Present exploration suggests the existence of a unified stochastic dynamical framework both near and far from equilibrium

Advanced adsorption cooling cum desalination cycle: A thermodynamic framework

KAUST Repository

Chakraborty, Anutosh

2011-01-01

We have developed a thermodynamic framework to calculate adsorption cooling cum desalination cycle performances as a function of pore widths and pore volumes of highly porous adsorbents, which are formulated from the rigor of thermodynamic property surfaces of adsorbent-adsorbate system and the adsorption interaction potential between them. Employing the proposed formulations, the coefficient of performance (COP) and overall performance ratio (OPR) of adsorption cycle are computed for various pore widths of solid adsorbents. These results are compared with experimental data for verifying the proposed thermodynamic formulations. It is found from the present analysis that the COP and OPR of adsorption cooling cum desalination cycle is influenced by (i) the physical characteristics of adsorbents, (ii) characteristics energy and (iii) the surface-structural heterogeneity factor of adsorbent-water system. The present study confirms that there exists a special type of adsorbents having optimal physical characteristics that allows us to obtain the best performance.

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

40 CFR Table 1a to Subpart Zzzz of... - Emission Limitations for Existing, New, and Reconstructed Spark Ignition, 4SRB Stationary RICE...

Science.gov (United States)

2010-07-01

..., and Reconstructed Spark Ignition, 4SRB Stationary RICE >500 HP Located at a Major Source of HAP... Limitations for Existing, New, and Reconstructed Spark Ignition, 4SRB Stationary RICE >500 HP Located at a... emission limitations for existing, new and reconstructed 4SRB stationary RICE at 100 percent load plus or...

40 CFR Table 1b to Subpart Zzzz of... - Operating Limitations for Existing, New, and Reconstructed Spark Ignition, 4SRB Stationary RICE...

Science.gov (United States)

2010-07-01

..., New, and Reconstructed Spark Ignition, 4SRB Stationary RICE >500 HP Located at a Major Source of HAP... Limitations for Existing, New, and Reconstructed Spark Ignition, 4SRB Stationary RICE >500 HP Located at a... following operating emission limitations for existing, new and reconstructed 4SRB stationary RICE >500 HP...

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.

Thermodynamic calculation on the stability of (Fe,Mn)3AlC carbide in high aluminum steels

International Nuclear Information System (INIS)

Chin, Kwang-Geun; Lee, Hyuk-Joong; Kwak, Jai-Hyun; Kang, Jung-Yoon; Lee, Byeong-Joo

2010-01-01

A CALPHAD type thermodynamic description for the Fe-Mn-Al-C quaternary system has been constructed by combining a newly assessed Mn-Al-C ternary description and a partly modified Fe-Al-C description to an existing thermodynamic database for steels. A special attention was paid to reproduce experimentally reported phase stability of κ carbide in high Al and high Mn steels. This paper demonstrates that the proposed thermodynamic description makes it possible to predict phase equilibria in corresponding alloys with a practically acceptable accuracy. The applicability of the thermodynamic calculation is also demonstrated for the interpretation of microstructural and constitutional evolution during industrial processes for high Al steels.

Lanczos-Lovelock gravity from a thermodynamic perspective

International Nuclear Information System (INIS)

Chakraborty, Sumanta

2015-01-01

The deep connection between gravitational dynamics and horizon thermodynamics leads to several intriguing features both in general relativity and in Lanczos-Lovelock theories of gravity. Recently in http://arxiv.org/abs/1312.3253 several additional results strengthening the above connection have been established within the framework of general relativity. In this work we provide a generalization of the above setup to Lanczos-Lovelock gravity as well. To our expectation it turns out that most of the results obtained in the context of general relativity generalize to Lanczos-Lovelock gravity in a straightforward but non-trivial manner. First, we provide an alternative and more general derivation of the connection between Noether charge for a specific time evolution vector field and gravitational heat density of the boundary surface. This will lead to holographic equipartition for static spacetimes in Lanczos-Lovelock gravity as well. Taking a cue from this, we have introduced naturally defined four-momentum current associated with gravity and matter energy momentum tensor for both Lanczos-Lovelock Lagrangian and its quadratic part. Then, we consider the concepts of Noether charge for null boundaries in Lanczos-Lovelock gravity by providing a direct generalization of previous results derived in the context of general relativity. Another very interesting feature for gravity is that gravitational field equations for arbitrary static and spherically symmetric spacetimes with horizon can be written as a thermodynamic identity in the near horizon limit. This result holds in both general relativity and in Lanczos-Lovelock gravity as well. In a previous work [http://arxiv.org/abs/1505.05297] we have shown that, for an arbitrary spacetime, the gravitational field equations near any null surface generically leads to a thermodynamic identity. In this work, we have also generalized this result to Lanczos-Lovelock gravity by showing that gravitational field equations for Lanczos

Thermodynamic Bethe Ansatz for the Spin-1/2 Staggered XXZ- Model

OpenAIRE

Mkhitaryan, V. V.; Sedrakyan, A. G.

2003-01-01

We develop the technique of Thermodynamic Bethe Ansatz to investigate the ground state and the spectrum in the thermodynamic limit of the staggered $XXZ$ models proposed recently as an example of integrable ladder model. This model appeared due to staggered inhomogeneity of the anisotropy parameter $\\Delta$ and the staggered shift of the spectral parameter. We give the structure of ground states and lowest lying excitations in two different phases which occur at zero temperature.

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...

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...

Existence of 121 limit cycles in a perturbed planar polynomial Hamiltonian vector field of degree 11

International Nuclear Information System (INIS)

Wang, S.; Yu, P.

2006-01-01

In this article, a systematic procedure has been explored to studying general Z q -equivariant planar polynomial Hamiltonian vector fields for the maximal number of closed orbits and the maximal number of limit cycles after perturbation. Following the procedure by taking special consideration of Z 12 -equivariant vector fields of degree 11, the maximal of 99 closed orbits are obtained under a well-defined coefficient group. Consequently, perturbation parameter control in limit cycle computation leads to the existence of 121 limit cycles in the perturbed Hamiltonian vector field, which gives rise to the lower bound of Hilbert number of 11th-order systems as H(11) ≥ 11 2 . Two conjectures are proposed regarding the maximal number of closed orbits for equivariant polynomial Hamiltonian vector fields and the maximal number of limit cycles bifurcated from the well defined Hamiltonian vector fields after perturbation

Thermodynamic curvature of soft-sphere fluids and solids

Science.gov (United States)

Brańka, A. C.; Pieprzyk, S.; Heyes, D. M.

2018-02-01

The influence of the strength of repulsion between particles on the thermodynamic curvature scalar R for the fluid and solid states is investigated for particles interacting with the inverse power (r-n) potential, where r is the pair separation and 1 /n is the softness. Exact results are obtained for R in certain limiting cases, and the R behavior determined for the systems in the fluid and solid phases. It is found that in such systems the thermodynamic curvature can be positive for very soft particles, negative for steeply repulsive (or large n ) particles across almost the entire density range, and can change sign between negative and positive at a certain density. The relationship between R and the form of the interaction potential is more complex than previously suggested, and it may be that R is an indicator of the relative importance of energy and entropy contributions to the thermodynamic properties of the system.

Correlating thermodynamic and kinetic parameters with amorphous stability

DEFF Research Database (Denmark)

Graeser, Kirsten A; Patterson, James E; Zeitler, J Axel

2009-01-01

Poor physical stability is one of the single most important factors limiting the widespread use of the amorphous state in pharmaceutics. The purpose of this study is to move away from the case study approach by investigating thermodynamic and kinetic parameters as potential predictors of physical...

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.

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.

High-temperature of thermodynamic properties of sodium

Energy Technology Data Exchange (ETDEWEB)

Padilla, A. Jr.

1977-01-01

The set of high-temperature thermodynamic properties for sodium in the two-phase and subcooled-liquid regions which was previously recommended, has been modified to incorporate recent experimental data. In particular, replacement of the previously estimated critical constants with experimentally-determined values has resulted in substantial differences in the region of the critical point. The following thermodynamic properties were determined: pressure, density, enthalpy, entropy, internal energy, compressibility (adiabatic and isothermal), thermal expansion coefficient, thermal pressure coefficient, and specific heat (constant-pressure and constant-volume). These properties were determined for the saturated liquid, saturated vapor, subcooled liquid, and superheated vapor. The superheated vapor properties are limited to low pressures and more work is required to extend them to higher pressures. The supercritical region was not investigated.

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

Thermodynamics of dilute gases: application to submonolayer He films

International Nuclear Information System (INIS)

Vetrovec, M.B.; Carneiro, G.M.

1979-01-01

The thermodynamic properties of submonolayer He films are calculated. Expressions are first obtained for the thermodynamic properties of dilute systems of particles interacting through a short range potential taking into account binary interactions between the particles. These expressions are exact in the limit n→0, n being the particle number density, and are valid at all temperatures. At high temperatures these expressions are reduced to those obtained using the virial expansion truncated after the second term. These expressions are next applied to He in two dimensions and the results compared with experiment and with previous calculations [pt

Thermodynamic stability of warped AdS3 black holes

International Nuclear Information System (INIS)

Birmingham, Danny; Mokhtari, Susan

2011-01-01

We study the thermodynamic stability of warped black holes in three-dimensional topologically massive gravity. The spacelike stretched black hole is parametrized by its mass and angular momentum. We determine the local and global stability properties in the canonical and grand canonical ensembles. The presence of a Hawking-Page type transition is established, and the critical temperature is determined. The thermodynamic metric of Ruppeiner is computed, and the curvature is shown to diverge in the extremal limit. The consequences of these results for the classical stability properties of warped black holes are discussed within the context of the correlated stability conjecture.

Kinetic and thermodynamic control of butyrate conversion in non-defined methanogenic communities.

Science.gov (United States)

Junicke, H; van Loosdrecht, M C M; Kleerebezem, R

2016-01-01

Many anaerobic conversions proceed close to thermodynamic equilibrium and the microbial groups involved need to share their low energy budget to survive at the thermodynamic boundary of life. This study aimed to investigate the kinetic and thermodynamic control mechanisms of the electron transfer during syntrophic butyrate conversion in non-defined methanogenic communities. Despite the rather low energy content of butyrate, results demonstrate unequal energy sharing between the butyrate-utilizing species (17 %), the hydrogenotrophic methanogens (9-10 %), and the acetoclastic methanogens (73-74 %). As a key finding, the energy disproportion resulted in different growth strategies of the syntrophic partners. Compared to the butyrate-utilizing partner, the hydrogenotrophic methanogens compensated their lower biomass yield per mole of electrons transferred with a 2-fold higher biomass-specific electron transfer rate. Apart from these thermodynamic control mechanisms, experiments revealed a ten times lower hydrogen inhibition constant on butyrate conversion than proposed by the Anaerobic Digestion Model No. 1, suggesting a much stronger inhibitory effect of hydrogen on anaerobic butyrate conversion. At hydrogen partial pressures exceeding 40 Pa and at bicarbonate limited conditions, a shift from methanogenesis to reduced product formation was observed which indicates an important role of the hydrogen partial pressure in redirecting electron fluxes towards reduced products such as butanol. The findings of this study demonstrate that a careful consideration of thermodynamics and kinetics is required to advance our current understanding of flux regulation in energy-limited syntrophic ecosystems.

Simulation and Domain Identification of Sea Ice Thermodynamic System

Directory of Open Access Journals (Sweden)

Bing Tan

2012-01-01

Full Text Available Based on the measured data and characteristics of sea ice temperature distribution in space and time, this study is intended to consider a parabolic partial differential equation of the thermodynamic field of sea ice (coupled by snow, ice, and sea water layers with a time-dependent domain and its parameter identification problem. An optimal model with state constraints is presented with the thicknesses of snow and sea ice as parametric variables and the deviation between the calculated and measured sea ice temperatures as the performance criterion. The unique existence of the weak solution of the thermodynamic system is proved. The properties of the identification problem and the existence of the optimal parameter are discussed, and the one-order necessary condition is derived. Finally, based on the nonoverlapping domain decomposition method and semi-implicit difference scheme, an optimization algorithm is proposed for the numerical simulation. Results show that the simulated temperature of sea ice fit well with the measured data, and the better fit is corresponding to the deeper sea ice.

Multi-Regge limit of the n-gluon bubble ansatz

Energy Technology Data Exchange (ETDEWEB)

Bartels, J. [Hamburg Univ. (Germany). 2. Inst. fuer Theoretische Physik; Schomerus, V.; Sprenger, M. [Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)

2012-07-15

We investigate n-gluon scattering amplitudes in the multi-Regge region of N=4 supersymmetric Yang-Mills theory at strong coupling. Through a careful analysis of the thermodynamic bubble ansatz (TBA) for surfaces in AdS{sub 5} with n-g(lu)on boundary conditions we demonstrate that the multi-Regge limit probes the large volume regime of the TBA. In reaching the multi-Regge regime we encounter wall-crossing in the TBA for all n>6. Our results imply that there exists an auxiliary system of algebraic Bethe ansatz equations which encode valuable information on the analytical structure of amplitudes at strong coupling.

Thermodynamic calculation on the stability of (Fe,Mn){sub 3}AlC carbide in high aluminum steels

Energy Technology Data Exchange (ETDEWEB)

Chin, Kwang-Geun [Automotive Steel Products Research Group, POSCO Technical Research Laboratories, POSCO, Jeonnam 545-090 (Korea, Republic of); School of Materials Science and Engineering, Pusan National University, Pusan, 609-735 (Korea, Republic of); Lee, Hyuk-Joong [Department of Materials Science and Engineering, Pohang University of Science and Technology (POSTECH), Pohang 790-784 (Korea, Republic of); Kwak, Jai-Hyun [Automotive Steel Products Research Group, POSCO Technical Research Laboratories, POSCO, Jeonnam 545-090 (Korea, Republic of); Kang, Jung-Yoon [School of Materials Science and Engineering, Pusan National University, Pusan, 609-735 (Korea, Republic of); Lee, Byeong-Joo, E-mail: calphad@postech.ac.k [Department of Materials Science and Engineering, Pohang University of Science and Technology (POSTECH), Pohang 790-784 (Korea, Republic of)

2010-08-27

A CALPHAD type thermodynamic description for the Fe-Mn-Al-C quaternary system has been constructed by combining a newly assessed Mn-Al-C ternary description and a partly modified Fe-Al-C description to an existing thermodynamic database for steels. A special attention was paid to reproduce experimentally reported phase stability of {kappa} carbide in high Al and high Mn steels. This paper demonstrates that the proposed thermodynamic description makes it possible to predict phase equilibria in corresponding alloys with a practically acceptable accuracy. The applicability of the thermodynamic calculation is also demonstrated for the interpretation of microstructural and constitutional evolution during industrial processes for high Al steels.

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.

Generalized Geometric Quantum Speed Limits

Directory of Open Access Journals (Sweden)

Diego Paiva Pires

2016-06-01

Full Text Available The attempt to gain a theoretical understanding of the concept of time in quantum mechanics has triggered significant progress towards the search for faster and more efficient quantum technologies. One of such advances consists in the interpretation of the time-energy uncertainty relations as lower bounds for the minimal evolution time between two distinguishable states of a quantum system, also known as quantum speed limits. We investigate how the nonuniqueness of a bona fide measure of distinguishability defined on the quantum-state space affects the quantum speed limits and can be exploited in order to derive improved bounds. Specifically, we establish an infinite family of quantum speed limits valid for unitary and nonunitary evolutions, based on an elegant information geometric formalism. Our work unifies and generalizes existing results on quantum speed limits and provides instances of novel bounds that are tighter than any established one based on the conventional quantum Fisher information. We illustrate our findings with relevant examples, demonstrating the importance of choosing different information metrics for open system dynamics, as well as clarifying the roles of classical populations versus quantum coherences, in the determination and saturation of the speed limits. Our results can find applications in the optimization and control of quantum technologies such as quantum computation and metrology, and might provide new insights in fundamental investigations of quantum thermodynamics.

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.

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.)

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

Method of core thermodynamic reliability determination in pressurized water reactors

Energy Technology Data Exchange (ETDEWEB)

Ackermann, G.; Horche, W. (Ingenieurhochschule Zittau (German Democratic Republic). Sektion Kraftwerksanlagenbau und Energieumwandlung)

1983-01-01

A statistical model appropriate to determine the thermodynamic reliability and the power-limiting parameter of PWR cores is described for cases of accidental transients. The model is compared with the hot channel model hitherto applied.

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.

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.

The Effect Of The Original Acquisition Of Ownership Of Immovable Property On Existing Limited Real Rights

Directory of Open Access Journals (Sweden)

Gerrit Pienaar

2015-12-01

Full Text Available It is an accepted principle in South African law that movable property acquired in an original way (by operation of law is not burdened by any limited real rights, as previous limited real rights are extinguished on the vesting of ownership (mobilia non habent sequelam. It is assumed by some South African writers that the same principles are applicable to the original acquisition of immovable property and that all existing limited real rights fall away on original acquisition of ownership. In this article the nature of limited real rights to immovable property is examined, and the notion that ownership is the "mother" right on which all limited real rights are based is scrutinised critically. The nature and establishment of limited real rights are used to distinguish between the essence and effect of limited real rights in the case of immovable property. The recognition of limited real rights as constitutional property is used as a further argument that limited real rights cannot be extinguished automatically by the original acquisition of immovable property, as such common law or statutory measures will constitute an arbitrary deprivation of property in terms of section 25 of the Constitution. The statutory provisions regarding limited real rights in the case of prescription and expropriation are then analysed as an indication that it is not a general principle that limited real rights are extinguished automatically on the original acquisition of ownership of immovable property.

Role of sufficient statistics in stochastic thermodynamics and its implication to sensory adaptation

Science.gov (United States)

Matsumoto, Takumi; Sagawa, Takahiro

2018-04-01

A sufficient statistic is a significant concept in statistics, which means a probability variable that has sufficient information required for an inference task. We investigate the roles of sufficient statistics and related quantities in stochastic thermodynamics. Specifically, we prove that for general continuous-time bipartite networks, the existence of a sufficient statistic implies that an informational quantity called the sensory capacity takes the maximum. Since the maximal sensory capacity imposes a constraint that the energetic efficiency cannot exceed one-half, our result implies that the existence of a sufficient statistic is inevitably accompanied by energetic dissipation. We also show that, in a particular parameter region of linear Langevin systems there exists the optimal noise intensity at which the sensory capacity, the information-thermodynamic efficiency, and the total entropy production are optimized at the same time. We apply our general result to a model of sensory adaptation of E. coli and find that the sensory capacity is nearly maximal with experimentally realistic parameters.

Method of core thermodynamic reliability determination in pressurized water reactors

International Nuclear Information System (INIS)

Ackermann, G.; Horche, W.

1983-01-01

A statistical model appropriate to determine the thermodynamic reliability and the power-limiting parameter of PWR cores is described for cases of accidental transients. The model is compared with the hot channel model hitherto applied. (author)

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

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

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

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

Black hole enthalpy and an entropy inequality for the thermodynamic volume

International Nuclear Information System (INIS)

Cvetic, M.; Gibbons, G. W.; Kubiznak, D.; Pope, C. N.

2011-01-01

In a theory where the cosmological constant Λ or the gauge coupling constant g arises as the vacuum expectation value, its variation should be included in the first law of thermodynamics for black holes. This becomes dE=TdS+Ω i dJ i +Φ α dQ α +ΘdΛ, where E is now the enthalpy of the spacetime, and Θ, the thermodynamic conjugate of Λ, is proportional to an effective volume V=-(16πΘ/D-2)''inside the event horizon.'' Here we calculate Θ and V for a wide variety of D-dimensional charged rotating asymptotically anti-de Sitter (AdS) black hole spacetimes, using the first law or the Smarr relation. We compare our expressions with those obtained by implementing a suggestion of Kastor, Ray, and Traschen, involving Komar integrals and Killing potentials, which we construct from conformal Killing-Yano tensors. We conjecture that the volume V and the horizon area A satisfy the inequality R≡ ((D-1)V/A D-2 ) 1/(D-1) (A D-2 /A) 1/(D-2) ≥1, where A D-2 is the volume of the unit (D-2) sphere, and we show that this is obeyed for a wide variety of black holes, and saturated for Schwarzschild-AdS. Intriguingly, this inequality is the ''inverse'' of the isoperimetric inequality for a volume V in Euclidean (D-1) space bounded by a surface of area A, for which R≤1. Our conjectured reverse isoperimetric inequality can be interpreted as the statement that the entropy inside a horizon of a given ''volume''V is maximized for Schwarzschild-AdS. The thermodynamic definition of V requires a cosmological constant (or gauge coupling constant). However, except in seven dimensions, a smooth limit exists where Λ or g goes to zero, providing a definition of V even for asymptotically flat black holes.

Thermodynamic bounds for existence of normal shock in compressible fluid flow in pipes

Directory of Open Access Journals (Sweden)

SERGIO COLLE

Full Text Available Abstract The present paper is concerned with the thermodynamic theory of the normal shock in compressible fluid flow in pipes, in the lights of the pioneering works of Lord Rayleigh and G. Fanno. The theory of normal shock in pipes is currently presented in terms of the Rayleigh and Fanno curves, which are shown to cross each other in two points, one corresponding to a subsonic flow and the other corresponding to a supersonic flow. It is proposed in this paper a novel differential identity, which relates the energy flux density, the linear momentum flux density, and the entropy, for constant mass flow density. The identity so obtained is used to establish a theorem, which shows that Rayleigh and Fanno curves become tangent to each other at a single sonic point. At the sonic point the entropy reaches a maximum, either as a function of the pressure and the energy density flux or as a function of the pressure and the linear momentum density flux. A Second Law analysis is also presented, which is fully independent of the Second Law analysis based on the Rankine-Hugoniot adiabatic carried out by Landau and Lifshitz (1959.

On the laws of thermodynamics from the escort average and on the uniqueness of statistical factors

International Nuclear Information System (INIS)

Yamano, Takuya

2003-01-01

We consider the relation between the statistical weight and the laws of thermodynamics. Our path bases on the infinitesimal perturbation from outside of the thermodynamical system. It is fair to say that the form of the first laws of thermodynamics and the Clausius' definition of thermodynamic entropy are commensurately altered once we employ the escort average of statistical weight but preserves the forms in the limit of the usual weight. We also see an example for the unique determination of the statistical factor (so-called the Gibbs theorem) in addition to the Boltzmann and the Tsallis ones

Thermodynamic basis for the emergence of genomes during prebiotic evolution.

Directory of Open Access Journals (Sweden)

Hyung-June Woo

2012-05-01

Full Text Available The RNA world hypothesis views modern organisms as descendants of RNA molecules. The earliest RNA molecules must have been random sequences, from which the first genomes that coded for polymerase ribozymes emerged. The quasispecies theory by Eigen predicts the existence of an error threshold limiting genomic stability during such transitions, but does not address the spontaneity of changes. Following a recent theoretical approach, we applied the quasispecies theory combined with kinetic/thermodynamic descriptions of RNA replication to analyze the collective behavior of RNA replicators based on known experimental kinetics data. We find that, with increasing fidelity (relative rate of base-extension for Watson-Crick versus mismatched base pairs, replications without enzymes, with ribozymes, and with protein-based polymerases are above, near, and below a critical point, respectively. The prebiotic evolution therefore must have crossed this critical region. Over large regions of the phase diagram, fitness increases with increasing fidelity, biasing random drifts in sequence space toward 'crystallization.' This region encloses the experimental nonenzymatic fidelity value, favoring evolutions toward polymerase sequences with ever higher fidelity, despite error rates above the error catastrophe threshold. Our work shows that experimentally characterized kinetics and thermodynamics of RNA replication allow us to determine the physicochemical conditions required for the spontaneous crystallization of biological information. Our findings also suggest that among many potential oligomers capable of templated replication, RNAs may have evolved to form prebiotic genomes due to the value of their nonenzymatic fidelity.

Thermodynamics of pellet-cladding interaction

International Nuclear Information System (INIS)

Kyoh, Bunkei; Fuji, Kensho

1987-01-01

Equilibrium thermodynamic calculations are performed on the U-Zr-Cs-I-O system that is assumed to exist in the fuel-cladding gap of light water reactor (LWR) fuel under pellet-cladding interaction (PCI) failure condition. For this purpose a computer program called SOLGASMIX-PV for the calculation of complex multi-component equilibria is used, and the results of postirradiation examination are interpreted. The analysis of the thermodynamics of the system U-Zr-Cs-I-O indicates that cesium and iodine are assumed to be released from fuel pellet into the fuel-cladding gap as CsI, therefore, the Cs/I ratio in fuel-cladding bonding zone is one. The important condensed phases in this region are UO 2 , U 3 O 8 , Cs 2 U 2 O 7 , Cs 2 U 15 O 46 , ZrO 2 and CsI, and the major gaseous species are CsI, I 2 and I. Under this situation where Cs/I ratio is one, cesium-zirconate is not present. If, however, cesium rich phase is partially present then cesium will be associated with zirconium, possibly as Cs 2 ZrO 3 . (author)

Partition functions. I. Improved partition functions and thermodynamic quantities for normal, equilibrium, and ortho and para molecular hydrogen

Science.gov (United States)

Popovas, A.; Jørgensen, U. G.

2016-11-01

Context. Hydrogen is the most abundant molecule in the Universe. Its thermodynamic quantities dominate the physical conditions in molecular clouds, protoplanetary disks, etc. It is also of high interest in plasma physics. Therefore thermodynamic data for molecular hydrogen have to be as accurate as possible in a wide temperature range. Aims: We here rigorously show the shortcomings of various simplifications that are used to calculate the total internal partition function. These shortcomings can lead to errors of up to 40 percent or more in the estimated partition function. These errors carry on to calculations of thermodynamic quantities. Therefore a more complicated approach has to be taken. Methods: Seven possible simplifications of various complexity are described, together with advantages and disadvantages of direct summation of experimental values. These were compared to what we consider the most accurate and most complete treatment (case 8). Dunham coefficients were determined from experimental and theoretical energy levels of a number of electronically excited states of H2. Both equilibrium and normal hydrogen was taken into consideration. Results: Various shortcomings in existing calculations are demonstrated, and the reasons for them are explained. New partition functions for equilibrium, normal, and ortho and para hydrogen are calculated and thermodynamic quantities are reported for the temperature range 1-20 000 K. Our results are compared to previous estimates in the literature. The calculations are not limited to the ground electronic state, but include all bound and quasi-bound levels of excited electronic states. Dunham coefficients of these states of H2 are also reported. Conclusions: For most of the relevant astrophysical cases it is strongly advised to avoid using simplifications, such as a harmonic oscillator and rigid rotor or ad hoc summation limits of the eigenstates to estimate accurate partition functions and to be particularly careful when

Thermodynamic performance assessment of wind energy systems: An application

International Nuclear Information System (INIS)

Redha, Adel Mohammed; Dincer, Ibrahim; Gadalla, Mohamed

2011-01-01

In this paper, the performance of wind energy system is assessed thermodynamically, from resource and technology perspectives. The thermodynamic characteristics of wind through energy and exergy analyses are considered and both energetic and exergetic efficiencies are studied. Wind speed is affected by air temperature and pressure and has a subsequent effect on wind turbine performance based on wind reference temperature and Bernoulli's equation. VESTAS V52 wind turbine is selected for (Sharjah/UAE). Energy and exergy efficiency equations for wind energy systems are further developed for practical applications. The results show that there are noticeable differences between energy and exergy efficiencies and that exergetic efficiency reflects the right/actual performance. Finally, exergy analysis has been proven to be the right tool used in design, simulation, and performance evaluation of all renewable energy systems. -- Highlights: → In this research the performance of wind energy system is assessed thermodynamically, from resource and technology perspectives. → Energy and exergy equations for wind energy systems are further developed for practical applications. → Thermodynamic characteristics of wind turbine systems through energetic and exergetic efficiencies are evaluated from January till March 2010. → Exergy efficiency describes the system irreversibility and the minimum irreversibility exists when the wind speed reaches 11 m/s. → The power production during March was about 17% higher than the month of February and 66% higher than January.

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

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

Science.gov (United States)

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

2018-02-01

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

ZINC MITIGATION INTERIM REPORT - THERMODYNAMIC STUDY

Energy Technology Data Exchange (ETDEWEB)

Korinko, P.

2010-12-17

An experimental program was initiated in order to develop and validate conditions that will effectively trap Zn vapors that are released during extraction. The proposed work is broken down into three tasks. The first task is to determine the effectiveness of various pore sizes of filter elements. The second task is to determine the effect of filter temperature on zinc vapor deposition. The final task is to determine whether the zinc vapors can be chemically bound. The approach for chemically binding the zinc vapors has two subtasks, the first is a review of literature and thermodynamic calculations and the second is an experimental approach using the best candidates. This report details the results of the thermodynamic calculations to determine feasibility of chemically binding the zinc vapors within the furnace module, specifically the lithium trap (1). A review of phase diagrams, literature, and thermodynamic calculations was conducted to determine if there are suitable materials to capture zinc vapor within the lithium trap of the extraction basket. While numerous elements exist that form compounds with zinc, many of these also form compounds with hydrogen or the water that is present in the TPBARs. This relatively comprehensive review of available data indicates that elemental cobalt and copper and molybdenum trioxide (MoO3) may have the requisite properties to capture zinc and yet not be adversely affected by the extraction gases and should be considered for testing.

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.

Thermodynamics of long-run economic innovation and growth

OpenAIRE

Garrett, Timothy J.

2013-01-01

This article derives prognostic expressions for the evolution of globally aggregated economic wealth, productivity, inflation, technological change, innovation and growth. The approach is to treat civilization as an open, non-equilibrium thermodynamic system that dissipates energy and diffuses matter in order to sustain existing circulations and to further its material growth. Appealing to a prior result that established a fixed relationship between a very general representation of global eco...

Modelling grain growth in the framework of Rational Extended Thermodynamics

International Nuclear Information System (INIS)

Kertsch, Lukas; Helm, Dirk

2016-01-01

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

Modelling grain growth in the framework of Rational Extended Thermodynamics

Science.gov (United States)

Kertsch, Lukas; Helm, Dirk

2016-05-01

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

Toward Improved Force-Field Accuracy through Sensitivity Analysis of Host-Guest Binding Thermodynamics

Science.gov (United States)

Yin, Jian; Fenley, Andrew T.; Henriksen, Niel M.; Gilson, Michael K.

2015-01-01

Improving the capability of atomistic computer models to predict the thermodynamics of noncovalent binding is critical for successful structure-based drug design, and the accuracy of such calculations remains limited by non-optimal force field parameters. Ideally, one would incorporate protein-ligand affinity data into force field parametrization, but this would be inefficient and costly. We now demonstrate that sensitivity analysis can be used to efficiently tune Lennard-Jones parameters of aqueous host-guest systems for increasingly accurate calculations of binding enthalpy. These results highlight the promise of a comprehensive use of calorimetric host-guest binding data, along with existing validation data sets, to improve force field parameters for the simulation of noncovalent binding, with the ultimate goal of making protein-ligand modeling more accurate and hence speeding drug discovery. PMID:26181208

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.

A thermodynamic perspective to study energy performance of vacuum-based membrane dehumidification

KAUST Repository

Bui, Thuan Duc; Kum Ja, M.; Gordon, Jeffrey M.; Ng, Kim Choon; Chua, Kian Jon

2017-01-01

In humid environments, decoupling the latent and sensible cooling loads - dehumidifying - can significantly improve chiller efficiency. Here, a basic limit for dehumidification efficiency is established from fundamental thermodynamics

Thermodynamic limits to the conversion of blackbody radiation by quantum systems. [with application to solar energy conversion devices

Science.gov (United States)

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

1982-01-01

Using general thermodynamic arguments, we analyze the conversion of the energy contained in the radiation from a blackbody to useful work by a quantum system. We show that the energy available for conversion is bounded above by the change in free energy in the incident and reradiated fields and that this free energy change depends upon the temperature of the receiving device. Universal efficiency curves giving the ultimate thermodynamic conversion efficiency of the quantum system are presented in terms of the blackbody temperature and the temperature and threshold energy of the quantum system. Application of these results is made to a variety of systems including biological photosynthetic, photovoltaic, and photoelectrochemical systems.

Thermodynamic stability of warped AdS{sub 3} black holes

Energy Technology Data Exchange (ETDEWEB)

Birmingham, Danny, E-mail: dbirmingham@pacific.ed [Department of Physics, University of the Pacific, Stockton, CA 95211 (United States); Mokhtari, Susan, E-mail: susan@science.csustan.ed [Department of Physics, California State University Stanislaus, Turlock, CA 95382 (United States)

2011-02-21

We study the thermodynamic stability of warped black holes in three-dimensional topologically massive gravity. The spacelike stretched black hole is parametrized by its mass and angular momentum. We determine the local and global stability properties in the canonical and grand canonical ensembles. The presence of a Hawking-Page type transition is established, and the critical temperature is determined. The thermodynamic metric of Ruppeiner is computed, and the curvature is shown to diverge in the extremal limit. The consequences of these results for the classical stability properties of warped black holes are discussed within the context of the correlated stability conjecture.

Earthquake Protection of Existing Structures with Limited Seismic Joint: Base Isolation with Supplemental Damping versus Rotational Inertia

Directory of Open Access Journals (Sweden)

Dario De Domenico

2018-01-01

Full Text Available Existing civil engineering structures having strategic importance, such as hospitals, fire stations, and power plants, often do not comply with seismic standards in force today, as they were designed and built based on past structural guidelines. On the other hand, due to their special importance, structural integrity of such buildings is of vital importance during and after earthquakes, which puts demands on strategies for their seismic protection. In this regard, seismic base isolation has been widely employed; however, the existing limited seismic joint between adjacent buildings may hamper this application because of the large displacements concentrated at the isolation floor. In this paper, we compare two possible remedies: the former is to provide supplemental damping in conventional base isolation systems and the latter consists in a combination of base isolation with supplemental rotational inertia. For the second strategy, a mechanical device, called inerter, is arranged in series with spring and dashpot elements to form the so-called tuned-mass-damper-inerter (TMDI directly connected to an isolation floor. Several advantages of this second system as compared to the first one are outlined, especially with regard to the limitation of floor accelerations and interstory drifts, which may be an issue for nonstructural elements and equipment, in addition to disturbing occupants. Once the optimal design of the TMDI is established, possible implementation of this system into existing structures is discussed.

Mass-independent area (or entropy) and thermodynamic volume products in conformal gravity

Science.gov (United States)

Pradhan, Parthapratim

2017-06-01

In this work, we investigate the thermodynamic properties of conformal gravity in four dimensions. We compute the area (or entropy) functional relation for this black hole (BH). We consider both de Sitter (dS) and anti-de Sitter (AdS) cases. We derive the Cosmic-Censorship-Inequality which is an important relation in general relativity that relates the total mass of a spacetime to the area of all the BH horizons. Local thermodynamic stability is studied by computing the specific heat. The second-order phase transition occurs at a certain condition. Various types of second-order phase structure have been given for various values of a and the cosmological constant Λ in the Appendix. When a = 0, one obtains the result of Schwarzschild-dS and Schwarzschild-AdS cases. In the limit aM ≪ 1, one obtains the result of Grumiller spacetime, where a is nontrivial Rindler parameter or Rindler acceleration and M is the mass parameter. The thermodynamic volume functional relation is derived in the extended phase space, where the cosmological constant is treated as a thermodynamic pressure and its conjugate variable as a thermodynamic volume. The mass-independent area (or entropy) functional relation and thermodynamic volume functional relation that we have derived could turn out to be a universal quantity.

Improved actions for QCD thermodynamics on the lattice

CERN Document Server

Beinlich, B; Laermann, E

1996-01-01

Finite cut-off effects strongly influence the thermodynamics of lattice regularized QCD at high temperature in the standard Wilson formulation. We analyze the reduction of finite cut-off effects in formulations of the thermodynamics of SU(N) gauge theories with three different O(a^2) and O(a^4) improved actions. We calculate the energy density and pressure on finite lattices in leading order weak coupling perturbation theory (T\\rightarrow \\infty) and perform Monte Carlo simulations with improved SU(3) actions at non-zero g^2. Already on lattices with temporal extent N_\\tau=4 we find a strong reduction of finite cut-off effects in the high temperature limit, which persists also down to temperatures a few times the deconfinement transition temperature.

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...

Life, hierarchy, and the thermodynamic machinery of planet Earth.

Science.gov (United States)

Kleidon, Axel

2010-12-01

substantial amounts of chemical free energy which essentially skips the limitations and inefficiencies associated with the transfer of power within the thermodynamic hierarchy of the planet. This perspective allows us to view life as being the means to transform many aspects of planet Earth to states even further away from thermodynamic equilibrium than is possible by purely abiotic means. In this perspective pockets of low-entropy life emerge from the overall trend of the Earth system to increase the entropy of the universe at the fastest possible rate. The implications of the theory are discussed regarding fundamental deficiencies in Earth system modeling, applications of the theory to reconstructions of Earth system history, and regarding the role of human activity for the future of the planet. Copyright © 2010 Elsevier B.V. All rights reserved.

Consideration on thermodynamic data for predicting solubility and chemical species of elements in groundwater. Part 2: Np, Pu

International Nuclear Information System (INIS)

Yamaguchi, Tetsuji

2000-11-01

The solubility determines the release of a radionuclide from waste form and is used as a source term in radionuclide migration analysis in performance assessment of radioactive waste repository. Complexations of the radionuclide by ligands in groundwater affect the interaction between radionuclides and geologic media, thus affect their migration behavior. It is essential to estimate the solubility and to predict the chemical species for the radionuclide based on thermodynamic data. The thermodynamic data of aqueous species and compounds were reviewed and compiled for Np and Pu. Thermodynamic data were reviewed with emphasis on the hydrolysis and carbonate complexation that can dominate the speciation in groundwater. Thermodynamic data for other species were selected based on existing databases. Thermodynamic data for other important elements are under investigation, thus shown in an appendix for temporary use. (author)

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.

Thermodynamics of complexity and pattern manipulation

Science.gov (United States)

Garner, Andrew J. P.; Thompson, Jayne; Vedral, Vlatko; Gu, Mile

2017-04-01

Many organisms capitalize on their ability to predict the environment to maximize available free energy and reinvest this energy to create new complex structures. This functionality relies on the manipulation of patterns—temporally ordered sequences of data. Here, we propose a framework to describe pattern manipulators—devices that convert thermodynamic work to patterns or vice versa—and use them to build a "pattern engine" that facilitates a thermodynamic cycle of pattern creation and consumption. We show that the least heat dissipation is achieved by the provably simplest devices, the ones that exhibit desired operational behavior while maintaining the least internal memory. We derive the ultimate limits of this heat dissipation and show that it is generally nonzero and connected with the pattern's intrinsic crypticity—a complexity theoretic quantity that captures the puzzling difference between the amount of information the pattern's past behavior reveals about its future and the amount one needs to communicate about this past to optimally predict the future.

ThermoCycle: A Modelica library for the simulation of thermodynamic systems

DEFF Research Database (Denmark)

Quoilin, Sylvain; Desideri, Adriano; Wronski, Jorrit

2014-01-01

This paper presents the results of an on-going project to develop ThermoCycle, an open Modelica library for the simulation of low-capacity thermodynamic cycles and thermal systems. Special attention is paid to robustness and simulation speed since dynamic simulations are often limited by numerical...... constraints and failures, either during initialization or during integration. Furthermore, the use of complex equations of state (EOS) to compute thermodynamic properties significantly decreases the simulation speed. In this paper, the approach adopted in the library to overcome these challenges is presented...

Thermodynamic and Process Modelling of Gas Hydrate Systems in CO2 Capture Processes

DEFF Research Database (Denmark)

Herslund, Peter Jørgensen

A novel gas separation technique based on gas hydrate formation (solid precipitation) is investigated by means of thermodynamic modeling and experimental investigations. This process has previously been proposed for application in post-combustion carbon dioxide capture from power station flue gases...... formation may be performed at pressures of approximately 20 MPa and temperatures below 280 K. Thermodynamic promoters are needed, to reduce the pressure requirement of the process, thereby making it competitive to existing capture technologies. A literature study is presented focusing mainly...... on thermodynamic gas hydrate promotion by hydrate formers stabilising the classical gas clathrate hydrate structures (sI, sII and sH) at low to moderate pressures. Much literature is available on this subject. Both experimental and theoretical studies presented in the literature have pointed out cyclopentane...

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

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).

A note on the laws of thermodynamics

International Nuclear Information System (INIS)

Dunning-Davies, J.

1984-01-01

It is shown that, while links exist between the second and third laws, between the zeroth and proposed fourther laws and between the zeroth and second laws, no equivalences have been proved. Moreover, for positive absolute temperatures, the second law is seen to imply the zeroth law, provided the validity of the first law is assumed. However, since this result does not hold for negative absolute temperatures, no redundancy among the laws of thermodynamics can be claimed to have been established

Thermodynamic signatures of fragment binding: Validation of direct versus displacement ITC titrations.

Science.gov (United States)

Rühmann, Eggert; Betz, Michael; Fricke, Marie; Heine, Andreas; Schäfer, Martina; Klebe, Gerhard

2015-04-01

Detailed characterization of the thermodynamic signature of weak binding fragments to proteins is essential to support the decision making process which fragments to take further for the hit-to-lead optimization. Isothermal titration calorimetry (ITC) is the method of choice to record thermodynamic data, however, weak binding ligands such as fragments require the development of meaningful and reliable measuring protocols as usually sigmoidal titration curves are hardly possible to record due to limited solubility. Fragments can be titrated either directly under low c-value conditions (no sigmoidal curve) or indirectly by use of a strong binding ligand displacing the pre-incubated weak fragment from the protein. The determination of Gibbs free energy is reliable and rather independent of the applied titration protocol. Even though the displacement method achieves higher accuracy, the obtained enthalpy-entropy profile depends on the properties of the used displacement ligand. The relative enthalpy differences across different displacement experiments reveal a constant signature and can serve as a thermodynamic fingerprint for fragments. Low c-value titrations are only reliable if the final concentration of the fragment in the sample cell exceeds 2-10 fold its K(D) value. Limited solubility often prevents this strategy. The present study suggests an applicable protocol to characterize the thermodynamic signature of protein-fragment binding. It shows however, that such measurements are limited by protein and fragment solubility. Deviating profiles obtained by use of different displacement ligands indicate that changes in the solvation pattern and protein dynamics most likely take influence on the resulting overall binding signature. Copyright © 2014 Elsevier B.V. All rights reserved.

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

Stochastic thermodynamics of quantum maps with and without equilibrium.

Science.gov (United States)

Barra, Felipe; Lledó, Cristóbal

2017-11-01

We study stochastic thermodynamics for a quantum system of interest whose dynamics is described by a completely positive trace-preserving (CPTP) map as a result of its interaction with a thermal bath. We define CPTP maps with equilibrium as CPTP maps with an invariant state such that the entropy production due to the action of the map on the invariant state vanishes. Thermal maps are a subgroup of CPTP maps with equilibrium. In general, for CPTP maps, the thermodynamic quantities, such as the entropy production or work performed on the system, depend on the combined state of the system plus its environment. We show that these quantities can be written in terms of system properties for maps with equilibrium. The relations that we obtain are valid for arbitrary coupling strengths between the system and the thermal bath. The fluctuations of thermodynamic quantities are considered in the framework of a two-point measurement scheme. We derive the entropy production fluctuation theorem for general maps and a fluctuation relation for the stochastic work on a system that starts in the Gibbs state. Some simplifications for the probability distributions in the case of maps with equilibrium are presented. We illustrate our results by considering spin 1/2 systems under thermal maps, nonthermal maps with equilibrium, maps with nonequilibrium steady states, and concatenations of them. Finally, and as an important application, we consider a particular limit in which the concatenation of maps generates a continuous time evolution in Lindblad form for the system of interest, and we show that the concept of maps with and without equilibrium translates into Lindblad equations with and without quantum detailed balance, respectively. The consequences for the thermodynamic quantities in this limit are discussed.

Thermodynamically Tuned Nanophase Materials for reversible Hydrogen storage

Energy Technology Data Exchange (ETDEWEB)

Ping Liu; John J. Vajo

2010-02-28

This program was devoted to significantly extending the limits of hydrogen storage technology for practical transportation applications. To meet the hydrogen capacity goals set forth by the DOE, solid-state materials consisting of light elements were developed. Many light element compounds are known that have high capacities. However, most of these materials are thermodynamically too stable, and they release and store hydrogen much too slowly for practical use. In this project we developed new light element chemical systems that have high hydrogen capacities while also having suitable thermodynamic properties. In addition, we developed methods for increasing the rates of hydrogen exchange in these new materials. The program has significantly advanced (1) the application of combined hydride systems for tuning thermodynamic properties and (2) the use of nanoengineering for improving hydrogen exchange. For example, we found that our strategy for thermodynamic tuning allows both entropy and enthalpy to be favorably adjusted. In addition, we demonstrated that using porous supports as scaffolds to confine hydride materials to nanoscale dimensions could improve rates of hydrogen exchange by > 50x. Although a hydrogen storage material meeting the requirements for commercial development was not achieved, this program has provided foundation and direction for future efforts. More broadly, nanoconfinment using scaffolds has application in other energy storage technologies including batteries and supercapacitors. The overall goal of this program was to develop a safe and cost-effective nanostructured light-element hydride material that overcomes the thermodynamic and kinetic barriers to hydrogen reaction and diffusion in current materials and thereby achieve > 6 weight percent hydrogen capacity at temperatures and equilibrium pressures consistent with DOE target values.

Thermodynamic study of the mixed phase in YBa_2Cu_3O_7_-_δ

International Nuclear Information System (INIS)

Bouquet, Frederic

1998-01-01

The mixed phase of type II superconductors is characterised by the existence of vortices of supercurrent that each enclose a magnetic flux quantum. Whereas the vortices order themselves in a lattice for most fields and temperatures in the mixed phase of conventional superconductors, the phase diagram for the high critical temperature superconductors is much more complex. We present here a thermodynamic study of the system of vortices for YBa_2Cu_30_7_-_δ, mainly based on specific heat experiments, but also on magnetisation measurements. To carry out the experimental work a modulated temperature calorimeter was developed, allowing us to achieve a very good resolution over a wide range of magnetic field. Our results confirm the existence of a first order thermodynamic transition in the mixed phase. We also present an original way to test the presence of a possible hysteresis associated with this transition by exploiting the oscillatory principle of our technique. The question of the existence of a low temperature high field vortex phase is discussed. Above a characteristic field B_c_r, which can reach very high values depending on the sample (up to 26 T), we find the latent heat associated with the first order transition disappears and the transition becomes continuous. By performing both magnetisation and specific heat experiments we show that Ber is related to pinning of the vortices. The existence of a third thermodynamically stable vortex phase at high field, different from the two phases at low field separated by the first order transition, does not seem to be compatible with our data. (author) [fr

Thermodynamic Analysis of the Static Spherically Symmetric Field Equations in Rastall Theory

International Nuclear Information System (INIS)

Moradpour, Hooman; Salako, Ines G.

2016-01-01

The restrictions on the Rastall theory due to application of the Newtonian limit to the theory are derived. In addition, we use the zero-zero component of the Rastall field equations as well as the unified first law of thermodynamics to find the Misner-Sharp mass content confined to the event horizon of the spherically symmetric static spacetimes in the Rastall framework. The obtained relation is calculated for the Schwarzschild and de-Sitter back holes as two examples. Bearing the obtained relation for the Misner-Sharp mass in mind together with recasting the one-one component of the Rastall field equations into the form of the first law of thermodynamics, we obtain expressions for the horizon entropy and the work term. Finally, we also compare the thermodynamic quantities of system, including energy, entropy, and work, with their counterparts in the Einstein framework to have a better view about the role of the Rastall hypothesis on the thermodynamics of system.

Bethe ansatz approach to quantum sine Gordon thermodynamics and finite temperature excitations

International Nuclear Information System (INIS)

Zotos, X.

1982-01-01

Takahashi and Suzuki (TS) using the Bethe ansatz method developed a formalism for the thermodynamics of the XYZ spin chain. Translating their formalism to the quantum sine-Gordon system, the thermodynamics and finite temperature elementary excitations are analyzed. Criteria imposed by TS on the allowed states simply correspond to the condition of normalizability of the wave functions. A set of coupled nonlinear integral equations for the thermodynamic equilibrium densities for particular values of the coupling constant in the attractive regime is derived. Solving numerically these Bethe ansatz equations, curves of the specific heat as a function of temperature are obtained. The soliton contribution peaks at a temperature of about 0.4 soliton masses shifting downward as the classical limit is approached. The weak coupling regime is analyzed by deriving the Bethe ansatz equations including the charged vacuum excitations. It is shown that they are necessary for a consistent presentation of the thermodynamics

A thermodynamic reference database for nuclear waste disposal

Energy Technology Data Exchange (ETDEWEB)

Brendler, V. [Helmholtz-Zentrum Dresden-Rossendorf, Dresden (Germany); Altmaier, M. [Karlsruhe Institute of Technology, Karlsruhe (Germany); Moog, H. [Gesellschaft fuer Anlagen- und Reaktorsicherheit mbH, Braunschweig (Germany); Voigt, W. [TU Bergakademie Freiberg (Germany); Wilhelm, S. [AF Consult Switzerland AG, Baden (Switzerland)

2015-07-01

Safety analysis for a geological repository for radioactive waste as well as remediation measures for uranium mining and processing legacies share an essential: the need for a reliable, traceable and accurate assessment of potential migration of toxic constituents into the biosphere. The respective computational codes require site-independent thermodynamic data concerning aqueous speciation, solubility limiting solid phases and ion-interaction parameters. Such databases, however, show several constraints: - Incompleteness in terms of major and trace elements - Inconsistencies between species considered and corresponding formation constants - Restricted variation ranges of intensive parameters (temperature, density, pressure) - Limitations with respect to solution compositions (ionic strength). To overcome these limitations to a significant degree, an ambitious database project - THEREDA - has been launched in 2006 by institutions leading in the field of safety research for nuclear waste disposal in Germany. The main objective is a centrally administrated and maintained database of verified thermodynamic parameters for environmental applications in general and radiochemical issues in particular. During the last year, the most important point was the official release of four more datasets (adding carbonate, An(III), Np(V) and Cs to the hexary system of oceanic salts), all based on the Pitzer model describing the ion-ion interactions. They can all be downloaded as separate files from the project web site www.thereda.de (navigation menu: THEREDA Data Query → Tailored Databases) as generic ASCII type, and in formats specific to the geochemical speciation codes PhreeqC, EQ3/6, ChemApp and Geochemist Workbench. Moreover, access to data records is now also possible through interactive forms (menu: THEREDA Data Query → Single Data Query // Complex Systems), both with export options as CSV or MS Excel file. Additional releases of thermodynamic data for Th(IV), U(IV) and

A thermodynamic reference database for nuclear waste disposal

International Nuclear Information System (INIS)

Brendler, V.; Altmaier, M.; Moog, H.; Voigt, W.; Wilhelm, S.

2015-01-01

Safety analysis for a geological repository for radioactive waste as well as remediation measures for uranium mining and processing legacies share an essential: the need for a reliable, traceable and accurate assessment of potential migration of toxic constituents into the biosphere. The respective computational codes require site-independent thermodynamic data concerning aqueous speciation, solubility limiting solid phases and ion-interaction parameters. Such databases, however, show several constraints: - Incompleteness in terms of major and trace elements - Inconsistencies between species considered and corresponding formation constants - Restricted variation ranges of intensive parameters (temperature, density, pressure) - Limitations with respect to solution compositions (ionic strength). To overcome these limitations to a significant degree, an ambitious database project - THEREDA - has been launched in 2006 by institutions leading in the field of safety research for nuclear waste disposal in Germany. The main objective is a centrally administrated and maintained database of verified thermodynamic parameters for environmental applications in general and radiochemical issues in particular. During the last year, the most important point was the official release of four more datasets (adding carbonate, An(III), Np(V) and Cs to the hexary system of oceanic salts), all based on the Pitzer model describing the ion-ion interactions. They can all be downloaded as separate files from the project web site www.thereda.de (navigation menu: THEREDA Data Query → Tailored Databases) as generic ASCII type, and in formats specific to the geochemical speciation codes PhreeqC, EQ3/6, ChemApp and Geochemist Workbench. Moreover, access to data records is now also possible through interactive forms (menu: THEREDA Data Query → Single Data Query // Complex Systems), both with export options as CSV or MS Excel file. Additional releases of thermodynamic data for Th(IV), U(IV) and

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.

Thermodynamics of (d+1)-dimensional NUT-charged AdS spacetimes

International Nuclear Information System (INIS)

Clarkson, R.; Fatibene, L.; Mann, R.B.

2003-01-01

We consider the thermodynamic properties of (d+1)-dimensional spacetimes with NUT charges. Such spacetimes are asymptotically locally anti-de Sitter (or flat), with non-trivial topology in their spatial sections, and can have fixed point sets of the Euclidean time symmetry that are either (d-1)-dimensional (called 'bolts') or of lower dimensionality (pure 'NUTs'). We compute the free energy, conserved mass, and entropy for 4, 6, 8 and 10 dimensions for each, using both Noether charge methods and the AdS/CFT-inspired counterterm approach. We then generalize these results to arbitrary dimensionality. We find in 4k+2 dimensions that there are no regions in parameter space in the pure NUT case for which the entropy and specific heat are both positive, and so all such spacetimes are thermodynamically unstable. For the pure NUT case in 4k dimensions a region of stability exists in parameter space that decreases in size with increasing dimensionality. All bolt cases have some region of parameter space for which thermodynamic stability can be realized

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.

Singularity-free interpretation of the thermodynamics of supercooled water

International Nuclear Information System (INIS)

Sastry, S.; Debenedetti, P.G.; Sciortino, F.; Stanley, H.E.

1996-01-01

The pronounced increases in isothermal compressibility, isobaric heat capacity, and in the magnitude of the thermal expansion coefficient of liquid water upon supercooling have been interpreted either in terms of a continuous, retracing spinodal curve bounding the superheated, stretched, and supercooled states of liquid water, or in terms of a metastable, low-temperature critical point. Common to these two scenarios is the existence of singularities associated with diverging density fluctuations at low temperature. We show that the increase in compressibility upon lowering the temperature of a liquid that expands on cooling, like water, is not contingent on any singular behavior, but rather is a thermodynamic necessity. We perform a thermodynamic analysis for an anomalous liquid (i.e., one that expands when cooled) in the absence of a retracing spinodal and show that one may in general expect a locus of compressibility extrema in the anomalous regime. Our analysis suggests that the simplest interpretation of the behavior of supercooled water consistent with experimental observations is free of singularities. We then develop a waterlike lattice model that exhibits no singular behavior, while capturing qualitative aspects of the thermodynamics of water. copyright 1996 The American Physical Society

The estimated possibilities of process monitoring in milk production by the simple thermodynamic sensors

Directory of Open Access Journals (Sweden)

Martin Adámek

2016-12-01

Full Text Available The characterization and monitoring of thermal processes in thermodynamic systems can be performed using the thermodynamic sensors (TDS. The basic idea of thermodynamic sensor is possible to use in many various applications (eq. monitoring of frictional heat, thermal radiation, pollution of cleaning fluid, etc.. One of application areas, where the thermodynamic sensor can find the new area for a using, is a production of milk products - cheese, yogurt, kefir, etc. This paper describes the estimated possibilities, advantages and disadvantages of the use of thermodynamic sensors in diary productions and simple experiments for characterization and monitoring of basic operations in milk production process by thermodynamic sensors. The milk products are often realized by fermenting or renneting process. Final stages of fermentation and renneting processes are often determined on the base of sensory evaluation, pH measurement or by analytical method. The exact time of the fermentation process completion is dependent on various parameters and is often the company know-how. The fast, clean and simple non-analytical non-contact method for monitoring and for the determination of process final stages does not exist in this time. Tests of fermentation process, renneting process and yoghurt process by thermodynamic sensors were characterized and measured in this work. Measurement of activity yeasts was tested in first series of experiments. In second series of experiments, measurement of processes in milk production was tested. First results of simple experiments show that the thermodynamic sensors might be used for determination of time behaviour of these processes. Therefore, the milk products (cheese, yogurt, kefir, etc. is opened as a one of new application areas, where the thermodynamic sensor can be used.

Searching the laws of thermodynamics in the Lorentz-invariant thermal energy propagation equation

International Nuclear Information System (INIS)

Szőllősi, Tibor; Márkus, Ferenc

2015-01-01

Highlights: • We study the laws of thermodynamics in a Lorentz-invariant Lagrangian model. • We calculate the canonical momenta and tensor. • We give the correspondents of the laws of thermodynamics in the model. • The developed theory is considered to be coherent with the laws of thermodynamics. - Abstract: In earlier works it has been shown that the Lorentz-invariant description of thermal energy transfer can be deduced from a Lagrangian description, by which the definition of a dynamic temperature is involved at the same time. It is also proved that this formulation includes the classical Fourier heat propagation as a natural limit. However, the relation of the elaborated theory to the basic laws of thermodynamics remained open. This connection is studied in details in the present paper. It is posted that though strictly speaking the model is meaningless in equilibrium and corresponds only to the non-equilibrium parts of the temperature, it respects the laws of thermodynamics and provides a way to transfer some form of them into the validity-area of the model

Computation of Thermodynamic Equilibria Pertinent to Nuclear Materials in Multi-Physics Codes

Science.gov (United States)

Piro, Markus Hans Alexander

Nuclear energy plays a vital role in supporting electrical needs and fulfilling commitments to reduce greenhouse gas emissions. Research is a continuing necessity to improve the predictive capabilities of fuel behaviour in order to reduce costs and to meet increasingly stringent safety requirements by the regulator. Moreover, a renewed interest in nuclear energy has given rise to a "nuclear renaissance" and the necessity to design the next generation of reactors. In support of this goal, significant research efforts have been dedicated to the advancement of numerical modelling and computational tools in simulating various physical and chemical phenomena associated with nuclear fuel behaviour. This undertaking in effect is collecting the experience and observations of a past generation of nuclear engineers and scientists in a meaningful way for future design purposes. There is an increasing desire to integrate thermodynamic computations directly into multi-physics nuclear fuel performance and safety codes. A new equilibrium thermodynamic solver is being developed with this matter as a primary objective. This solver is intended to provide thermodynamic material properties and boundary conditions for continuum transport calculations. There are several concerns with the use of existing commercial thermodynamic codes: computational performance; limited capabilities in handling large multi-component systems of interest to the nuclear industry; convenient incorporation into other codes with quality assurance considerations; and, licensing entanglements associated with code distribution. The development of this software in this research is aimed at addressing all of these concerns. The approach taken in this work exploits fundamental principles of equilibrium thermodynamics to simplify the numerical optimization equations. In brief, the chemical potentials of all species and phases in the system are constrained by estimates of the chemical potentials of the system

Exact solution and thermodynamics of a spin chain with long-range elliptic interactions

International Nuclear Information System (INIS)

Finkel, Federico; González-López, Artemio

2014-01-01

We solve in closed form the simplest (su(1|1)) supersymmetric version of Inozemtsev's elliptic spin chain, as well as its infinite (hyperbolic) counterpart. The solution relies on the equivalence of these models to a system of free spinless fermions and on the exact computation of the Fourier transform of the resulting elliptic hopping amplitude. We also compute the thermodynamic functions of the finite (elliptic) chain and their low temperature limit and show that the energy levels become normally distributed in the thermodynamic limit. Our results indicate that at low temperatures the su(1|1) elliptic chain behaves as a critical XX model and deviates in an essential way from the Haldane–Shastry chain. (paper)

Thermodynamic Optimality criteria for biological systems in linear irreversible thermodynamics

International Nuclear Information System (INIS)

Chimal, J C; Sánchez, N; Ramírez, PR

2017-01-01

In this paper the methodology of the so-called Linear Irreversible Thermodynamics (LIT) is applied; although traditionally used locally to study general systems in non-equilibrium states in which it is consider both internal and external contributions to the entropy increments in order to analyze the efficiency of two coupled processes with generalized fluxes J 1 , J 2 and their corresponding forces X 1 , X 2 . We extend the former analysis to takes into account two different operating regimes namely: Omega Function and Efficient Power criterion, respectively. Results show analogies in the optimal performance between and we can say that there exist a criteria of optimization which can be used specially for biological systems where a good design of the biological parameters made by nature at maximum efficient power conditions lead to more efficient engines than those at the maximum power conditions or ecological conditions. (paper)

A re-assessment of the thermodynamic properties of iodine condensed phases

International Nuclear Information System (INIS)

Arblaster, J.W.

2011-01-01

Highlights: → In the low temperature region below 298.15 K all previous reviews included highly discrepant experimental data points which should have been rejected. In the present review these data points have been rejected leading to a smooth specific heat curve similar to that obtained for solid bromine. The current values, especially at 298.15 K therefore differ considerably from other reviews but it is suggested are more acceptable. → For temperatures above 298.15 K previous reviews carried out unnecessary corrections to the experimental enthalpy measurements and therefore arrived at distorted values for the thermodynamic properties and since these corrections differed from one review to the next then the situation existed where different sets of thermodynamic tables existed and there was no way to suggest which was the correct one. In the present review the experimental values have been used without correction for calibration and therefore again represent a superior set of tables. → Since iodine is solid at room temperature then the question arises as to whether or not to divide the thermodynamic tables in to low temperature values based on 0 K and high temperature values based on 298.15 K. In this paper the values are based on 0 K only to be consistent with the analogues chlorine and bromine. However if in the opinion of the referees the divide ought to be used in this can be achieved quite easily. - Abstract: Thermodynamic properties of iodine have been calculated to 500 K. Specific heat anomalies accepted for the solid phase in previous reviews have been eliminated and a smooth specific heat curve derived. Corrections previously applied to high temperature solid and liquid enthalpy measurements were shown to be unnecessary.

Vicious random walkers in the limit of a large number of walkers

International Nuclear Information System (INIS)

Forrester, P.J.

1989-01-01

The vicious random walker problem on a line is studied in the limit of a large number of walkers. The multidimensional integral representing the probability that the p walkers will survive a time t (denoted P t (p) ) is shown to be analogous to the partition function of a particular one-component Coulomb gas. By assuming the existence of the thermodynamic limit for the Coulomb gas, one can deduce asymptotic formulas for P t (p) in the large-p, large-t limit. A straightforward analysis gives rigorous asymptotic formulas for the probability that after a time t the walkers are in their initial configuration (this event is termed a reunion). Consequently, asymptotic formulas for the conditional probability of a reunion, given that all walkers survive, are derived. Also, an asymptotic formula for the conditional probability density that any walker will arrive at a particular point in time t, given that all p walkers survive, is calculated in the limit t >> p

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.

40 CFR 63.6602 - What emission limitations must I meet if I own or operate an existing stationary CI RICE with a...

Science.gov (United States)

2010-07-01

... if I own or operate an existing stationary CI RICE with a site rating of equal to or less than 500....6602 What emission limitations must I meet if I own or operate an existing stationary CI RICE with a... own or operate an existing stationary CI RICE with a site rating of equal to or less than 500 brake HP...

Radial flow in non-extensive thermodynamics and study of particle spectra at LHC in the limit of small (q - 1)

International Nuclear Information System (INIS)

Bhattacharyya, Trambak; Khuntia, Arvind; Pareek, Pooja; Sahoo, Raghunath; Cleymans, Jean

2016-01-01

We expand the Tsallis distribution in a Taylor series of powers of (q - 1), where q is the Tsallis parameter, assuming q is very close to 1. This helps in studying the degree of deviation of transverse momentum spectra and other thermodynamic quantities from a thermalized Boltzmann distribution. After checking thermodynamic consistency, we provide analytical results for the Tsallis distribution in the presence of collective flow up to the first order of (q - 1). The formulae are compared with the experimental data. (orig.)

Radial flow in non-extensive thermodynamics and study of particle spectra at LHC in the limit of small (q - 1)

Energy Technology Data Exchange (ETDEWEB)

Bhattacharyya, Trambak; Khuntia, Arvind; Pareek, Pooja; Sahoo, Raghunath [Indian Institute of Technology Indore, Discipline of Physics, School of Basic Sciences, Simrol (India); Cleymans, Jean [University of Cape Town, UCT-CERN Research Centre and Department of Physics, Rondebosch (South Africa)

2016-02-15

We expand the Tsallis distribution in a Taylor series of powers of (q - 1), where q is the Tsallis parameter, assuming q is very close to 1. This helps in studying the degree of deviation of transverse momentum spectra and other thermodynamic quantities from a thermalized Boltzmann distribution. After checking thermodynamic consistency, we provide analytical results for the Tsallis distribution in the presence of collective flow up to the first order of (q - 1). The formulae are compared with the experimental data. (orig.)

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...

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.

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

Thermodynamic fluctuations within the Gibbs and Einstein approaches

International Nuclear Information System (INIS)

Rudoi, Yurii G; Sukhanov, Alexander D

2000-01-01

A comparative analysis of the descriptions of fluctuations in statistical mechanics (the Gibbs approach) and in statistical thermodynamics (the Einstein approach) is given. On this basis solutions are obtained for the Gibbs and Einstein problems that arise in pressure fluctuation calculations for a spatially limited equilibrium (or slightly nonequilibrium) macroscopic system. A modern formulation of the Gibbs approach which allows one to calculate equilibrium pressure fluctuations without making any additional assumptions is presented; to this end the generalized Bogolyubov - Zubarev and Hellmann - Feynman theorems are proved for the classical and quantum descriptions of a macrosystem. A statistical version of the Einstein approach is developed which shows a fundamental difference in pressure fluctuation results obtained within the context of two approaches. Both the 'genetic' relation between the Gibbs and Einstein approaches and the conceptual distinction between their physical grounds are demonstrated. To illustrate the results, which are valid for any thermodynamic system, an ideal nondegenerate gas of microparticles is considered, both classically and quantum mechanically. Based on the results obtained, the correspondence between the micro- and macroscopic descriptions is considered and the prospects of statistical thermodynamics are discussed. (reviews of topical problems)

Thermodynamic Resistance to Matter Flow at The Interface of a Porous Membrane.

Science.gov (United States)

Glavatskiy, K S; Bhatia, Suresh K

2016-04-12

Nanoporous materials are important in industrial separation, but their application is subject to strong interfacial barriers to the entry and transport of fluids. At certain conditions the fluid inside and outside the nanoporous material can be viewed as a two-phase system, with an interface between them, which poses an excess resistance to matter flow. We show that there exist two kinds of phenomena which influence the interfacial resistance: hydrodynamic effects and thermodynamic effects, which are independent of each other. Here, we investigate the role of the thermodynamic effects in carbon nanotubes (CNTs) and slit pores and compare the associated thermodynmic resistance with that due to hydrodynamic effects traditionally modeled by the established Sampson expression. Using CH4 and CO2 as model fluids, we show that the thermodynamic resistance is especially important for moderate to high pressures, at which the fluid within the CNT or slit pore is in the condensed state. Further, we show that at such pressures the thermodynamic resistance becomes comparable with the internal resistance to fluid transport at length scales typical of membranes used in fuel cells, and of importance in membrane-based separation, and nanofluidics in general.

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

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...

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)

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.

Magnetic properties and thermodynamics in a metallic nanotube

International Nuclear Information System (INIS)

Jiang, Wei; Li, Xiao-Xi; Guo, An-Bang; Guan, Hong-Yu; Wang, Zan; Wang, Kai

2014-01-01

A metallic nanotube composed of the ferromagnetic spin-3/2 inner shell and spin-1 outer shell with a ferrimagnetic interlayer coupling has been studied by using the effective-field theory with correlations (EFT). With both existence of the magnetic anisotropy and transverse field, we have studied effects of them on the magnetic properties and the thermodynamics. Some interesting phenomena have been found in the phase diagrams. At low temperature, the magnetization curves present different behaviors. Two compensation points have been found for the certain values of the system parameters in the system. The research results of metallic nanotubes may have potential applications in the fields of biomedicine and molecular devices. - Highlights: • A hexagonal metallic nanotube is composed of spin-3/2 inner layer and spin-1 outer layer. • Various types of magnetization curves depend on physical parameters and temperature. • We study the effects of physical parameters on the magnetic properties and thermodynamics

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

Infrared Cloaking, Stealth, and the Second Law of Thermodynamics

Directory of Open Access Journals (Sweden)

Daniel P. Sheehan

2012-10-01

Full Text Available Infrared signature management (IRSM has been a primary aeronautical concern for over 50 years. Most strategies and technologies are limited by the second law of thermodynamics. In this article, IRSM is considered in light of theoretical developments over the last 15 years that have put the absolute status of the second law into doubt and that might open the door to a new class of broadband IR stealth and cloaking techniques. Following a brief overview of IRSM and its current thermodynamic limitations, theoretical and experimental challenges to the second law are reviewed. One proposal is treated in detail: a high power density, solid-state power source to convert thermal energy into electrical or chemical energy. Next, second-law based infrared signature management (SL-IRSM strategies are considered for two representative military scenarios: an underground installation and a SL-based jet engine. It is found that SL-IRSM could be technologically disruptive across the full spectrum of IRSM modalities, including camouflage, surveillance, night vision, target acquisition, tracking, and homing.

Thermodynamic and elastic properties of hexagonal ZnO under high temperature

International Nuclear Information System (INIS)

Wang, Feng; Wu, Jinghe; Xia, Chuanhui; Hu, Chenghua; Hu, Chunlian; Zhou, Ping; Shi, Lingna; Ji, Yanling; Zheng, Zhou; Liu, Xiankun

2014-01-01

Highlights: • A new method is applied to predict crystal constants of hexagonal crystal under high temperature. • Elastic properties of ZnO under high temperature are obtained exactly. • Thermodynamic properties of ZnO under high temperature are attained too. - Abstract: Studies on thermodynamic and elastic properties of hexagonal ZnO (wurtzite structure) under high temperature have not been reported usually from no matter experimental or theoretic methods. In this work, we study these properties by ab-initio together with quasi-harmonic Debye model. The value of C v tends to the Petit and Dulong limit at high temperature under any pressure, 49.73 J/mol K. And C v is greatly limited by pressure at intermediate temperatures. Nevertheless, the limit effect on C v caused by pressure is not obvious under low as well as very high temperature. The thermal expansions along a or c axis are almost same under temperature, which increase with temperature like a parabola. C 11 , C 33 , C 12 and C 13 decrease with temperature a little, which means that mechanics properties are weakened respectively

40 CFR Table 1 to Subpart Oooo of... - Emission Limits for New or Reconstructed and Existing Affected Sources in the Printing, Coating...

Science.gov (United States)

2010-07-01

... Reconstructed and Existing Affected Sources in the Printing, Coating and Dyeing of Fabrics and Other Textiles... SOURCE CATEGORIES National Emission Standards for Hazardous Air Pollutants: Printing, Coating, and Dyeing...—Emission Limits for New or Reconstructed and Existing Affected Sources in the Printing, Coating and Dyeing...

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

Thermodynamic and transport properties of liquid gallium

International Nuclear Information System (INIS)

Park, H.Y.; Jhon, M.S.

1982-01-01

The significant structure theory of liquids has been successfully applied to liquid gallium. In this work, we have assumed that two structures exist simultaneously in liquid gallium. One is considerec as loosely close packed β-Ga-like structure and the other is remainder of solid α-Ga or α-Ga-like structure. This two structural model is introduced to construct the liquid partition function. Using the partition function, the thermodynamic and transport properties are calculated ever a wide temperature range. The calculated results are quite satisfactory when compared with the experimental results. (Author)

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)

WATEQ3 geochemical model: thermodynamic data for several additional solids

International Nuclear Information System (INIS)

Krupka, K.M.; Jenne, E.A.

1982-09-01

Geochemical models such as WATEQ3 can be used to model the concentrations of water-soluble pollutants that may result from the disposal of nuclear waste and retorted oil shale. However, for a model to competently deal with these water-soluble pollutants, an adequate thermodynamic data base must be provided that includes elements identified as important in modeling these pollutants. To this end, several minerals and related solid phases were identified that were absent from the thermodynamic data base of WATEQ3. In this study, the thermodynamic data for the identified solids were compiled and selected from several published tabulations of thermodynamic data. For these solids, an accepted Gibbs free energy of formation, ΔG 0 /sub f,298/, was selected for each solid phase based on the recentness of the tabulated data and on considerations of internal consistency with respect to both the published tabulations and the existing data in WATEQ3. For those solids not included in these published tabulations, Gibbs free energies of formation were calculated from published solubility data (e.g., lepidocrocite), or were estimated (e.g., nontronite) using a free-energy summation method described by Mattigod and Sposito (1978). The accepted or estimated free energies were then combined with internally consistent, ancillary thermodynamic data to calculate equilibrium constants for the hydrolysis reactions of these minerals and related solid phases. Including these values in the WATEQ3 data base increased the competency of this geochemical model in applications associated with the disposal of nuclear waste and retorted oil shale. Additional minerals and related solid phases that need to be added to the solubility submodel will be identified as modeling applications continue in these two programs

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.

Fluctuating States: What is the Probability of a Thermodynamical Transition?

Directory of Open Access Journals (Sweden)

Álvaro M. Alhambra

2016-10-01

Full Text Available If the second law of thermodynamics forbids a transition from one state to another, then it is still possible to make the transition happen by using a sufficient amount of work. But if we do not have access to this amount of work, can the transition happen probabilistically? In the thermodynamic limit, this probability tends to zero, but here we find that for finite-sized and quantum systems it can be finite. We compute the maximum probability of a transition or a thermodynamical fluctuation from any initial state to any final state and show that this maximum can be achieved for any final state that is block diagonal in the energy eigenbasis. We also find upper and lower bounds on this transition probability, in terms of the work of transition. As a by-product, we introduce a finite set of thermodynamical monotones related to the thermomajorization criteria which governs state transitions and compute the work of transition in terms of them. The trade-off between the probability of a transition and any partial work added to aid in that transition is also considered. Our results have applications in entanglement theory, and we find the amount of entanglement required (or gained when transforming one pure entangled state into any other.

Temporal Asymmetry, Entropic Irreversibility, and Finite-Time Thermodynamics: From Parmenides–Einstein Time-Reversal Symmetry to the Heraclitan Entropic Arrow of Time

Directory of Open Access Journals (Sweden)

Wassim M. Haddad

2012-02-01

Full Text Available In this paper, we combine the two universalisms of thermodynamics and dynamical systems theory to develop a dynamical system formalism for classical thermodynamics. Specifically, using a compartmental dynamical system energy flow model we develop a state-space dynamical system model that captures the key aspects of thermodynamics, including its fundamental laws. In addition, we establish the existence of a unique, continuously differentiable global entropy function for our dynamical system model, and using Lyapunov stability theory we show that the proposed thermodynamic model has finite-time convergent trajectories to Lyapunov stable equilibria determined by the system initial energies. Finally, using the system entropy, we establish the absence of Poincaré recurrence for our thermodynamic model and develop clear and rigorous connections between irreversibility, the second law of thermodynamics, and the entropic arrow of time.

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...

40 CFR Table 4 to Subpart Bbbb of... - Model Rule-Class II Emission Limits for Existing Small Municipal Waste Combustion Unit a

Science.gov (United States)

2010-07-01

... Existing Small Municipal Waste Combustion Unit a 4 Table 4 to Subpart BBBB of Part 60 Protection of... NEW STATIONARY SOURCES Emission Guidelines and Compliance Times for Small Municipal Waste Combustion... Part 60—Model Rule—Class II Emission Limits for Existing Small Municipal Waste Combustion Unit a For...

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.

Thermodynamics and general relativity could determine the symmetry of the universe

International Nuclear Information System (INIS)

Bayin, S.S.

1986-01-01

Behavior of black hole parameters (area, surface gravity, and so on), like certain thermodynamic quantities (entropy, temperature, and so on), motivated Bekenstein to conjecture the existence of black hole thermodynamics. Later, the discovery of black hole radiation by Hawking established the physical link between these parameters and their thermodynamic counterparts. However, despite the success of black hole thermodynamics, the relation between general relativity and thermodynamics remains to be established for more general metrics. In this paper, in order to explore this relation the author considers the possibility of the Bianchi symmetry of a Friedmann model changing as the universe evolves. The suggestive model he uses is the one in which the radius of curvature of the three-dimensional space is treated like the inverse of the temperature and where rho(P,T) plays the role of the Gibbs potential energy density. He shows that for the transitions between Bianchi I and V and Bianchi I and IX symmetric Friedmann models, there is only one Gibbs function and the transformation is of second order. For the transformations between Bianchi V and Bianchi IV symmetric models, he has two distinct Gibbs functions and in general this leads us to first order phase transitions. These conclusions are obtained independently of the details of the local equation of state. He also discusses two specific cases to demonstrate some of the properties of the model. One of these properties is that this model gives us a new way of determining the symmetry of the universe. By using a well-known equation of state (P = αrho), he shows that with respect to the thermodynamics he has defined, it is advantageous for the universe to be open (Bianchi V symmetric)

Equilibrium econophysics: A unified formalism for neoclassical economics and equilibrium thermodynamics

Science.gov (United States)

Sousa, Tânia; Domingos, Tiago

2006-11-01

We develop a unified conceptual and mathematical structure for equilibrium econophysics, i.e., the use of concepts and tools of equilibrium thermodynamics in neoclassical microeconomics and vice versa. Within this conceptual structure the results obtained in microeconomic theory are: (1) the definition of irreversibility in economic behavior; (2) the clarification that the Engel curve and the offer curve are not descriptions of real processes dictated by the maximization of utility at constant endowment; (3) the derivation of a relation between elasticities proving that economic elasticities are not all independent; (4) the proof that Giffen goods do not exist in a stable equilibrium; (5) the derivation that ‘economic integrability’ is equivalent to the generalized Le Chatelier principle and (6) the definition of a first order phase transition, i.e., a transition between separate points in the utility function. In thermodynamics the results obtained are: (1) a relation between the non-dimensional isothermal and adiabatic compressibilities and the increase or decrease in the thermodynamic potentials; (2) the distinction between mathematical integrability and optimization behavior and (3) the generalization of the Clapeyron equation.

Thermodynamics in finite time: A chemically driven engine

International Nuclear Information System (INIS)

Ondrechen, M.J.; Berry, R.S.; Andresen, B.

1980-01-01

The methods of finite time thermodynamics are applied to processes whose relaxation parameters are chemical rate coefficients within the working fluid. The direct optimization formalism used previously for heat engines with friction and finite heat transfer rates: termed the tricycle method: is extended to heat engines driven by exothermic reactions. The model is a flow reactor coupled by a heat exchanger to an engine. Conditions are established for the achievement of maximum power from such a system. Emphasis is on how the chemical kinetics control the finite-time thermodynamic extrema; first order, first order reversible, and second order reaction kinetics are analyzed. For the types of reactions considered here, there is always a finite positive flow rate in the reactor that yields maximum engine power. Maximum fuel efficiency is always attained in these systems at the uninteresting limit of zero flow rate

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.

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

Experimental and thermodynamic investigation of Al-Cu-Nd ternary system

Energy Technology Data Exchange (ETDEWEB)

Bai, W.M. [School of Materials Science and Engineering, Central South University, Changsha, 410083 (China); Jiang, Y. [Hunan Sushi Guangbo Testing Techniques Co. LTD, Changsha (China); Guo, Z.Y.; Zeng, L.J.; Tan, M.Y. [School of Materials Science and Engineering, Central South University, Changsha, 410083 (China); Meggs, C. [School of Metallurgy and Materials, The University of Birmingham, Edgbaston, Birmingham, B15 2TT (United Kingdom); Zhang, L.G., E-mail: ligangzhang@csu.edu.cn [School of Materials Science and Engineering, Central South University, Changsha, 410083 (China); Liu, L.B., E-mail: pdc@csu.edu.cn [School of Materials Science and Engineering, Central South University, Changsha, 410083 (China); Jin, Z.P. [School of Materials Science and Engineering, Central South University, Changsha, 410083 (China)

2017-07-01

The phase relationships in the Al–Cu-Nd ternary system at 673 K have been investigated by X-ray powder diffraction (XRD) and scanning electron microscope (SEM) with energy disperse X-ray spectroscopy (EDS) in backscattered electron imaging (BSE) modes. The existence of six ternary Stoichiometric compounds, namely τ{sub 1}-Al{sub 8}Cu{sub 4}Nd, τ{sub 2}-Al{sub 9}Cu{sub 8}Nd{sub 2}, τ{sub 3}-Al{sub 6}Cu{sub 7}Nd, τ{sub 4}-Al{sub 2.4}Cu{sub 8.6}Nd, τ{sub 5}-Al{sub 3}CuNd, τ{sub 6}-AlCuNd, have been confirmed. A complete thermodynamic description of the Al–Cu-Nd ternary system coupled with the CALPHAD method is obtained based on experimental results and first-principles calculations. The calculated phase equilibria were in agreement with the available experimental data. - Highlights: • Phase relationships in the Al-Cu-Nd system has been systematically investigated. • 9 three-phase regions and 4 two-phase regions are confirmed. • A complete thermodynamic description of the Al-Cu-Nd system is obtained. • Results of first-principle calculation consist with thermodynamic calculation.

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

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...

Consideration on thermodynamic data for predicting solubility and chemical species of elements in groundwater. Part 1: Tc, U, Am

Energy Technology Data Exchange (ETDEWEB)

Yamaguchi, Tetsuji; Takeda, Seiji [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

1999-01-01

The solubility determines the release of radionuclides from waste form and is used as a source term in radionuclide migration analysis in performance assessment of radioactive waste repository. Complexations of radionuclides by ligands in groundwater affect the interaction between radionuclides and geologic media, thus affect their migration behavior. Thermodynamic data for Tc, Am and U were reviewed and compiled to be used for predicting the solubility and chemical species in groundwater. Thermodynamic data were reviewed with emphasis on the hydrolysis and carbonate complexation that can dominate the speciation in typical groundwater. Thermodynamic data for other species were selected based on existing database. Thermodynamic data for other important elements are under investigation, thus shown in an appendix for temporary use. (author)

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.

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...

Self-interacting, boson, quantum field theory, and the thermodynamic limit in d dimensions

International Nuclear Information System (INIS)

Baker, G.A. Jr.

1975-01-01

By use of a finite volume, lattice approximation, an approximation to the analytic continuation of a polynomial, self-interacting boson quantum field theory from Minkowski space to Euclidean space was set up. The infinite volume limit for various boundary conditions is shown to exist and to be asymptotic to the perturbation expansion in the coupling constant g at g = 0. For g: phi 4 : d theory mass renormalizability is proved and it is shown how, by use of Nelson's reconstruction theorem, the corresponding Minkowski space quantum field theory can be obtained. It is discussed, at least for d greater than or equal to 4, how statistical mechanical techniques, used to analyze the Ising model in the critical region just above the critical temperature, can be used to compute the properties of quantum field theory. (U.S.)

Thermodynamics and structure of liquid alkali metals from the charged-hard-sphere reference fluid

International Nuclear Information System (INIS)

Lai, S.K.; Akinlade, O.; Tosi, M.P.

1989-12-01

The evaluation of thermodynamic properties of liquid alkali metals is re-examined in the approach based on the Gibbs-Bogoliubov inequality and using the fluid of charged hard spheres in the mean spherical approximation as reference system, with a view to achieving consistency with the liquid structure factor. The perturbative variational calculation of the Helmholtz free energy is based on an ab initio and highly reliable nonlocal pseudopotential. Only limited improvement is found in the calculated thermodynamic functions, even when full advantage is taken of the two variational parameters inherent in this approach. The role of thermodynamic self-consistency between the equations of state of the reference fluid derived from the routes of the internal energy and of the virial theorem is then discussed, using previous results by Hoye and Stell. An approximate evaluation of the corresponding contribution to the free energy of liquid alkali metals yields appreciable improvements in both the thermodynamic functions and the liquid structure factor. It thus appears that an accurate treatment of thermodynamic self-consistency in the charged-hard-sphere system may help to resolve some of the difficulties that are commonly met in the evaluation of thermodynamic and structural properties of liquid metals. (author). 55 refs, 4 figs, 4 tabs

Detailed Balance Limit of Efficiency of Broadband-Pumped Lasers.

Science.gov (United States)

Nechayev, Sergey; Rotschild, Carmel

2017-09-13

Broadband light sources are a wide class of pumping schemes for lasers including LEDs, sunlight and flash lamps. Recently, efficient coupling of broadband light to high-quality micro-cavities has been demonstrated for on-chip applications and low-threshold solar-pumped lasers via cascade energy transfer. However, the conversion of incoherent to coherent light comes with an inherent price of reduced efficiency, which has yet to be assessed. In this paper, we derive the detailed balance limit of efficiency of broadband-pumped lasers and discuss how it is affected by the need to maintain a threshold population inversion and thermodynamically dictated minimal Stokes' shift. We show that lasers' slope efficiency is analogous to the nominal efficiency of solar cells, limited by thermalisation losses and additional unavoidable Stokes' shift. The lasers' power efficiency is analogous to the detailed balance limit of efficiency of solar cells, affected by the cavity mirrors and impedance matching factor, respectively. As an example we analyze the specific case of solar-pumped sensitized Nd 3+ :YAG-like lasers and define the conditions to reach their thermodynamic limit of efficiency. Our work establishes an upper theoretical limit for the efficiency of broadband-pumped lasers. Our general, yet flexible model also provides a way to incorporate other optical and thermodynamic losses and, hence, to estimate the efficiency of non-ideal broadband-pumped lasers.

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

Science.gov (United States)

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

2018-05-01

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

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.

On Limitations of Existing Methods for Location Privacy

DEFF Research Database (Denmark)

Andersen, Mads Schaarup

This paper argues that there are some limitations when applying location privacy methods developed for point-ofinterest services to newer classes of location based services. We support the argument by categorizing methods for location privacy and identifying the issues. It is hypothesized...

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

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.

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 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.

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

Ergodic properties and thermodynamic behavior of elementary reversible cellular automata. I. Basic properties

International Nuclear Information System (INIS)

Takesue, Shinji

1989-01-01

This is the first part of a series devoted to the study of thermodynamic behavior of large dynamical systems with the use of a family of full-discrete and conservative models named elementary reversible cellular automata (ERCAs). In this paper, basic properties such as conservation laws and phase space structure are investigated in preparation for the later studies. ERCAs are a family of one-dimensional reversible cellular automata having two Boolean variables on each site. Reflection and Boolean conjugation symmetries divide them into 88 equivalence classes. For each rule, additive conserved quantities written in a certain form are regarded as a kind of energy, if they exist. By the aid of the discreteness of the variables, every ERCA satisfies the Liouville theorem or the preservation of phase space volume. Thus, if an energy exists in the above sense, statistical mechanics of the model can formally be constructed. If a locally defined quantity is conserved, however, it prevents the realization of statistical mechanics. The existence of such a quantity is examined for each class and a number of rules which have at least one energy but no local conservation laws are selected as hopeful candidates for the realization of thermodynamic behavior. In addition, the phase space structure of ERCAs is analyzed by enumerating cycles exactly in the phase space for systems of comparatively small sizes. As a result, it is revealed that a finite ERCA is not ergodic, that is, a large number of orbits coexist on an energy surface. It is argued that this fact does not necessarily mean the failure of thermodynamic behavior on the basis of an analogy with the ergodic nature of infinite systems

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.

Fluctuations and thermodynamic response functions in a Lennard-Jones solid

International Nuclear Information System (INIS)

Li, M.; Johnson, W.L.

1992-01-01

Thermodynamic response functions of a nearest-neighbor Lennard-Jones solid--heat capacity, thermal-expansion coefficient, compressibility, and elastic constants--are calculated directly from fluctuations using molecular-dynamics simulations. The algorithm used is the earlier Parrinello-Rahman molecular dynamics modified to take into account symmetry and rotation invariance of the system under investigation. The convergence is very fast and results are in good agreement with existing Monte Carlo and molecular-dynamics results

Finite time thermodynamics of power and refrigeration cycles

CERN Document Server

Kaushik, Shubhash C; Kumar, Pramod

2017-01-01

This book addresses the concept and applications of Finite Time Thermodynamics to various thermal energy conversion systems including heat engines, heat pumps, and refrigeration and air-conditioning systems. The book is the first of its kind, presenting detailed analytical formulations for the design and optimisation of various power producing and cooling cycles including but not limited to: • Vapour power cycles • Gas power cycles • Vapour compression cycles • Vapour absorption cycles • Rankine cycle coupled refrigeration systems Further, the book addresses the thermoeconomic analysis for the optimisation of thermal cycles, an important field of study in the present age and which is characterised by multi-objective optimization regarding energy, ecology, the environment and economics. Lastly, the book provides the readers with key techniques associated with Finite Time Thermodynamics, allowing them to understand the relevance of irreversibilitie s associated with real processes and the scientific r...

Thermodynamic evaluation of the Cu-Mg-Zr system

International Nuclear Information System (INIS)

Haemaelaeinen, M.; Zeng, K.

1999-01-01

The thermodynamic evaluation of the Cu-Mg-Zr system is presented in this paper. A literature survey was carried out first based on the most recent literature, which was scanned from the THERMET literature database. The evaluation of the thermodynamic parameters was carried out using Thermo-Calc (version H) software. The evaluation of the Cu-Mg-Zr system was carried out using the most recent experimental data from the literature and a set of DTA measurements. DTA measurements were done using alumina (Al 2 O 3 ) crucibles under helium atmosphere with the niobium (Nb) reference crucible. The evaluated Cu-Mg-Zr phase diagram fitted well with experimental data with the liquidus data in a limited range of composition. There were two miscibility gaps observe in the system. New τ phase was detected using the X-ray and microscopic analysis and the data was used in this evaluation. (orig.)

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

Thermodynamic properties of vanadium

International Nuclear Information System (INIS)

Desai, P.D.

1986-01-01

This work reviews and discusses the data and information on the various thermodynamic properties of vanadium available through March 1985. These include the heat capacity and enthalpy, enthalpy of melting, vapor pressure, and enthalpy of vaporization. The existing data have been critically evaluated and analyzed, and the recommended values for heat capacity, enthalpy, entropy, and Gibbs energy function covering the temperature range from 1 to 3800 K have been generated. These values are referred to tempertures based on IPTS-1968. The units used for various properties are joules per mole (J. mol - 1 ). The estimated uncertainties in the heat capacity are +/-3% below 15 K, +/-10% from 15 to 150 K, +/-3% from 150 to 298.15 K, +/-2% from 298.15 to 1000 K, +/-3% from 1000 to the melting point (2202 K), and +/-5% in the liquid region

Non-Equilibrium Thermodynamic Chemistry and the Composition of the Atmosphere of Mars

Science.gov (United States)

Levine, J. S.; Summers, M. E.

2003-01-01

A high priority objective of the Mars Exploration Program is to Determine if life exists today (MEPAG Goal I, Objective A). The measurement of gases of biogenic origin may be an approach to detect the presence of microbial life on the surface or subsurface of Mars. Chemical thermodynamic calculations indicate that on both Earth and Mars, certain gases should exist in extremely low concentrations, if at all. Microbial metabolic activity is an important non-equilibrium chemistry process on Earth, and if microbial life exists on Mars, may be an important nonequilibrium chemistry process on Mars. The non-equilibrium chemistry of the atmosphere of Mars is discussed in this paper.

40 CFR Table 3 to Subpart Bbbb of... - Model Rule-Class I Nitrogen Oxides Emission Limits for Existing Small Municipal Waste Combustion...

Science.gov (United States)

2010-07-01

... Emission Limits for Existing Small Municipal Waste Combustion Unitsa,b,c 3 Table 3 to Subpart BBBB of Part... Municipal Waste Combustion Units Constructed on or Before August 30, 1999 Pt. 60, Subpt. BBBB, Table 3 Table... Municipal Waste Combustion Unitsa,b,c Municipal waste combustion technology Limits for class I municipal...

Entropy, limits to growth, and the prospects for weak sustainability

International Nuclear Information System (INIS)

Krysiak, Frank C.

2006-01-01

In this paper, we analyze the consequences of mass and energy conservation and the second law of thermodynamics for economic activity. In contrast to former studies, we deduce our results formally from a general model of production and consumption. We show that in a static setting for economies containing irreversible processes, a non-zero resource input as well as non-zero emissions are necessary to sustain a positive level of consumption. We generalize this result to a dynamic setting and apply it to the growth discussion and the sustainability discourse. Thereby we show that limits to growth of production and consumption are likely to exist and that the concept of weak sustainability is either morally unattractive or physically infeasible. (author)

Hamiltonian mechanics limits microscopic engines

Science.gov (United States)

Anglin, James; Gilz, Lukas; Thesing, Eike

2015-05-01

We propose a definition of fully microscopic engines (micro-engines) in terms of pure mechanics, without reference to thermodynamics, equilibrium, or cycles imposed by external control, and without invoking ergodic theory. This definition is pragmatically based on the observation that what makes engines useful is energy transport across a large ratio of dynamical time scales. We then prove that classical and quantum mechanics set non-trivial limits-of different kinds-on how much of the energy that a micro-engine extracts from its fuel can be converted into work. Our results are not merely formal; they imply manageable design constraints on micro-engines. They also suggest the novel possibility that thermodynamics does not emerge from mechanics in macroscopic regimes, but rather represents the macroscopic limit of a generalized theory, valid on all scales, which governs the important phenomenon of energy transport across large time scale ratios. We propose experimental realizations of the dynamical mechanisms we identify, with trapped ions and in Bose-Einstein condensates (``motorized bright solitons'').

Thermodynamics of soluble fission products cesium and iodine in the Molten Salt Reactor

NARCIS (Netherlands)

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

2018-01-01

The present study describes the full thermodynamic assessment of the Li,Cs,Th//F,I system. The existing database for the relevant fluoride salts considered as fuel for the Molten Salt Reactor (MSR) has been extended with two key fission products, cesium and iodine. A complete evaluation of all

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.

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

International Nuclear Information System (INIS)

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

2013-01-01

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

Thermodynamic phase transition in the rainbow Schwarzschild black hole

International Nuclear Information System (INIS)

Gim, Yongwan; Kim, Wontae

2014-01-01

We study the thermodynamic phase transition in the rainbow Schwarzschild black hole where the metric depends on the energy of the test particle. Identifying the black hole temperature with the energy from the modified dispersion relation, we obtain the modified entropy and thermodynamic energy along with the modified local temperature in the cavity to provide well defined black hole states. It is found that apart from the conventional critical temperature related to Hawking-Page phase transition there appears an additional critical temperature which is of relevance to the existence of a locally stable tiny black hole; however, the off-shell free energy tells us that this black hole should eventually tunnel into the stable large black hole. Finally, we discuss the reason why the temperature near the horizon is finite in the rainbow black hole by employing the running gravitational coupling constant, whereas it is divergent near the horizon in the ordinary Schwarzschild black hole

Variational discretization of the nonequilibrium thermodynamics of simple systems

Science.gov (United States)

Gay-Balmaz, François; Yoshimura, Hiroaki

2018-04-01

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

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.

Thermodynamical Approach for The Determination of The Speed of Heat Propagation in Heat Conduction

International Nuclear Information System (INIS)

Shnaid, I.

1998-01-01

In this work, a thermodynamical approach for the determination of the speed of heat propagation in a heat conductive body is developed. It employs equations of the First and the Second Laws of thermodynamics. The present analyses show that no time delay exists between time moments of heat extraction and heat supply. Therefore, an infinite speed of heat propagation is proven. It is also predicted that there is no time lag between heat flow and temperature difference. A theoretical approach straightforwardly leading from basic equations of the First and the Second Laws of thermodynamics to a kinetic equation describing heat conduction in an isotropic continuum is also developed. It is shown that Fourier's equation is a particular case of the derived kinetic equation. Based on the kinetic equation, the governing heat conduction equation is of tile parabolic type, thus, confirming that speed of heat propagation is infinite

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.

Some thermodynamic aspects of the solubility of iron in sodium

International Nuclear Information System (INIS)

Awasthi, S.P.; Sundaresan, M.

1984-01-01

Because of the use of liquid sodium as a heat transfer fluid in fast breeder reactors, its interaction with Fe and some alloying elements, has assumed great importance. Solubility is an important manifestation of this interaction, but there exists in literature a wide divergence in the data on the solubility of iron, which is known to have an intimate relationship with temperature and the concentration of available oxygen in sodium. An attempt has been made, here, to arrive at the mechanism of the observed enhanced solubility of iron in presence of oxygen by analysing the available experimental isothermal and athermal data on solubilities in literature by computing the relevant thermodynamic parameters for various probable interactions in the Na-O-Fe system. From comparison of these with the sign and magnitude of the theoretically calculated thermodynamic values, it has been shown that the predominant iron species existing in liquid sodium in presence of higher concentrations of oxygen is the soluble compound Na 4 FeO 3 . The most probable mechanism of the enhanced solubility of iron can be explained in terms of a sequence involving the initial formation of iron oxide (FeO) in liquid sodium, followed by its conversion to the compound Na 4 FeO 3 . (author)

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.

On the long wavelength thermodynamic limit of a neutron diffraction experiment in the vicinity of a liquid-liquid critical point. Application to the concentration fluctuations in the Li-ND3 system

International Nuclear Information System (INIS)

Chieux, P.; Damay, P.

1978-01-01

A quantitative comparison is made between the thermodynamics as obtained from the long wavelength limit of a small angle neutron scattering experiment in the vicinity of a liquid-liquid critical point for the Li-ND 3 system and the data obtained from vapour pressure measurements. The agreement is fair. It is shown how the comparison always implies an underlying model of the interacting species leading to the liquid-liquid phase separation. (Auth.)

Fission product thermodynamic data: technical progress report 1 January-30 June 1991

International Nuclear Information System (INIS)

Ball, R.G.J.; Yates, A.D.; Bowsher, B.R.; Dickinson, S.; Freemantle, N.E.; Day, T.; Ogden, J.S.

1991-07-01

Thermodynamic data are being determined for a number of compounds formed from specific fission products and reactor materials. The compounds selected for experimental study and critical assessment were chosen because their thermodynamic data were inadequate or did not exist, as assessed and recommended at a specialists' meeting. These data can be used in the appropriate computer code so that the speciation and transport properties of the fission products can be predicted during a severe reactor accident. Experimental studies have focussed on the vaporization of tellurium dioxide, caesium ruthenate, strontium borate and indium hydroxide. Critical evaluations have begun for a number of tellurides of importance in severe accident assessments, and preliminary analyses have been made of the Fe-Te, Ni-Te and Cr-Te systems. (author)

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.

Geometric Thermodynamics: Black Holes and the Meaning of the Scalar Curvature

Directory of Open Access Journals (Sweden)

Miguel Ángel García-Ariza

2014-12-01

Full Text Available In this paper we show that the vanishing of the scalar curvature of Ruppeiner-like metrics does not characterize the ideal gas. Furthermore, we claim through an example that flatness is not a sufficient condition to establish the absence of interactions in the underlying microscopic model of a thermodynamic system, which poses a limitation on the usefulness of Ruppeiner’s metric and conjecture. Finally, we address the problem of the choice of coordinates in black hole thermodynamics. We propose an alternative energy representation for Kerr-Newman black holes that mimics fully Weinhold’s approach. The corresponding Ruppeiner’s metrics become degenerate only at absolute zero and have non-vanishing scalar curvatures.

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

Science.gov (United States)

Abramov, Yuriy A

2015-06-01

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

Molecular structure and thermodynamic predictions to create highly sensitive microRNA biosensors

International Nuclear Information System (INIS)

Larkey, Nicholas E.; Brucks, Corinne N.; Lansing, Shan S.; Le, Sophia D.; Smith, Natasha M.; Tran, Victoria; Zhang, Lulu; Burrows, Sean M.

2016-01-01

Many studies have established microRNAs (miRNAs) as post-transcriptional regulators in a variety of intracellular molecular processes. Abnormal changes in miRNA have been associated with several diseases. However, these changes are sometimes subtle and occur at nanomolar levels or lower. Several biosensing hurdles for in situ cellular/tissue analysis of miRNA limit detection of small amounts of miRNA. Of these limitations the most challenging are selectivity and sensor degradation creating high background signals and false signals. Recently we developed a reporter+probe biosensor for let-7a that showed potential to mitigate false signal from sensor degradation. Here we designed reporter+probe biosensors for miR-26a-2-3p and miR-27a-5p to better understand the effect of thermodynamics and molecular structures of the biosensor constituents on the analytical performance. Signal changes from interactions between Cy3 and Cy5 on the reporters were used to understand structural aspects of the reporter designs. Theoretical thermodynamic values, single stranded conformations, hetero- and homodimerization structures, and equilibrium concentrations of the reporters and probes were used to interpret the experimental observations. Studies of the sensitivity and selectivity revealed 5–9 nM detection limits in the presence and absence of interfering off-analyte miRNAs. These studies will aid in determining how to rationally design reporter+probe biosensors to overcome hurdles associated with highly sensitive miRNA biosensing. - Highlights: • Challenges facing highly sensitive miRNA biosensor designs are addressed. • Thermodynamic and molecular structure design metrics for reporter+probe biosensors are proposed. • The influence of ideal and non-ideal reporter hairpin structures on reporter+probe formation and signal change are discussed. • 5–9 nM limits of detection were observed with no interference from off-analytes.

Molecular structure and thermodynamic predictions to create highly sensitive microRNA biosensors

Energy Technology Data Exchange (ETDEWEB)

Larkey, Nicholas E.; Brucks, Corinne N.; Lansing, Shan S.; Le, Sophia D.; Smith, Natasha M.; Tran, Victoria; Zhang, Lulu; Burrows, Sean M., E-mail: sean.burrows@oregonstate.edu

2016-02-25

Many studies have established microRNAs (miRNAs) as post-transcriptional regulators in a variety of intracellular molecular processes. Abnormal changes in miRNA have been associated with several diseases. However, these changes are sometimes subtle and occur at nanomolar levels or lower. Several biosensing hurdles for in situ cellular/tissue analysis of miRNA limit detection of small amounts of miRNA. Of these limitations the most challenging are selectivity and sensor degradation creating high background signals and false signals. Recently we developed a reporter+probe biosensor for let-7a that showed potential to mitigate false signal from sensor degradation. Here we designed reporter+probe biosensors for miR-26a-2-3p and miR-27a-5p to better understand the effect of thermodynamics and molecular structures of the biosensor constituents on the analytical performance. Signal changes from interactions between Cy3 and Cy5 on the reporters were used to understand structural aspects of the reporter designs. Theoretical thermodynamic values, single stranded conformations, hetero- and homodimerization structures, and equilibrium concentrations of the reporters and probes were used to interpret the experimental observations. Studies of the sensitivity and selectivity revealed 5–9 nM detection limits in the presence and absence of interfering off-analyte miRNAs. These studies will aid in determining how to rationally design reporter+probe biosensors to overcome hurdles associated with highly sensitive miRNA biosensing. - Highlights: • Challenges facing highly sensitive miRNA biosensor designs are addressed. • Thermodynamic and molecular structure design metrics for reporter+probe biosensors are proposed. • The influence of ideal and non-ideal reporter hairpin structures on reporter+probe formation and signal change are discussed. • 5–9 nM limits of detection were observed with no interference from off-analytes.

Exact analytical thermodynamic expressions for a Brownian heat engine

Science.gov (United States)

Taye, Mesfin Asfaw

2015-09-01

The nonequilibrium thermodynamics feature of a Brownian motor operating between two different heat baths is explored as a function of time t . Using the Gibbs entropy and Schnakenberg microscopic stochastic approach, we find exact closed form expressions for the free energy, the rate of entropy production, and the rate of entropy flow from the system to the outside. We show that when the system is out of equilibrium, it constantly produces entropy and at the same time extracts entropy out of the system. Its entropy production and extraction rates decrease in time and saturate to a constant value. In the long time limit, the rate of entropy production balances the rate of entropy extraction, and at equilibrium both entropy production and extraction rates become zero. Furthermore, via the present model, many thermodynamic theories can be checked.

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.

Thermodynamics of the Apparent Horizon in FRW Universe with Massive Gravity

International Nuclear Information System (INIS)

Li Hui; Zhang Yi

2013-01-01

Applying Clausius relation with energy-supply defined by the unified first law of thermodynamics formalism to the apparent horizon of a massive gravity model in cosmology proposed lately, the corrected entropic formula of the apparent horizon is obtained with the help of the modified Friedmann equations. This entropy-area relation, together with the identified Misner-Sharp internal energy, verifies the first law of thermodynamics for the apparent horizon with a volume change term for consistency. On the other hand, by means of the corrected entropy-area formula and the Clausius relation δQ = T d S, where the heat Bow δQ is the energy-supply of pure matter projecting on the vector ξ tangent to the apparent horizon and should be looked on as the amount of energy crossing the apparent horizon during the time interval dt and the temperature of the apparent horizon for energy crossing during the same interval is 1/(2πr A ), the modified Friedmann equations governing the dynamical evolution of the universe are reproduced with the known energy density and pressure of massive graviton. The integration constant is found to correspond to a cosmological term which could be absorbed into the energy density of matter. Having established the correspondence of massive cosmology with the unified first law of thermodynamics on the apparent horizon, the validity of the generalized second law of thermodynamics is also discussed by assuming the thermal equilibrium between the apparent horizon and the matter field bounded by the apparent horizon. It is found that, in the limit H c → 0, which recovers the Minkowski reference metric solution in the fiat case, the generalized second law of thermodynamics holds if α 3 + 4α 4 3 = α 4 = 0, the generalized second law of thermodynamics could be violated. (general)

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

Science.gov (United States)

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

2014-01-01

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

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)

Existence of limit cycles in a three level trophic chain with Lotka–Volterra and Holling type II functional responses

International Nuclear Information System (INIS)

Castellanos, Víctor; Chan-López, Ramón E.

2017-01-01

In this paper we analyze a three level trophic chain model, considering a logistic growth for the lowest trophic level, a Lotka–Volterra and Holling type II functional responses for predators in the middle and in the cusp in the chain, respectively. The differential system is based on the Leslie–Gower scheme. We establish conditions on the parameters that guarantee the coexistence of populations in the habitat. We find that an Andronov–Hopf bifurcation takes place. The first Lyapunov coefficient is computed explicitly and we show the existence of a stable limit cycle. Numerically, we observe a strange attractor and there exist evidence of the model to exhibit chaotic dynamics.

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

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...

40 CFR Table 4 to Subpart Jjj of... - Class II Emission Limits for Existing Small Municipal Waste Combustion Unitsa

Science.gov (United States)

2010-07-01

... Small Municipal Waste Combustion Unitsa 4 Table 4 to Subpart JJJ of Part 62 Protection of Environment... Combustion Units Constructed on or Before August 30, 1999 Pt. 62, Subpt. JJJ, Table 4 Table 4 to Subpart JJJ of Part 62—Class II Emission Limits for Existing Small Municipal Waste Combustion Unitsa ER31JA03.009...

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.

Neutrality Versus Materiality: A Thermodynamic Theory of Neutral Surfaces

Directory of Open Access Journals (Sweden)

Rémi Tailleux

2016-09-01

Full Text Available In this paper, a theory for constructing quasi-neutral density variables γ directly in thermodynamic space is formulated, which is based on minimising the absolute value of a purely thermodynamic quantity J n . Physically, J n has a dual dynamic/thermodynamic interpretation as the quantity controlling the energy cost of adiabatic and isohaline parcel exchanges on material surfaces, as well as the dependence of in-situ density on spiciness, in a description of water masses based on γ, spiciness and pressure. Mathematically, minimising | J n | in thermodynamic space is showed to be equivalent to maximising neutrality in physical space. The physics of epineutral dispersion is also reviewed and discussed. It is argued, in particular, that epineutral dispersion is best understood as the aggregate effect of many individual non-neutral stirring events (being understood here as adiabatic and isohaline events with non-zero buoyancy, so that it is only the net displacement aggregated over many events that is approximately neutral. This new view resolves an apparent paradox between the focus in neutral density theory on zero-buoyancy motions and the overwhelming evidence that lateral dispersion in the ocean is primarily caused by non-zero buoyancy processes such as tides, residual currents and sheared internal waves. The efficiency by which a physical process contributes to lateral dispersion can be characterised by its energy signature, with those processes releasing available potential energy (negative energy cost being more efficient than purely neutral processes with zero energy cost. The latter mechanism occurs in the wedge of instability, and its source of energy is the coupling between baroclinicity, thermobaricity, and density compensated temperature/salinity anomalies. Such a mechanism, which can only exist in a salty ocean, is speculated to be important for dissipating spiciness anomalies and neutral helicity. The paper also discusses potential

Amine donor and acceptor influence on the thermodynamics of ω-transaminase reactions

DEFF Research Database (Denmark)

Gundersen, Maria T.; Abu, Rohana; Schürmann, Martin

2015-01-01

In recent years biocatalytic transamination using ω-transaminase has become established as one of the most interesting routes to synthesize chiral amines with a high enantiomeric purity, especially in the pharmaceutical sector where the demand for such compounds is high. Nevertheless, one limitat...... of such reactions because it may be used to help select suitable donor/acceptor combinations. The results presented here give guidance, with respect to thermodynamics, in order to further extend the application of biocatalytic transamination....... limitation for successful implementation and scale-up is that the thermodynamics of such conversions are frequently found unfavourable. Herein we report experimental measurements of apparent equilibrium constants for several industrially relevant transamination reactions in a systematic manner to better...... understand the effect of amine acceptor and donor choice. For example, we have found that ortho-substitution of acetophenone like molecules, had a significant impact on the thermodynamic equilibrium. Likewise, the effect of cyclic amine acceptors was evaluated and compared to similar non-cyclic structures...

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

Mechanical, thermodynamic and electronic properties of wurtzite and zinc-blende GaN crystals

NARCIS (Netherlands)

Qin, Hongbo; Luan, Xinghe; Feng, Chuang; Yang, Daoguo; Zhang, G.Q.

2017-01-01

For the limitation of experimental methods in crystal characterization, in this study, the mechanical, thermodynamic and electronic properties of wurtzite and zinc-blende GaN crystals were investigated by first-principles calculations based on density functional theory. Firstly, bulk moduli,

Linear and nonlinear thermodynamics of a kinetic heat engine with fast transformations

Science.gov (United States)

Cerino, Luca; Puglisi, Andrea; Vulpiani, Angelo

2016-04-01

We investigate a kinetic heat engine model composed of particles enclosed in a box where one side acts as a thermostat and the opposite side is a piston exerting a given pressure. Pressure and temperature are varied in a cyclical protocol of period τ : their relative excursions, δ and ɛ , respectively, constitute the thermodynamic forces dragging the system out of equilibrium. The analysis of the entropy production of the system allows us to define the conjugated fluxes, which are proportional to the extracted work and the consumed heat. In the limit of small δ and ɛ the fluxes are linear in the forces through a τ -dependent Onsager matrix whose off-diagonal elements satisfy a reciprocal relation. The dynamics of the piston can be approximated, through a coarse-graining procedure, by a Klein-Kramers equation which—in the linear regime—yields analytic expressions for the Onsager coefficients and the entropy production. A study of the efficiency at maximum power shows that the Curzon-Ahlborn formula is always an upper limit which is approached at increasing values of the thermodynamic forces, i.e., outside of the linear regime. In all our analysis the adiabatic limit τ →∞ and the the small-force limit δ ,ɛ →0 are not directly related.

Thermodynamic analysis of fermentation and anaerobic growth of baker's yeast for ethanol production.

Science.gov (United States)

Teh, Kwee-Yan; Lutz, Andrew E

2010-05-17

Thermodynamic concepts have been used in the past to predict microbial growth yield. This may be the key consideration in many industrial biotechnology applications. It is not the case, however, in the context of ethanol fuel production. In this paper, we examine the thermodynamics of fermentation and concomitant growth of baker's yeast in continuous culture experiments under anaerobic, glucose-limited conditions, with emphasis on the yield and efficiency of bio-ethanol production. We find that anaerobic metabolism of yeast is very efficient; the process retains more than 90% of the maximum work that could be extracted from the growth medium supplied to the chemostat reactor. Yeast cells and other metabolic by-products are also formed, which reduces the glucose-to-ethanol conversion efficiency to less than 75%. Varying the specific ATP consumption rate, which is the fundamental parameter in this paper for modeling the energy demands of cell growth, shows the usual trade-off between ethanol production and biomass yield. The minimum ATP consumption rate required for synthesizing cell materials leads to biomass yield and Gibbs energy dissipation limits that are much more severe than those imposed by mass balance and thermodynamic equilibrium constraints. 2010 Elsevier B.V. All rights reserved.

DEMONIC programming: a computational language for single-particle equilibrium thermodynamics, and its formal semantics.

Directory of Open Access Journals (Sweden)

Samson Abramsky

2015-11-01

Full Text Available Maxwell's Demon, 'a being whose faculties are so sharpened that he can follow every molecule in its course', has been the centre of much debate about its abilities to violate the second law of thermodynamics. Landauer's hypothesis, that the Demon must erase its memory and incur a thermodynamic cost, has become the standard response to Maxwell's dilemma, and its implications for the thermodynamics of computation reach into many areas of quantum and classical computing. It remains, however, still a hypothesis. Debate has often centred around simple toy models of a single particle in a box. Despite their simplicity, the ability of these systems to accurately represent thermodynamics (specifically to satisfy the second law and whether or not they display Landauer Erasure, has been a matter of ongoing argument. The recent Norton-Ladyman controversy is one such example. In this paper we introduce a programming language to describe these simple thermodynamic processes, and give a formal operational semantics and program logic as a basis for formal reasoning about thermodynamic systems. We formalise the basic single-particle operations as statements in the language, and then show that the second law must be satisfied by any composition of these basic operations. This is done by finding a computational invariant of the system. We show, furthermore, that this invariant requires an erasure cost to exist within the system, equal to kTln2 for a bit of information: Landauer Erasure becomes a theorem of the formal system. The Norton-Ladyman controversy can therefore be resolved in a rigorous fashion, and moreover the formalism we introduce gives a set of reasoning tools for further analysis of Landauer erasure, which are provably consistent with the second law of thermodynamics.

Thermodynamic exergy analysis for small modular reactor in nuclear hybrid energy system

Directory of Open Access Journals (Sweden)

Boldon Lauren

2016-01-01

Full Text Available Small modular reactors (SMRs provide a unique opportunity for future nuclear development with reduced financial risks, allowing the United States to meet growing energy demands through safe, reliable, clean air electricity generation while reducing greenhouse gas emissions and the reliance on unstable fossil fuel prices. A nuclear power plant is comprised of several complex subsystems which utilize materials from other subsystems and their surroundings. The economic utility of resources, or thermoeconomics, is extremely difficult to analyze, particularly when trying to optimize resources and costs among individual subsystems and determine prices for products. Economics and thermodynamics cannot provide this information individually. Thermoeconomics, however, provides a method of coupling the quality of energy available based on exergy and the value of this available energy – “exergetic costs”. For an SMR exergy analysis, both the physical and economic environments must be considered. The physical environment incorporates the energy, raw materials, and reference environment, where the reference environment refers to natural resources available without limit and without cost, such as air input to a boiler. The economic environment includes market influences and prices in addition to installation, operation, and maintenance costs required for production to occur. The exergetic cost or the required exergy for production may be determined by analyzing the physical environment alone. However, to optimize the system economics, this environment must be coupled with the economic environment. A balance exists between enhancing systems to improve efficiency and optimizing costs. Prior research into SMR thermodynamics has not detailed methods on improving exergetic costs for an SMR coupled with storage technologies and renewable energy such as wind or solar in a hybrid energy system. This process requires balancing technological efficiencies and

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

Computational Thermodynamics of Materials Zi-Kui Liu and Yi Wang

Energy Technology Data Exchange (ETDEWEB)

Devanathan, Ram

2017-02-01

This authoritative volume introduces the reader to computational thermodynamics and the use of this approach to the design of material properties by tailoring the chemical composition. The text covers applications of this approach, introduces the relevant computational codes, and offers exercises at the end of each chapter. The book has nine chapters and two appendices that provide background material on computer codes. Chapter 1 covers the first and second laws of thermodynamics, introduces the spinodal as the limit of stability, and presents the Gibbs-Duhem equation. Chapter 2 focuses on the Gibbs energy function. Starting with a homogeneous system with a single phase, the authors proceed to phases with variable compositions, and polymer blends. The discussion includes the contributions of external electric and magnetic fields to the Gibbs energy. Chapter 3 deals with phase equilibria in heterogeneous systems, the Gibbs phase rule, and phase diagrams. Chapter 4 briefly covers experimental measurements of thermodynamic properties used as input for thermodynamic modeling by Calculation of Phase Diagrams (CALPHAD). Chapter 5 discusses the use of density functional theory to obtain thermochemical data and fill gaps where experimental data is missing. The reader is introduced to the Vienna Ab Initio Simulation Package (VASP) for density functional theory and the YPHON code for phonon calculations. Chapter 6 introduces the modeling of Gibbs energy of phases with the CALPHAD method. Chapter 7 deals with chemical reactions and the Ellingham diagram for metal-oxide systems and presents the calculation of the maximum reaction rate from equilibrium thermodynamics. Chapter 8 is devoted to electrochemical reactions and Pourbaix diagrams with application examples. Chapter 9 concludes this volume with the application of a model of multiple microstates to Ce and Fe3Pt. CALPHAD modeling is briefly discussed in the context of genomics of materials. The book introduces basic

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

Thermodynamic Upper Bound on Broadband Light Coupling with Photonic Structures

KAUST Repository

Yu, Zongfu

2012-10-01

The coupling between free space radiation and optical media critically influences the performance of optical devices. We show that, for any given photonic structure, the sum of the external coupling rates for all its optical modes are subject to an upper bound dictated by the second law of thermodynamics. Such bound limits how efficient light can be coupled to any photonic structure. As one example of application, we use this upper bound to derive the limit of light absorption in broadband solar absorbers. © 2012 American Physical Society.

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.

Thermodynamic Data for Geochemical Modeling of Carbonate Reactions Associated with CO2 Sequestration - Literature Review

International Nuclear Information System (INIS)

Krupka, Kenneth M.; Cantrell, Kirk J.; McGrail, B. Peter

2010-01-01

Permanent storage of anthropogenic CO 2 in deep geologic formations is being considered as a means to reduce the concentration of atmospheric CO 2 and thus its contribution to global climate change. To ensure safe and effective geologic sequestration, numerous studies have been completed of the extent to which the CO 2 migrates within geologic formations and what physical and geochemical changes occur in these formations when CO 2 is injected. Sophisticated, computerized reservoir simulations are used as part of field site and laboratory CO 2 sequestration studies. These simulations use coupled multiphase flow-reactive chemical transport models and/or standalone (i.e., no coupled fluid transport) geochemical models to calculate gas solubility, aqueous complexation, reduction/oxidation (redox), and/or mineral solubility reactions related to CO 2 injection and sequestration. Thermodynamic data are critical inputs to modeling geochemical processes. The adequacy of thermodynamic data for carbonate compounds has been identified as an important data requirement for the successful application of these geochemical reaction models to CO 2 sequestration. A review of thermodynamic data for CO 2 gas and carbonate aqueous species and minerals present in published data compilations and databases used in geochemical reaction models was therefore completed. Published studies that describe mineralogical analyses from CO 2 sequestration field and natural analogue sites and laboratory studies were also reviewed to identify specific carbonate minerals that are important to CO 2 sequestration reactions and therefore require thermodynamic data. The results of the literature review indicated that an extensive thermodynamic database exists for CO 2 and CH 4 gases, carbonate aqueous species, and carbonate minerals. Values of Δ f G 298 o and/or log K r,298 o are available for essentially all of these compounds. However, log K r,T o or heat capacity values at temperatures above 298 K exist

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

Thermodynamic and surface properties of liquid Co–Cr–Ni alloys

International Nuclear Information System (INIS)

Costa, C.; Delsante, S.; Borzone, G.; Zivkovic, D.; Novakovic, R.

2014-01-01

Highlights: • The liquid phases of Co–Cr, Co–Ni and Cr–Ni were modelled by the Quasi Chemical Approximation for regular solutions. • The excess Gibbs free energy of mixing of the liquid Co–Cr–Ni phase is estimated by the three thermodynamic models. • Prediction of structure can compensate the lack of structural data of Co–Cr, Co–Ni and Cr–Ni melts. • Thermodynamic modelling of the surface properties of Co–Cr–Ni melts. • Weak effects of short range ordering among nearest neighbours in Co–Cr, Co–Ni and Cr–Ni liquid alloys can be deduced. -- Abstract: Direct measurements of bulk and surface properties of liquid alloys at elevated temperatures are often technically difficult or even impossible, and therefore, theoretical models can be used to estimate missing property values. The energetics of mixing in liquid Co–Cr, Cr–Ni and Co–Ni systems has been analysed through the study of the concentration dependence of various thermodynamic, surface (surface tension and surface composition) and structural properties (concentration fluctuations in the long-wavelength limit and chemical short-range order parameter) by the first or the Quasi-Chemical Approximation (QCA) for regular solutions, developed by Bhatia and Singh, in the framework of statistical mechanical theory in conjunction with the Quasi-Lattice Theory (QLT). The results obtained for these binary systems have been extended to study the thermodynamics and surface properties of ternary Co–Cr–Ni liquid alloys

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...

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 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

Simple thermodynamic model of the extension of solid solution of Cu-Mo alloys processed by mechanical alloying

International Nuclear Information System (INIS)

Aguilar, C.; Guzman, D.; Rojas, P.A.; Ordonez, Stella; Rios, R.

2011-01-01

Highlights: → Extension of solid solution in Cu-Mo systems achieved by mechanical alloying. → Simple thermodynamic model to explain extension of solid solution of Mo in Cu. → Model gives results that are consistent with the solubility limit extension reported in other works. - Abstract: The objective of this work is proposing a simple thermodynamic model to explain the increase in the solubility limit of the powders of the Cu-Mo systems or other binary systems processed by mechanical alloying. In the regular solution model, the effects of crystalline defects, such as; dislocations and grain boundary produced during milling were introduced. The model gives results that are consistent with the solubility limit extension reported in other works for the Cu-Cr, Cu-Nb and Cu-Fe systems processed by mechanical alloying.

Quantitative Assessment of Thermodynamic Constraints on the Solution Space of Genome-Scale Metabolic Models

Science.gov (United States)

Hamilton, Joshua J.; Dwivedi, Vivek; Reed, Jennifer L.

2013-01-01

Constraint-based methods provide powerful computational techniques to allow understanding and prediction of cellular behavior. These methods rely on physiochemical constraints to eliminate infeasible behaviors from the space of available behaviors. One such constraint is thermodynamic feasibility, the requirement that intracellular flux distributions obey the laws of thermodynamics. The past decade has seen several constraint-based methods that interpret this constraint in different ways, including those that are limited to small networks, rely on predefined reaction directions, and/or neglect the relationship between reaction free energies and metabolite concentrations. In this work, we utilize one such approach, thermodynamics-based metabolic flux analysis (TMFA), to make genome-scale, quantitative predictions about metabolite concentrations and reaction free energies in the absence of prior knowledge of reaction directions, while accounting for uncertainties in thermodynamic estimates. We applied TMFA to a genome-scale network reconstruction of Escherichia coli and examined the effect of thermodynamic constraints on the flux space. We also assessed the predictive performance of TMFA against gene essentiality and quantitative metabolomics data, under both aerobic and anaerobic, and optimal and suboptimal growth conditions. Based on these results, we propose that TMFA is a useful tool for validating phenotypes and generating hypotheses, and that additional types of data and constraints can improve predictions of metabolite concentrations. PMID:23870272

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.

Thermodynamic properties and entropy scaling law for diffusivity in soft spheres.

Science.gov (United States)

Pieprzyk, S; Heyes, D M; Brańka, A C

2014-07-01

The purely repulsive soft-sphere system, where the interaction potential is inversely proportional to the pair separation raised to the power n, is considered. The Laplace transform technique is used to derive its thermodynamic properties in terms of the potential energy and its density derivative obtained from molecular dynamics simulations. The derived expressions provide an analytic framework with which to explore soft-sphere thermodynamics across the whole softness-density fluid domain. The trends in the isochoric and isobaric heat capacity, thermal expansion coefficient, isothermal and adiabatic bulk moduli, Grüneisen parameter, isothermal pressure, and the Joule-Thomson coefficient as a function of fluid density and potential softness are described using these formulas supplemented by the simulation-derived equation of state. At low densities a minimum in the isobaric heat capacity with density is found, which is a new feature for a purely repulsive pair interaction. The hard-sphere and n = 3 limits are obtained, and the low density limit specified analytically for any n is discussed. The softness dependence of calculated quantities indicates freezing criteria based on features of the radial distribution function or derived functions of it are not expected to be universal. A new and accurate formula linking the self-diffusion coefficient to the excess entropy for the entire fluid softness-density domain is proposed, which incorporates the kinetic theory solution for the low density limit and an entropy-dependent function in an exponential form. The thermodynamic properties (or their derivatives), structural quantities, and diffusion coefficient indicate that three regions specified by a convex, concave, and intermediate density dependence can be expected as a function of n, with a narrow transition region within the range 5 < n < 8.

Thermodynamics-based Metabolite Sensitivity Analysis in metabolic networks.

Science.gov (United States)

Kiparissides, A; Hatzimanikatis, V

2017-01-01

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

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

Thermodynamic stability of modified Schwarzschild-AdS black hole in rainbow gravity

Energy Technology Data Exchange (ETDEWEB)

Kim, Yong-Wan [Chonbuk National University, Research Institute of Physics and Chemistry, Jeonju (Korea, Republic of); Kim, Seung Kook [Seonam University, Department of Physical Therapy, Namwon (Korea, Republic of); Park, Young-Jai [Sogang University, Department of Physics, Seoul (Korea, Republic of)

2016-10-15

In this paper, we have extended the previous study of the thermodynamics and phase transition of the Schwarzschild black hole in the rainbow gravity to the Schwarzschild-AdS black hole where metric depends on the energy of a probe. Making use of the Heisenberg uncertainty principle and the modified dispersion relation, we have obtained the modified local Hawking temperature and thermodynamic quantities in an isothermal cavity. Moreover, we carry out the analysis of constant temperature slices of a black hole. As a result, we have shown that there also exists another Hawking-Page-like phase transition in which case a locally stable small black hole tunnels into a globally stable large black hole as well as the standard Hawking-Page phase transition from a hot flat space to a black hole. (orig.)

Thermodynamic properties of minerals: Macroscopic and microscopic approaches

International Nuclear Information System (INIS)

Richet, P.; Gillet, P.; Fiquet, G.

1992-01-01

Thermodynamic modeling of experimental or natural-phase equilibria has become an integral part of petrology. In this respect, the isobaric heat capacity (C p ) has manifold importance. First, C p data constitute the basis of third-law determinations of the entropy of minerals. Second, these data are needed to calculate the variation with temperature of the entropy, the entropy, and the Gibbs free energy. As a result, it necessary to know accurately heat capacities when retrieving thermodynamic information from phase equilibria data, especially when trying to separate the effects of the enthalpies and entropies of transformation. In this paper, we broadly review the main empiricial and theoretical aspects of the heat capacity of minerals. We begin with a brief review of the three main techniques that are currently in use for determining heat capacities from 0 to 2000 K, namely, adiabatic, differential scanning (DSC), and drop colarimetry, paying attention to the experimental constraints that limit measurements to certain conditions. When minerals can be subjected at best to limited calorimetric measurements, either because of lack of gram-sized samples or of instability at high temperatures (as if often the case with high-pressure minerals), other ways have to be found for predicting standard entropies and high-temperature properties. The validity of empiricial methods of prediction of the heat capacity as a function of temperature and composition will thus be discussed

Thermodynamic properties of chemical species of waste radionuclides

International Nuclear Information System (INIS)

Silva, R.J.; Nitsche, H.

1984-01-01

The object of the experimental program at Lawrence Berkeley Laboratory is to identify gaps or conflicts in thermodynamic data on the solubilities of compounds and on the formation of solution complexes of waste radionuclides needed for the reliable prediction of solution concentrations. It involves laboratory measurements necessary to (1) generate specific new data, where none exists, in order to demonstrate the importance of a particular solution species, compound or solution parameter (e.g., temperature, Eh) and to (2) resolve conflicts in existing thermodynamic data on important species or compounds. The measurement of the solubility of AmOHCO 3 in 0.1 M NaClO 4 at 25 0 C and 1 atmosphere pressure has been completed. From the experimental data, an average solubility product quotient, Qsp, was evaluated for the reaction, AmOHCO 3 (S) + 2H + = Am 3+ + HCO 3 - + H 2 O. The logarithm of Qsp was calculated to be 2.74 +/- .17. Speciation calculations, using this new data plus reported data on the solubility of Am(OH) 3 and the hydrolysis and carbonate complexation of Am 3+ , indicate that the presence of carbonate can have a substantial effect on the nature of compounds and solution species formed by americium in ground waters. Since actinides in a given oxidation state tend to exhibit similar chemical properties, this result should apply to other actinides in the trivalent state. Thus, the effect of carbonate on the solubilities and complexation of trivalent actinides should be included in any predictive modelling studies required for licensing. 27 references, 4 figures, 5 tables

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

Gauss-Bonnet coupling constant as a free thermodynamical variable and the associated criticality

International Nuclear Information System (INIS)

Xu, Wei; Xu, Hao; Zhao, Liu

2014-01-01

The thermodynamic phase space of Gauss-Bonnet (GB) AdS black holes is extended, taking the inverse of the GB coupling constant as a new thermodynamic pressure P GB . We studied the critical behavior associated with P GB in the extended thermodynamic phase space at fixed cosmological constant and electric charge. The result shows that when the black holes are neutral, the associated critical points can only exist in five dimensional GB-AdS black holes with spherical topology, and the corresponding critical exponents are identical to those for the Van der Waals system. For charged GB-AdS black holes, it is shown that there can be only one critical point in five dimensions (for black holes with either spherical or hyperbolic topologies), which also requires the electric charge to be bounded within some appropriate range; while in d < 5 dimensions, there can be up to two different critical points at the same electric charge, and the phase transition can occur only at temperatures which are not in between the two critical values. (orig.)

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)

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

Science.gov (United States)

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

2016-09-01