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.
Thermodynamics of Crystalline States
Fujimoto, Minoru
2010-01-01
Thermodynamics is a well-established discipline of physics for properties of matter in thermal equilibrium surroundings. Applying to crystals, however, the laws encounter undefined properties of crystal lattices, which therefore need to be determined for a clear and well-defined description of crystalline states. Thermodynamics of Crystalline States explores the roles played by order variables and dynamic lattices in crystals in a wholly new way. This book is divided into three parts. The book begins by clarifying basic concepts for stable crystals. Next, binary phase transitions are discussed to study collective motion of order variables, as described mostly as classical phenomena. In the third part, the multi-electron system is discussed theoretically, as a quantum-mechanical example, for the superconducting state in metallic crystals. Throughout the book, the role played by the lattice is emphasized and examined in-depth. Thermodynamics of Crystalline States is an introductory treatise and textbook on meso...
Thermodynamic approach to the inelastic state variable theories
International Nuclear Information System (INIS)
Dashner, P.A.
1978-06-01
A continuum model is proposed as a theoretical foundation for the inelastic state variable theory of Hart. The model is based on the existence of a free energy function and the assumption that a strained material element recalls two other local configurations which are, in some specified manner, descriptive of prior deformation. A precise formulation of these material hypotheses within the classical thermodynamical framework leads to the recovery of a generalized elastic law and the specification of evolutionary laws for the remembered configurations which are frame invariant and formally valid for finite strains. Moreover, the precise structure of Hart's theory is recovered when strains are assumed to be small
Thermodynamics of Crystalline States
Fujimoto, Minoru
2013-01-01
Thermodynamics is a well-established discipline of physics for properties of matter in thermal equilibrium with the surroundings. Applying to crystals, however, the laws encounter undefined properties of crystal lattice, which therefore need to be determined for a clear and well-defined description of crystalline states. Thermodynamics of Crystalline States explores the roles played by order variables and dynamic lattices in crystals in a wholly new way. The book begins by clarifying basic concepts for stable crystals. Next, binary phase transitions are discussed to study collective motion of order variables, as described mostly as classical phenomena. New to this edition is the examination of magnetic crystals, where magnetic symmetry is essential for magnetic phase transitions. The multi-electron system is also discussed theoretically, as a quantum-mechanical example, for superconductivity in metallic crystals. Throughout the book, the role played by the lattice is emphasized and studied in-depth. Thermod...
On the derivation of thermodynamic restrictions for materials with internal state variables
International Nuclear Information System (INIS)
Malmberg, T.
1987-07-01
Thermodynamic restrictions for the constitutive relations of an internal variable model are derived by evaluating the Clausius-Duhem entropy inequality with two different approaches. The classical Coleman-Noll argumentation of Rational Thermodynamics applied by Coleman and Gurtin to an internal variable model is summarized. This approach requires an arbitrary modulation of body forces and heat supply in the interior of the body which is subject to criticism. The second approach applied in this presentation is patterned after a concept of Mueller and Liu, originally developed within the context of a different entropy inequality and different classes of constitutive models. For the internal variable model the second approach requires only the modulation of initial values on the boundary of the body. In the course of the development of the second approach certain differences to the argumentation of Mueller and Liu become evident and are pointed out. Finally, the results demonstrate that the first and second approach give the same thermodynamic restrictions for the internal variable model. The derived residual entropy inequality requires further analysis. (orig.) [de
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
Thermodynamics of the variable modified Chaplygin gas
Energy Technology Data Exchange (ETDEWEB)
Panigrahi, D. [Sree Chaitanya College, Habra 743268 (India); Chatterjee, S., E-mail: dibyendupanigrahi@yahoo.co.in, E-mail: chat_sujit1@yahoo.com [Relativity and Cosmology Research Centre, Jadavpur University, Kolkata – 700032 (India)
2016-05-01
A cosmological model with a new variant of Chaplygin gas obeying an equation of state (EoS), P = A ρ − B /ρ{sup α} where B = B {sub 0} a {sup n} is investigated in the context of its thermodynamical behaviour. Here B {sub 0} and n are constants and a is the scale factor. We show that the equation of state of this 'Variable Modified Chaplygin gas' (VMCG) can describe the current accelerated expansion of the universe. Following standard thermodynamical criteria we mainly discuss the classical thermodynamical stability of the model and find that the new parameter, n introduced in VMCG plays a crucial role in determining the stability considerations and should always be negative. We further observe that although the earlier model of Lu explains many of the current observational findings of different probes it fails the desirable tests of thermodynamical stability. We also note that for 0 n < our model points to a phantom type of expansion which, however, is found to be compatible with current SNe Ia observations and CMB anisotropy measurements. Further the third law of thermodynamics is obeyed in our case. Our model is very general in the sense that many of earlier works in this field may be obtained as a special case of our solution. An interesting point to note is that the model also apparently suggests a smooth transition from the big bang to the big rip in its whole evaluation process.
The Markov process admits a consistent steady-state thermodynamic formalism
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.
The Matrix model, a driven state variables approach to non-equilibrium thermodynamics
Jongschaap, R.J.J.
2001-01-01
One of the new approaches in non-equilibrium thermodynamics is the so-called matrix model of Jongschaap. In this paper some features of this model are discussed. We indicate the differences with the more common approach based upon internal variables and the more sophisticated Hamiltonian and GENERIC
Integrated stoichiometric, thermodynamic and kinetic modelling of steady state metabolism.
Fleming, R M T; Thiele, I; Provan, G; Nasheuer, H P
2010-06-07
The quantitative analysis of biochemical reactions and metabolites is at frontier of biological sciences. The recent availability of high-throughput technology data sets in biology has paved the way for new modelling approaches at various levels of complexity including the metabolome of a cell or an organism. Understanding the metabolism of a single cell and multi-cell organism will provide the knowledge for the rational design of growth conditions to produce commercially valuable reagents in biotechnology. Here, we demonstrate how equations representing steady state mass conservation, energy conservation, the second law of thermodynamics, and reversible enzyme kinetics can be formulated as a single system of linear equalities and inequalities, in addition to linear equalities on exponential variables. Even though the feasible set is non-convex, the reformulation is exact and amenable to large-scale numerical analysis, a prerequisite for computationally feasible genome scale modelling. Integrating flux, concentration and kinetic variables in a unified constraint-based formulation is aimed at increasing the quantitative predictive capacity of flux balance analysis. Incorporation of experimental and theoretical bounds on thermodynamic and kinetic variables ensures that the predicted steady state fluxes are both thermodynamically and biochemically feasible. The resulting in silico predictions are tested against fluxomic data for central metabolism in Escherichia coli and compare favourably with in silico prediction by flux balance analysis. Copyright (c) 2010 Elsevier Ltd. All rights reserved.
Teaching Differentials in Thermodynamics Using Spatial Visualization
Wang, Chih-Yueh; Hou, Ching-Han
2012-01-01
The greatest difficulty that is encountered by students in thermodynamics classes is to find relationships between variables and to solve a total differential equation that relates one thermodynamic state variable to two mutually independent state variables. Rules of differentiation, including the total differential and the cyclic rule, are…
Quantum thermodynamics of nanoscale steady states far from equilibrium
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.
Thermodynamic state ensemble models of cis-regulation.
Directory of Open Access Journals (Sweden)
Marc S Sherman
Full Text Available A major goal in computational biology is to develop models that accurately predict a gene's expression from its surrounding regulatory DNA. Here we present one class of such models, thermodynamic state ensemble models. We describe the biochemical derivation of the thermodynamic framework in simple terms, and lay out the mathematical components that comprise each model. These components include (1 the possible states of a promoter, where a state is defined as a particular arrangement of transcription factors bound to a DNA promoter, (2 the binding constants that describe the affinity of the protein-protein and protein-DNA interactions that occur in each state, and (3 whether each state is capable of transcribing. Using these components, we demonstrate how to compute a cis-regulatory function that encodes the probability of a promoter being active. Our intention is to provide enough detail so that readers with little background in thermodynamics can compose their own cis-regulatory functions. To facilitate this goal, we also describe a matrix form of the model that can be easily coded in any programming language. This formalism has great flexibility, which we show by illustrating how phenomena such as competition between transcription factors and cooperativity are readily incorporated into these models. Using this framework, we also demonstrate that Michaelis-like functions, another class of cis-regulatory models, are a subset of the thermodynamic framework with specific assumptions. By recasting Michaelis-like functions as thermodynamic functions, we emphasize the relationship between these models and delineate the specific circumstances representable by each approach. Application of thermodynamic state ensemble models is likely to be an important tool in unraveling the physical basis of combinatorial cis-regulation and in generating formalisms that accurately predict gene expression from DNA sequence.
Rational extended thermodynamics
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...
International Nuclear Information System (INIS)
Malmberg, T.
1993-09-01
The objective of this study is to derive and investigate thermodynamic restrictions for a particular class of internal variable models. Their evolution equations consist of two contributions: the usual irreversible part, depending only on the present state, and a reversible but path dependent part, linear in the rates of the external variables (evolution equations of ''mixed type''). In the first instance the thermodynamic analysis is based on the classical Clausius-Duhem entropy inequality and the Coleman-Noll argument. The analysis is restricted to infinitesimal strains and rotations. The results are specialized and transferred to a general class of elastic-viscoplastic material models. Subsequently, they are applied to several viscoplastic models of ''mixed type'', proposed or discussed in the literature (Robinson et al., Krempl et al., Freed et al.), and it is shown that some of these models are thermodynamically inconsistent. The study is closed with the evaluation of the extended Clausius-Duhem entropy inequality (concept of Mueller) where the entropy flux is governed by an assumed constitutive equation in its own right; also the constraining balance equations are explicitly accounted for by the method of Lagrange multipliers (Liu's approach). This analysis is done for a viscoplastic material model with evolution equations of the ''mixed type''. It is shown that this approach is much more involved than the evaluation of the classical Clausius-Duhem entropy inequality with the Coleman-Noll argument. (orig.) [de
Thermodynamic Ground States of Complex Oxide Heterointerfaces
DEFF Research Database (Denmark)
Gunkel, F.; Hoffmann-Eifert, S.; Heinen, R. A.
2017-01-01
The formation mechanism of 2-dimensional electron gases (2DEGs) at heterointerfaces between nominally insulating oxides is addressed with a thermodynamical approach. We provide a comprehensive analysis of the thermodynamic ground states of various 2DEG systems directly probed in high temperature...
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.
Methods for thermodynamic evaluation of battery state of health
Yazami, Rachid; McMenamin, Joseph; Reynier, Yvan; Fultz, Brent T
2013-05-21
Described are systems and methods for accurately characterizing thermodynamic and materials properties of electrodes and battery systems and for characterizing the state of health of electrodes and battery systems. Measurement of physical attributes of electrodes and batteries corresponding to thermodynamically stabilized electrode conditions permit determination of thermodynamic parameters, including state functions such as the Gibbs free energy, enthalpy and entropy of electrode/electrochemical cell reactions, that enable prediction of important performance attributes of electrode materials and battery systems, such as energy, power density, current rate, cycle life and state of health. Also provided are systems and methods for charging a battery according to its state of health.
On Equivalence of Nonequilibrium Thermodynamic and Statistical Entropies
Directory of Open Access Journals (Sweden)
Purushottam D. Gujrati
2015-02-01
Full Text Available We review the concept of nonequilibrium thermodynamic entropy and observables and internal variables as state variables, introduced recently by us, and provide a simple first principle derivation of additive statistical entropy, applicable to all nonequilibrium states by treating thermodynamics as an experimental science. We establish their numerical equivalence in several cases, which includes the most important case when the thermodynamic entropy is a state function. We discuss various interesting aspects of the two entropies and show that the number of microstates in the Boltzmann entropy includes all possible microstates of non-zero probabilities even if the system is trapped in a disjoint component of the microstate space. We show that negative thermodynamic entropy can appear from nonnegative statistical entropy.
Tischer, Alexander; Auton, Matthew
2013-01-01
We have analyzed the thermodynamic properties of the von Willebrand factor (VWF) A3 domain using urea-induced unfolding at variable temperature and thermal unfolding at variable urea concentrations to generate a phase diagram that quantitatively describes the equilibrium between native and denatured states. From this analysis, we were able to determine consistent thermodynamic parameters with various spectroscopic and calorimetric methods that define the urea–temperature parameter plane from cold denaturation to heat denaturation. Urea and thermal denaturation are experimentally reversible and independent of the thermal scan rate indicating that all transitions are at equilibrium and the van't Hoff and calorimetric enthalpies obtained from analysis of individual thermal transitions are equivalent demonstrating two-state character. Global analysis of the urea–temperature phase diagram results in a significantly higher enthalpy of unfolding than obtained from analysis of individual thermal transitions and significant cross correlations describing the urea dependence of and that define a complex temperature dependence of the m-value. Circular dichroism (CD) spectroscopy illustrates a large increase in secondary structure content of the urea-denatured state as temperature increases and a loss of secondary structure in the thermally denatured state upon addition of urea. These structural changes in the denatured ensemble make up ∼40% of the total ellipticity change indicating a highly compact thermally denatured state. The difference between the thermodynamic parameters obtained from phase diagram analysis and those obtained from analysis of individual thermal transitions illustrates that phase diagrams capture both contributions to unfolding and denatured state expansion and by comparison are able to decipher these contributions. PMID:23813497
International thermodynamic tables of the fluid state propylene (propene)
Angus, S; De Reuck, K M
2013-01-01
International Thermodynamic Tables of the Fluid State - 7 Propylene (Propene) is a compilation of internationally agreed values of the equilibrium thermodynamic properties of propylene. This book is composed of three chapters, and begins with the presentation of experimental result of thermodynamic studies compared with the equations used to generate the tables. The succeeding chapter deals with correlating equations for thermodynamic property determination of propylene. The last chapter provides the tabulations of the propylene's thermodynamic properties and constants. This book will prove
Thermodynamic picture of the glassy state
Nieuwenhuizen, T.M.
2000-01-01
A picture for the thermodynamics of the glassy state is introduced. It assumes that one extra parameter, the effective temperature, is needed to describe the glassy state. This explains the classical paradoxes concerning the Ehrenfest relations and the Prigogine-Defay ratio. As a second feature, the
International thermodynamic tables of the fluid state helium-4
de Reuck, K M; McCarty, R D
2013-01-01
International Thermodynamic Tables of the Fluid State Helium-4 presents the IUPAC Thermodynamic Tables for the thermodynamic properties of helium. The IUPAC Thermodynamic Tables Project has therefore encouraged the critical analysis of the available thermodynamic measurements for helium and their synthesis into tables. This book is divided into three chapters. The first chapter discusses the experimental results and compares with the equations used to generate the tables. These equations are supplemented by a vapor pressure equation, which represents the 1958 He-4 scale of temperature that is
Thermodynamic behavior of glassy state of structurally related compounds.
Kaushal, Aditya Mohan; Bansal, Arvind Kumar
2008-08-01
Thermodynamic properties of amorphous pharmaceutical forms are responsible for enhanced solubility as well as poor physical stability. The present study was designed to investigate the differences in thermodynamic parameters arising out of disparate molecular structures and associations for four structurally related pharmaceutical compounds--celecoxib, valdecoxib, rofecoxib, and etoricoxib. Conventional and modulated temperature differential scanning calorimetry were employed to study glass forming ability and thermodynamic behavior of the glassy state of model compounds. Glass transition temperature of four glassy compounds was in a close range of 327.6-331.8 K, however, other thermodynamic parameters varied considerably. Kauzmann temperature, strength parameter and fragility parameter showed rofecoxib glass to be most fragile of the four compounds. Glass forming ability of the compounds fared similar in the critical cooling rate experiments, suggesting that different factors were determining the glass forming ability and subsequent behavior of the compounds in glassy state. A comprehensive understanding of such thermodynamic facets of amorphous form would help in rationalizing the approaches towards development of stable glassy pharmaceuticals.
Thermodynamic Fluid Equations-of-State
Directory of Open Access Journals (Sweden)
Leslie V. Woodcock
2018-01-01
Full Text Available As experimental measurements of thermodynamic properties have improved in accuracy, to five or six figures, over the decades, cubic equations that are widely used for modern thermodynamic fluid property data banks require ever-increasing numbers of terms with more fitted parameters. Functional forms with continuity for Gibbs density surface ρ(p,T which accommodate a critical-point singularity are fundamentally inappropriate in the vicinity of the critical temperature (Tc and pressure (pc and in the supercritical density mid-range between gas- and liquid-like states. A mesophase, confined within percolation transition loci that bound the gas- and liquid-state by third-order discontinuities in derivatives of the Gibbs energy, has been identified. There is no critical-point singularity at Tc on Gibbs density surface and no continuity of gas and liquid. When appropriate functional forms are used for each state separately, we find that the mesophase pressure functions are linear. The negative and positive deviations, for both gas and liquid states, on either side of the mesophase, are accurately represented by three or four-term virial expansions. All gaseous states require only known virial coefficients, and physical constants belonging to the fluid, i.e., Boyle temperature (TB, critical temperature (Tc, critical pressure (pc and coexisting densities of gas (ρcG and liquid (ρcL along the critical isotherm. A notable finding for simple fluids is that for all gaseous states below TB, the contribution of the fourth virial term is negligible within experimental uncertainty. Use may be made of a symmetry between gas and liquid states in the state function rigidity (dp/dρT to specify lower-order liquid-state coefficients. Preliminary results for selected isotherms and isochores are presented for the exemplary fluids, CO2, argon, water and SF6, with focus on the supercritical mesophase and critical region.
A constitutive model for magnetostriction based on thermodynamic framework
International Nuclear Information System (INIS)
Ho, Kwangsoo
2016-01-01
This work presents a general framework for the continuum-based formulation of dissipative materials with magneto–mechanical coupling in the viewpoint of irreversible thermodynamics. The thermodynamically consistent model developed for the magnetic hysteresis is extended to include the magnetostrictive effect. The dissipative and hysteretic response of magnetostrictive materials is captured through the introduction of internal state variables. The evolution rate of magnetostrictive strain as well as magnetization is derived from thermodynamic and dissipative potentials in accordance with the general principles of thermodynamics. It is then demonstrated that the constitutive model is competent to describe the magneto-mechanical behavior by comparing simulation results with the experimental data reported in the literature. - Highlights: • A thermodynamically consistent model is proposed to describe the magneto-mechanical coupling effect. • Internal state variables are introduced to capture the dissipative material response. • The evolution rate of the magnetostrictive strain is derived through thermodynamic and dissipation potentials.
Methods and systems for thermodynamic evaluation of battery state of health
Yazami, Rachid; McMenamin, Joseph; Reynier, Yvan; Fultz, Brent T
2014-12-02
Described are systems and methods for accurately characterizing thermodynamic and materials properties of electrodes and battery systems and for characterizing the state of health of electrodes and battery systems. Measurement of physical attributes of electrodes and batteries corresponding to thermodynamically stabilized electrode conditions permit determination of thermodynamic parameters, including state functions such as the Gibbs free energy, enthalpy and entropy of electrode/electrochemical cell reactions, that enable prediction of important performance attributes of electrode materials and battery systems, such as energy, power density, current rate, cycle life and state of health. Also provided are systems and methods for charging a battery according to its state of health.
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.
Thermodynamics of bread baking: A two-state model
Zürcher, Ulrich
2014-03-01
Bread baking can be viewed as a complex physico-chemical process. It is governed by transport of heat and is accompanied by changes such as gelation of starch, the expansion of air cells within dough, and others. We focus on the thermodynamics of baking and investigate the heat flow through dough and find that the evaporation of excess water in dough is the rate-limiting step. We consider a simplified one-dimensional model of bread, treating the excess water content as a two-state variable that is zero for baked bread and a fixed constant for unbaked dough. We arrive at a system of coupled, nonlinear ordinary differential equations, which are solved using a standard Runge-Kutta integration method. The calculated baking times are consistent with common baking experience.
Stability of black holes based on horizon thermodynamics
Directory of Open Access Journals (Sweden)
Meng-Sen Ma
2015-12-01
Full Text Available On the basis of horizon thermodynamics we study the thermodynamic stability of black holes constructed in general relativity and Gauss–Bonnet gravity. In the framework of horizon thermodynamics there are only five thermodynamic variables E, P, V, T, S. It is not necessary to consider concrete matter fields, which may contribute to the pressure of black hole thermodynamic system. In non-vacuum cases, we can derive the equation of state, P=P(V,T. According to the requirements of stable equilibrium in conventional thermodynamics, we start from these thermodynamic variables to calculate the heat capacity at constant pressure and Gibbs free energy and analyze the local and global thermodynamic stability of black holes. It is shown that P>0 is the necessary condition for black holes in general relativity to be thermodynamically stable, however this condition cannot be satisfied by many black holes in general relativity. For black hole in Gauss–Bonnet gravity negative pressure can be feasible, but only local stable black hole exists in this case.
Thermodynamic analysis of elastic-plastic deformation
International Nuclear Information System (INIS)
Lubarda, V.
1981-01-01
The complete set of constitutive equations which fully describes the behaviour of material in elastic-plastic deformation is derived on the basis of thermodynamic analysis of the deformation process. The analysis is done after the matrix decomposition of the deformation gradient is introduced into the structure of thermodynamics with internal state variables. The free energy function, is decomposed. Derive the expressions for the stress response, entropy and heat flux, and establish the evolution equation. Finally, we establish the thermodynamic restrictions of the deformation process. (Author) [pt
Energy Technology Data Exchange (ETDEWEB)
Fei, Yiyan; Landry, James P.; Zhu, X. D., E-mail: xdzhu@physics.ucdavis.edu [Department of Physics, University of California, One Shields Avenue, Davis, California 95616 (United States); Li, Yanhong; Yu, Hai; Lau, Kam; Huang, Shengshu; Chokhawala, Harshal A.; Chen, Xi [Department of Chemistry, University of California, One Shields Avenue, Davis, California 95616 (United States)
2013-11-15
A biological state is equilibrium of multiple concurrent biomolecular reactions. The relative importance of these reactions depends on physiological temperature typically between 10 °C and 50 °C. Experimentally the temperature dependence of binding reaction constants reveals thermodynamics and thus details of these biomolecular processes. We developed a variable-temperature opto-fluidic system for real-time measurement of multiple (400–10 000) biomolecular binding reactions on solid supports from 10 °C to 60 °C within ±0.1 °C. We illustrate the performance of this system with investigation of binding reactions of plant lectins (carbohydrate-binding proteins) with 24 synthetic glycans (i.e., carbohydrates). We found that the lectin-glycan reactions in general can be enthalpy-driven, entropy-driven, or both, and water molecules play critical roles in the thermodynamics of these reactions.
Life, hierarchy, and the thermodynamic machinery of planet Earth.
Kleidon, Axel
2010-12-01
Throughout Earth's history, life has increased greatly in abundance, complexity, and diversity. At the same time, it has substantially altered the Earth's environment, evolving some of its variables to states further and further away from thermodynamic equilibrium. For instance, concentrations in atmospheric oxygen have increased throughout Earth's history, resulting in an increased chemical disequilibrium in the atmosphere as well as an increased redox gradient between the atmosphere and the Earth's reducing crust. These trends seem to contradict the second law of thermodynamics, which states for isolated systems that gradients and free energy are dissipated over time, resulting in a state of thermodynamic equilibrium. This seeming contradiction is resolved by considering planet Earth as a coupled, hierarchical and evolving non-equilibrium thermodynamic system that has been substantially altered by the input of free energy generated by photosynthetic life. Here, I present this hierarchical thermodynamic theory of the Earth system. I first present simple considerations to show that thermodynamic variables are driven away from a state of thermodynamic equilibrium by the transfer of power from some other process and that the resulting state of disequilibrium reflects the past net work done on the variable. This is applied to the processes of planet Earth to characterize the generation and transfer of free energy and its dissipation, from radiative gradients to temperature and chemical potential gradients that result in chemical, kinetic, and potential free energy and associated dynamics of the climate system and geochemical cycles. The maximization of power transfer among the processes within this hierarchy yields thermodynamic efficiencies much lower than the Carnot efficiency of equilibrium thermodynamics and is closely related to the proposed principle of Maximum Entropy Production (MEP). The role of life is then discussed as a photochemical process that generates
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
A Thermodynamical Theory with Internal Variables Describing Thermal Effects in Viscous Fluids
Ciancio, Vincenzo; Palumbo, Annunziata
2018-04-01
In this paper the heat conduction in viscous fluids is described by using the theory of classical irreversible thermodynamics with internal variables. In this theory, the deviation from the local equilibrium is characterized by vectorial internal variables and a generalized entropy current density expressed in terms of so-called current multipliers. Cross effects between heat conduction and viscosity are also considered and some phenomenological generalizations of Fourier's and Newton's laws are obtained.
Surface dependency in thermodynamics of ideal gases
International Nuclear Information System (INIS)
Sisman, Altug
2004-01-01
The Casimir-like size effect rises in ideal gases confined in a finite domain due to the wave character of atoms. By considering this effect, thermodynamic properties of an ideal gas confined in spherical and cylindrical geometries are derived and compared with those in rectangular geometry. It is seen that an ideal gas exhibits an unavoidable quantum surface free energy and surface over volume ratio becomes a control variable on thermodynamic state functions in microscale. Thermodynamics turns into non-extensive thermodynamics and geometry difference becomes a driving force since the surface over volume ratio depends on the geometry
International Nuclear Information System (INIS)
Udovskij, A.L.; Karpushkin, V.N.; Nikishina, E.A.
1991-01-01
Method of non-interacting thermodynamic calculation of state diagram of binary systems contacting p disordered phases with variable composition and q phases with constant composition for (p, q) ≤ 10 case is developed. Determination of all possible solutions of phase equilibrium equations is realized in the method. Certain application examples of computer-realized method of T-x thermodynamic calculation using PC for Cr-W, Ni-W, Ni-Al, Ni-Re binary systems are given
Hamiltonian and Thermodynamic Modeling of Quantum Turbulence
Grmela, Miroslav
2010-10-01
The state variables in the novel model introduced in this paper are the fields playing this role in the classical Landau-Tisza model and additional fields of mass, entropy (or temperature), superfluid velocity, and gradient of the superfluid velocity, all depending on the position vector and another tree dimensional vector labeling the scale, describing the small-scale structure developed in 4He superfluid experiencing turbulent motion. The fluxes of mass, momentum, energy, and entropy in the position space as well as the fluxes of energy and entropy in scales, appear in the time evolution equations as explicit functions of the state variables and of their conjugates. The fundamental thermodynamic relation relating the fields to their conjugates is left in this paper undetermined. The GENERIC structure of the equations serves two purposes: (i) it guarantees that solutions to the governing equations, independently of the choice of the fundamental thermodynamic relation, agree with the observed compatibility with thermodynamics, and (ii) it is used as a guide in the construction of the novel model.
Irreversible thermodynamics, parabolic law and self-similar state in grain growth
International Nuclear Information System (INIS)
Rios, P.R.
2004-01-01
The formalism of the thermodynamic theory of irreversible processes is applied to grain growth to investigate the nature of the self-similar state and its corresponding parabolic law. Grain growth does not reach a steady state in the sense that the entropy production remains constant. However, the entropy production can be written as a product of two factors: a scale factor that tends to zero for long times and a scaled entropy production. It is suggested that the parabolic law and the self-similar state may be associated with the minimum of this scaled entropy production. This result implies that the parabolic law and the self-similar state have a sound irreversible thermodynamical basis
International Nuclear Information System (INIS)
Kelley, Neil D.
1999-01-01
This paper makes the case for establishing efficient predictor variables for atmospheric thermodynamics that can be used to statistically correlate the fatigue accumulation seen on wind turbines. Recently, two approaches to this issue have been reported. One uses multiple linear-regression analysis to establish the relative causality between a number of predictors related to the turbulent inflow and turbine loads. The other approach, using many of the same predictors, applies the technique of principal component analysis. An examination of the ensemble of predictor variables revealed that they were all kinematic in nature; i.e., they were only related to the description of the velocity field. Boundary-layer turbulence dynamics depends upon a description of the thermal field and its interaction with the velocity distribution. We used a series of measurements taken within a multi-row wind farm to demonstrate the need to include atmospheric thermodynamic variables as well as velocity-related ones in the search for efficient turbulence loading predictors in various turbine-operating environments. Our results show that a combination of vertical stability and hub-height mean shearing stress variables meet this need over a period of 10 minutes
Thermodynamic properties by Equation of state of liquid sodium under pressure
Li, Huaming; Sun, Yongli; Zhang, Xiaoxiao; Li, Mo
Isothermal bulk modulus, molar volume and speed of sound of molten sodium are calculated through an equation of state of a power law form within good precision as compared with the experimental data. The calculated internal energy data show the minimum along the isothermal lines as the previous result but with slightly larger values. The calculated values of isobaric heat capacity show the unexpected minimum in the isothermal compression. The temperature and pressure derivative of various thermodynamic quantities in liquid Sodium are derived. It is discussed about the contribution from entropy to the temperature and pressure derivative of isothermal bulk modulus. The expressions for acoustical parameter and nonlinearity parameter are obtained based on thermodynamic relations from the equation of state. Both parameters for liquid Sodium are calculated under high pressure along the isothermal lines by using the available thermodynamic data and numeric derivations. By comparison with the results from experimental measurements and quasi-thermodynamic theory, the calculated values are found to be very close at melting point at ambient condition. Furthermore, several other thermodynamic quantities are also presented. Scientific Research Starting Foundation from Taiyuan university of Technology, Shanxi Provincial government (``100-talents program''), China Scholarship Council and National Natural Science Foundation of China (NSFC) under Grant No. 11204200.
Thermodynamic study of fluid in terms of equation of state containing physical parameters
International Nuclear Information System (INIS)
Khasare, S. B.
2015-01-01
We introduce a simple condition for one mole fluid by considering the thermodynamics of molecules pointing towards the effective potential for the cluster. Efforts are made to estimate new physical parameter f in liquid state using the equation of state containing only two physical parameters such as the hard sphere diameter and binding energy. The temperature dependence of the structural properties and the thermodynamic behavior of the clusters are studied. Computations based on f predict the variation of numbers of particles at the contact point of the molecular cavity (radial distribution function). From the thermodynamic profile of the fluid, the model results are discussed in terms of the cavity due to the closed surface along with suitable energy. The present calculation is based upon the sample thermodynamic data for n-hexanol, such as the ultrasonic wave, density, volume expansion coefficient, and ratio of specific heat in the liquid state, and it is consistent with the thermodynamic relations containing physical parameters such as size and energy. Since the data is restricted to n-hexanol, we avoid giving the physical meaning of f, which is the key parameter studied in the present work. (paper)
Thermodynamic and Quantum Thermodynamic Analyses of Brownian Movement
Gyftopoulos, Elias P.
2006-01-01
Thermodynamic and quantum thermodynamic analyses of Brownian movement of a solvent and a colloid passing through neutral thermodynamic equilibrium states only. It is shown that Brownian motors and E. coli do not represent Brownian movement.
On the thermodynamics of the McMillan-Mayer state function
DEFF Research Database (Denmark)
Mollerup, Jørgen; Breil, Martin Peter
2009-01-01
to develop the McMillan-Mayer framework in a classical thermodynamic context for which we develop the relationship between the state function of the McMillan-Mayer framework and the Helmholtz state function. A Taylor expansion method can be applied to the osmotic pressure of a solution which is dilute...
Directory of Open Access Journals (Sweden)
Wassim M. Haddad
2013-05-01
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 involving heat flow, work energy, and chemical reactions, we develop a state-space dynamical system model that captures the key aspects of thermodynamics, including its fundamental laws. In addition, we show that our thermodynamically consistent dynamical system model is globally semistable with system states converging to a state of temperature equipartition. Furthermore, in the presence of chemical reactions, we use the law of mass-action and the notion of chemical potential to show that the dynamic system states converge to a state of temperature equipartition and zero affinity corresponding to a state of chemical equilibrium.
Stationary Distribution and Thermodynamic Relation in Nonequilibrium Steady States
Komatsu, Teruhisa S.; Nakagawa, Naoko; Sasa, Shin-ichi; Tasaki, Hal; Ito, Nobuyasu
2010-01-01
We describe our recent attempts toward statistical mechanics and thermodynamics for nonequilibrium steady states (NESS) realized, e.g., in a heat conducting system. Our first result is a simple expression of the probability distribution (of microscopic states) of a NESS. Our second result is a natural extension of the thermodynamic Clausius relation and a definition of an accompanying entropy in NESS. This entropy coincides with the normalization constant appearing in the above mentioned microscopic expression of NESS, and has an expression similar to the Shannon entropy (with a further symmetrization). The NESS entropy proposed here is a clearly defined measurable quantity even in a system with a large degrees of freedom. We numerically measure the NESS entropy in hardsphere fluid systems with a heat current, by observing energy exchange between the system and the heat baths when the temperatures of the baths are changed according to specified protocols.
Hartree-Fock states in the thermodynamic limit
International Nuclear Information System (INIS)
Aguilera-Navarro, V.C.; Llano, M. de; Peltier, S.; Plastino, A.
1976-01-01
Two infinite families of two-parameter generalized Overhauser orbitals are introduced and shown to explicitly satisfy, for occupied states, the self-consistent Hartree-Fock equations in the thermodynamic limit. For an attractive delta interaction, they give lower Hartree-Fock energy than the usual plane-wave solutions, even for relatively weak coupling and/or low density. The limiting members (possessing an infinite number of harmonics) of both families appear to tend to a 'classical static lattice' state. The related density profiles and energy expressions are calculated as functions of the two new parameters. A direct-variation with respect to these parameters was done numerically and results are presented graphically. (Author) [pt
The thermodynamic basis of entransy and entransy dissipation
International Nuclear Information System (INIS)
Xu, Mingtian
2011-01-01
In the present work, the entransy and entransy dissipation are defined from the thermodynamic point of view. It is shown that the entransy is a state variable and can be employed to describe the second law of thermodynamics. For heat conduction, a principle of minimum entransy dissipation is established based on the second law of thermodynamics in terms of entransy dissipation, which leads to the governing equation of the steady Fourier heat conduction without heat source. Furthermore, we derive the expressions of the entransy dissipation in duct flows and heat exchangers from the second law of thermodynamics, which paves the way for applications of the entransy dissipation theory in heat exchanger design. -- Highlights: → The concepts of entransy and entransy dissipation are defined from the thermodynamic point of view. → We find that the entransy is a new thermodynamic property. → The second law of thermodynamics can be described by the entransy and entransy dissipation. → The expressions of entransy dissipation in duct flows and heat exchangers are derived from the second law of thermodynamics.
Thermodynamics of de Sitter black holes: Thermal cosmological constant
International Nuclear Information System (INIS)
Sekiwa, Y.
2006-01-01
We study the thermodynamic properties associated with the black hole event horizon and the cosmological horizon for black hole solutions in asymptotically de Sitter spacetimes. We examine thermodynamics of these horizons on the basis of the conserved charges according to Teitelboim's method. In particular, we have succeeded in deriving the generalized Smarr formula among thermodynamical quantities in a simple and natural way. We then show that cosmological constant must decrease when one takes into account the quantum effect. These observations have been obtained if and only if the cosmological constant plays the role of a thermodynamical state variable. We also touch upon the relation between inflation of our universe and a phase transition of black holes
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
The Donnan equilibrium: I. On the thermodynamic foundation of the Donnan equation of state
International Nuclear Information System (INIS)
Philipse, A; Vrij, A
2011-01-01
The thermodynamic equilibrium between charged colloids and an electrolyte reservoir is named after Frederic Donnan who first published on it one century ago (Donnan 1911 Z. Electrochem. 17 572). One of the intriguing features of the Donnan equilibrium is the ensuing osmotic equation of state which is a nonlinear one, even when both colloids and ions obey Van 't Hoff's ideal osmotic pressure law. The Donnan equation of state, nevertheless, is internally consistent; we demonstrate it to be a rigorous consequence of the phenomenological thermodynamics of a neutral bulk suspension equilibrating with an infinite salt reservoir. Our proof is based on an exact thermodynamic relation between osmotic pressure and salt adsorption which, when applied to ideal ions, does indeed entail the Donnan equation of state. Our derivation also shows that, contrary to what is often assumed, the Donnan equilibrium does not require ideality of the colloids: the Donnan model merely evaluates the osmotic pressure of homogeneously distributed ions, in excess of the pressure exerted by an arbitrary reference fluid of uncharged colloids. We also conclude that results from the phenomenological Donnan model coincide with predictions from statistical thermodynamics in the limit of weakly charged, point-like colloids.
Thermodynamics of adaptive molecular resolution.
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).
1976-01-01
The entropy of a gas system with the number of particles subject to external control is maximized to derive relations between the thermodynamic variables that obtain at equilibrium. These relations are described in terms of the chemical potential, defined as equivalent partial derivatives of entropy, energy, enthalpy, free energy, or free enthalpy. At equilibrium, the change in total chemical potential must vanish. This fact is used to derive the equilibrium constants for chemical reactions in terms of the partition functions of the species involved in the reaction. Thus the equilibrium constants can be determined accurately, just as other thermodynamic properties, from a knowledge of the energy levels and degeneracies for the gas species involved. These equilibrium constants permit one to calculate the equilibrium concentrations or partial pressures of chemically reacting species that occur in gas mixtures at any given condition of pressure and temperature or volume and temperature.
Twenty lectures on thermodynamics
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
Thermodynamically constrained correction to ab initio equations of state
International Nuclear Information System (INIS)
French, Martin; Mattsson, Thomas R.
2014-01-01
We show how equations of state generated by density functional theory methods can be augmented to match experimental data without distorting the correct behavior in the high- and low-density limits. The technique is thermodynamically consistent and relies on knowledge of the density and bulk modulus at a reference state and an estimation of the critical density of the liquid phase. We apply the method to four materials representing different classes of solids: carbon, molybdenum, lithium, and lithium fluoride. It is demonstrated that the corrected equations of state for both the liquid and solid phases show a significantly reduced dependence of the exchange-correlation functional used.
International Nuclear Information System (INIS)
Soldatova, Je.D.; Snegyir'ov, M.G.
2001-01-01
The thermodynamical method for studing a critical state is illustrated by the example of critical behavior of metallic cerium in the frameworks of the improved Rainford-Edwards model. Thermodynamical stability of the model is investigated, and behavior of the whole complex of thermodynamical characteristics of the system is analyzed. It is concluded that the model has the first type of critical behaviour
Fahrenbach, Albert C; Bruns, Carson J; Cao, Dennis; Stoddart, J Fraser
2012-09-18
Fashioned through billions of years of evolution, biological molecular machines, such as ATP synthase, myosin, and kinesin, use the intricate relative motions of their components to drive some of life's most essential processes. Having control over the motions in molecules is imperative for life to function, and many chemists have designed, synthesized, and investigated artificial molecular systems that also express controllable motions within molecules. Using bistable mechanically interlocked molecules (MIMs), based on donor-acceptor recognition motifs, we have sought to imitate the sophisticated nanoscale machines present in living systems. In this Account, we analyze the thermodynamic characteristics of a series of redox-switchable [2]rotaxanes and [2]catenanes. Control and understanding of the relative intramolecular movements of components in MIMs have been vital in the development of a variety of applications of these compounds ranging from molecular electronic devices to drug delivery systems. These bistable donor-acceptor MIMs undergo redox-activated switching between two isomeric states. Under ambient conditions, the dominant translational isomer, the ground-state coconformation (GSCC), is in equilibrium with the less favored translational isomer, the metastable-state coconformation (MSCC). By manipulating the redox state of the recognition site associated with the GSCC, we can stimulate the relative movements of the components in these bistable MIMs. The thermodynamic parameters of model host-guest complexes provide a good starting point to rationalize the ratio of GSCC to MSCC at equilibrium. The bistable [2]rotaxanes show a strong correlation between the relative free energies of model complexes and the ground-state distribution constants (K(GS)). This relationship does not always hold for bistable [2]catenanes, most likely because of the additional steric and electronic constraints present when the two rings are mechanically interlocked with each other
Thermodynamic and kinetic properties of amorphous and liquid states
International Nuclear Information System (INIS)
Granato, A.V.
1998-01-01
The magnitude and temperature dependence of the liquid state shear modulus G, specific heat C p , diffusivity D, and viscosity η should all be closely related, according to the interstitialcy model, if a recent proposal by Dyre et al. is generally true. They suppose that the viscosity is given by η = η 0 exp (F/kT), where η 0 is a reference viscosity and F is given by the work required to shove aside neighboring particle in a diffusion process, where F = GV c and V c is a characteristic volume. In the interstitialcy model the high frequency thermodynamic liquid state shear modulus is given by G(T) = G 0 exp [-γ(T/T 0 - 1)], where G 0 is the shear modulus at a reference temperature T 0 , which can be taken as the glass temperature. The resulting non-Arrhenius behavior of the viscosity is compared with experimental data. A critical quantitative analysis for a Zr 41.2 Ti 13.8 Cu 12.5 Ni 10 Be 225 alloy does not support the shoving model, but the thermodynamic properties can be understood in terms of mixed interstitials composed of metal-beryllium complexes
Thermodynamic functions of element 105 in neutral and ionized states
International Nuclear Information System (INIS)
Pershina, V.; Fricke, B.; Ionova, G.V.; Johnson, E.
1994-01-01
The basic thermodynamic functions, the entropy, free energy, and enthalpy, for element 105 (hahnium) in electronic configurations d 3 s 2 , d 3 sp, and d 4 s 1 and for its + 5 ionized state (5f 14 ) have been calculated as a function of temperature. The data are based on the results of the calculations of the corresponding electronic states of element 105 using the multiconfiguration Dirac-Fock method. 19 refs., 1 fig., 11 tabs
Irreversible Thermodynamics of the Universe: Constraints from Planck Data
International Nuclear Information System (INIS)
Saha, Subhajit; Chakraborty, Subenoy; Biswas, Atreyee
2014-01-01
The present work deals with irreversible universal thermodynamics. The homogenous and isotropic flat model of the universe is chosen as open thermodynamical system and nonequilibrium thermodynamics comes into picture. For simplicity, entropy flow is considered only due to heat conduction. Further, due to Maxwell-Cattaneo modified Fourier law for nonequilibrium phenomenon, the temperature satisfies damped wave equation instead of heat conduction equation. Validity of generalized second law of thermodynamics (GSLT) has been investigated for universe bounded by apparent or event horizon with cosmic substratum as perfect fluid with constant or variable equation of state or interacting dark species. Finally, we have used three Planck data sets to constrain the thermal conductivity λ and the coupling parameter b 2 . These constraints must be satisfied in order for GSLT to hold for universe bounded by apparent or event horizons
Thermodynamic ocean-atmosphere Coupling and the Predictability of Nordeste rainfall
Chang, P.; Saravanan, R.; Giannini, A.
2003-04-01
The interannual variability of rainfall in the northeastern region of Brazil, or Nordeste, is known to be very strongly correlated with sea surface temperature (SST) variability, of Atlantic and Pacific origin. For this reason the potential predictability of Nordeste rainfall is high. The current generation of state-of-the-art atmospheric models can replicate the observed rainfall variability with high skill when forced with the observed record of SST variability. The correlation between observed and modeled indices of Nordeste rainfall, in the AMIP-style integrations with two such models (NSIPP and CCM3) analyzed here, is of the order of 0.8, i.e. the models explain about 2/3 of the observed variability. Assuming that thermodynamic, ocean-atmosphere heat exchange plays the dominant role in tropical Atlantic SST variability on the seasonal to interannual time scale, we analyze its role in Nordeste rainfall predictability using an atmospheric general circulation model coupled to a slab ocean model. Predictability experiments initialized with observed December SST show that thermodynamic coupling plays a significant role in enhancing the persistence of SST anomalies, both in the tropical Pacific and in the tropical Atlantic. We show that thermodynamic coupling is sufficient to provide fairly accurate forecasts of tropical Atlantic SST in the boreal spring that are significantly better than the persistence forecasts. The consequences for the prediction of Nordeste rainfall are analyzed.
Energy Technology Data Exchange (ETDEWEB)
Martinez Reyes, Jose; Gonzalez Partida, Eduardo; Jorge, A [Centro de Geociencias, Universidad National Autonoma de Mexico Campo de Juriquilla, Qro., Mexico, apartado postal 76230 (Mexico); Perez, Renee J [Department of Chemical and Petroleum Engineering, University of Calgary, 500 University Drive, Calgary Alberta, T2N 1N4 (Canada); Tinoco, Michel
2008-10-01
Based on information of enthalpies of the fluids of wells from the geothermal reservoir of Los Humeros, Puebla, Mexico, we determined the thermodynamic conditions of the reservoir comparing the values of enthalpies of the fluids of discharge of the wells with the values published in the literature for different thermodynamic state of fluids.
Thermodynamics of an Attractive 2D Fermi Gas
Fenech, K.; Dyke, P.; Peppler, T.; Lingham, M. G.; Hoinka, S.; Hu, H.; Vale, C. J.
2016-01-01
Thermodynamic properties of matter are conveniently expressed as functional relations between variables known as equations of state. Here we experimentally determine the compressibility, density, and pressure equations of state for an attractive 2D Fermi gas in the normal phase as a function of temperature and interaction strength. In 2D, interacting gases exhibit qualitatively different features to those found in 3D. This is evident in the normalized density equation of state, which peaks at intermediate densities corresponding to the crossover from classical to quantum behavior.
International Nuclear Information System (INIS)
Gilles, D.
2005-01-01
This report is devoted to illustrate the power of a Monte Carlo (MC) simulation code to study the thermodynamical properties of a plasma, composed of classical point particles at thermodynamical equilibrium. Such simulations can help us to manage successfully the challenge of taking into account 'exactly' all classical correlations between particles due to density effects, unlike analytical or semi-analytical approaches, often restricted to low dense plasmas. MC simulations results allow to cover, for laser or astrophysical applications, a wide range of thermodynamical conditions from more dense (and correlated) to less dense ones (where potentials are long ranged type). Therefore Yukawa potentials, with a Thomas-Fermi temperature- and density-dependent screening length, are used to describe the effective ion-ion potentials. In this report we present two MC codes ('PDE' and 'PUCE') and applications performed with these codes in different fields (spectroscopy, opacity, equation of state). Some examples of them are discussed and illustrated at the end of the report. (author)
Chlorine international thermodynamic tables of the fluid state
Angus, S; de Reuck, K M
1985-01-01
Chlorine: International Thermodynamic Tables of the Fluid State-8 is a four-chapter book that covers available and estimated data on chlorine; estimation of the element's properties; the correlating equations for the element; and how the tabulated properties are calculated from chosen equation. The tables in this book give the volume, entropy, enthalpy, isobaric heat capacity, compression factor, fugacity/pressure ratio, Joule-Thomson coefficient, ratio of the heat capacities, and speed of sound as a function of pressure and temperature. Given in the tables as well are the pressure, entropy, i
International Nuclear Information System (INIS)
Li, Guijiang; Eriksson, Olle; Johansson, Börje; Vitos, Levente
2015-01-01
We have found that thermodynamic state and kinetic process co-determine the dual ferromagnetic (FM) orders in high-Si content FeMnP 1−x Si x (0.25 < x < 0.5). Alloys undergoing high temperature annealing and quenching process prefer a high magnetic moment FM state in a chemically partial disordered structure with low c/a ratio. This mechanism is suggested to be responsible for the often discussed virgin effect as well. A chemically ordered structure obtained by a slow cooling process from a relatively low annealing temperature and the increase in Si content stabilize a metastable lattice with high c/a ratio and FM order with low magnetic moment. The non-simultaneity of the magnetic and structural transitions can be responsible for the occurrence of FM state in the high c/a range. Thus, a c/a ratio that changes from high to low is physically plausible to stabilize the metastable FM order at low temperature. Our theoretical observations indicate that suitable thermodynamic state and kinetic diffusion process is crucial for optimizing magnetocaloric properties and exploring feasible magnetocaloric materials
Variable-speed-of-light cosmology and second law of thermodynamics
International Nuclear Information System (INIS)
Youm, Donam
2002-01-01
We examine whether cosmologies with a varying speed of light (VSL) are compatible with the second law of thermodynamics. We find that the VSL cosmology with a varying fundamental constant is severely constrained by the second law of thermodynamics, whereas the bimetric cosmological models are less constrained
Variable-speed-of-light cosmology and second law of thermodynamics
International Nuclear Information System (INIS)
Youm, Donam
2002-03-01
We examine whether the cosmologies with varying speed of light (VSL) are compatible with the second law of thermodynamics. We find that the VSL cosmology with varying fundamental constant is severely constrained by the second law of thermodynamics, whereas the bimetric cosmological models are less constrained. (author)
Nonequilibrium thermodynamic potentials for continuous-time Markov chains.
Verley, Gatien
2016-01-01
We connect the rare fluctuations of an equilibrium (EQ) process and the typical fluctuations of a nonequilibrium (NE) stationary process. In the framework of large deviation theory, this observation allows us to introduce NE thermodynamic potentials. For continuous-time Markov chains, we identify the relevant pairs of conjugated variables and propose two NE ensembles: one with fixed dynamics and fluctuating time-averaged variables, and another with fixed time-averaged variables, but a fluctuating dynamics. Accordingly, we show that NE processes are equivalent to conditioned EQ processes ensuring that NE potentials are Legendre dual. We find a variational principle satisfied by the NE potentials that reach their maximum in the NE stationary state and whose first derivatives produce the NE equations of state and second derivatives produce the NE Maxwell relations generalizing the Onsager reciprocity relations.
Nonequilibrium thermodynamics of the Kovacs effect
Bouchbinder, Eran; Langer, J. S.
We present a thermodynamic theory of the Kovacs effect based on the idea that the configurational degrees of freedom of a glass-forming material are driven out of equilibrium with the heat bath by irreversible thermal contraction and expansion. We assume that the slowly varying configurational subsystem, i.e. the part of the system that is described by inherent structures, is characterized by an effective temperature, and contains a volume-related internal variable. We examine mechanisms by which irreversible dynamics of the fast, kinetic-vibrational degrees of freedom can cause the entropy and the effective temperature of the configurational subsystem to increase during sufficiently rapid changes in the bath temperature. We then use this theory to interpret the numerical simulations by Mossa and Sciortino (MS), who observe the Kovacs effect in more detail than is feasible in laboratory experiments. Our analysis highlights two mechanisms for the equilibration of internal variables. In one of these, an internal variable first relaxes toward a state of quasi-equilibrium determined by the effective temperature, and then approaches true thermodynamic equilibrium as the effective temperature slowly relaxes toward the bath temperature. In the other mechanism, an internal variable directly equilibrates with the bath temperature on intermediate timescales, without equilibrating with the effective temperature at any stage. Both mechanisms appear to be essential for understanding the MS results.
Energy Technology Data Exchange (ETDEWEB)
Baudisch, H.
1968-03-15
The tables presented in this report contain the thermodynamic values of isentropic change of state for water in the two-phase region starting from the saturation line down to 0.01 at. The variables have been computed in the pressure range from 5-100 at. in equal pressure intervals of 5 at. and in the range from 100-170 at. in intervals of 10 at. Assuming a one-dimensional flow and a known saturation pressure, the dimensions of a discharge nozzle may be determined by interpolation of the calculated values for an isentropic discharge. 4 figs., 29 tabs., 23 refs.
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.
Predicting structural properties of fluids by thermodynamic extrapolation
Mahynski, Nathan A.; Jiao, Sally; Hatch, Harold W.; Blanco, Marco A.; Shen, Vincent K.
2018-05-01
We describe a methodology for extrapolating the structural properties of multicomponent fluids from one thermodynamic state to another. These properties generally include features of a system that may be computed from an individual configuration such as radial distribution functions, cluster size distributions, or a polymer's radius of gyration. This approach is based on the principle of using fluctuations in a system's extensive thermodynamic variables, such as energy, to construct an appropriate Taylor series expansion for these structural properties in terms of intensive conjugate variables, such as temperature. Thus, one may extrapolate these properties from one state to another when the series is truncated to some finite order. We demonstrate this extrapolation for simple and coarse-grained fluids in both the canonical and grand canonical ensembles, in terms of both temperatures and the chemical potentials of different components. The results show that this method is able to reasonably approximate structural properties of such fluids over a broad range of conditions. Consequently, this methodology may be employed to increase the computational efficiency of molecular simulations used to measure the structural properties of certain fluid systems, especially those used in high-throughput or data-driven investigations.
Mathematical foundations of thermodynamics
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
Ab initio molecular dynamics simulation of hydrogen fluoride at several thermodynamic states
DEFF Research Database (Denmark)
Kreitmeir, M.; Bertagnolli, H.; Mortensen, Jens Jørgen
2003-01-01
Liquid hydrogen fluoride is a simple but interesting system for studies of the influence of hydrogen bonds on physical properties. We have performed ab initio molecular dynamics simulations of HF at several thermodynamic states, where we examine the microscopic structure of the liquid as well...
Braun-Le Chatelier principle in dissipative thermodynamics
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.
Thermodynamics and equations of state of matter from ideal gas to quark-gluon plasma
Fortov, Vladimir E
2016-01-01
The monograph presents a comparative analysis of different thermodynamic models of the equations of state. The basic ideological premises of the theoretical methods and the experiment are considered. The principal attention is on the description of states that are of greatest interest for the physics of high energy concentrations which are either already attained or can be reached in the near future in controlled terrestrial conditions, or are realized in astrophysical objects at different stages of their evolution. Ultra-extreme astrophysical and nuclear-physical applications are also analyzed where the thermodynamics of matter is affected substantially by relativism, high-power gravitational and magnetic fields, thermal radiation, transformation of nuclear particles, nucleon neutronization, and quark deconfinement. The book is intended for a wide range of specialists engaged in the study of the equations of state of matter and high energy density physics, as well as for senior students and postgraduates.
Nieuwenhuizen, T.M.
2001-01-01
Glass is an under-cooled liquid that very slowly relaxes towards the equilibrium crystalline state. Its energy balance is ill understood, since it is widely believed that the glassy state cannot be described thermodynamically. However, the classical paradoxes involving the Ehrenfest relations and
The vitreous state thermodynamics, structure, rheology, and crystallization
Gutzow, Ivan S
2013-01-01
This book summarizes the experimental evidence and modern classical and theoretical approaches in understanding the vitreous state, from structural problems, over equilibrium and non-equilibrium thermodynamics, to statistical physics. Glasses, and especially silicate glasses, are only the best known representatives of this particular physical state of matter. Other typical representatives include organic polymer glasses, and many other easily vitrifying organic and inorganic substances, technically important materials, amidst them vitreous water and vitrified aqueous solutions, and also many metallic alloy systems. Some of these systems only form glasses under particular conditions, e.g. through ultra-rapid cooling. This book describes the properties and the formation of both every-day technical glasses and especially of such more exotic forms of vitreous matter. It is a unique source of knowledge and new ideas for materials scientists, engineers and researchers working on condensed matter. The new edition e...
Investigation of the thermodynamics governing metal hydride synthesis in the molten state process
International Nuclear Information System (INIS)
Stowe, Ashley C.; Berseth, Polly A.; Farrell, Thomas P.; Laughlin, Laura; Anton, Donald; Zidan, Ragaiy
2008-01-01
This work is aimed at utilizing a new synthetic technique to form novel complex hydrides for hydrogen storage. This technique is based on fusing different complex hydrides at elevated temperatures and pressures to form new species with improved hydrogen storage properties. Under conditions of elevated hydrogen overpressures and temperatures the starting materials can reach melting or near-melting point without decomposing (molten state processing), allowing for enhanced diffusion and exchange of elements among the starting materials. The formation and stabilization of these compounds, using the molten state process, is driven by the thermodynamic and kinetic properties of the starting and resulting compounds. Complex hydrides (e.g. NaK 2 AlH 6 , Mg(AlH 4 ) 2 ) were formed, structurally characterized and their hydrogen desorption properties were tested. In this paper we report on investigations of the thermodynamic aspects governing the process and products. We also report on the role of molar ratio in determining the final products. The effectiveness of the molten state process is compared with chemomechanical synthetic methods (ball milling)
A thermodynamic approach to nonlinear ultrasonics for material state awareness and prognosis
Chillara, Vamshi Krishna
2017-11-01
We develop a thermodynamic framework for modeling nonlinear ultrasonic damage sensing and prognosis in materials undergoing progressive damage. The framework is based on the internal variable approach and relies on the construction of a pseudo-elastic strain energy function that captures the energetics associated with the damage progression. The pseudo-elastic strain energy function is composed of two energy functions—one that describes how a material stores energy in an elastic fashion and the other describes how material dissipates energy or stores it in an inelastic fashion. Experimental motivation for the choice of the above two functionals is discussed and some specific choices pertaining to damage progression during fatigue and creep are presented. The thermodynamic framework is employed to model the nonlinear response of material undergoing stress relaxation and creep-like degradation. For each of the above cases, evolution of the nonlinearity parameter with damage as well as with macroscopic measurables like accumulated plastic strain is obtained.
Li, Huaming; Tian, Yanting; Sun, Yongli; Li, Mo; Nonequilibrium materials; physics Team; Computational materials science Team
In this work, we apply a general equation of state of liquid and Ab initio molecular-dynamics method to study thermodynamic properties in liquid potassium under high pressure. Isothermal bulk modulus and molar volume of molten sodium are calculated within good precision as compared with the experimental data. The calculated internal energy data and the calculated values of isobaric heat capacity of molten potassium show the minimum along the isothermal lines as the previous result obtained in liquid sodium. The expressions for acoustical parameter and nonlinearity parameter are obtained based on thermodynamic relations from the equation of state. Both parameters for liquid potassium are calculated under high pressure along the isothermal lines by using the available thermodynamic data and numeric derivations. Furthermore, Ab initio molecular-dynamics simulations are used to calculate some thermodynamic properties of liquid potassium along the isothermal lines. Scientific Research Starting Foundation from Taiyuan university of Technology, Shanxi Provincial government (``100-talents program''), China Scholarship Council and National Natural Science Foundation of China (NSFC) under Grant No. 51602213.
Electrochemical thermodynamic measurement system
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 and dynamics of the hard-sphere system: From stable to metastable states
Energy Technology Data Exchange (ETDEWEB)
Bomont, Jean-Marc, E-mail: jean-marc.bomont@univ-lorraine.fr; Bretonnet, Jean-Louis
2014-08-17
Highlights: • Three different scaling laws, devoted to transport properties of hard-sphere system, are investigated over a wide range of packing fractions. • A new semiempirical relation linking the transport properties to the excess pressure is derived. • The present relation allows to better understand the link between the thermodynamic and the dynamic properties of the hard-sphere system. - Abstract: A set of three different scaling laws is investigated, which are devoted to link the transport properties, i.e. diffusion coefficient, shear viscosity, bulk viscosity and thermal conductivity, to the thermodynamic properties for the athermal hard-sphere system, over the wider range of packing fraction covering the stable and metastable regimes. Except for the thermal conductivity, the Rosenfeld (1999) [15] relation is found to be applicable to the stable states while the Adam and Gibbs (1965) [24] relation holds well for the metastable states. In contrast, the modified Cohen and Turnbull (1959) [25] relation proposed here gives sound support for a universal scaling law connecting the dynamic and thermodynamic properties, over the domain of packing fraction including the stable and metastable states. In particular, it is found that the most relevant control parameter is not the excess entropy, but the logarithm derivative of the excess entropy with respect to the packing fraction. In the same context, the Stokes–Einstein relation between the diffusion coefficient and the shear viscosity is also examined. The possible violation of the Stokes–Einstein relation is investigated over a large domain of packing fractions.
Thermodynamics and dynamics of the hard-sphere system: From stable to metastable states
International Nuclear Information System (INIS)
Bomont, Jean-Marc; Bretonnet, Jean-Louis
2014-01-01
Highlights: • Three different scaling laws, devoted to transport properties of hard-sphere system, are investigated over a wide range of packing fractions. • A new semiempirical relation linking the transport properties to the excess pressure is derived. • The present relation allows to better understand the link between the thermodynamic and the dynamic properties of the hard-sphere system. - Abstract: A set of three different scaling laws is investigated, which are devoted to link the transport properties, i.e. diffusion coefficient, shear viscosity, bulk viscosity and thermal conductivity, to the thermodynamic properties for the athermal hard-sphere system, over the wider range of packing fraction covering the stable and metastable regimes. Except for the thermal conductivity, the Rosenfeld (1999) [15] relation is found to be applicable to the stable states while the Adam and Gibbs (1965) [24] relation holds well for the metastable states. In contrast, the modified Cohen and Turnbull (1959) [25] relation proposed here gives sound support for a universal scaling law connecting the dynamic and thermodynamic properties, over the domain of packing fraction including the stable and metastable states. In particular, it is found that the most relevant control parameter is not the excess entropy, but the logarithm derivative of the excess entropy with respect to the packing fraction. In the same context, the Stokes–Einstein relation between the diffusion coefficient and the shear viscosity is also examined. The possible violation of the Stokes–Einstein relation is investigated over a large domain of packing fractions
Thermodynamics of manganese oxides: Sodium, potassium, and calcium birnessite and cryptomelane
Birkner, Nancy; Navrotsky, Alexandra
2017-01-01
Manganese oxides with layer and tunnel structures occur widely in nature and inspire technological applications. Having variable compositions, these structures often are found as small particles (nanophases). This study explores, using experimental thermochemistry, the role of composition, oxidation state, structure, and surface energy in the their thermodynamic stability. The measured surface energies of cryptomelane, sodium birnessite, potassium birnessite and calcium birnessite are all significantly lower than those of binary manganese oxides (Mn3O4, Mn2O3, and MnO2), consistent with added stabilization of the layer and tunnel structures at the nanoscale. Surface energies generally decrease with decreasing average manganese oxidation state. A stabilizing enthalpy contribution arises from increasing counter-cation content. The formation of cryptomelane from birnessite in contact with aqueous solution is favored by the removal of ions from the layered phase. At large surface area, surface-energy differences make cryptomelane formation thermodynamically less favorable than birnessite formation. In contrast, at small to moderate surface areas, bulk thermodynamics and the energetics of the aqueous phase drive cryptomelane formation from birnessite, perhaps aided by oxidation-state differences. Transformation among birnessite phases of increasing surface area favors compositions with lower surface energy. These quantitative thermodynamic findings explain and support qualitative observations of phase-transformation patterns gathered from natural and synthetic manganese oxides. PMID:28130549
Ma, Y.M.; Menenti, M.; Feddes, R.A.; Wang, J.M.
2008-01-01
The land surface heterogeneity has a very significant impact on atmospheric variables (air temperature T-a, wind speed u, and humidity q), the aerodynamic roughness length z(0m), thermodynamic roughness length z(0h), and the excess resistance to heat transfer kB(-1). First, in this study the land
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
Approximate thermodynamic state relations in partially ionized gas mixtures
International Nuclear Information System (INIS)
Ramshaw, John D.
2004-01-01
Thermodynamic state relations for mixtures of partially ionized nonideal gases are often approximated by artificially partitioning the mixture into compartments or subvolumes occupied by the pure partially ionized constituent gases, and requiring these subvolumes to be in temperature and pressure equilibrium. This intuitively reasonable procedure is easily shown to reproduce the correct thermal and caloric state equations for a mixture of neutral (nonionized) ideal gases. The purpose of this paper is to point out that (a) this procedure leads to incorrect state equations for a mixture of partially ionized ideal gases, whereas (b) the alternative procedure of requiring that the subvolumes all have the same temperature and free electron density reproduces the correct thermal and caloric state equations for such a mixture. These results readily generalize to the case of partially degenerate and/or relativistic electrons, to a common approximation used to represent pressure ionization effects, and to two-temperature plasmas. This suggests that equating the subvolume electron number densities or chemical potentials instead of pressures is likely to provide a more accurate approximation in nonideal plasma mixtures
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.
About the role of constraints in the linear relaxational behaviour of thermodynamic systems
Jongschaap, R.J.J.
1978-01-01
A formalism is presented by which the linear relaxational behaviour of thermodynamic systems can be described. Instead of using the concept of internal variables of state a set of so-called constraint equations is introduced. These equations represent structural properties of the system and turn out
Some problems on the thermodynamic state of the metallogenetic systems
International Nuclear Information System (INIS)
Mingarro, E.
1965-01-01
In order to get a classification of the uranium deposits, the geological processes have been ordered in thermodynamic systems according to the independent parameters that define their equilibrium state. Also, to apply the phase rule, we suppose that the ore forming elements are always ideally mobile components; that is, in the geological systems, these components are defined by their chemical potentials. In this paper, we show that in random conditions, i. e.; for any possible value of the factors of equilibrium or state the stable mineralizations are formed only in metasomatic regimes; so that the mineralogical sequence is a function both of the Helmholtz's free energy and the crystallisation pressure of the minerals. (Author) 7 refs
Thermodynamical properties of dark energy with the equation of state ω=ω0+ω1z
International Nuclear Information System (INIS)
Zhang Yongping; Yi Zelong; Zhang Tongjie; Liu Wenbiao
2008-01-01
The thermodynamical properties of dark energy are usually investigated with the equation of state ω=ω 0 +ω 1 z. Recent observations show that our Universe is accelerating, and the apparent horizon and the event horizon vary with redshift z. Because definitions of the temperature and entropy of a black hole are used to describe the two horizons of the Universe, we examine the thermodynamical properties of the Universe, which is enveloped by the apparent horizon and the event horizon, respectively. We show that the first and the second laws of thermodynamics inside the apparent horizon in any redshift are satisfied, while they are broken down inside the event horizon in some redshifts. Therefore, the apparent horizon for the Universe may be the boundary of thermodynamical equilibrium for the Universe like the event horizon for a black hole
International Nuclear Information System (INIS)
Karow, H.U.
1977-02-01
The properties have been determined by means of statistical mechanics. The discussion of the thermodynamic state includes the evaluation of the plasma state and its contribution to the caloric variables-of-state of saturated oxide fuel vapor. Because of the extremely high ion and electron density due to thermal ionization, the ionized component of the fuel vapor does no more represent a perfect kinetic plasma. At temperatures around 5,000 K, UO 2 vapor reaches the collective plasma state and becomes increasingly 'metallic'. - Moreover, the nonuniform molecular equilibrium composition of UO 2 vapor has been taken into account in calculating its caloric functions-of-state. The contribution to specific heat and enthalpy of thermally excited electronic states of the vapor molecules has been derived by means of a Rydberg orbital model of the UO 2 molecule. The resulting enthalpy functions and specific heats for saturated UO 2 vapor of equilibrium composition and that for pure UO 2 gas are compared with the enthalpy and specific heat data of gaseous UO 2 at lower temperatures known from literature. (orig./HP) [de
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...
Latella, Ivan; Pérez-Madrid, Agustín
2013-10-01
The local thermodynamics of a system with long-range interactions in d dimensions is studied using the mean-field approximation. Long-range interactions are introduced through pair interaction potentials that decay as a power law in the interparticle distance. We compute the local entropy, Helmholtz free energy, and grand potential per particle in the microcanonical, canonical, and grand canonical ensembles, respectively. From the local entropy per particle we obtain the local equation of state of the system by using the condition of local thermodynamic equilibrium. This local equation of state has the form of the ideal gas equation of state, but with the density depending on the potential characterizing long-range interactions. By volume integration of the relation between the different thermodynamic potentials at the local level, we find the corresponding equation satisfied by the potentials at the global level. It is shown that the potential energy enters as a thermodynamic variable that modifies the global thermodynamic potentials. As a result, we find a generalized Gibbs-Duhem equation that relates the potential energy to the temperature, pressure, and chemical potential. For the marginal case where the power of the decaying interaction potential is equal to the dimension of the space, the usual Gibbs-Duhem equation is recovered. As examples of the application of this equation, we consider spatially uniform interaction potentials and the self-gravitating gas. We also point out a close relationship with the thermodynamics of small systems.
Thermodynamics of Bioreactions.
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.
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.
Thermodynamic properties and equation of state of zircon ZrSiO4
International Nuclear Information System (INIS)
Mittal, R.; Chaplot, S.L.; Choudhury, N.
1998-01-01
The silicate mineral zircon is a host material for radioactive materials in the earth's crust and is a natural candidate for usage as a nuclear waste storage material. Lattice dynamical calculations have been carried out to understand its thermodynamic properties and high pressure behavior. The calculated phonon density of states, variation of phonon frequencies with pressure and equation of state are in good agreement with the available experimental data. One of the zone center optic mode involving SiO 4 rotations becomes soft at 47 GPa
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
Thermodynamics of small systems two volumes bound as one
Hill, Terrel L
1994-01-01
This authoritative summary of the basics of small system, or nonmacroscopic, thermodynamics was written by the field's founder. Originally published in two volumes, the text remains essential reading in an area in which the practical aim is to derive equations that provide interconnections among various thermodynamic functions. Part I introduces the basics of small system thermodynamics, exploring environmental variables, noting throughout the ways in which small thermodynamic systems differ operationally from macroscopic systems. Part II explores binding on macromolecules and aggregation, completes the discussion of environmental variables, and includes brief summaries of certain special topics, including electric and magnetic fields, spherical drops and bubbles, and polydisperse systems.
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
McCarty, J; Clark, A J; Copperman, J; Guenza, M G
2014-05-28
Structural and thermodynamic consistency of coarse-graining models across multiple length scales is essential for the predictive role of multi-scale modeling and molecular dynamic simulations that use mesoscale descriptions. Our approach is a coarse-grained model based on integral equation theory, which can represent polymer chains at variable levels of chemical details. The model is analytical and depends on molecular and thermodynamic parameters of the system under study, as well as on the direct correlation function in the k → 0 limit, c0. A numerical solution to the PRISM integral equations is used to determine c0, by adjusting the value of the effective hard sphere diameter, dHS, to agree with the predicted equation of state. This single quantity parameterizes the coarse-grained potential, which is used to perform mesoscale simulations that are directly compared with atomistic-level simulations of the same system. We test our coarse-graining formalism by comparing structural correlations, isothermal compressibility, equation of state, Helmholtz and Gibbs free energies, and potential energy and entropy using both united atom and coarse-grained descriptions. We find quantitative agreement between the analytical formalism for the thermodynamic properties, and the results of Molecular Dynamics simulations, independent of the chosen level of representation. In the mesoscale description, the potential energy of the soft-particle interaction becomes a free energy in the coarse-grained coordinates which preserves the excess free energy from an ideal gas across all levels of description. The structural consistency between the united-atom and mesoscale descriptions means the relative entropy between descriptions has been minimized without any variational optimization parameters. The approach is general and applicable to any polymeric system in different thermodynamic conditions.
Martino, Piera Di; Magnoni, Federico; Peregrina, Dolores Vargas; Gigliobianco, Maria Rosa; Censi, Roberta; Malaj, Ledjan
2016-01-01
Drugs and excipients used for pharmaceutical applications generally exist in the solid (crystalline or amorphous) state, more rarely as liquid materials. In some cases, according to the physicochemical nature of the molecule, or as a consequence of specific technological processes, a compound may exist exclusively in the amorphous state. In other cases, as a consequence of specific treatments (freezing and spray drying, melting and co-melting, grinding and compression), the crystalline form may convert into a completely or partially amorphous form. An amorphous material shows physical and thermodynamic properties different from the corresponding crystalline form, with profound repercussions on its technological performance and biopharmaceutical properties. Several physicochemical techniques such as X-ray powder diffraction, thermal methods of analysis, spectroscopic techniques, gravimetric techniques, and inverse gas chromatography can be applied to characterize the amorphous form of a compound (drug or excipient), and to evaluate its thermodynamic stability. This review offers a survey of the technologies used to convert a crystalline solid into an amorphous form, and describes the most important techniques for characterizing the amorphous state of compounds of pharmaceutical interest.
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
Quantum thermodynamics of general quantum processes.
Binder, Felix; Vinjanampathy, Sai; Modi, Kavan; Goold, John
2015-03-01
Accurately describing work extraction from a quantum system is a central objective for the extension of thermodynamics to individual quantum systems. The concepts of work and heat are surprisingly subtle when generalizations are made to arbitrary quantum states. We formulate an operational thermodynamics suitable for application to an open quantum system undergoing quantum evolution under a general quantum process by which we mean a completely positive and trace-preserving map. We derive an operational first law of thermodynamics for such processes and show consistency with the second law. We show that heat, from the first law, is positive when the input state of the map majorizes the output state. Moreover, the change in entropy is also positive for the same majorization condition. This makes a strong connection between the two operational laws of thermodynamics.
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)
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
Thermodynamic treatment of nonphysical systems: formalism and an example (single-lane traffic)
International Nuclear Information System (INIS)
Reiss, H.; Hammerich, A.D.; Montroll, E.W.
1986-01-01
An effort is made to introduce thermodynamic and statistical thermodynamic methods into the treatment of nonphysical (e.g., social, economic, etc.) systems. Emphasis is placed on the use of the entire thermodynamic framework, not merely entropy. Entropy arises naturally, related in a simple manner to other measurables, but does not occupy a primary position in the theory. However, the maximum entropy formalism is a convenient procedure for deriving the thermodynamic analog framework in which undetermined multipliers are thermodynamic-like variables which summarize the collective behavior of the system. The authors discuss the analysis of Levine and his coworkers showing that the maximum entropy formalism is the unique algorithm for achieving consistent inference of probabilities. The thermodynamic-like formalism for treating a single lane of vehicular traffic is developed and applied to traffic in which the interaction between cars is chosen to be a particular form of the ''follow-the-leader'' type. The equation of state of the traffic, the distributions of velocity and headway, and the various thermodynamic-like parameters, e.g., temperature (collective sensitivity), pressure, etc. are determined for the example of the Holland Tunnel. Nearest-neighbor and pair correlation functions for the vehicles are also determined. Interesting and suggestive results are obtained
Thermodynamic analysis of biochemical systems
International Nuclear Information System (INIS)
Yuan, Y.; Fan, L.T.; Shieh, J.H.
1989-01-01
Introduction of the concepts of the availability (or exergy), datum level materials, and the dead state has been regarded as some of the most significant recent developments in classical thermodynamics. Not only the available energy balance but also the material and energy balances of a biological system may be established in reference to the datum level materials in the dead state or environment. In this paper these concepts are illustrated with two examples of fermentation and are shown to be useful in identifying sources of thermodynamic inefficiency, thereby leading naturally to the rational definition of thermodynamic efficiency of a biochemical process
Applied chemical engineering thermodynamics
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.
Statistical thermodynamics of supercapacitors and blue engines
van Roij, R.H.H.G.
2013-01-01
We study the thermodynamics of electrode-electrolyte systems, for instance supercapacitors filled with an ionic liquid or blue-energy devices filled with river- or sea water. By a suitable mapping of thermodynamic variables, we identify a strong analogy with classical heat engines. We introduce
Theoretical physics 5 thermodynamics
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...
Institute of Scientific and Technical Information of China (English)
吴金平
1991-01-01
The relation between the excess entropy production criterion of thermodynamic stabilityfor nonequilibrium states and kinetic linear stability principle is discussed. It is shown thatthe condition required by the excess entropy production criterion generally is sufficient, butnot necessary to judge the system stability. The condition required by the excess entropyproduction criterion is stronger than that of the linear stability principle. Only when theproduct matrix between the linearized matrix of kinetic equations and matrix of quadraticform of second-order excess entropy is symmetric, is the condition required by the excessentropy production criterion that the steady steate is asymptotically stable (δ_xP>0) necessaryand sufficient. The counterexample given by Fox to prove that the excess entropy, (δ~2S)ss,is not a Liapunov function is incorrect. Contradictory to his conclusion, the counterexampleis just a positive one that proves that the excess entropy is a Liapunov function. Moreover,the excess entropy production criterion is not limited by symmetric conditions of the linear-ized matrix of kinetic equations. The excess entropy around nonequilibrium steady states,(δ~2S)ss, is a Liapunov function of thermodynamic system.
Cycle kinetics, steady state thermodynamics and motors-a paradigm for living matter physics
International Nuclear Information System (INIS)
Qian, Hong
2005-01-01
An integration of the stochastic mathematical models for motor proteins with Hill's steady state thermodynamics yields a rather comprehensive theory for molecular motors as open systems in the nonequilibrium steady state. This theory, a natural extension of Gibbs' approach to isothermal molecular systems in equilibrium, is compared with other existing theories with dissipative structures and dynamics. The theory of molecular motors might be considered as an archetype for studying more complex open biological systems such as biochemical reaction networks inside living cells
The Donnan equilibrium: I. On the thermodynamic foundation of the Donnan equation of state
Philipse, A.P.; Vrij, A.
2011-01-01
The thermodynamic equilibrium between charged colloids and an electrolyte reservoir is named after Frederic Donnan who first published on it one century ago (Donnan 1911 Z. Electrochem. 17 572). One of the intriguing features of the Donnan equilibrium is the ensuing osmotic equation of state which
Thermodynamic volume and the extended Smarr relation
Energy Technology Data Exchange (ETDEWEB)
Hyun, Seungjoon; Jeong, Jaehoon; Park, Sang-A; Yi, Sang-Heon [Department of Physics, College of Science, Yonsei University,Seoul 120-749 (Korea, Republic of)
2017-04-10
We continue to explore the scaling transformation in the reduced action formalism of gravity models. As an extension of our construction, we consider the extended forms of the Smarr relation for various black holes, adopting the cosmological constant as the bulk pressure as in some literatures on black holes. Firstly, by using the quasi-local formalism for charges, we show that, in a general theory of gravity, the volume in the black hole thermodynamics could be defined as the thermodynamic conjugate variable to the bulk pressure in such a way that the first law can be extended consistently. This, so called, thermodynamic volume can be expressed explicitly in terms of the metric and field variables. Then, by using the scaling transformation allowed in the reduced action formulation, we obtain the extended Smarr relation involving the bulk pressure and the thermodynamic volume. In our approach, we do not resort to Euler’s homogeneous scaling of charges while incorporating the would-be hairy contribution without any difficulty.
Thermodynamics for Chemists, Physicists and Engineers
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...
Akiba, Hiroki; Tsumoto, Kouhei
2015-07-01
Antibodies (immunoglobulins) bind specific molecules (i.e. antigens) with high affinity and specificity. In order to understand their mechanisms of recognition, interaction analysis based on thermodynamic and kinetic parameters, as well as structure determination is crucial. In this review, we focus on mutational analysis which gives information about the role of each amino acid residue in antibody-antigen interaction. Taking anti-hen egg lysozyme antibodies and several anti-small molecule antibodies, the energetic contribution of hot-spot and non-hot-spot residues is discussed in terms of thermodynamics. Here, thermodynamics of the contribution from aromatic, charged and hydrogen bond-forming amino acids are discussed, and their different characteristics have been elucidated. The information gives fundamental understanding of the antibody-antigen interaction. Furthermore, the consequences of antibody engineering are analysed from thermodynamic viewpoints: humanization to reduce immunogenicity and rational design to improve affinity. Amino acid residues outside hot-spots in the interface play important roles in these cases, and thus thermodynamic and kinetic parameters give much information about the antigen recognition. Thermodynamic analysis of mutant antibodies thus should lead to advanced strategies to design and select antibodies with high affinity. © The Authors 2015. Published by Oxford University Press on behalf of the Japanese Biochemical Society. All rights reserved.
Statistical mechanics and the foundations of thermodynamics
International Nuclear Information System (INIS)
Loef, A.M.
1979-01-01
An introduction to classical statistical mechanics and its relation to thermodynamics is presented. Emphasis is put on getting a detailed and logical presentation of the foundations of thermodynamics based on the maximum entropy principles which govern the values taken by macroscopic variables according to the laws of large numbers
Eichhorn, Ralf; Aurell, Erik
2014-04-01
theory for small deviations from equilibrium, in which a general framework is constructed from the analysis of non-equilibrium states close to equilibrium. In a next step, Prigogine and others developed linear irreversible thermodynamics, which establishes relations between transport coefficients and entropy production on a phenomenological level in terms of thermodynamic forces and fluxes. However, beyond the realm of linear response no general theoretical results were available for quite a long time. This situation has changed drastically over the last 20 years with the development of stochastic thermodynamics, revealing that the range of validity of thermodynamic statements can indeed be extended deep into the non-equilibrium regime. Early developments in that direction trace back to the observations of symmetry relations between the probabilities for entropy production and entropy annihilation in non-equilibrium steady states [5-8] (nowadays categorized in the class of so-called detailed fluctuation theorems), and the derivations of the Bochkov-Kuzovlev [9, 10] and Jarzynski relations [11] (which are now classified as so-called integral fluctuation theorems). Apart from its fundamental theoretical interest, the developments in stochastic thermodynamics have experienced an additional boost from the recent experimental progress in fabricating, manipulating, controlling and observing systems on the micro- and nano-scale. These advances are not only of formidable use for probing and monitoring biological processes on the cellular, sub-cellular and molecular level, but even include the realization of a microscopic thermodynamic heat engine [12] or the experimental verification of Landauer's principle in a colloidal system [13]. The scientific program Stochastic Thermodynamics held between 4 and 15 March 2013, and hosted by The Nordic Institute for Theoretical Physics (Nordita), was attended by more than 50 scientists from the Nordic countries and elsewhere, amongst them
International Nuclear Information System (INIS)
Ackermann, R.J.; Chandrasekharaiah, M.S.
1975-01-01
The thermodynamic data for the actinide metals and oxides (thorium to curium ) have been assessed, examined for consistency, and compared with the lanthanides. Correlations relating the enthalpies of formation of the solid oxides with the corresponding aquo ions make possible the estimation of the thermodynamic properties of AmO 2 (s) and Am 2 O 3 (s) which are in accordance with vaporization data. The known thermodynamic properties of the substoichiometric dioxides MOsub(2-x)(s) at high temperatures demonstrate the relative stabilities of valence states less than 4+ and lead to the examination of stability requirements for the sesquioxides M 2 O 3 (s) and the monoxides MO(s). Sequential trends in the gaseous metals, monoxides and dioxides are examined, compared, and contrasted with the lanthanides. (author)
Equation of state and thermodynamic properties of BCC metals
Directory of Open Access Journals (Sweden)
Vu Van Hung, N.T. Hoa
2017-10-01
Full Text Available The moment method in statistical dynamics is used to study the equation of state and thermodynamic properties of the bcc metals taking into account the anharmonicity effects of the lattice vibrations and hydrostatic pressures. The explicit expressions of the lattice constant, thermal expansion oefficient, and the specific heats of the bcc metals are derived within the fourth order moment approximation. The termodynamic quantities of W, Nb, Fe,and Ta metals are calculated as a function of the pressure, and they are in good agreement with the corresponding results obtained from the first principles calculations and experimental results. The effective pair potentials work well for the calculations of bcc metals.
Thermodynamic and transport properties of gaseous tetrafluoromethane in chemical equilibrium
Hunt, J. L.; Boney, L. R.
1973-01-01
Equations and in computer code are presented for the thermodynamic and transport properties of gaseous, undissociated tetrafluoromethane (CF4) in chemical equilibrium. The computer code calculates the thermodynamic and transport properties of CF4 when given any two of five thermodynamic variables (entropy, temperature, volume, pressure, and enthalpy). Equilibrium thermodynamic and transport property data are tabulated and pressure-enthalpy diagrams are presented.
International Nuclear Information System (INIS)
Zanchini, E.
1988-01-01
The definition of energy, in thermodynamics, is dependent by starting operative definitions of the basic concepts of physics on which it rests, such as those of isolated systems, ambient of a system, separable system and set of separable states. Then the definition of energy is rigorously extended to open systems. The extension gives a clear physical meaning to the concept of energy difference between two states with arbitrary different compositions
Black hole thermodynamics under the microscope
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.
Extended Irreversible Thermodynamics
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...
On thermodynamic limits of entropy densities
Moriya, H; Van Enter, A
We give some sufficient conditions which guarantee that the entropy density in the thermodynamic limit is equal to the thermodynamic limit of the entropy densities of finite-volume (local) Gibbs states.
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)
Directory of Open Access Journals (Sweden)
Raji HeyrovskÃƒÂ¡
2004-03-01
Full Text Available Abstract: Recently, the author suggested a simple and composite equation of state by incorporating fundamental thermodynamic properties like heat capacities into her earlier concise equation of state for gases based on free volume and molecular association / dissociation. This work brings new results for aqueous solutions, based on the analogy of the equation of state for gases and solutions over wide ranges of pressures (for gases and concentrations (for solutions. The definitions of entropy and heat energy through the equation of state for gases, also holds for solutions.
New methods of thermodynamics; Nouvelles methodes en thermodynamique
Energy Technology Data Exchange (ETDEWEB)
NONE
2001-07-01
This day, organized by the SFT French Society of Thermology, took stock on the new methods in the domain of the thermodynamics. Eight papers have been presented during this day: new developments of the thermodynamics in finite time; the optimal efficiency of energy converters; a version of non-equilibrium thermodynamics with entropy and information as positive and negative thermal change; the role of thermodynamics in process integration; application of the thermodynamics to critical nuclear accidents; the entropic analysis help in the case of charge and discharge state of an energy storage process; fluid flow threw a stable state in the urban hydraulic; a computer code for phase diagram prediction. (A.L.B.)
International Nuclear Information System (INIS)
Hamm, L.L.; Van Brunt, V.
1982-08-01
The Christiansen and Fredenslund programs for calculating vapor-liquid equilibria have been modified by replacing the Soave-Redlich-Kwong equation of state with the newly developed Peng-Robinson equation of state. This modification was shown to be a decided improvement for high pressure systems, especially in the critical and upper retrograde regions. Thermodynamic consistency tests were developed and used to evaluate and compare calculated values from both the modified and unmodified programs with reported experimental data for several vapor-liquid systems
Kulinskii, V.L.; Malomuzh, N.P.; Matvejchuk, O.I.
2009-01-01
The applicability of the Principle of Corresponding States (PCS) for the noble fluids is discussed. We give the thermodynamic evidence for the dimerization of the liquid phase in heavy noble gases like argon, krypton etc. which manifests itself in deviations from the PCS. The behavior of the
Limits of predictions in thermodynamic systems: a review
Marsland, Robert, III; England, Jeremy
2018-01-01
The past twenty years have seen a resurgence of interest in nonequilibrium thermodynamics, thanks to advances in the theory of stochastic processes and in their thermodynamic interpretation. Fluctuation theorems provide fundamental constraints on the dynamics of systems arbitrarily far from thermal equilibrium. Thermodynamic uncertainty relations bound the dissipative cost of precision in a wide variety of processes. Concepts of excess work and excess heat provide the basis for a complete thermodynamics of nonequilibrium steady states, including generalized Clausius relations and thermodynamic potentials. But these general results carry their own limitations: fluctuation theorems involve exponential averages that can depend sensitively on unobservably rare trajectories; steady-state thermodynamics makes use of a dual dynamics that lacks any direct physical interpretation. This review aims to present these central results of contemporary nonequilibrium thermodynamics in such a way that the power of each claim for making physical predictions can be clearly assessed, using examples from current topics in soft matter and biophysics.
The second laws of quantum thermodynamics.
Brandão, Fernando; Horodecki, Michał; Ng, Nelly; Oppenheim, Jonathan; Wehner, Stephanie
2015-03-17
The second law of thermodynamics places constraints on state transformations. It applies to systems composed of many particles, however, we are seeing that one can formulate laws of thermodynamics when only a small number of particles are interacting with a heat bath. Is there a second law of thermodynamics in this regime? Here, we find that for processes which are approximately cyclic, the second law for microscopic systems takes on a different form compared to the macroscopic scale, imposing not just one constraint on state transformations, but an entire family of constraints. We find a family of free energies which generalize the traditional one, and show that they can never increase. The ordinary second law relates to one of these, with the remainder imposing additional constraints on thermodynamic transitions. We find three regimes which determine which family of second laws govern state transitions, depending on how cyclic the process is. In one regime one can cause an apparent violation of the usual second law, through a process of embezzling work from a large system which remains arbitrarily close to its original state. These second laws are relevant for small systems, and also apply to individual macroscopic systems interacting via long-range interactions. By making precise the definition of thermal operations, the laws of thermodynamics are unified in this framework, with the first law defining the class of operations, the zeroth law emerging as an equivalence relation between thermal states, and the remaining laws being monotonicity of our generalized free energies.
Directory of Open Access Journals (Sweden)
B. Hussain
2018-02-01
Full Text Available Mixture phase equilibrium and thermodynamic properties have a significant role in industry. Numerical analysis of flash calculation generates an appropriate solution for the problem. In this research, a comparison of Soave Redlich Kwong (SRK and Peng-Robinson (PR equations of state predicting the thermodynamic properties of a mixture of hydrocarbon and related compounds in a critical region at phase equilibrium is performed. By applying mathematical modeling of both equations of states, the behavior of binary gases mixtures is monitored. The numerical analysis of isothermal flash calculations is applied to study the pressure behavior with volume and mole fraction. The approach used in this research shows considerable convergence with experimental results available in the literature.
International Nuclear Information System (INIS)
Morrison, J.D.; Barley, M.H.; Parker, I.B.
1995-01-01
This paper reports on the development and application of a thermodynamic model based on the second-order Modified Huron Vidal equation of state (MHV-2) to predict the properties of ternary mixtures of the refrigerants R32, R125, and R134a. The mixing rules of this equation of state have been used to incorporate directly an activity-coefficient model for the excess Gibbs free energy. The parameters for the activity-coefficient model have been derived from experimental VLE data for binary mixtures. This methodology has enabled the production of a thermodynamically consistent model which can be used to predict the phase equilibria of R32/R125/R134a mixtures. The input data used in the model are presented in the paper and the predictions of the model are compared with available experimental data. The model has been used to predict the behavior of ternary refrigerant blends of R32/R125/R134a in fractionation scenarios, such as liquid charging and vapor leakage, which are of direct interest to the refrigeration industry. Details of these applications and comparisons with experimental data are discussed, along with other general uses of the thermodynamic model
Thermodynamic behaviour of ruthenium at high temperatures
International Nuclear Information System (INIS)
Garisto, F.
1988-01-01
Thermodynamic equilibrium calculations are used to determine the chemical speciation of ruthenium under postulated reactor accident conditions. The speciation of ruthenium is determined for various values of temperature, pressure, oxygen partial pressure and ruthenium concentration. The importance of these variables, in particular the oxygen partial pressure, in determining the volatility of ruthenium is clearly demonstrated in this report. Reliable thermodynamic data are required to determine the behaviour of ruthenium using equilibrium calculations. Therefore, it was necessary to compile a thermodynamic database for the ruthenium species that can be formed under reactor accident conditions. The origin of the thermodynamic data for the ruthenium species included in our calculations is discussed in detail in Appendix A. 23 refs
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...
International Nuclear Information System (INIS)
Buy, Francois; Voltz, Christophe; Llorca, Fabrice
2006-01-01
This work is devoted to the evaluation of complex behavior of metals under shock wave loading. It presents a methodology for the design of specific experiments performed for validation of models and the evaluation of a multiphase equation of state for tin. This material has been selected because of the numerous works completed during the past years on its equation of state. We focus on the solid diagram which presents two solid phases. A thermodynamically based equation of state is developed which gives the opportunity to search for singularities which could be activated under particular shock wave loading. In the temperature -- pressure diagram, the superimposed Hugoniot and release paths make apparent a double shock, release shock configurations. We propose the design and the VISAR results of a calibrated shock -- reshock test for investigating the validity and the efficiency of the model for predicting the thermodynamical state of tin (phases mixing, temperature...). Comparison between numerical and experimental data shows the good accuracy of the results given by the EOS
Chemical Thermodynamics and Information Theory with Applications
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
Some consideration on the thermodynamics of the universe
International Nuclear Information System (INIS)
Hoenl, H.
1977-01-01
It is shown that the thermodynamics of the universe display certain features that are foreign to classical thermodynamics, the discrepancy having its origin in the cosmic expansion of the universe. This is apparent, for example, in the outstanding fact that in the early stages of the universe (some 10 5 or 10 6 years after the Big Bang) the distribution of matter was essentially homogeneous and, owing to the extremely high density and temperature, was in thermodynamic equilibrium. However, in its present state, after the formation of the celestial bodies, (the inhomogeneous phase of the universe), it has moved far away from thermodynamic equilibrium. It is stated that to prove entropy conservation during the homogeneous phase of the universe, one only needs the most general thermodynamical-statistical principles. (U,K)
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
Concise chemical thermodynamics
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
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...
Covariant Thermodynamics of Quantum Systems: Passivity, Semipassivity, and the Unruh Effect
Kuckert, Bernd
2001-01-01
According to the Second Law of Thermodynamics, cycles applied to thermodynamic equilibrium states cannot perform any work (passivity property of thermodynamic equilibrium states). In the presence of matter this can hold only in the rest frame of the matter, as moving matter makes windmills and
Thermodynamic metrics and optimal paths.
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.
Applied Thermodynamics: Grain Boundary Segregation
Directory of Open Access Journals (Sweden)
Pavel Lejček
2014-03-01
Full Text Available Chemical composition of interfaces—free surfaces and grain boundaries—is generally described by the Langmuir–McLean segregation isotherm controlled by Gibbs energy of segregation. Various components of the Gibbs energy of segregation, the standard and the excess ones as well as other thermodynamic state functions—enthalpy, entropy and volume—of interfacial segregation are derived and their physical meaning is elucidated. The importance of the thermodynamic state functions of grain boundary segregation, their dependence on volume solid solubility, mutual solute–solute interaction and pressure effect in ferrous alloys is demonstrated.
Quantum Coherence, Time-Translation Symmetry, and Thermodynamics
Directory of Open Access Journals (Sweden)
Matteo Lostaglio
2015-04-01
Full Text Available The first law of thermodynamics imposes not just a constraint on the energy content of systems in extreme quantum regimes but also symmetry constraints related to the thermodynamic processing of quantum coherence. We show that this thermodynamic symmetry decomposes any quantum state into mode operators that quantify the coherence present in the state. We then establish general upper and lower bounds for the evolution of quantum coherence under arbitrary thermal operations, valid for any temperature. We identify primitive coherence manipulations and show that the transfer of coherence between energy levels manifests irreversibility not captured by free energy. Moreover, the recently developed thermomajorization relations on block-diagonal quantum states are observed to be special cases of this symmetry analysis.
Kou, Jisheng; Sun, Shuyu
2017-01-01
In this paper, we consider a diffuse-interface gas-liquid two-phase flow model with inhomogeneous temperatures, in which we employ the Peng-Robinson equation of state and the temperature-dependent influence parameter instead of the van der Waals equation of state and the constant influence parameter used in the existing models. As a result, our model can characterize accurately the physical behaviors of numerous realistic gas-liquid fluids, especially hydrocarbons. Furthermore, we prove a relation associating the pressure gradient with the gradients of temperature and chemical potential, and thereby derive a new formulation of the momentum balance equation, which shows that gradients of the chemical potential and temperature become the primary driving force of the fluid motion. It is rigorously proved that the new formulations of the model obey the first and second laws of thermodynamics. To design efficient numerical methods, we prove that Helmholtz free energy density is a concave function with respect to the temperature under certain physical conditions. Based on the proposed modeling formulations and the convex-concave splitting of Helmholtz free energy density, we propose a novel thermodynamically stable numerical scheme. We rigorously prove that the proposed method satisfies the first and second laws of thermodynamics. Finally, numerical tests are carried out to verify the effectiveness of the proposed simulation method.
Kou, Jisheng
2017-12-06
In this paper, we consider a diffuse-interface gas-liquid two-phase flow model with inhomogeneous temperatures, in which we employ the Peng-Robinson equation of state and the temperature-dependent influence parameter instead of the van der Waals equation of state and the constant influence parameter used in the existing models. As a result, our model can characterize accurately the physical behaviors of numerous realistic gas-liquid fluids, especially hydrocarbons. Furthermore, we prove a relation associating the pressure gradient with the gradients of temperature and chemical potential, and thereby derive a new formulation of the momentum balance equation, which shows that gradients of the chemical potential and temperature become the primary driving force of the fluid motion. It is rigorously proved that the new formulations of the model obey the first and second laws of thermodynamics. To design efficient numerical methods, we prove that Helmholtz free energy density is a concave function with respect to the temperature under certain physical conditions. Based on the proposed modeling formulations and the convex-concave splitting of Helmholtz free energy density, we propose a novel thermodynamically stable numerical scheme. We rigorously prove that the proposed method satisfies the first and second laws of thermodynamics. Finally, numerical tests are carried out to verify the effectiveness of the proposed simulation method.
Calculating Stress: From Entropy to a Thermodynamic Concept of Health and Disease
Nečesánek, Ivo; Konečný, David; Vasku, Anna
2016-01-01
To date, contemporary science has lacked a satisfactory tool for the objective expression of stress. This text thus introduces a new–thermodynamically derived–approach to stress measurement, based on entropy production in time and independent of the quality or modality of a given stressor or a combination thereof. Hereto, we propose a novel model of stress response based on thermodynamic modelling of entropy production, both in the tissues/organs and in regulatory feedbacks. Stress response is expressed in our model on the basis of stress entropic load (SEL), a variable we introduced previously; the mathematical expression of SEL, provided here for the first time, now allows us to describe the various states of a living system, including differentiating between states of health and disease. The resulting calculation of stress response regardless of the type of stressor(s) in question is thus poised to become an entirely new tool for predicting the development of a living system. PMID:26771542
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
Non-equilibrium thermodynamics, maximum entropy production and Earth-system evolution.
Kleidon, Axel
2010-01-13
The present-day atmosphere is in a unique state far from thermodynamic equilibrium. This uniqueness is for instance reflected in the high concentration of molecular oxygen and the low relative humidity in the atmosphere. Given that the concentration of atmospheric oxygen has likely increased throughout Earth-system history, we can ask whether this trend can be generalized to a trend of Earth-system evolution that is directed away from thermodynamic equilibrium, why we would expect such a trend to take place and what it would imply for Earth-system evolution as a whole. The justification for such a trend could be found in the proposed general principle of maximum entropy production (MEP), which states that non-equilibrium thermodynamic systems maintain steady states at which entropy production is maximized. Here, I justify and demonstrate this application of MEP to the Earth at the planetary scale. I first describe the non-equilibrium thermodynamic nature of Earth-system processes and distinguish processes that drive the system's state away from equilibrium from those that are directed towards equilibrium. I formulate the interactions among these processes from a thermodynamic perspective and then connect them to a holistic view of the planetary thermodynamic state of the Earth system. In conclusion, non-equilibrium thermodynamics and MEP have the potential to provide a simple and holistic theory of Earth-system functioning. This theory can be used to derive overall evolutionary trends of the Earth's past, identify the role that life plays in driving thermodynamic states far from equilibrium, identify habitability in other planetary environments and evaluate human impacts on Earth-system functioning. This journal is © 2010 The Royal Society
The OpenCalphad thermodynamic software interface
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 properties of cryogenic fluids
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...
Zaidi, Sobia; Haque, Md Anzarul; Ubaid-Ullah, Shah; Prakash, Amresh; Hassan, Md Imtaiyaz; Islam, Asimul; Batra, Janendra K; Ahmad, Faizan
2017-05-01
A sequence alignment of mammalian cytochromes c with yeast iso-1-cytochrome c (y-cyt-c) shows that the yeast protein contains five extra N-terminal residues. We have been interested in understanding the question: What is the role of these five extra N-terminal residues in folding and stability of the protein? To answer this question we have prepared five deletants of y-cyt-c by sequentially removing these extra residues. During our studies on the wild type (WT) protein and its deletants, we observed that the amount of secondary structure in the guanidinium chloride (GdmCl)-induced denatured (D) state of each protein is different from that of the heat-induced denatured (H) state. This finding is confirmed by the observation of an additional cooperative transition curve of optical properties between H and D states on the addition of different concentrations of GdmCl to the already heat denatured WT y-cyt-c and its deletants at pH 6.0 and 68°C. For each protein, analysis of transition curves representing processes, native (N) state ↔ D state, N state ↔ H state, and H state ↔ D state, was done to obtain Gibbs free energy changes associated with all the three processes. This analysis showed that, for each protein, thermodynamic cycle accommodates Gibbs free energies associated with transitions between N and D states, N and H states, and H and D states, the characteristics required for a thermodynamic function. All these experimental observations have been supported by our molecular dynamics simulation studies.
Coupled thermodynamic-dynamic semi-analytical model of free piston Stirling engines
Energy Technology Data Exchange (ETDEWEB)
Formosa, F., E-mail: fabien.formosa@univ-savoie.f [Laboratoire SYMME, Universite de Savoie, BP 80439, 74944 Annecy le Vieux Cedex (France)
2011-05-15
Research highlights: {yields} The free piston Stirling behaviour relies on its thermal and dynamic features. {yields} A global semi-analytical model for preliminary design is developed. {yields} The model compared with NASA-RE1000 experimental data shows good correlations. -- Abstract: The study of free piston Stirling engine (FPSE) requires both accurate thermodynamic and dynamic modelling to predict its performances. The steady state behaviour of the engine partly relies on non linear dissipative phenomena such as pressure drop loss within heat exchangers which is dependant on the temperature within the associated components. An analytical thermodynamic model which encompasses the effectiveness and the flaws of the heat exchangers and the regenerator has been previously developed and validated. A semi-analytical dynamic model of FPSE is developed and presented in this paper. The thermodynamic model is used to define the thermal variables that are used in the dynamic model which evaluates the kinematic results. Thus, a coupled iterative strategy has been used to perform a global simulation. The global modelling approach has been validated using the experimental data available from the NASA RE-1000 Stirling engine prototype. The resulting coupled thermodynamic-dynamic model using a standardized description of the engine allows efficient and realistic preliminary design of FPSE.
Coupled thermodynamic-dynamic semi-analytical model of free piston Stirling engines
International Nuclear Information System (INIS)
Formosa, F.
2011-01-01
Research highlights: → The free piston Stirling behaviour relies on its thermal and dynamic features. → A global semi-analytical model for preliminary design is developed. → The model compared with NASA-RE1000 experimental data shows good correlations. -- Abstract: The study of free piston Stirling engine (FPSE) requires both accurate thermodynamic and dynamic modelling to predict its performances. The steady state behaviour of the engine partly relies on non linear dissipative phenomena such as pressure drop loss within heat exchangers which is dependant on the temperature within the associated components. An analytical thermodynamic model which encompasses the effectiveness and the flaws of the heat exchangers and the regenerator has been previously developed and validated. A semi-analytical dynamic model of FPSE is developed and presented in this paper. The thermodynamic model is used to define the thermal variables that are used in the dynamic model which evaluates the kinematic results. Thus, a coupled iterative strategy has been used to perform a global simulation. The global modelling approach has been validated using the experimental data available from the NASA RE-1000 Stirling engine prototype. The resulting coupled thermodynamic-dynamic model using a standardized description of the engine allows efficient and realistic preliminary design of FPSE.
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
Thermodynamics of Fluids Under Flow Second Edition
Jou, David; Criado-Sancho, Manuel
2011-01-01
This is the second edition of the book “Thermodynamics of Fluids under Flow,” which was published in 2000 and has now been corrected, expanded and updated. This is a companion book to our other title Extended irreversible thermodynamics (D. Jou, J. Casas-Vázquez and G. Lebon, Springer, 4th edition 2010), and of the textbook Understanding non-equilibrium thermodynamics (G. Lebon, D. Jou and J. Casas-Vázquez, Springer, 2008. The present book is more specialized than its counterpart, as it focuses its attention on the non-equilibrium thermodynamics of flowing fluids, incorporating non-trivial thermodynamic contributions of the flow, going beyond local equilibrium theories, i.e., including the effects of internal variables and of external forcing due to the flow. Whereas the book's first edition was much more focused on polymer solutions, with brief glimpses into ideal and real gases, the present edition covers a much wider variety of systems, such as: diluted and concentrated polymer solutions, polymer ble...
Li, Guanchen; von Spakovsky, Michael R.
2016-01-01
This paper presents a study of the nonequilibrium relaxation process of chemically reactive systems using steepest-entropy-ascent quantum thermodynamics (SEAQT). The trajectory of the chemical reaction, i.e., the accessible intermediate states, is predicted and discussed. The prediction is made using a thermodynamic-ensemble approach, which does not require detailed information about the particle mechanics involved (e.g., the collision of particles). Instead, modeling the kinetics and dynamics of the relaxation process is based on the principle of steepest-entropy ascent (SEA) or maximum-entropy production, which suggests a constrained gradient dynamics in state space. The SEAQT framework is based on general definitions for energy and entropy and at least theoretically enables the prediction of the nonequilibrium relaxation of system state at all temporal and spatial scales. However, to make this not just theoretically but computationally possible, the concept of density of states is introduced to simplify the application of the relaxation model, which in effect extends the application of the SEAQT framework even to infinite energy eigenlevel systems. The energy eigenstructure of the reactive system considered here consists of an extremely large number of such levels (on the order of 10130) and yields to the quasicontinuous assumption. The principle of SEA results in a unique trajectory of system thermodynamic state evolution in Hilbert space in the nonequilibrium realm, even far from equilibrium. To describe this trajectory, the concepts of subsystem hypoequilibrium state and temperature are introduced and used to characterize each system-level, nonequilibrium state. This definition of temperature is fundamental rather than phenomenological and is a generalization of the temperature defined at stable equilibrium. In addition, to deal with the large number of energy eigenlevels, the equation of motion is formulated on the basis of the density of states and a set of
Is applicable thermodynamics of negative temperature for living organisms?
Atanasov, Atanas Todorov
2017-11-01
During organismal development the moment of sexual maturity can be characterizes by nearly maximum basal metabolic rate and body mass. Once the living organism reaches extreme values of the mass and the basal metabolic rate, it reaches near equilibrium thermodynamic steady state physiological level with maximum organismal complexity. Such thermodynamic systems that reach equilibrium steady state level at maximum mass-energy characteristics can be regarded from the prospective of thermodynamics of negative temperature. In these systems the increase of the internal and free energy is accompanied with decrease of the entropy. In our study we show the possibility the living organisms to regard as thermodynamic system with negative temperature
Thermodynamics of perfect fluids from scalar field theory
Ballesteros, Guillermo; Pilo, Luigi
2016-01-01
The low-energy dynamics of relativistic continuous media is given by a shift-symmetric effective theory of four scalar fields. These scalars describe the embedding in spacetime of the medium and play the role of Stuckelberg fields for spontaneously broken spatial and time translations. Perfect fluids are selected imposing a stronger symmetry group or reducing the field content to a single scalar. We explore the relation between the field theory description of perfect fluids to thermodynamics. By drawing the correspondence between the allowed operators at leading order in derivatives and the thermodynamic variables, we find that a complete thermodynamic picture requires the four Stuckelberg fields. We show that thermodynamic stability plus the null energy condition imply dynamical stability. We also argue that a consistent thermodynamic interpretation is not possible if any of the shift symmetries is explicitly broken.
Statistical thermodynamics of supercapacitors and blue engines
van Roij, René
2012-01-01
We study the thermodynamics of electrode-electrolyte systems, for instance supercapacitors filled with an ionic liquid or blue-energy devices filled with river- or sea water. By a suitable mapping of thermodynamic variables, we identify a strong analogy with classical heat engines. We introduce several Legendre transformations and Maxwell relations. We argue that one should distinguish between the differential capacity at constant ion number and at constant ion chemical potential, and derive ...
International Nuclear Information System (INIS)
Garcia-Morales, Vladimir; Pellicer, Julio; Manzanares, Jose A.
2008-01-01
We present some novel thermodynamic ideas based on the Maupertuis principle. By considering Hamiltonians written in terms of appropriate action-angle variables we show that thermal states can be characterized by the action variables and by their evolution in time when the system is nonintegrable. We propose dynamical definitions for the equilibrium temperature and entropy as well as an expression for the nonequilibrium entropy valid for isolated systems with many degrees of freedom. This entropy is shown to increase in the relaxation to equilibrium of macroscopic systems with short-range interactions, which constitutes a dynamical justification of the Second Law of Thermodynamics. Several examples are worked out to show that this formalism yields the right microcanonical (equilibrium) quantities. The relevance of this approach to nonequilibrium situations is illustrated with an application to a network of coupled oscillators (Kuramoto model). We provide an expression for the entropy production in this system finding that its positive value is directly related to dissipation at the steady state in attaining order through synchronization
Smith, Brent
2002-01-01
Describes equations of state as a supplement to an introductory thermodynamics undergraduate course. Uses rubber-elastic materials (REM) which have strong analogies to the concept of an ideal gas and explains the molar basis of REM. Provides examples of the analogies between ideal gas and REM and mathematical analogies. (Contains 22 references.)…
A statistical model for instable thermodynamical systems
International Nuclear Information System (INIS)
Sommer, Jens-Uwe
2003-01-01
A generic model is presented for statistical systems which display thermodynamic features in contrast to our everyday experience, such as infinite and negative heat capacities. Such system are instable in terms of classical equilibrium thermodynamics. Using our statistical model, we are able to investigate states of instable systems which are undefined in the framework of equilibrium thermodynamics. We show that a region of negative heat capacity in the adiabatic environment, leads to a first order like phase transition when the system is coupled to a heat reservoir. This phase transition takes place without a phase coexistence. Nevertheless, all intermediate states are stable due to fluctuations. When two instable system are brought in thermal contact, the temperature of the composed system is lower than the minimum temperature of the individual systems. Generally, the equilibrium states of instable system cannot be simply decomposed into equilibrium states of the individual systems. The properties of instable system depend on the environment, ensemble equivalence is broken
Coherence and measurement in quantum thermodynamics.
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.
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 geometry and phase transitions of AdS braneworld black holes
Energy Technology Data Exchange (ETDEWEB)
Chaturvedi, Pankaj, E-mail: cpankaj@iitk.ac.in; Sengupta, Gautam, E-mail: sengupta@iitk.ac.in
2017-02-10
The thermodynamics and phase transitions of charged RN–AdS and rotating Kerr–AdS black holes in a generalized Randall–Sundrum braneworld are investigated in the framework of thermodynamic geometry. A detailed analysis of the thermodynamics, stability and phase structures in the canonical and the grand canonical ensembles for these AdS braneworld black holes are described. The thermodynamic curvatures for both these AdS braneworld black holes are computed and studied as a function of the thermodynamic variables. Through this analysis we illustrate an interesting dependence of the phase structures on the braneworld parameter for these black holes.
Understanding the Thermodynamics of Biological Order
Peterson, Jacob
2012-01-01
By growth in size and complexity (i.e., changing from more probable to less probable states), plants and animals appear to defy the second law of thermodynamics. The usual explanation describes the input of nutrient and sunlight energy into open thermodynamic systems. However, energy input alone does not address the ability to organize and create…
Size- and shape-dependent surface thermodynamic properties of nanocrystals
Fu, Qingshan; Xue, Yongqiang; Cui, Zixiang
2018-05-01
As the fundamental properties, the surface thermodynamic properties of nanocrystals play a key role in the physical and chemical changes. However, it remains ambiguous about the quantitative influence regularities of size and shape on the surface thermodynamic properties of nanocrystals. Thus by introducing interface variables into the Gibbs energy and combining Young-Laplace equation, relations between the surface thermodynamic properties (surface Gibbs energy, surface enthalpy, surface entropy, surface energy and surface heat capacity), respectively, and size of nanocrystals with different shapes were derived. Theoretical estimations of the orders of the surface thermodynamic properties of nanocrystals agree with available experimental values. Calculated results of the surface thermodynamic properties of Au, Bi and Al nanocrystals suggest that when r > 10 nm, the surface thermodynamic properties linearly vary with the reciprocal of particle size, and when r < 10 nm, the effect of particle size on the surface thermodynamic properties becomes greater and deviates from linear variation. For nanocrystals with identical equivalent diameter, the more the shape deviates from sphere, the larger the surface thermodynamic properties (absolute value) are.
Structure and thermodynamics of molten salts
International Nuclear Information System (INIS)
Papatheodorou, G.N.
1983-01-01
This chapter investigates single-component molten salts and multicomponent salt mixtures. Molten salts provide an important testing ground for theories of liquids, solutions, and plasmas. Topics considered include molten salts as liquids (the pair potential, the radial distribution function, methods of characterization), single salts (structure, thermodynamic correlations), and salt mixtures (the thermodynamics of mixing; spectroscopy and structure). Neutron and X-ray scattering techniques are used to determine the structure of molten metal halide salts. The corresponding-states theory is used to obtain thermodynamic correlations on single salts. Structural information on salt mixtures is obtained by using vibrational (Raman) and electronic absorption spectroscopy. Charge-symmetrical systems and charge-unsymmetrical systems are used to examine the thermodynamics of salt mixtures
The virial equation of state for unitary fermion thermodynamics with non-Gaussian correlations
International Nuclear Information System (INIS)
Chen Jisheng; Li Jiarong; Wang Yanping; Xia Xiangjun
2008-01-01
We study the roles of the dynamical high order perturbation and statistically non-linear infrared fluctuation/correlation in the virial equation of state for the Fermi gas in the unitary limit. Incorporating the quantum level crossing rearrangement effects, the spontaneously generated entropy departing from the mean-field theory formalism leads to concise thermodynamical expressions. The dimensionless virial coefficients with complex non-local correlations are calculated up to the fourth order for the first time. The virial coefficients of unitary Fermi gas are found to be proportional to those of the ideal quantum gas with integer ratios through a general term formula. Counterintuitively, contrary to those of the ideal bosons (a (0) 2 =-(1/4√2)) or fermions (a (0) 2 =(1/4√2)), the second virial coefficient a 2 of Fermi gas at unitarity is found to be equal to zero. With the vanishing leading order quantum correction, the BCS–BEC crossover thermodynamics manifests the famous pure classical Boyle's law in the Boltzmann regime. The non-Gaussian correlation phenomena can be validated by studying the Joule–Thomson effect
Action–angle variables, ladder operators and coherent states
International Nuclear Information System (INIS)
Campoamor-Stursberg, R.; Gadella, M.; Kuru, Ş.; Negro, J.
2012-01-01
This Letter is devoted to the building of coherent states from arguments based on classical action–angle variables. First, we show how these classical variables are associated to an algebraic structure in terms of Poisson brackets. In the quantum context these considerations are implemented by ladder type operators and a structure known as spectrum generating algebra. All this allows to generate coherent states and thereby the correspondence of classical–quantum properties by means of the aforementioned underlying structure. This approach is illustrated with the example of the one-dimensional Pöschl–Teller potential system. -- Highlights: ► We study the building of coherent states from classical action–angle variables arguments. ► The classical variables are associated to an algebraic structure in terms of Poisson brackets. ► In the quantum context these considerations are implemented by ladder type operators. ► All this allows to formulate coherent states and the correspondence of classical–quantum properties.
Global thermodynamics of confined inhomogeneous dilute gases: A semi-classical approach
Poveda-Cuevas, F. J.; Reyes-Ayala, I.; Seman, J. A.; Romero-Rochín, V.
2018-04-01
In this work we present our contribution to the Latin American School of Physics "Marcos Moshinsky" 2017 on Quantum Correlations which was held in Mexico City during the summer of 2017. We review the efforts that have been done to construct a global thermodynamic description of ultracold dilute gases confined in inhomogeneous potentials. This is difficult because the presence of this non-uniform trap makes the pressure of the gas to be a spatially dependent variable and its volume an ambiguously defined quantity. In this paper we introduce new global thermodynamic variables, equivalent to pressure and volume, and propose a realistic model of the equation of state of the system. This model is based on a mean-field approach which asymptotically reaches the Thomas-Fermi limit for a weakly interacting Bose gas. We put special emphasis to the transition between the normal and superfluid phases by studying the behavior of the isothermal compressibility across the transition. We reveal how the potential modifies the critical properties of the transition by determining the critical exponents associated to the divergences not of the susceptibilities but of their derivatives.
Friction Force: From Mechanics to Thermodynamics
Ferrari, Christian; Gruber, Christian
2010-01-01
We study some mechanical problems in which a friction force is acting on a system. Using the fundamental concepts of state, time evolution and energy conservation, we explain how to extend Newtonian mechanics to thermodynamics. We arrive at the two laws of thermodynamics and then apply them to investigate the time evolution and heat transfer of…
International Nuclear Information System (INIS)
Bernhoeft, N.; Lander, G.H.; Colineau, E.
2003-01-01
An asymmetric shift in the position of the magnetic Bragg peak with respect to the fiducial lattice has been observed by resonant X-ray scattering in a diverse series of antiferromagnetic compounds. This apparent violation of Bragg's law is interpreted in terms of a dynamically phased order parameter. We demonstrate the use of this effect as a novel probe of fragile or dynamic thermodynamic order in strongly correlated electronic systems. In particular, fresh light is shed on the paradoxical situation encountered in URu 2 Si 2 where the measured entropy gain on passing through T Neel is incompatible with the ground state moment estimated by neutron diffraction. The intrinsic space-time averaging of the probe used to characterise the thermodynamic macroscopic state may play a crucial and previously neglected role. In turn, this suggests the further use of resonant X-ray scattering in investigations of systems dominated by quantum fluctuations. (author)
Chemical engineering and thermodynamics using Mat lab
International Nuclear Information System (INIS)
Kim Heon; Kim, Moon Gap; Lee, Hak Yeong; Yeo, Yeong Gu; Ham, Seong Won
2002-02-01
This book consists of twelve chapters and four appendixes about chemical engineering and thermodynamics using Mat lab, which deals with introduction, energy budget, entropy, thermodynamics process, generalization on any fluid, engineering equation of state for PVT properties, deviation of the function, phase equilibrium of pure fluid, basic of multicomponent, phase equilibrium of compound by state equation, activity model and reaction system. The appendixes is about summary of computer program, related mathematical formula and material property of pure component.
Unified geometric description of black hole thermodynamics
International Nuclear Information System (INIS)
Alvarez, Jose L.; Quevedo, Hernando; Sanchez, Alberto
2008-01-01
In the space of thermodynamic equilibrium states we introduce a Legendre invariant metric which contains all the information about the thermodynamics of black holes. The curvature of this thermodynamic metric becomes singular at those points where, according to the analysis of the heat capacities, phase transitions occur. This result is valid for the Kerr-Newman black hole and all its special cases and, therefore, provides a unified description of black hole phase transitions in terms of curvature singularities.
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.
Relativistic thermodynamics of Fluids. l
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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
International Nuclear Information System (INIS)
Djamali, Essmaiil; Cobble, James W.
2009-01-01
Standard state thermodynamic properties for fully ionized aqueous perrhenic acid at temperature in the range of (298.15 to 598.15) K and at p sat were determined by high dilution solution calorimetry (10 -4 m). A comparison of the standard state thermodynamic properties for fully ionized aqueous perrhenic acid, HReO 4 (aq), and sodium perrhenate, NaReO 4 (aq), establishes for the first time the quantitative values for the differences between H + (aq) and Na + (aq) from temperature of (298.15 to 598.15) K. Perrhenic acid is believed to be the first strong acid to be thermodynamically well characterized under standard state conditions to date from measurements down to 10 -4 m. The value of the Debye-Hueckel limiting slope for enthalpies of dilution at temperature of 596.30 K of 122 ± 6 kJ . mol -3/2 . kg 1/2 , obtained from the integral heats of solution measurement at various concentrations, is in good agreement with theoretical value in literature, 121 kJ . mol -3/2 . kg 1/2 . This agreement verifies that HReO 4 (aq) obeys the simple limiting law for strong electrolytes. Many thermodynamic properties of soluble sodium electrolytes can now be converted to the corresponding acid form.
Thermodynamical properties of dark energy
International Nuclear Information System (INIS)
Gong Yungui; Wang Bin; Wang Anzhong
2007-01-01
We have investigated the thermodynamical properties of dark energy. Assuming that the dark energy temperature T∼a -n and considering that the volume of the Universe enveloped by the apparent horizon relates to the temperature, we have derived the dark energy entropy. For dark energy with constant equation of state w>-1 and the generalized Chaplygin gas, the derived entropy can be positive and satisfy the entropy bound. The total entropy, including those of dark energy, the thermal radiation, and the apparent horizon, satisfies the generalized second law of thermodynamics. However, for the phantom with constant equation of state, the positivity of entropy, the entropy bound, and the generalized second law cannot be satisfied simultaneously
Thermodynamics of Horndeski black holes with non-minimal derivative coupling
Energy Technology Data Exchange (ETDEWEB)
Miao, Yan-Gang [Nankai University, School of Physics, Tianjin (China); Max-Planck-Institut fuer Gravitationsphysik (Albert-Einstein-Institut), Potsdam (Germany); Xu, Zhen-Ming [Nankai University, School of Physics, Tianjin (China)
2016-11-15
We explore thermodynamic properties of a new class of Horndeski black holes whose action contains a non-minimal kinetic coupling of a massless real scalar and the Einstein tensor. Our treatment is based on the well-accepted consideration, where the cosmological constant is dealt with as thermodynamic pressure and the mass of black holes as thermodynamic enthalpy. We resort to a newly introduced intensive thermodynamic variable, i.e., the coupling strength of the scalar and tensor whose dimension is length square, and thus yield both the generalized first law of thermodynamics and the generalized Smarr relation. Our result indicates that this class of Horndeski black holes presents rich thermodynamic behaviors and critical phenomena. Especially in the case of the presence of an electric field, these black holes undergo two phase transitions. Once the charge parameter exceeds its critical value, or the cosmological parameter does not exceed its critical value, no phase transitions happen and the black holes are stable. As a by-product, we point out, the coupling strength acts as the thermodynamic pressure in thermodynamics. (orig.)
Thermodynamics of Horndeski black holes with non-minimal derivative coupling
International Nuclear Information System (INIS)
Miao, Yan-Gang; Xu, Zhen-Ming
2016-01-01
We explore thermodynamic properties of a new class of Horndeski black holes whose action contains a non-minimal kinetic coupling of a massless real scalar and the Einstein tensor. Our treatment is based on the well-accepted consideration, where the cosmological constant is dealt with as thermodynamic pressure and the mass of black holes as thermodynamic enthalpy. We resort to a newly introduced intensive thermodynamic variable, i.e., the coupling strength of the scalar and tensor whose dimension is length square, and thus yield both the generalized first law of thermodynamics and the generalized Smarr relation. Our result indicates that this class of Horndeski black holes presents rich thermodynamic behaviors and critical phenomena. Especially in the case of the presence of an electric field, these black holes undergo two phase transitions. Once the charge parameter exceeds its critical value, or the cosmological parameter does not exceed its critical value, no phase transitions happen and the black holes are stable. As a by-product, we point out, the coupling strength acts as the thermodynamic pressure in thermodynamics. (orig.)
Thermodynamics of U(VI) complexation by succinate at variable temperatures
Energy Technology Data Exchange (ETDEWEB)
Rawat, Neetika [Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Tomar, B.S., E-mail: bstomar@barc.gov.in [Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Manchanda, V.K. [Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India)
2011-07-15
Research highlights: > lg {beta} and {Delta}H{sub C} for U(VI)-succinate determined at variable temperatures. > Increase in lg {beta} with temperature well explained by Born equation. > {Delta}S{sub C} plays the dominant role in variation of {Delta}G{sub C} with temperature. > {Delta}H{sub C} for U(VI)-succinate increases linearly with temperature. > {Delta}C{sub P} of U(VI)-succinate is higher than that of oxalate and malonate complexes. - Abstract: Complexation of U(VI) by succinate has been studied at various temperatures in the range of (298 to 338) K by potentiometry and isothermal titration calorimetry at constant ionic strength (1.0 M). The potentiometric titrations revealed the formation of 1:1 uranyl succinate complex in the pH range of 1.5 to 4.5. The stability constant of uranyl succinate complex was found to increase with temperature. Similar trend was observed in the case of enthalpy of complex formation. However, the increase in entropy with temperature over-compensated the increase in enthalpy, thereby favouring the complexation reaction at higher temperatures. The linear increase of enthalpy of complexation with temperature indicates constancy of the change in heat capacity during complexation. The temperature dependence of stability constant data was well explained with the help of Born equation for electrostatic interaction between the metal ion and the ligand. The data have been compared with those for uranyl complexes with malonate and oxalate to study the effect of ligand size and hydrophobicity on the temperature dependence of thermodynamic quantities.
Introduction to the thermodynamics of solids
International Nuclear Information System (INIS)
Ericksen, J.L.
1992-01-01
This book addresses issues of thermodynamics associated with solids from a unique point of view. Professor Ericksen provides a perspective of thermodynamics which is based in material science and solid mechanics, and attempts to apply basic thermodynamics to a wide range of phenomena. The book is not written as a text-book, as it does not contain example problems or exercises, is directed primarily at researchers in solids. The author states that much of the book is controversial, and that many of his treatments of thermodynamics are not traditional. The author's assessment is accurate on both counts. However, there are several reasons to believe that many of the issues raised in the book are not so much controversial, but rather simply not well described, either by the author or by thermodynamicists, in general. The primary references for much of the thermodynamics in the book are historic in nature, and certainly worthy of consideration, but only a few current references are provided
Equation of state for thermodynamic properties of pure and mixtures liquid alkali metals
International Nuclear Information System (INIS)
Mousazadeh, M.H.; Faramarzi, E.; Maleki, Z.
2010-01-01
We developed an equation of state based on statistical-mechanical perturbation theory for pure and mixtures alkali metals. Thermodynamic properties were calculated by the equation of state, based on the perturbed-chain statistical associating fluid theory (PC-SAFT). The model uses two parameters for a monatomic system, segment size, σ, and segment energy, ε. In this work, we calculate the saturation and compressed liquid density, heat capacity at constant pressure and constant volume, isobaric expansion coefficient, for which accurate experimental data exist in the literatures. Results on the density of binary and ternary alkali metal alloys of Cs-K, Na-K, Na-K-Cs, at temperatures from the freezing point up to several hundred degrees above the boiling point are presented. The calculated results are in good agreement with experimental 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.)
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.
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.
First law of thermodynamics on holographic screens in entropic force frame
International Nuclear Information System (INIS)
Chen Yixin; Li Jianlong
2011-01-01
Imposing a mathematical definition of holographic screen, in the spirit of Verlinde's entropic force proposal (E.P. Verlinde, (arXiv:1001.0785)), we give the differential and integral form of the first law of thermodynamics on the holographic screen enclosing a spherical symmetric black hole. It is consistent with equipartition principle and the form of Komar mass. There are also other version of first law, which are equivalent up to a Legendre transformation. The holographic screen thermodynamics is defined in a quasi-local form, which is the main difference to black hole thermodynamics. Thus, the physical interpretation of holographic screen thermodynamics might be different from black hole thermodynamics. We argue that the entropy of the holographic screen determines its area, i.e. S=A/4 . And the metric can be expressed by thermodynamics variables, which is an illustration of how the space is foliated by the thermodynamical potentials.
Peaceful nuclear explosions and thermodynamics
International Nuclear Information System (INIS)
Prieto, F.E.
1975-01-01
Some theoretical advances in the thermodynamics of very high pressures are reviewed. A universal (system-independent) formulation of the thermodynamics is sketched, and some of the equations more frequently used are written in system-independent form. Among these equations are: Hugoniot pressure and temperature as functions of volume; the Mie-Gruneisen equation; and an explicit form for the equation of state. It is also shown that this formalism can be used to interpret and predict results from peaceful nuclear explosions. (author)
Universality of P−V criticality in horizon thermodynamics
Energy Technology Data Exchange (ETDEWEB)
Hansen, Devin; Kubizňák, David [Perimeter Institute,31 Caroline St. N., Waterloo, Ontario, N2L 2Y5 (Canada); Department of Physics and Astronomy, University of Waterloo,Waterloo, Ontario, N2L 3G1 (Canada); Mann, Robert B. [Department of Physics and Astronomy, University of Waterloo,Waterloo, Ontario, N2L 3G1 (Canada)
2017-01-11
We study P−V criticality of black holes in Lovelock gravities in the context of horizon thermodynamics. The corresponding first law of horizon thermodynamics emerges as one of the Einstein-Lovelock equations and assumes the universal (independent of matter content) form δE=TδS−PδV, where P is identified with the total pressure of all matter in the spacetime (including a cosmological constant Λ if present). We compare this approach to recent advances in extended phase space thermodynamics of asymptotically AdS black holes where the ‘standard’ first law of black hole thermodynamics is extended to include a pressure-volume term, where the pressure is entirely due to the (variable) cosmological constant. We show that both approaches are quite different in interpretation. Provided there is sufficient non-linearity in the gravitational sector, we find that horizon thermodynamics admits the same interesting black hole phase behaviour seen in the extended case, such as a Hawking-Page transition, Van der Waals like behaviour, and the presence of a triple point. We also formulate the Smarr formula in horizon thermodynamics and discuss the interpretation of the quantity E appearing in the horizon first law.
Universality of P−V criticality in horizon thermodynamics
International Nuclear Information System (INIS)
Hansen, Devin; Kubizňák, David; Mann, Robert B.
2017-01-01
We study P−V criticality of black holes in Lovelock gravities in the context of horizon thermodynamics. The corresponding first law of horizon thermodynamics emerges as one of the Einstein-Lovelock equations and assumes the universal (independent of matter content) form δE=TδS−PδV, where P is identified with the total pressure of all matter in the spacetime (including a cosmological constant Λ if present). We compare this approach to recent advances in extended phase space thermodynamics of asymptotically AdS black holes where the ‘standard’ first law of black hole thermodynamics is extended to include a pressure-volume term, where the pressure is entirely due to the (variable) cosmological constant. We show that both approaches are quite different in interpretation. Provided there is sufficient non-linearity in the gravitational sector, we find that horizon thermodynamics admits the same interesting black hole phase behaviour seen in the extended case, such as a Hawking-Page transition, Van der Waals like behaviour, and the presence of a triple point. We also formulate the Smarr formula in horizon thermodynamics and discuss the interpretation of the quantity E appearing in the horizon first law.
Stochastic Thermodynamics: A Dynamical Systems Approach
Directory of Open Access Journals (Sweden)
Tanmay Rajpurohit
2017-12-01
Full Text Available In this paper, we develop an energy-based, large-scale dynamical system model driven by Markov diffusion processes to present a unified framework for statistical thermodynamics predicated on a stochastic dynamical systems formalism. Specifically, using a stochastic state space formulation, we develop a nonlinear stochastic compartmental dynamical system model characterized by energy conservation laws that is consistent with statistical thermodynamic principles. In particular, we show that the difference between the average supplied system energy and the average stored system energy for our stochastic thermodynamic model is a martingale with respect to the system filtration. In addition, we show that the average stored system energy is equal to the mean energy that can be extracted from the system and the mean energy that can be delivered to the system in order to transfer it from a zero energy level to an arbitrary nonempty subset in the state space over a finite stopping time.
Systematic vibration thermodynamic properties of bromine
Liu, G. Y.; Sun, W. G.; Liao, B. T.
2015-11-01
Based on the analysis of the maturity and finiteness of vibrational levels of bromine molecule in ground state and evaluating the effect on statistical computation, according to the elementary principles of quantum statistical theorem, using the full set of bromine molecular vibrational levels determined with algebra method, the statistical contribution for bromine systematical macroscopic thermodynamic properties is discussed. Thermodynamic state functions Helmholtz free energy, entropy and observable vibration heat capacity are calculated. The results show that the determination of full set of vibrational levels and maximum vibrational quantum number is the key in the correct statistical analysis of bromine systematical thermodynamic property. Algebra method results are clearly different from data of simple harmonic oscillator and the related algebra method results are no longer analytical but numerical and are superior to simple harmonic oscillator results. Compared with simple harmonic oscillator's heat capacities, the algebra method's heat capacities are more consistent with the experimental data in the given temperature range of 600-2100 K.
Precision measurement of the speed of sound and thermodynamic properties of gases
International Nuclear Information System (INIS)
Benedetto, G.; Gavioso, R.M.; Spagnolo, R.
1999-01-01
The speed of sound in pure fluids and mixtures is a characteristic and important physical propriety which depends of several intensive thermodynamic variables. This fact indicates that it can be calculated using the appropriate thermodynamic properties of the fluid. Alternatively, experimental evaluation of the speed of sound can be used to determine several fundamental thermophysical properties. Recently, very accurate measurements of the speed of sound in dilute gases have found relevant applications: 1) the last experimental determinations of the value of the universal gas constant R, by measurements in argon, at the triple point of water (1,2); 2) revision of the thermodynamic temperature scales in different temperature ranges (3-5); 3) derivation of the state of many pure gases, which includes methane, helium and ethylene (6-7); 4)determination of the heat capacities and densities of pure gases and mixture (8-16). The aim of this paper is to provide an extensive review of the measurement of the speed of sound in gases and of its theoretical basis, giving prominence to the relevant metrological aspects involved in the determination of this physical quantity
International Nuclear Information System (INIS)
Li, Guanchen; Spakovsky, Michael R. von
2016-01-01
Conventional first principle approaches for studying nonequilibrium or far-from-equilibrium processes depend on the mechanics of individual particles or quantum states. They also require many details of the mechanical features of a system to arrive at a macroscopic property. In contrast, thermodynamics provides an approach for determining macroscopic property values without going into these details, because the overall effect of particle dynamics results, for example, at stable equilibrium in an invariant pattern of the “Maxwellian distribution”, which in turn leads to macroscopic properties. However, such an approach is not generally applicable to a nonequilibrium process except in the near-equilibrium realm. To adequately address these drawbacks, steepest-entropy-ascent quantum thermodynamics (SEAQT) provides a first principle, thermodynamic-ensemble approach applicable to the entire nonequilibrium realm. Based on prior developments by the authors, this paper applies the SEAQT framework to modeling the nonquasi-equilibrium cycle, which a system with variable volume undergoes. Using the concept of hypoequilibrium state and nonequilibrium intensive properties, this framework provides a complete description of the nonequilibrium evolution in state of the system. Results presented here reveal how nonequilibrium effects influence the performance of the cycle. - Highlights: • First-principles nonequilibrium model of thermodynamic cycles. • Study of thermal efficiency losses due to nonequilibrium effects. • Study of systems undergoing nonquasi-equilibrium processes. • Study of the coupling of system relaxation and interaction with a reservoir.
Calculation and analysis of thermodynamic relations for superconductors
International Nuclear Information System (INIS)
Nazarenko, A.B.
1989-01-01
The absorption coefficients of high-frequency and low-frequency sound have been calculated on the basis of the Ginzburg-Landau theory. This sound is a wave of periodic adiabatic bulk compressions and rarefactions of the frequency ω in an isotropic superconductor near the transition temperature. Thermodynamic relations have been obtained for abrupt changes in the physical quantities produced as a result of a transition from the normal state to the superconducting state. These relations are similar to the Ehrenfest relations. The above--mentioned thermodynamic quantities are compared with the published experimental results on YBa 2 Cu 3 O 7-δ . The experiments on the absorption of ultrasound in recently discovered superconductors mainformation on the phase transition type and thermodynamic relations for these superconductors, in particular, the T c -vs-dp curve. Similar calculations have been carried out for 2 He-transition experiments with ferromagnetic materials. The order parameter in the thermodynamic potential was assumed to be isotropic
Shchekin, Alexander K; Shabaev, Ilya V; Hellmuth, Olaf
2013-02-07
Thermodynamic and kinetic peculiarities of nucleation, deliquescence and efflorescence transitions in the ensemble of droplets formed on soluble condensation nuclei from a solvent vapor have been considered. The interplay of the effects of solubility and the size of condensation nuclei has been analyzed. Activation barriers for the deliquescence and phase transitions and for the reverse efflorescence transition have been determined as functions of the relative humidity of the vapor-gas atmosphere, initial size, and solubility of condensation nuclei. It has been demonstrated that, upon variations in the relative humidity of the atmosphere, the crossover in thermodynamically stable and unstable variables of the droplet state takes place. The physical meaning of stable and unstable variables has been clarified. The kinetic equations for establishing equilibrium and steady distributions of binary droplets have been solved. The specific times for relaxation, deliquescence and efflorescence transitions have been calculated.
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.
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.
Evaluation of the Thermodynamic Models for the Thermal Diffusion Factor
DEFF Research Database (Denmark)
Gonzalez-Bagnoli, Mariana G.; Shapiro, Alexander; Stenby, Erling Halfdan
2003-01-01
Over the years, several thermodynamic models for the thermal diffusion factors for binary mixtures have been proposed. The goal of this paper is to test some of these models in combination with different equations of state. We tested the following models: those proposed by Rutherford and Drickamer...... we applied different thermodynamic models, such as the Soave-Redlich-Kwong and the Peng-Robinson equations of state. The necessity to try different thermo-dynamic models is caused by the high sensitivity of the thermal diffusion factors to the values of the partial molar properties. Two different...... corrections for the determination of the partial molar volumes have been implemented; the Peneloux correction and the correction based on the principle of corresponding states....
The utility of affine variables and affine coherent states
International Nuclear Information System (INIS)
Klauder, John R
2012-01-01
Affine coherent states are generated by affine kinematical variables much like canonical coherent states are generated by canonical kinematical variables. Although all classical and quantum formalisms normally entail canonical variables, it is shown that affine variables can serve equally well for many classical and quantum studies. This general purpose analysis provides tools to discuss two major applications: (1) the completely successful quantization of a nonrenormalizable scalar quantum field theory by affine techniques, in complete contrast to canonical techniques which only offer triviality; and (2) a formulation of the kinematical portion of quantum gravity that favors affine kinematical variables over canonical kinematical variables, and which generates a framework in which a favorable analysis of the constrained dynamical issues can take place. All this is possible because of the close connection between the affine and the canonical stories, while the few distinctions can be used to advantage when appropriate. This article is part of a special issue of Journal of Physics A: Mathematical and Theoretical devoted to ‘Coherent states: mathematical and physical aspects’. (review)
Analysis of radioactive-matter interaction near thermodynamical equilibrium states
International Nuclear Information System (INIS)
Damamme, G.
1993-01-01
We study the absorption/emission process of photon by matter in the framework of a radiativo-collisionnal model of atom, a thermodynamical approach being used. The considered matter description is the atomic sphere one. First we give the expression of the balance equation around an equilibrium state. Then we express the atomic populations in function of the characteristics of the radiation and of the free electrons and of their time history. This permit us to interpret the photon balance as being due to true emission/absorption process of photons as well as fluorescence terms, all these processes being affected by relaxation effects. The total energy balance between matter and radiation can also be analyzed in the same way and conduct to introduce one photon effective interactions terms for each radiative proper mode, terms also affected by retardation effects. Such a taking into account of atom populations has no consequence on the radiative flux equation (i.e. the transfer opacity) but can considerably modify the energy balance between matter and radiation. (author). 11 refs., 3 figs
Systemic analysis of thermodynamic properties of lanthanide halides
International Nuclear Information System (INIS)
Mirsaidov, U.; Badalov, A.; Marufi, V.K.
1992-01-01
System analysis of thermodynamic characteristics of lanthanide halides was carried out. A method making allowances for the influence of spin and orbital moments of momentum of the main states of lanthanide trivalent ions in their natural series was employed. Unknown in literature thermodynamic values were calculated and corrected for certain compounds. The character of lanthanide halide thermodynamic parameter change depending on ordinal number of the metals was ascertained. Pronouncement of tetrad-effect in series of compounds considered was pointed out
Hybrid ANN–PLS approach to scroll compressor thermodynamic performance prediction
International Nuclear Information System (INIS)
Tian, Z.; Gu, B.; Yang, L.; Lu, Y.
2015-01-01
In this paper, a scroll compressor thermodynamic performance prediction was carried out by applying a hybrid ANN–PLS model. Firstly, an experimental platform with second-refrigeration calorimeter was set up and steady-state scroll compressor data sets were collected from experiments. Then totally 148 data sets were introduced to train and verify the validity of the ANN–PLS model for predicting the scroll compressor parameters such as volumetric efficiency, refrigerant mass flow rate, discharge temperature and power consumption. The ANN–PLS model was determined with 5 hidden neurons and 7 latent variables through the training process. Ultimately, the ANN–PLS model showed better performance than the ANN model and the PLS model working separately. ANN–PLS predictions agree well with the experimental values with mean relative errors (MREs) in the range of 0.34–1.96%, correlation coefficients (R 2 ) in the range of 0.9703–0.9999 and very low root mean square errors (RMSEs). - Highlights: • Hybrid ANN–PLS is utilized to predict the thermodynamic performance of scroll compressor. • ANN–PLS model is determined with 5 hidden neurons and 7 latent variables. • ANN–PLS model demonstrates better performance than ANN and PLS working separately. • The values of MRE and RMSE are in the range of 0.34–1.96% and 0.9703–0.9999, respectively
Thermodynamic properties of water solvating biomolecular surfaces
Heyden, Matthias
Changes in the potential energy and entropy of water molecules hydrating biomolecular interfaces play a significant role for biomolecular solubility and association. Free energy perturbation and thermodynamic integration methods allow calculations of free energy differences between two states from simulations. However, these methods are computationally demanding and do not provide insights into individual thermodynamic contributions, i.e. changes in the solvent energy or entropy. Here, we employ methods to spatially resolve distributions of hydration water thermodynamic properties in the vicinity of biomolecular surfaces. This allows direct insights into thermodynamic signatures of the hydration of hydrophobic and hydrophilic solvent accessible sites of proteins and small molecules and comparisons to ideal model surfaces. We correlate dynamic properties of hydration water molecules, i.e. translational and rotational mobility, to their thermodynamics. The latter can be used as a guide to extract thermodynamic information from experimental measurements of site-resolved water dynamics. Further, we study energy-entropy compensations of water at different hydration sites of biomolecular surfaces. This work is supported by the Cluster of Excellence RESOLV (EXC 1069) funded by the Deutsche Forschungsgemeinschaft.
First principles thermodynamics of alloys
International Nuclear Information System (INIS)
Ducastelle, F.
1993-01-01
We present a brief report on the methods of solid state physics (electronic structure, statistical thermodynamics) that allow us to discuss the phase stability of alloys and to determine their phase diagrams. (orig.)
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
Thermodynamics of gravitationally induced particle creation scenario in DGP braneworld
Energy Technology Data Exchange (ETDEWEB)
Jawad, Abdul; Rani, Shamaila; Rafique, Salman [COMSATS Institute of Information Technology, Department of Mathematics, Lahore (Pakistan)
2018-01-15
In this paper, we discuss the thermodynamical analysis for gravitationally induced particle creation scenario in the framework of DGP braneworld model. For this purpose, we consider apparent horizon as the boundary of the universe. We take three types of entropy such as Bakenstein entropy, logarithmic corrected entropy and power law corrected entropy with ordinary creation rate Γ. We analyze the first law and generalized second law of thermodynamics analytically for these entropies which hold under some constraints. The behavior of total entropy in each case is also discussed which implies the validity of generalized second law of thermodynamics. Also, we check the thermodynamical equilibrium condition for two phases of creation rate, that is constant and variable Γ and found its vitality in all cases of entropy. (orig.)
Thermodynamics of gravitationally induced particle creation scenario in DGP braneworld
International Nuclear Information System (INIS)
Jawad, Abdul; Rani, Shamaila; Rafique, Salman
2018-01-01
In this paper, we discuss the thermodynamical analysis for gravitationally induced particle creation scenario in the framework of DGP braneworld model. For this purpose, we consider apparent horizon as the boundary of the universe. We take three types of entropy such as Bakenstein entropy, logarithmic corrected entropy and power law corrected entropy with ordinary creation rate Γ. We analyze the first law and generalized second law of thermodynamics analytically for these entropies which hold under some constraints. The behavior of total entropy in each case is also discussed which implies the validity of generalized second law of thermodynamics. Also, we check the thermodynamical equilibrium condition for two phases of creation rate, that is constant and variable Γ and found its vitality in all cases of entropy. (orig.)
On the thermodynamic stability of the generalized Chaplygin gas
International Nuclear Information System (INIS)
Santos, F.C.; Bedran, M.L.; Soares, V.
2006-01-01
The main purpose of this Letter is to discuss the temperature behavior and the thermodynamic stability of an exotic fluid known as generalized Chaplygin gas considering only general thermodynamics. This fluid is considered a perfect fluid which obeys an adiabatic equation of state like P=-A/ρ α , where P and ρ are respectively the pressure and energy density; the parameter A is a positive universal constant and α>0. It is remarked that if the energy density of the fluid is a function of volume only, the temperature of the fluid remains zero at any pressure or volume, violating the third law of thermodynamics. We have determined a scenario where its thermal equation of state depends on temperature only and the fluid presents thermodynamic stability during any expansion process. Such a scenario also reveals that the fluid cools down through the expansion without facing any critical point or phase transition
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.)
Positive Nonlinear Dynamical Group Uniting Quantum Mechanics and Thermodynamics
Beretta, Gian Paolo
2006-01-01
We discuss and motivate the form of the generator of a nonlinear quantum dynamical group 'designed' so as to accomplish a unification of quantum mechanics (QM) and thermodynamics. We call this nonrelativistic theory Quantum Thermodynamics (QT). Its conceptual foundations differ from those of (von Neumann) quantum statistical mechanics (QSM) and (Jaynes) quantum information theory (QIT), but for thermodynamic equilibrium (TE) states it reduces to the same mathematics, and for zero entropy stat...
pycalphad: CALPHAD-based Computational Thermodynamics in Python
Directory of Open Access Journals (Sweden)
Richard Otis
2017-01-01
Full Text Available The pycalphad software package is a free and open-source Python library for designing thermodynamic models, calculating phase diagrams and investigating phase equilibria using the CALPHAD method. It provides routines for reading thermodynamic databases and solving the multi-component, multi-phase Gibbs energy minimization problem. The pycalphad software project advances the state of thermodynamic modeling by providing a flexible yet powerful interface for manipulating CALPHAD data and models. The key feature of the software is that the thermodynamic models of individual phases and their associated databases can be programmatically manipulated and overridden at run-time without modifying any internal solver or calculation code. Because the models are internally decoupled from the equilibrium solver and the models themselves are represented symbolically, pycalphad is an ideal tool for CALPHAD database development and model prototyping.
Stochastic approach to equilibrium and nonequilibrium thermodynamics.
Tomé, Tânia; de Oliveira, Mário J
2015-04-01
We develop the stochastic approach to thermodynamics based on stochastic dynamics, which can be discrete (master equation) and continuous (Fokker-Planck equation), and on two assumptions concerning entropy. The first is the definition of entropy itself and the second the definition of entropy production rate, which is non-negative and vanishes in thermodynamic equilibrium. Based on these assumptions, we study interacting systems with many degrees of freedom in equilibrium or out of thermodynamic equilibrium and how the macroscopic laws are derived from the stochastic dynamics. These studies include the quasiequilibrium processes; the convexity of the equilibrium surface; the monotonic time behavior of thermodynamic potentials, including entropy; the bilinear form of the entropy production rate; the Onsager coefficients and reciprocal relations; and the nonequilibrium steady states of chemical reactions.
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 charged Lovelock: AdS black holes
International Nuclear Information System (INIS)
Prasobh, C.B.; Suresh, Jishnu; Kuriakose, V.C.
2016-01-01
We investigate the thermodynamic behavior of maximally symmetric charged, asymptotically AdS black hole solutions of Lovelock gravity. We explore the thermodynamic stability of such solutions by the ordinary method of calculating the specific heat of the black holes and investigating its divergences which signal second-order phase transitions between black hole states. We then utilize the methods of thermodynamic geometry of black hole spacetimes in order to explain the origin of these points of divergence. We calculate the curvature scalar corresponding to a Legendre-invariant thermodynamic metric of these spacetimes and find that the divergences in the black hole specific heat correspond to singularities in the thermodynamic phase space. We also calculate the area spectrum for large black holes in the model by applying the Bohr-Sommerfeld quantization to the adiabatic invariant calculated for the spacetime. (orig.)
Thermodynamics of charged Lovelock: AdS black holes
Prasobh, C. B.; Suresh, Jishnu; Kuriakose, V. C.
2016-04-01
We investigate the thermodynamic behavior of maximally symmetric charged, asymptotically AdS black hole solutions of Lovelock gravity. We explore the thermodynamic stability of such solutions by the ordinary method of calculating the specific heat of the black holes and investigating its divergences which signal second-order phase transitions between black hole states. We then utilize the methods of thermodynamic geometry of black hole spacetimes in order to explain the origin of these points of divergence. We calculate the curvature scalar corresponding to a Legendre-invariant thermodynamic metric of these spacetimes and find that the divergences in the black hole specific heat correspond to singularities in the thermodynamic phase space. We also calculate the area spectrum for large black holes in the model by applying the Bohr-Sommerfeld quantization to the adiabatic invariant calculated for the spacetime.
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
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
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
Fundamental aspects of plasma chemical physics Thermodynamics
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...
International Nuclear Information System (INIS)
Salvestrini, Stefano; Leone, Vincenzo; Iovino, Pasquale; Canzano, Silvana; Capasso, Sante
2014-01-01
Highlights: • Different methods to derive sorption thermodynamic parameters have been discussed. • ΔG° and, ΔS° values depend on the selected standard states. • Isosteric heat values help in evaluating the applicability of the sorption models. -- Abstract: This is a comparative analysis of popular methods currently in use to derive sorption thermodynamic parameters from temperature dependence of sorption isotherms. It is emphasized that the standard and isosteric thermodynamic parameters have sharply different meanings. Moreover, it is shown with examples how the sorption model adopted conditions the standard state and consequently the value of ΔG° and ΔS°. These trivial but often neglected aspects should carefully be considered when comparing thermodynamic parameters from different literature sources. An effort by the scientific community is needed to define criteria for the choice of the standard state in sorption processes
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.)
A fresh look at the thermodynamic consistency of vapour-liquid equilibria data
International Nuclear Information System (INIS)
Wisniak, Jaime; Ortega, Juan; Fernández, Luis
2017-01-01
Highlights: • The thermodynamic consistency tests commonly used to evaluate VLE data are presented and discussed. • Advantages/disadvantages for each one of test are listed using actual examples. • All manuscripts should include information about VLE variables and test results. • In any case, the Herington test should not be used for VLE data evaluation. • Simultaneous application of several tests is recommended. - Abstract: Design of a separation unit requires real information about the phase equilibrium of the system being handled. Accurate equilibrium data allows the best design from a thermodynamic viewpoint and contributes to a better knowledge about the behaviour of fluids and their mixtures. The principles behind the concept of thermodynamic consistency are presented and discussed. The present state of the art shows that no definite test is available for insuring the quality of the measured values. The main available procedures for testing the consistency of vapour-liquid equilibrium (VLE) data at constant temperature or pressure are reviewed and analysed and recommendations provided for their proper use, for the presentation of VLE results, and also some possible means for determining their quality. Suitable examples are provided about the adequate use of the available tests and about their misuse.
Directory of Open Access Journals (Sweden)
Francesco Oliveri
2016-01-01
Full Text Available The exploitation of second law of thermodynamics for a mixture of two fluids with a scalar internal variable and a first order nonlocal state space is achieved by using the extended Liu approach. This method requires to insert as constraints in the entropy inequality either the field equations or their gradient extensions. Consequently, the thermodynamic restrictions imposed by the entropy principle are derived without introducing extra terms neither in the energy balance equation nor in the entropy inequality.
Thermodynamic assessment of the Cu–Fe–Ni system
International Nuclear Information System (INIS)
Dreval, Liya A.; Turchanin, Mikhail A.; Agraval, Pavel G.
2014-01-01
Highlights: • The thermodynamic description of the Cu–Fe–Ni system has been updated. • The new experimental data have been used to refine thermodynamic model of the system. • The four-sublattice model has been adopted to predict the equilibria involving the ordered L1 2 phase. • A significant improvement in comparison with the previous assessments has been achieved. • The liquidus and solidus projections have been presented. -- Abstract: The thermodynamic description of the Cu–Fe–Ni system has been updated considering the newly available experimental data, as well as compatibility of the present modeling with those used for the Cu and Fe systems. All of the experimental data available in the literature have been critically reviewed, and the inconsistent information has been excluded. The thermodynamic parameters have been evaluated in order to properly describe the thermodynamic properties of the liquid phase and miscibility gap in the solid state. A significant improvement in comparison with the previous thermodynamic descriptions has been achieved. Additionally, for the ordered L1 2 phase the four-sublattice model has been adopted to predict the ternary phase equilibria involving this phase. A set of thermodynamic parameters for the phases is given
Huang, Jinfeng; Zhu, Yali; Sun, Bin; Yao, Yuan; Liu, Junjun
2016-03-01
The protonation state of the Asp dyad is important as it can reveal enzymatic mechanisms, and the information this provides can be used in the development of drugs for proteins such as memapsin 2 (BACE-1), HIV-1 protease, and rennin. Conventional molecular dynamics (MD) simulations have been successfully used to determine the preferred protonation state of the Asp dyad. In the present work, we demonstrate that the results obtained from conventional MD simulations can be greatly influenced by the particular force field applied or the values used for control parameters. In principle, free-energy changes between possible protonation states can be used to determine the protonation state. We show that protonation state prediction by the thermodynamic integration (TI) method is insensitive to force field version or to the cutoff for calculating nonbonded interactions (a control parameter). In the present study, the protonation state of the Asp dyad predicted by TI calculations was the same regardless of the force field and cutoff value applied. Contrary to the intuition that conventional MD is more efficient, our results clearly show that the TI method is actually more efficient and more reliable for determining the protonation state of the Asp dyad.
Continuous variable quantum key distribution with modulated entangled states
DEFF Research Database (Denmark)
Madsen, Lars S; Usenko, Vladyslav C.; Lassen, Mikael
2012-01-01
Quantum key distribution enables two remote parties to grow a shared key, which they can use for unconditionally secure communication over a certain distance. The maximal distance depends on the loss and the excess noise of the connecting quantum channel. Several quantum key distribution schemes...... based on coherent states and continuous variable measurements are resilient to high loss in the channel, but are strongly affected by small amounts of channel excess noise. Here we propose and experimentally address a continuous variable quantum key distribution protocol that uses modulated fragile...... entangled states of light to greatly enhance the robustness to channel noise. We experimentally demonstrate that the resulting quantum key distribution protocol can tolerate more noise than the benchmark set by the ideal continuous variable coherent state protocol. Our scheme represents a very promising...
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
Black Hole Thermodynamics in an Undergraduate Thermodynamics Course.
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)
Thermodynamic tables to accompany Modern engineering thermodynamics
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.
Coupling-parameter expansion in thermodynamic perturbation theory.
Ramana, A Sai Venkata; Menon, S V G
2013-02-01
An approach to the coupling-parameter expansion in the liquid state theory of simple fluids is presented by combining the ideas of thermodynamic perturbation theory and integral equation theories. This hybrid scheme avoids the problems of the latter in the two phase region. A method to compute the perturbation series to any arbitrary order is developed and applied to square well fluids. Apart from the Helmholtz free energy, the method also gives the radial distribution function and the direct correlation function of the perturbed system. The theory is applied for square well fluids of variable ranges and compared with simulation data. While the convergence of perturbation series and the overall performance of the theory is good, improvements are needed for potentials with shorter ranges. Possible directions for further developments in the coupling-parameter expansion are indicated.
Onsager's reciprocity theorem in extended irreversible thermodynamics
International Nuclear Information System (INIS)
Garcia-Colin, L.S.; Velasco, R.M.
1992-01-01
In this paper we shall discuss the Onsager relations for the transport coefficients in a dilute monatomic gas described by the extended irreversible thermodynamics. Our discussion is based on a 26 variables description of the system and its corresponding comparison with the kinetic reciprocity between coefficients is shown (Author)
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 aspects of dynamical calibration of microbarometers used for IMS applications
International Nuclear Information System (INIS)
Starovojt, Yu.O.; Martysevich, P.N.; Kunakov, A.V.
2006-01-01
This paper describes the method of dynamical calibration of a microbarometer using the chamber with variable volume. The physics of this method is based on the thermodynamic process occurring inside the closed volume and on the corresponding relationships between pressure, volume and temperature changes caused by the movement of the piston attached to the inlet of the chamber. The method has been already used in several applications, however we consider essential to analyze its physical details. The paper gives the description of thermodynamic processes inside the calibration volume, the discussion of thermodynamics need and its effect on the calibration accuracy. (author)
Thermodynamic data development using the solubility method (Joint research)
International Nuclear Information System (INIS)
Rai, Dhanpat; Yui, Mikazu
2013-05-01
The solubility method is one of the most powerful tools to obtain reliable thermodynamic data for 1) solubility products of discrete solids and double salts, 2) complexation constants for various ligands, 3) development of data in a wide range of pH values, 4) evaluation of data for metals that form very insoluble solids (e.g. tetravalent actinides), 5) determining solubility-controlling solids in different types of wastes and 6) elevated temperatures for redox sensitive systems. This document is focused on describing various aspects of obtaining thermodynamic data using the solubility method. This manuscript deals with various aspects of conducting solubility studies, including selecting the study topic, modeling to define important variables, selecting the range of variables and experimental parameters, anticipating results, general equipment requirements, conducting experiments, and interpreting experimental data. (author)
Outcalt, Stephanie L.; McLinden, Mark O.
1996-03-01
A modified Benedict-Webb-Rubin (MBWR) equation of state has been developed for R152a (1,1-difluoroethane). The correlation is based on a selection of available experimental thermodynamic property data. Single-phase pressure-volume-temperature (PVT), heat capacity, and sound speed data, as well as second virial coefficient, vapor pressure, and saturated liquid and saturated vapor density data, were used with multi-property linear least-squares fitting to determine the 32 adjustable coefficients of the MBWR equation. Ancillary equations representing the vapor pressure, saturated liquid and saturated vapor densities, and the ideal gas heat capacity were determined. Coefficients for the equation of state and the ancillary equations are given. Experimental data used in this work covered temperatures from 162 K to 453 K and pressures to 35 MPa. The MBWR equation established in this work may be used to predict thermodynamic properties of R152a from the triple-point temperature of 154.56 K to 500 K and for pressures up to 60 MPa except in the immediate vicinity of the critical point.
Mass transfer and thermodynamic modeling of carbon dioxide absorption into MEA aqueous solution
Directory of Open Access Journals (Sweden)
Ghaemi Ahad
2017-09-01
Full Text Available In this research, thermodynamic and absorption rate of carbon dioxide in monoethanolamine (MEA solution was investigated. A correlation based on both liquid and a gas phase variable for carbon dioxide absorption rate was presented using the π-Buckingham theorem. The correlation was constructed based on dimensionless numbers, including carbon dioxide loading, carbon dioxide partial pressure, film parameter and the ratio of liquid phase film thickness and gas phase film thickness. The film parameter is used to apply the effect of chemical reactions on absorption rate. A thermodynamic model based on the extended-UNIQUAC equations for the activity coefficients coupled with the Virial equation of state for representing the non-ideality of the vapor phase was used to predict the CO2 solubility in the CO2-MEA-H2O system. The average absolute error of the results for the correlation was 6.4%, which indicates the accuracy of the proposed correlation.
A Study of Universal Thermodynamics in Brane World Scenario
International Nuclear Information System (INIS)
Mitra, Saugata; Saha, Subhajit; Chakraborty, Subenoy
2015-01-01
A study of Universal thermodynamics is done in the framework of RSII brane model and DGP brane scenario. The Universe is chosen as FRW model bounded by apparent or event horizon. Assuming extended Hawking temperature on the horizon, the unified first law is examined for perfect fluid (with constant equation of state) and Modified Chaplygin Gas model. As a result there is a modification of Bekenstein entropy on the horizons. Further the validity of the generalized second law of thermodynamics and thermodynamical equilibrium are also investigated
Thermodynamics analysis of the rare earth metals and their alloys with indium in solid state
International Nuclear Information System (INIS)
Vassiliev, V.P.; Benaissa, Ablazeze; Taldrik, A.F.
2013-01-01
Graphical abstract: Gibbs energies of formation vs. RE atomic numbers in REIn 3 . Highlights: •Set of experimental values was collected for REIn 3 phases. •Thermodynamic functions of formation were calculated at 298 K and 775 K. •Experimental and calculated values were compared. -- Abstract: Nonlinear correlative analyses between thermodynamic and some physico-chemical properties of rare-earth metals (RE) and their alloys with indium are performed for the isostructural phases RE and REIn 3 . The thermodynamics values (Gibbs energies of formation, enthalpies of formation, and entropies of formation at 298 K and 775 K and standard entropies) of LnIn 3 phases are calculated on the basis of calorimetry and potentiometry results. The proposed correlation between physico-chemical and thermodynamic properties agrees for all the isostructural phases REX (X are others elements of the periodic table). The resulting thermodynamic data are recommended for metallurgical handbook
Lagrangian formulation of irreversible thermodynamics and the second law of thermodynamics.
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.
International Nuclear Information System (INIS)
Armas, Octavio; Ballesteros, Rosario; Cardenas, María Dolores
2012-01-01
Highlights: ► Thermodynamic diagnosis was applied to diesel combustion process during transient operation. ► Comparative analysis of thermodynamic results with different biodiesel fuels has been carried out. ► Biodiesel fuels studied have a slight effect on timing of the combustion process. ► Methodology used can be applied to improve engine control when using different alternative fuels. -- Abstract: The study of the diesel combustion process is a current topic by the need of thermal efficiency improving and the reduction of pollutant emissions. This circumstance has forced researchers and manufacturers to optimize this process not only in steady state operating conditions but also during transient operation. A zero dimensional thermodynamic diagnostic model, with three species (air, fuel evaporated and burned products), has been used to characterize the combustion process during load increase transient sequences at two different engine speed. In both sequences, three variables were studied: the valve position of the exhaust gas recirculation (EGR), the elapsed time of the transition process and the type of fuel. Three biodiesel fuels were tested pure: rapeseed, soybean and sunflower which were compared to a commercial diesel fuel used as reference. Results are presented comparing the in-cylinder average maximum pressure and temperature, and the phasing of the combustion process based on the calculation of heat release. This study has allowed the detection of the effect of the tested engine parameters and the biodiesel fuels used on the in-cylinder thermodynamic conditions during the load transient sequences studied.
Thermodynamics of higher spin black holes in AdS3
de Boer, Jan; Jottar, Juan I.
2014-01-01
We discuss the thermodynamics of recently constructed three-dimensional higher spin black holes in SL( N, ) × SL( N, ) Chern-Simons theory with generalized asymptotically-anti-de Sitter boundary conditions. From a holographic perspective, these bulk theories are dual to two-dimensional CFTs with WN symmetry algebras, and the black hole solutions are dual to thermal states with higher spin chemical potentials and charges turned on. Because the notion of horizon area is not gauge-invariant in the higher spin theory, the traditional approaches to the computation of black hole entropy must be reconsidered. One possibility, explored in the recent literature, involves demanding the existence of a partition function in the CFT, and consistency with the first law of thermodynamics. This approach is not free from ambiguities, however, and in particular different definitions of energy result in different expressions for the entropy. In the present work we show that there are natural definitions of the thermodynamically conjugate variables that follow from careful examination of the variational principle, and moreover agree with those obtained via canonical methods. Building on this intuition, we derive general expressions for the higher spin black hole entropy and free energy which are written entirely in terms of the Chern-Simons connections, and are valid for both static and rotating solutions. We compare our results to other proposals in the literature, and provide a new and efficient way to determine the generalization of the Cardy formula to a situation with higher spin charges.
Geometric Description of the Thermodynamics of the Noncommutative Schwarzschild Black Hole
Directory of Open Access Journals (Sweden)
Alexis Larrañaga
2013-01-01
Full Text Available The thermodynamics of the noncommutative Schwarzschild black hole is reformulated within the context of the recently developed formalism of geometrothermodynamics (GTD. Using a thermodynamic metric which is invariant with respect to Legendre transformations, we determine the geometry of the space of equilibrium states and show that phase transitions, which correspond to divergencies of the heat capacity, are represented geometrically as singularities of the curvature scalar. This further indicates that the curvature of the thermodynamic metric is a measure of thermodynamic interaction.
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
Exceptional thermodynamics. The equation of state of G2 gauge theory
International Nuclear Information System (INIS)
Bruno, Mattia; Panero, Marco; Pellegrini, Roberto
2014-10-01
We present a lattice study of the equation of state in Yang-Mills theory based on the exceptional G 2 gauge group. As is well-known, at zero temperature this theory shares many qualitative features with real-world QCD, including the absence of colored states in the spectrum and dynamical string breaking at large distances. In agreement with previous works, we show that at finite temperature this theory features a first-order deconfining phase transition, whose nature can be studied by a semi-classical computation. We also show that the equilibrium thermodynamic observables in the deconfined phase bear striking quantitative similarities with those found in SU(N) gauge theories: in particular, these quantities exhibit nearly perfect proportionality to the number of gluon degrees of freedom, and the trace anomaly reveals a characteristic quadratic dependence on the temperature, also observed in SU(N) Yang-Mills theories (both in four and in three spacetime dimensions). We compare our lattice data with analytical predictions from effective models, and discuss their implications for the deconfinement mechanism and high-temperature properties of strongly interacting, non-supersymmetric gauge theories. Our results give strong evidence for the conjecture that the thermal deconfining transition is governed by a universal mechanism, common to all simple gauge groups.
Quantum engineering of continuous variable quantum states
Energy Technology Data Exchange (ETDEWEB)
Sabuncu, Metin
2009-10-29
Quantum information with continuous variables is a field attracting increasing attention recently. In continuous variable quantum information one makes use of the continuous information encoded into the quadrature of a quantized light field instead of binary quantities such as the polarization state of a single photon. This brand new research area is witnessing exciting theoretical and experimental achievements such as teleportation, quantum computation and quantum error correction. The rapid development of the field is mainly due higher optical data rates and the availability of simple and efficient manipulation tools in continuous-variable quantum information processing. We in this thesis extend the work in continuous variable quantum information processing and report on novel experiments on amplification, cloning, minimal disturbance and noise erasure protocols. The promising results we obtain in these pioneering experiments indicate that the future of continuous variable quantum information is bright and many advances can be foreseen. (orig.)
Quantum engineering of continuous variable quantum states
International Nuclear Information System (INIS)
Sabuncu, Metin
2009-01-01
Quantum information with continuous variables is a field attracting increasing attention recently. In continuous variable quantum information one makes use of the continuous information encoded into the quadrature of a quantized light field instead of binary quantities such as the polarization state of a single photon. This brand new research area is witnessing exciting theoretical and experimental achievements such as teleportation, quantum computation and quantum error correction. The rapid development of the field is mainly due higher optical data rates and the availability of simple and efficient manipulation tools in continuous-variable quantum information processing. We in this thesis extend the work in continuous variable quantum information processing and report on novel experiments on amplification, cloning, minimal disturbance and noise erasure protocols. The promising results we obtain in these pioneering experiments indicate that the future of continuous variable quantum information is bright and many advances can be foreseen. (orig.)
A commentary on thermodynamics
Day, William Alan
1988-01-01
The aim of this book is to comment on, and clarify, the mathematical aspects of the theory of thermodynamics. The standard presentations of the subject are often beset by a number of obscurities associated with the words "state", "reversible", "irreversible", and "quasi-static". This book is written in the belief that such obscurities are best removed not by the formal axiomatization of thermodynamics, but by setting the theory in the wider context of a genuine field theory which incorporates the effects of heat conduction and intertia, and proving appropriate results about the governing differential equations of this field theory. Even in the simplest one-dimensional case it is a nontrivial task to carry through the details of this program, and many challenging problems remain open.
Thermodynamics of a periodically driven qubit
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.
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...
Derivation of the phase field equations from the thermodynamic extremal principle
International Nuclear Information System (INIS)
Svoboda, J.; Fischer, F.D.; McDowell, D.L.
2012-01-01
Thermodynamics employs quantities that characterize the state of the system and provides driving forces for system evolution. These quantities can be applied by means of the thermodynamic extremal principle to obtain models and consequently constitutive equations for the evolution of the thermodynamic systems. The phase field method is a promising tool for simulation of the microstructure evolution in complex systems but introduces several parameters that are not standard in thermodynamics. The purpose of this paper is to show how the phase field method equations can be derived from the thermodynamic extremal principle, allowing the common treatment of the phase field parameters together with standard thermodynamic parameters in future applications. Fixed values of the phase field parameters may, however, not guarantee fixed values of thermodynamic parameters. Conditions are determined, for which relatively stable values of the thermodynamic parameters are guaranteed during phase field method simulations of interface migration. Finally, analytical relations between the thermodynamic and phase field parameters are found and verified for these simulations. A slight dependence of the thermodynamic parameters on the driving force is determined for the cases examined.
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
Metal viscoplasticity with two-temperature thermodynamics and two dislocation densities
Roy Chowdhury, Shubhankar; Kar, Gurudas; Roy, Debasish; Reddy, J. N.
2018-03-01
Posed within the two-temperature theory of non-equilibrium thermodynamics, we propose a model for thermoviscoplastic deformation in metals. We incorporate the dynamics of dislocation densities-mobile and forest—that play the role of internal state variables in the formulation. The description based on two temperatures appears naturally when one recognizes that the thermodynamic system undergoing viscoplastic deformation is composed of two weakly interacting subsystems, viz. a kinetic-vibrational subsystem of the vibrating atomic lattices and a configurational subsystem of the slower degrees of freedom relating to defect motion, each with its own temperature. Starting with a basic model that involves only homogeneous deformation, a three-dimensional model for inhomogeneous viscoplasticity applicable to finite deformation is charted out in an overstress driven viscoplastic deformation framework. The model shows how the coupled evolutions of mobile and forest dislocation densities, which are critically influenced by the dynamics of configurational temperature, govern the strength and ductility of the metal. Unlike most contemporary models, the current proposal also affords a prediction of certain finer details as observed in the experimental data on stress-strain behaviour of metals and this in turn enhances the understanding of the evolving and interacting dislocation densities.
Statistical black-hole thermodynamics
International Nuclear Information System (INIS)
Bekenstein, J.D.
1975-01-01
Traditional methods from statistical thermodynamics, with appropriate modifications, are used to study several problems in black-hole thermodynamics. Jaynes's maximum-uncertainty method for computing probabilities is used to show that the earlier-formulated generalized second law is respected in statistically averaged form in the process of spontaneous radiation by a Kerr black hole discovered by Hawking, and also in the case of a Schwarzschild hole immersed in a bath of black-body radiation, however cold. The generalized second law is used to motivate a maximum-entropy principle for determining the equilibrium probability distribution for a system containing a black hole. As an application we derive the distribution for the radiation in equilibrium with a Kerr hole (it is found to agree with what would be expected from Hawking's results) and the form of the associated distribution among Kerr black-hole solution states of definite mass. The same results are shown to follow from a statistical interpretation of the concept of black-hole entropy as the natural logarithm of the number of possible interior configurations that are compatible with the given exterior black-hole state. We also formulate a Jaynes-type maximum-uncertainty principle for black holes, and apply it to obtain the probability distribution among Kerr solution states for an isolated radiating Kerr hole
Leveraging Environmental Correlations: The Thermodynamics of Requisite Variety
Boyd, Alexander B.; Mandal, Dibyendu; Crutchfield, James P.
2017-06-01
Key to biological success, the requisite variety that confronts an adaptive organism is the set of detectable, accessible, and controllable states in its environment. We analyze its role in the thermodynamic functioning of information ratchets—a form of autonomous Maxwellian Demon capable of exploiting fluctuations in an external information reservoir to harvest useful work from a thermal bath. This establishes a quantitative paradigm for understanding how adaptive agents leverage structured thermal environments for their own thermodynamic benefit. General ratchets behave as memoryful communication channels, interacting with their environment sequentially and storing results to an output. The bulk of thermal ratchets analyzed to date, however, assume memoryless environments that generate input signals without temporal correlations. Employing computational mechanics and a new information-processing Second Law of Thermodynamics (IPSL) we remove these restrictions, analyzing general finite-state ratchets interacting with structured environments that generate correlated input signals. On the one hand, we demonstrate that a ratchet need not have memory to exploit an uncorrelated environment. On the other, and more appropriate to biological adaptation, we show that a ratchet must have memory to most effectively leverage structure and correlation in its environment. The lesson is that to optimally harvest work a ratchet's memory must reflect the input generator's memory. Finally, we investigate achieving the IPSL bounds on the amount of work a ratchet can extract from its environment, discovering that finite-state, optimal ratchets are unable to reach these bounds. In contrast, we show that infinite-state ratchets can go well beyond these bounds by utilizing their own infinite "negentropy". We conclude with an outline of the collective thermodynamics of information-ratchet swarms.
Thermodynamics of freezing and melting
DEFF Research Database (Denmark)
Pedersen, Ulf Rørbæk; Costigliola, Lorenzo; Bailey, Nicholas
2016-01-01
phases at a single thermodynamic state point provide the basis for calculating the pressure, density and entropy of fusion as functions of temperature along the melting line, as well as the variation along this line of the reduced crystalline vibrational mean-square displacement (the Lindemann ratio...
Mechanics of deformations in terms of scalar variables
Ryabov, Valeriy A.
2017-05-01
Theory of particle and continuous mechanics is developed which allows a treatment of pure deformation in terms of the set of variables "coordinate-momentum-force" instead of the standard treatment in terms of tensor-valued variables "strain-stress." This approach is quite natural for a microscopic description of atomic system, according to which only pointwise forces caused by the stress act to atoms making a body deform. The new concept starts from affine transformation of spatial to material coordinates in terms of the stretch tensor or its analogs. Thus, three principal stretches and three angles related to their orientation form a set of six scalar variables to describe deformation. Instead of volume-dependent potential used in the standard theory, which requires conditions of equilibrium for surface and body forces acting to a volume element, a potential dependent on scalar variables is introduced. A consistent introduction of generalized force associated with this potential becomes possible if a deformed body is considered to be confined on the surface of torus having six genuine dimensions. Strain, constitutive equations and other fundamental laws of the continuum and particle mechanics may be neatly rewritten in terms of scalar variables. Giving a new presentation for finite deformation new approach provides a full treatment of hyperelasticity including anisotropic case. Derived equations of motion generate a new kind of thermodynamical ensemble in terms of constant tension forces. In this ensemble, six internal deformation forces proportional to the components of Irving-Kirkwood stress are controlled by applied external forces. In thermodynamical limit, instead of the pressure and volume as state variables, this ensemble employs deformation force measured in kelvin unit and stretch ratio.
Interphase thermodynamic bond in heterogeneous alloys: effects on alloy properties
International Nuclear Information System (INIS)
Savchenko, A.M.; Konovalov, Yu.V.; Yuferov, O.I.
2005-01-01
Inconsistency between a conventional thermodynamic description of alloys as a mechanical mixture of phases and a real alloys state as a common thermodynamic system in which there is a complicated physical-chemical phases interaction has been considered. It is supposed that in heterogeneous alloys (eutectic ones, for instance), so called interphase thermodynamic bond can become apparent due to a partial electron levels splitting under phase interaction. Thermodynamic description of phase equilibrium in alloys is proposed taking into account a thermodynamic bond for the system with phase diagram of eutectic type, and methods of the value of this bond estimation are presented. Experimental evidence (Al-Cu-Si, Al-Si-Mg-Cu, U-Mo + Al) of the effect of interphase thermodynamic bond on temperature and enthalpy of melting of alloys are produced as well as possibility of its effects on alloys electrical conduction, strength, heat and corrosion resistance is substantiated theoretically [ru
Nonequilibrium Thermodynamics of Driven Disordered Materials
Bouchbinder, Eran
2011-03-01
We present a nonequilibrium thermodynamic framework for describing the dynamics of driven disordered solids (noncrystalline solids near and below their glass temperature, soft glassy materials such as colloidal suspensions and heavily dislocated polycrystalline solids). A central idea in our approach is that the set of mechanically stable configurations, i.e. the part of the system that is described by inherent structures, evolves slowly as compared to thermal vibrations and is characterized by an effective disorder temperature. Our thermodynamics-motivated equations of motion for the flow of energy and entropy are supplemented by coarse-grained internal variables that carry information about the relevant microscopic physics. Applications of this framework to amorphous visco-plasticity (Shear-Transformation-Zone theory), glassy memory effects (the Kovacs effect) and dislocation-mediated polycrystalline plasticity will be briefly discussed.
A Novel Flood Forecasting Method Based on Initial State Variable Correction
Directory of Open Access Journals (Sweden)
Kuang Li
2017-12-01
Full Text Available The influence of initial state variables on flood forecasting accuracy by using conceptual hydrological models is analyzed in this paper and a novel flood forecasting method based on correction of initial state variables is proposed. The new method is abbreviated as ISVC (Initial State Variable Correction. The ISVC takes the residual between the measured and forecasted flows during the initial period of the flood event as the objective function, and it uses a particle swarm optimization algorithm to correct the initial state variables, which are then used to drive the flood forecasting model. The historical flood events of 11 watersheds in south China are forecasted and verified, and important issues concerning the ISVC application are then discussed. The study results show that the ISVC is effective and applicable in flood forecasting tasks. It can significantly improve the flood forecasting accuracy in most cases.
Continuous Variable Quantum Key Distribution Using Polarized Coherent States
Vidiella-Barranco, A.; Borelli, L. F. M.
We discuss a continuous variables method of quantum key distribution employing strongly polarized coherent states of light. The key encoding is performed using the variables known as Stokes parameters, rather than the field quadratures. Their quantum counterpart, the Stokes operators Ŝi (i=1,2,3), constitute a set of non-commuting operators, being the precision of simultaneous measurements of a pair of them limited by an uncertainty-like relation. Alice transmits a conveniently modulated two-mode coherent state, and Bob randomly measures one of the Stokes parameters of the incoming beam. After performing reconciliation and privacy amplification procedures, it is possible to distill a secret common key. We also consider a non-ideal situation, in which coherent states with thermal noise, instead of pure coherent states, are used for encoding.
A Thermodynamic Library for Simulation and Optimization of Dynamic Processes
DEFF Research Database (Denmark)
Ritschel, Tobias Kasper Skovborg; Gaspar, Jozsef; Jørgensen, John Bagterp
2017-01-01
Process system tools, such as simulation and optimization of dynamic systems, are widely used in the process industries for development of operational strategies and control for process systems. These tools rely on thermodynamic models and many thermodynamic models have been developed for different...... compounds and mixtures. However, rigorous thermodynamic models are generally computationally intensive and not available as open-source libraries for process simulation and optimization. In this paper, we describe the application of a novel open-source rigorous thermodynamic library, ThermoLib, which...... is designed for dynamic simulation and optimization of vapor-liquid processes. ThermoLib is implemented in Matlab and C and uses cubic equations of state to compute vapor and liquid phase thermodynamic properties. The novelty of ThermoLib is that it provides analytical first and second order derivatives...
International Nuclear Information System (INIS)
Lewis, A.E.; Khodabocus, F.; Dhokun, V.; Khalife, M.
2010-01-01
In a sugar refinery, the juice is concentrated through evaporation, with the objective of concentrating the juice to syrup as rapidly as possible. Because the heat of vaporization of water is relatively high, the evaporation process can be highly energy intensive, and therefore the economical use of steam is important in the refinery. This paper reports on the development of a simulation model for the evaporation sections of two Mauritian sugar refineries. The first objective was to use the simulation model to carry out an energy balance over the evaporators in order to assess the economy of steam usage over the refinery. The second objective was to examine to what extent a fundamental steady state model, based on thermodynamics (not kinetics) was capable of predicting the material and energy flows in two operating sugar refineries and thereby to evaluate the applicability of the modelling framework. The simulation model was validated using historical data as well as data from the plant DCS system. The simulation results generally correlated well with the measured values, except for one of the evaporators on one refinery. Some suggestions were made as to the cause of the discrepancy. On balance, it was found that both refineries are extremely efficient in terms of steam and equipment usage and that there is not much scope for energy optimisation within the present configuration - nor for much spare steam capacity for an additional refinery. It was also shown that steady state process simulation, using thermodynamic models, can generate a very useful representation of a working refinery. Besides being able to use the model to 'benchmark' the operation and thus evaluate its performance as a whole as well as across individual units, it could also be used to evaluate refinery performance across refineries, nationally as well as globally.
Thermodynamics of Fluid Polyamorphism
Directory of Open Access Journals (Sweden)
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.
International Nuclear Information System (INIS)
Cabrillo, C; Bermejo, F J; Maira-Vidal, A; Fernandez-Perea, R; Bennington, S M; Martin, D
2004-01-01
The advent of inelastic x-ray scattering techniques has prompted a reawakened interest in the dynamics of simple liquids. Such studies are often carried out using simplified models to account for the stochastic dynamics that give rise to quasielastic scattering. The vibrational and diffusive dynamics of molten potassium are studied here by an experiment using neutron scattering and are shown to provide some clues to understand the basic thermodynamics of the liquid state. The findings reported here suggest ways in which the true complementarity of neutron and x-ray scattering may be profitably exploited
Energy Technology Data Exchange (ETDEWEB)
Peleties, F. [Department of Chemical Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom); Segovia, J.J. [Grupo de Termodinamica y Calibracion (TERMOCAL), Dpto. Ingenieria Energetica y Fluidomecanica, E.T.S. de Ingenieros Industriales, Universidad de Valladolid, E-47011 Valladolid (Spain); Trusler, J.P.M., E-mail: m.trusler@imperial.ac.u [Department of Chemical Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom); Vega-Maza, D. [Grupo de Termodinamica y Calibracion (TERMOCAL), Dpto. Ingenieria Energetica y Fluidomecanica, E.T.S. de Ingenieros Industriales, Universidad de Valladolid, E-47011 Valladolid (Spain)
2010-05-15
We report measurements of the thermodynamic properties of liquid di-isodecyl phthalate (DIDP) and an equation of state determined therefrom. The speed of sound in DIDP was measured at temperatures between (293.15 and 413.15) K and a pressures between (0.1 and 140) MPa with a relative uncertainty of 0.1%. In addition, the isobaric specific heat capacity was measured at temperatures between (293.15 and 423.15) K at a pressure of 0.1 MPa with a relative uncertainty of 1%, and the density was measured at temperatures between (273.15 and 413.15) K at a pressure of 0.1 MPa with a relative uncertainty of 0.015%. The thermodynamic properties of DIDP were obtained from the measured speeds of sound by thermodynamic integration starting from the initial values of density and isobaric specific heat capacity obtained experimentally. The results have been represented by a new equation of state containing nine parameters with an uncertainty in density not worse than 0.025%. Comparisons with literature data are made.
International Nuclear Information System (INIS)
Peleties, F.; Segovia, J.J.; Trusler, J.P.M.; Vega-Maza, D.
2010-01-01
We report measurements of the thermodynamic properties of liquid di-isodecyl phthalate (DIDP) and an equation of state determined therefrom. The speed of sound in DIDP was measured at temperatures between (293.15 and 413.15) K and a pressures between (0.1 and 140) MPa with a relative uncertainty of 0.1%. In addition, the isobaric specific heat capacity was measured at temperatures between (293.15 and 423.15) K at a pressure of 0.1 MPa with a relative uncertainty of 1%, and the density was measured at temperatures between (273.15 and 413.15) K at a pressure of 0.1 MPa with a relative uncertainty of 0.015%. The thermodynamic properties of DIDP were obtained from the measured speeds of sound by thermodynamic integration starting from the initial values of density and isobaric specific heat capacity obtained experimentally. The results have been represented by a new equation of state containing nine parameters with an uncertainty in density not worse than 0.025%. Comparisons with literature data are made.
Barsuk, Alexandr A.; Paladi, Florentin
2018-04-01
The dynamic behavior of thermodynamic system, described by one order parameter and one control parameter, in a small neighborhood of ordinary and bifurcation equilibrium values of the system parameters is studied. Using the general methods of investigating the branching (bifurcations) of solutions for nonlinear equations, we performed an exhaustive analysis of the order parameter dependences on the control parameter in a small vicinity of the equilibrium values of parameters, including the stability analysis of the equilibrium states, and the asymptotic behavior of the order parameter dependences on the control parameter (bifurcation diagrams). The peculiarities of the transition to an unstable state of the system are discussed, and the estimates of the transition time to the unstable state in the neighborhood of ordinary and bifurcation equilibrium values of parameters are given. The influence of an external field on the dynamic behavior of thermodynamic system is analyzed, and the peculiarities of the system dynamic behavior are discussed near the ordinary and bifurcation equilibrium values of parameters in the presence of external field. The dynamic process of magnetization of a ferromagnet is discussed by using the general methods of bifurcation and stability analysis presented in the paper.
On the Spectral Entropy of Thermodynamic Paths for Elementary Systems
Directory of Open Access Journals (Sweden)
Daniel J. Graham
2009-12-01
Full Text Available Systems do not elect thermodynamic pathways on their own. They operate in tandem with their surroundings. Pathway selection and traversal require coordinated work and heat exchanges along with parallel tuning of the system variables. Previous research by the author (Reference [1] focused on the information expressed in thermodynamic pathways. Examined here is how spectral entropy is a by-product of information that depends intricately on the pathway structure. The spectral entropy has proven to be a valuable tool in diverse fields. This paper illustrates the contact between spectral entropy and the properties which distinguish ideal from non-ideal gases. The role of spectral entropy in the first and second laws of thermodynamics and heat → work conversions is also discussed.
Thermodynamic Bethe Ansatz for the Spin-1/2 Staggered XXZ- Model
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.
Determining Membrane Protein-Lipid Binding Thermodynamics Using Native Mass Spectrometry.
Cong, Xiao; Liu, Yang; Liu, Wen; Liang, Xiaowen; Russell, David H; Laganowsky, Arthur
2016-04-06
Membrane proteins are embedded in the biological membrane where the chemically diverse lipid environment can modulate their structure and function. However, the thermodynamics governing the molecular recognition and interaction of lipids with membrane proteins is poorly understood. Here, we report a method using native mass spectrometry (MS), to determine thermodynamics of individual ligand binding events to proteins. Unlike conventional methods, native MS can resolve individual ligand binding events and, coupled with an apparatus to control the temperature, determine binding thermodynamic parameters, such as for protein-lipid interactions. We validated our approach using three soluble protein-ligand systems (maltose binding protein, lysozyme, and nitrogen regulatory protein) and obtained similar results to those using isothermal titration calorimetry and surface plasmon resonance. We also determined for the first time the thermodynamics of individual lipid binding to the ammonia channel (AmtB), an integral membrane protein from Escherichia coli. Remarkably, we observed distinct thermodynamic signatures for the binding of different lipids and entropy-enthalpy compensation for binding lipids of variable chain length. Additionally, using a mutant form of AmtB that abolishes a specific phosphatidylglycerol (PG) binding site, we observed distinct changes in the thermodynamic signatures for binding PG, implying these signatures can identify key residues involved in specific lipid binding and potentially differentiate between specific lipid binding sites.
Nonequilibrium thermodynamics of dilute polymer solutions in flow.
Latinwo, Folarin; Hsiao, Kai-Wen; Schroeder, Charles M
2014-11-07
Modern materials processing applications and technologies often occur far from equilibrium. To this end, the processing of complex materials such as polymer melts and nanocomposites generally occurs under strong deformations and flows, conditions under which equilibrium thermodynamics does not apply. As a result, the ability to determine the nonequilibrium thermodynamic properties of polymeric materials from measurable quantities such as heat and work is a major challenge in the field. Here, we use work relations to show that nonequilibrium thermodynamic quantities such as free energy and entropy can be determined for dilute polymer solutions in flow. In this way, we determine the thermodynamic properties of DNA molecules in strong flows using a combination of simulations, kinetic theory, and single molecule experiments. We show that it is possible to calculate polymer relaxation timescales purely from polymer stretching dynamics in flow. We further observe a thermodynamic equivalence between nonequilibrium and equilibrium steady-states for polymeric systems. In this way, our results provide an improved understanding of the energetics of flowing polymer solutions.
Statistical thermodynamics understanding the properties of macroscopic systems
Fai, Lukong Cornelius
2012-01-01
Basic Principles of Statistical PhysicsMicroscopic and Macroscopic Description of StatesBasic PostulatesGibbs Ergodic AssumptionGibbsian EnsemblesExperimental Basis of Statistical MechanicsDefinition of Expectation ValuesErgodic Principle and Expectation ValuesProperties of Distribution FunctionRelative Fluctuation of an Additive Macroscopic ParameterLiouville TheoremGibbs Microcanonical EnsembleMicrocanonical Distribution in Quantum MechanicsDensity MatrixDensity Matrix in Energy RepresentationEntropyThermodynamic FunctionsTemperatureAdiabatic ProcessesPressureThermodynamic IdentityLaws of Th
Laser-irradiated thermodynamic behaviors of spallation and recombination at solid-state interface
International Nuclear Information System (INIS)
Lai, H.-Y.; Huang, P.-H.
2008-01-01
A microscopic insight of interfacial spallation and recombination behaviors at multilayer thin-film interface induced by incident femtosecond pulsed laser is presented in this paper. Such two different aforementioned behaviors are investigated via the thermodynamic trajectories obtained by using standard Lennard-Jones (L-J) molecular dynamics (MD) simulation. Based on the simulation results, the interfacial damages of multilayer thin film are dominated by a critical threshold that induces an extraordinary expansive dynamics and phase transitions leading to the structural softened and tensile spallation at interface. The critical damage threshold is evaluated at around 8.5 J/m 2 which governs the possible occurrence of two different regimes, i.e. interfacial spallaiton and recombination. In interfacial damage region, quasi-isothermal thermodynamic trajectories can be observed after the interfacial spallation occurs. Moreover, the result of thermodynamic trajectories analyses indicates that, the relaxation of pressure wave may cause the over-heated interfacial zone to reduce volumetric density, thus leading to structural softness and even weaken interfacial structural strength. The crucial effect leading to the phenomenon of low tension spallation is identified
A thermodynamic approach to model the caloric properties of semicrystalline polymers
Lion, Alexander; Johlitz, Michael
2016-05-01
It is well known that the crystallisation and melting behaviour of semicrystalline polymers depends in a pronounced manner on the temperature history. If the polymer is in the liquid state above the melting point, and the temperature is reduced to a level below the glass transition, the final degree of crystallinity, the amount of the rigid amorphous phase and the configurational state of the mobile amorphous phase strongly depend on the cooling rate. If the temperature is increased afterwards, the extents of cold crystallisation and melting are functions of the heating rate. Since crystalline and amorphous phases exhibit different densities, the specific volume depends also on the temperature history. In this article, a thermodynamically based phenomenological approach is developed which allows for the constitutive representation of these phenomena in the time domain. The degree of crystallinity and the configuration of the amorphous phase are represented by two internal state variables whose evolution equations are formulated under consideration of the second law of thermodynamics. The model for the specific Gibbs free energy takes the chemical potentials of the different phases and the mixture entropy into account. For simplification, it is assumed that the amount of the rigid amorphous phase is proportional to the degree of crystallinity. An essential outcome of the model is an equation in closed form for the equilibrium degree of crystallinity in dependence on pressure and temperature. Numerical simulations demonstrate that the process dependences of crystallisation and melting under consideration of the glass transition are represented.
Beyond heat baths II: framework for generalized thermodynamic resource theories
Yunger Halpern, Nicole
2018-03-01
Thermodynamics, which describes vast systems, has been reconciled with small scales, relevant to single-molecule experiments, in resource theories. Resource theories have been used to model exchanges of energy and information. Recently, particle exchanges were modeled; and an umbrella family of thermodynamic resource theories was proposed to model diverse baths, interactions, and free energies. This paper motivates and details the family’s structure and prospective applications. How to model electrochemical, gravitational, magnetic, and other thermodynamic systems is explained. Szilárd’s engine and Landauer’s Principle are generalized, as resourcefulness is shown to be convertible not only between information and gravitational energy, but also among diverse degrees of freedom. Extensive variables are associated with quantum operators that might fail to commute, introducing extra nonclassicality into thermodynamic resource theories. An early version of this paper partially motivated the later development of noncommutative thermalization. This generalization expands the theories’ potential for modeling realistic systems with which small-scale statistical mechanics might be tested experimentally.
Entropy, related thermodynamic properties, and structure of methylisocyanate
International Nuclear Information System (INIS)
Davis, Phil S.; Kilpatrick, John E.
2013-01-01
Highlights: ► The thermodynamic properties of methylisocyanate have been determined by isothermal calorimetry from 15 to 298.15 K. ► The third law entropy has been compared with the entropy calculated by statistical thermodynamics. ► The comparisons are consistent with selected proposed molecular structures and vibrational frequencies. -- Abstract: The entropy and related thermodynamic properties of methylisocyanate, CH 3 NCO, have been determined by isothermal calorimetry. The entropy in the ideal gas state at 298.15 K and 1 atmosphere is S m o = 284.3 ± 0.6 J/K · mol. Other thermodynamic properties determined include: the heat capacity from 15 to 300 K, the temperature of fusion (T fus = 178.461 ± 0.024 K), the enthalpy of fusion (ΔH fus = 7455.2 ± 14.0 J/mol), the enthalpy of vaporization at 298.15 K (ΔH vap = 28768 ± 54 J/mol), and the vapor pressure from fusion to 300 K. Using statistical thermodynamics, the entropy in this same state has been calculated for various assumed structures for methylisocyante which have been proposed based on several spectroscopic and ab initio results. Comparisons between the experimental and calculated entropy have led to the following conclusions concerning historical differences among problematic structural properties: (1) The CNC/CNO angles can have the paired values of 140/180° or 135/173° respectively. It is not possible to distinguish between the two by this thermodynamic analysis. (2) The methyl group functions as a free rotor or near free rotor against the NCO rigid frame. The barrier to internal rotation is less than 2100 J/mol. (3) The CNC vibrational bending frequency is consistent with the more recently observed assignments at 165 and 172 cm −1 with some degree of anharmonicity or with a pure harmonic at about 158 cm −1
Directory of Open Access Journals (Sweden)
B. H. Kahn
2017-08-01
Full Text Available The global-scale patterns and covariances of subtropical marine boundary layer (MBL cloud fraction and spatial variability with atmospheric thermodynamic and dynamic fields remain poorly understood. We describe an approach that leverages coincident NASA A-train and the Modern Era Retrospective-Analysis for Research and Applications (MERRA data to quantify the relationships in the subtropical MBL derived at the native pixel and grid resolution. A new method for observing four subtropical oceanic regions that capture transitions from stratocumulus to trade cumulus is demonstrated, where stratocumulus and cumulus regimes are determined from infrared-based thermodynamic phase. Visible radiances are normally distributed within stratocumulus and are increasingly skewed away from the coast, where trade cumulus dominates. Increases in MBL depth, wind speed, and effective radius (re, and reductions in 700–1000 hPa moist static energy differences and 700 and 850 hPa vertical velocity correspond with increases in visible radiance skewness. We posit that a more robust representation of the cloudy MBL is obtained using visible radiance rather than retrievals of optical thickness that are limited to a smaller subset of cumulus. The method using the combined A-train and MERRA data set has demonstrated that an increase in re within shallow cumulus is strongly related to higher MBL wind speeds that further correspond to increased precipitation occurrence according to CloudSat, previously demonstrated with surface observations. Hence, the combined data sets have the potential of adding global context to process-level understanding of the MBL.
Navrotsky, Alexandra
Thermodynamics of Crystals is a gold mine of a references bargain with more derivations of useful equations per dollar, or per page, than almost any other book I know. Useful to whom? To the solid state physicist, the solid state chemist working the geophysicist, the rock mechanic, the mineral physicist. Useful for what? For lattice dynamics, crystal potentials, band structure. For elegant, rigorous, and concise derivations of fundamental equations. For comparison of levels of approximation. For some data and physical insights, especially for metals and simple halides. This book is a reissue, with some changes and additions, of a 1970 treatise. It ages well, since the fundamentals do not change.
A Simple Statistical Thermodynamics Experiment
LoPresto, Michael C.
2010-01-01
Comparing the predicted and actual rolls of combinations of both two and three dice can help to introduce many of the basic concepts of statistical thermodynamics, including multiplicity, probability, microstates, and macrostates, and demonstrate that entropy is indeed a measure of randomness, that disordered states (those of higher entropy) are…
Haldar, Amritendu; Biswas, Ritabrata
2018-06-01
We investigate the effect of thermal fluctuations on the thermodynamics of a Lovelock-AdS black hole. Taking the first order logarithmic correction term in entropy we analyze the thermodynamic potentials like Helmholtz free energy, enthalpy and Gibbs free energy. We find that all the thermodynamic potentials are decreasing functions of correction coefficient α . We also examined this correction coefficient must be positive by analysing P{-}V diagram. Further we study the P{-}V criticality and stability and find that presence of logarithmic correction in it is necessary to have critical points and stable phases. When P{-}V criticality appears, we calculate the critical volume V_c, critical pressure P_c and critical temperature T_c using different equations and show that there is no critical point for this black hole without thermal fluctuations. We also study the geometrothermodynamics of this kind of black holes. The Ricci scalar of the Ruppeiner metric is graphically analysed.
Thermodynamic analysis of fatty acid esterification for fatty acid alkyl esters production
International Nuclear Information System (INIS)
Voll, Fernando A.P.; Silva, Camila da; Rossi, Carla C.R.S.; Guirardello, Reginaldo; Castilhos, Fernanda de; Oliveira, J. Vladimir; Cardozo-Filho, Lucio
2011-01-01
The development of renewable energy source alternatives has become a planet need because of the unavoidable fossil fuel scarcity and for that reason biodiesel production has attracted growing interest over the last decade. The reaction yield for obtaining fatty acid alkyl esters varies significantly according to the operating conditions such as temperature and the feed reactants ratio and thus investigation of the thermodynamics involved in such reactional systems may afford important knowledge on the effects of process variables on biodiesel production. The present work reports a thermodynamic analysis of fatty acid esterification reaction at low pressure. For this purpose, Gibbs free energy minimization was employed with UNIFAC and modified Wilson thermodynamic models through a nonlinear programming model implementation. The methodology employed is shown to reproduce the most relevant investigations involving experimental studies and thermodynamic analysis.
Thermodynamics of higher spin black holes in AdS3
International Nuclear Information System (INIS)
Boer, Jan de; Jottar, Juan I.
2014-01-01
We discuss the thermodynamics of recently constructed three-dimensional higher spin black holes in SL(N,ℝ)×SL(N,ℝ) Chern-Simons theory with generalized asymptotically-anti-de Sitter boundary conditions. From a holographic perspective, these bulk theories are dual to two-dimensional CFTs with W N symmetry algebras, and the black hole solutions are dual to thermal states with higher spin chemical potentials and charges turned on. Because the notion of horizon area is not gauge-invariant in the higher spin theory, the traditional approaches to the computation of black hole entropy must be reconsidered. One possibility, explored in the recent literature, involves demanding the existence of a partition function in the CFT, and consistency with the first law of thermodynamics. This approach is not free from ambiguities, however, and in particular different definitions of energy result in different expressions for the entropy. In the present work we show that there are natural definitions of the thermodynamically conjugate variables that follow from careful examination of the variational principle, and moreover agree with those obtained via canonical methods. Building on this intuition, we derive general expressions for the higher spin black hole entropy and free energy which are written entirely in terms of the Chern-Simons connections, and are valid for both static and rotating solutions. We compare our results to other proposals in the literature, and provide a new and efficient way to determine the generalization of the Cardy formula to a situation with higher spin charges
Unifying mechanical and thermodynamic descriptions across the thioredoxin protein family.
Mottonen, James M; Xu, Minli; Jacobs, Donald J; Livesay, Dennis R
2009-05-15
We compare various predicted mechanical and thermodynamic properties of nine oxidized thioredoxins (TRX) using a Distance Constraint Model (DCM). The DCM is based on a nonadditive free energy decomposition scheme, where entropic contributions are determined from rigidity and flexibility of structure based on distance constraints. We perform averages over an ensemble of constraint topologies to calculate several thermodynamic and mechanical response functions that together yield quantitative stability/flexibility relationships (QSFR). Applied to the TRX protein family, QSFR metrics display a rich variety of similarities and differences. In particular, backbone flexibility is well conserved across the family, whereas cooperativity correlation describing mechanical and thermodynamic couplings between the residue pairs exhibit distinctive features that readily standout. The diversity in predicted QSFR metrics that describe cooperativity correlation between pairs of residues is largely explained by a global flexibility order parameter describing the amount of intrinsic flexibility within the protein. A free energy landscape is calculated as a function of the flexibility order parameter, and key values are determined where the native-state, transition-state, and unfolded-state are located. Another key value identifies a mechanical transition where the global nature of the protein changes from flexible to rigid. The key values of the flexibility order parameter help characterize how mechanical and thermodynamic response is linked. Variation in QSFR metrics and key characteristics of global flexibility are related to the native state X-ray crystal structure primarily through the hydrogen bond network. Furthermore, comparison of three TRX redox pairs reveals differences in thermodynamic response (i.e., relative melting point) and mechanical properties (i.e., backbone flexibility and cooperativity correlation) that are consistent with experimental data on thermal stabilities
Local thermodynamics of a magnetized, anisotropic plasma
International Nuclear Information System (INIS)
Hazeltine, R. D.; Mahajan, S. M.; Morrison, P. J.
2013-01-01
An expression for the internal energy of a fluid element in a weakly coupled, magnetized, anisotropic plasma is derived from first principles. The result is a function of entropy, particle density and magnetic field, and as such plays the role of a thermodynamic potential: it determines in principle all thermodynamic properties of the fluid element. In particular it provides equations of state for the magnetized plasma. The derivation uses familiar fluid equations, a few elements of kinetic theory, the MHD version of Faraday's law, and certain familiar stability and regularity conditions.
Classical and statistical thermodynamics
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.
Stochastic thermodynamics of quantum maps with and without equilibrium.
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.
Non-hard sphere thermodynamic perturbation theory.
Zhou, Shiqi
2011-08-21
A non-hard sphere (HS) perturbation scheme, recently advanced by the present author, is elaborated for several technical matters, which are key mathematical details for implementation of the non-HS perturbation scheme in a coupling parameter expansion (CPE) thermodynamic perturbation framework. NVT-Monte Carlo simulation is carried out for a generalized Lennard-Jones (LJ) 2n-n potential to obtain routine thermodynamic quantities such as excess internal energy, pressure, excess chemical potential, excess Helmholtz free energy, and excess constant volume heat capacity. Then, these new simulation data, and available simulation data in literatures about a hard core attractive Yukawa fluid and a Sutherland fluid, are used to test the non-HS CPE 3rd-order thermodynamic perturbation theory (TPT) and give a comparison between the non-HS CPE 3rd-order TPT and other theoretical approaches. It is indicated that the non-HS CPE 3rd-order TPT is superior to other traditional TPT such as van der Waals/HS (vdW/HS), perturbation theory 2 (PT2)/HS, and vdW/Yukawa (vdW/Y) theory or analytical equation of state such as mean spherical approximation (MSA)-equation of state and is at least comparable to several currently the most accurate Ornstein-Zernike integral equation theories. It is discovered that three technical issues, i.e., opening up new bridge function approximation for the reference potential, choosing proper reference potential, and/or using proper thermodynamic route for calculation of f(ex-ref), chiefly decide the quality of the non-HS CPE TPT. Considering that the non-HS perturbation scheme applies for a wide variety of model fluids, and its implementation in the CPE thermodynamic perturbation framework is amenable to high-order truncation, the non-HS CPE 3rd-order or higher order TPT will be more promising once the above-mentioned three technological advances are established. © 2011 American Institute of Physics
Statistical thermodynamics and mean-field theory for the alloy under irradiation model
International Nuclear Information System (INIS)
Kamyshendo, V.
1993-01-01
A generalization of statistical thermodynamics to the open systems case, is discussed, using as an example the alloy-under-irradiation model. The statistical properties of stationary states are described with the use of generalized thermodynamic potentials and 'quasi-interactions' determined from the master equation for micro-configuration probabilities. Methods for resolving this equation are illustrated by the mean-field type calculations of correlators, thermodynamic potentials and phase diagrams for disordered alloys
Bayesian quantification of thermodynamic uncertainties in dense gas flows
International Nuclear Information System (INIS)
Merle, X.; Cinnella, P.
2015-01-01
A Bayesian inference methodology is developed for calibrating complex equations of state used in numerical fluid flow solvers. Precisely, the input parameters of three equations of state commonly used for modeling the thermodynamic behavior of the so-called dense gas flows, – i.e. flows of gases characterized by high molecular weights and complex molecules, working in thermodynamic conditions close to the liquid–vapor saturation curve – are calibrated by means of Bayesian inference from reference aerodynamic data for a dense gas flow over a wing section. Flow thermodynamic conditions are such that the gas thermodynamic behavior strongly deviates from that of a perfect gas. In the aim of assessing the proposed methodology, synthetic calibration data – specifically, wall pressure data – are generated by running the numerical solver with a more complex and accurate thermodynamic model. The statistical model used to build the likelihood function includes a model-form inadequacy term, accounting for the gap between the model output associated to the best-fit parameters and the true phenomenon. Results show that, for all of the relatively simple models under investigation, calibrations lead to informative posterior probability density distributions of the input parameters and improve the predictive distribution significantly. Nevertheless, calibrated parameters strongly differ from their expected physical values. The relationship between this behavior and model-form inadequacy is discussed. - Highlights: • Development of a Bayesian inference procedure for calibrating dense-gas flow solvers. • Complex thermodynamic models calibrated by using aerodynamic data for the flow. • Preliminary Sobol analysis used to reduce parameter space. • Piecewise polynomial surrogate model constructed to reduce computational cost. • Calibration results show the crucial role played by model-form inadequacies
Exceptional thermodynamics. The equation of state of G{sub 2} gauge theory
Energy Technology Data Exchange (ETDEWEB)
Bruno, Mattia [Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany). John von Neumann-Inst. fuer Computing NIC; Caselle, Michele [Torino Univ. (Italy). Dipt. di Fisica Teorica; INFN, Sezione di Torino (Italy); Panero, Marco [Univ. Autonoma de Madrid (Spain). Inst. de Fisica Teorica; Consejo Superior de Investigaciones Cientificas, Madrid (Spain); Pellegrini, Roberto [Swansea Univ. (United Kingdom). Dept. of Physics
2014-10-15
We present a lattice study of the equation of state in Yang-Mills theory based on the exceptional G{sub 2} gauge group. As is well-known, at zero temperature this theory shares many qualitative features with real-world QCD, including the absence of colored states in the spectrum and dynamical string breaking at large distances. In agreement with previous works, we show that at finite temperature this theory features a first-order deconfining phase transition, whose nature can be studied by a semi-classical computation. We also show that the equilibrium thermodynamic observables in the deconfined phase bear striking quantitative similarities with those found in SU(N) gauge theories: in particular, these quantities exhibit nearly perfect proportionality to the number of gluon degrees of freedom, and the trace anomaly reveals a characteristic quadratic dependence on the temperature, also observed in SU(N) Yang-Mills theories (both in four and in three spacetime dimensions). We compare our lattice data with analytical predictions from effective models, and discuss their implications for the deconfinement mechanism and high-temperature properties of strongly interacting, non-supersymmetric gauge theories. Our results give strong evidence for the conjecture that the thermal deconfining transition is governed by a universal mechanism, common to all simple gauge groups.
Thermodynamic analysis of chemical heat pumps
International Nuclear Information System (INIS)
Obermeier, Jonas; Müller, Karsten; Arlt, Wolfgang
2015-01-01
Thermal energy storages and heat pump units represent an important part of high efficient renewable energy systems. By using thermally driven, reversible chemical reactions a combination of thermal energy storage and heat pump can be realized. The influences of thermophysical properties of the involved components on the efficiency of a heat pump cycle is analysed and the relevance of the thermodynamic driving force is worked out. In general, the behaviour of energetic and exergetic efficiency is contrary. In a real cycle, higher enthalpies of reaction decrease the energetic efficiency but increase the exergetic efficiency. Higher enthalpies of reaction allow for lower offsets from equilibrium state for a default thermodynamic driving force of the reaction. - Highlights: • A comprehensive efficiency analysis of gas-solid heat pumps is proposed. • Link between thermodynamic driving force and equilibrium drop is shown. • Calculation of the equilibrium drop based on thermochemical properties. • Reaction equilibria of the decomposition reaction of salt hydrates. • Contrary behavior of energetic and exergetic efficiency
The Theory of Thermodynamics for Chemical Reactions in Dispersed Heterogeneous Systems
Yongqiang; Baojiao; Jianfeng
1997-07-01
In this paper, the expressions of Gibbs energy change, enthalpy change, entropy change, and equilibrium constant for chemical reactions in dispersed heterogeneous systems are derived using classical thermodynamics theory. The thermodynamical relations for the same reaction system between the dispersed and the block state are also derived. The effects of degree of dispersion on thermodynamical properties, reaction directions, and chemical equilibria are discussed. The results show that the present equation of thermodynamics for chemical reactions is only a special case of the above-mentioned formulas and that the effect of the dispersity of a heterogeneous system on the chemical reaction obeys the Le Chatelier principle of movement of equilibria.
Latent variable method for automatic adaptation to background states in motor imagery BCI
Dagaev, Nikolay; Volkova, Ksenia; Ossadtchi, Alexei
2018-02-01
Objective. Brain-computer interface (BCI) systems are known to be vulnerable to variabilities in background states of a user. Usually, no detailed information on these states is available even during the training stage. Thus there is a need in a method which is capable of taking background states into account in an unsupervised way. Approach. We propose a latent variable method that is based on a probabilistic model with a discrete latent variable. In order to estimate the model’s parameters, we suggest to use the expectation maximization algorithm. The proposed method is aimed at assessing characteristics of background states without any corresponding data labeling. In the context of asynchronous motor imagery paradigm, we applied this method to the real data from twelve able-bodied subjects with open/closed eyes serving as background states. Main results. We found that the latent variable method improved classification of target states compared to the baseline method (in seven of twelve subjects). In addition, we found that our method was also capable of background states recognition (in six of twelve subjects). Significance. Without any supervised information on background states, the latent variable method provides a way to improve classification in BCI by taking background states into account at the training stage and then by making decisions on target states weighted by posterior probabilities of background states at the prediction stage.
Description of quantum coherence in thermodynamic processes requires constraints beyond free energy
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.
Directory of Open Access Journals (Sweden)
A. Zuber
2015-09-01
Full Text Available AbstractThe correlation of thermodynamic properties of nonaqueous electrolyte solutions is relevant to design and operation of many chemical processes, as in fertilizer production and the pharmaceutical industry. In this work, the Q-electrolattice equation of state (EOS is used to model vapor pressure, mean ionic activity coefficient, osmotic coefficient, and liquid density of sixteen methanol and ten ethanol solutions containing single strong 1:1 and 2:1 salts. The Q-electrolattice comprises the lattice-based Mattedi-Tavares-Castier (MTC EOS, the Born term and the explicit MSA term. The model requires two adjustable parameters per ion, namely the ionic diameter and the solvent-ion interaction energy. Predictions of osmotic coefficient at 298.15 K and liquid density at different temperatures are also presented.
Nonequilibrium thermodynamics and information theory: basic concepts and relaxing dynamics
International Nuclear Information System (INIS)
Altaner, Bernhard
2017-01-01
Thermodynamics is based on the notions of energy and entropy. While energy is the elementary quantity governing physical dynamics, entropy is the fundamental concept in information theory. In this work, starting from first principles, we give a detailed didactic account on the relations between energy and entropy and thus physics and information theory. We show that thermodynamic process inequalities, like the second law, are equivalent to the requirement that an effective description for physical dynamics is strongly relaxing. From the perspective of information theory, strongly relaxing dynamics govern the irreversible convergence of a statistical ensemble towards the maximally non-commital probability distribution that is compatible with thermodynamic equilibrium parameters. In particular, Markov processes that converge to a thermodynamic equilibrium state are strongly relaxing. Our framework generalizes previous results to arbitrary open and driven systems, yielding novel thermodynamic bounds for idealized and real processes. (paper)
Work extraction and thermodynamics for individual quantum systems
Skrzypczyk, Paul; Short, Anthony J.; Popescu, Sandu
2014-06-01
Thermodynamics is traditionally concerned with systems comprised of a large number of particles. Here we present a framework for extending thermodynamics to individual quantum systems, including explicitly a thermal bath and work-storage device (essentially a ‘weight’ that can be raised or lowered). We prove that the second law of thermodynamics holds in our framework, and gives a simple protocol to extract the optimal amount of work from the system, equal to its change in free energy. Our results apply to any quantum system in an arbitrary initial state, in particular including non-equilibrium situations. The optimal protocol is essentially reversible, similar to classical Carnot cycles, and indeed, we show that it can be used to construct a quantum Carnot engine.
Generic Natural Systems Evaluation - Thermodynamic Database Development and Data Management
Energy Technology Data Exchange (ETDEWEB)
Wolery, T W; Sutton, M
2011-09-19
Thermodynamic data are essential for understanding and evaluating geochemical processes, as by speciation-solubility calculations, reaction-path modeling, or reactive transport simulation. These data are required to evaluate both equilibrium states and the kinetic approach to such states (via the affinity term or its equivalent in commonly used rate laws). These types of calculations and the data needed to carry them out are a central feature of geochemistry in many applications, including water-rock interactions in natural systems at low and high temperatures. Such calculations are also made in engineering studies, for example studies of interactions involving man-made materials such as metal alloys and concrete. They are used in a fairly broad spectrum of repository studies where interactions take place among water, rock, and man-made materials (e.g., usage on YMP and WIPP). Waste form degradation, engineered barrier system performance, and near-field and far-field transport typically incorporate some level of thermodynamic modeling, requiring the relevant supporting data. Typical applications of thermodynamic modeling involve calculations of aqueous speciation (which is of great importance in the case of most radionuclides), solubilities of minerals and related solids, solubilities of gases, and stability relations among the various possible phases that might be present in a chemical system at a given temperature and pressure. If a phase can have a variable chemical composition, then a common calculational task is to determine that composition. Thermodynamic modeling also encompasses ion exchange and surface complexation processes. Any and all of these processes may be important in a geochemical process or reactive transport calculation. Such calculations are generally carried out using computer codes. For geochemical modeling calculations, codes such as EQ3/6 and PHREEQC, are commonly used. These codes typically provide 'full service' geochemistry
Generic Natural Systems Evaluation - Thermodynamic Database Development and Data Management
International Nuclear Information System (INIS)
Wolery, T.W.; Sutton, M.
2011-01-01
Thermodynamic data are essential for understanding and evaluating geochemical processes, as by speciation-solubility calculations, reaction-path modeling, or reactive transport simulation. These data are required to evaluate both equilibrium states and the kinetic approach to such states (via the affinity term or its equivalent in commonly used rate laws). These types of calculations and the data needed to carry them out are a central feature of geochemistry in many applications, including water-rock interactions in natural systems at low and high temperatures. Such calculations are also made in engineering studies, for example studies of interactions involving man-made materials such as metal alloys and concrete. They are used in a fairly broad spectrum of repository studies where interactions take place among water, rock, and man-made materials (e.g., usage on YMP and WIPP). Waste form degradation, engineered barrier system performance, and near-field and far-field transport typically incorporate some level of thermodynamic modeling, requiring the relevant supporting data. Typical applications of thermodynamic modeling involve calculations of aqueous speciation (which is of great importance in the case of most radionuclides), solubilities of minerals and related solids, solubilities of gases, and stability relations among the various possible phases that might be present in a chemical system at a given temperature and pressure. If a phase can have a variable chemical composition, then a common calculational task is to determine that composition. Thermodynamic modeling also encompasses ion exchange and surface complexation processes. Any and all of these processes may be important in a geochemical process or reactive transport calculation. Such calculations are generally carried out using computer codes. For geochemical modeling calculations, codes such as EQ3/6 and PHREEQC, are commonly used. These codes typically provide 'full service' geochemistry, meaning that
State-space dimensionality in short-memory hidden-variable theories
International Nuclear Information System (INIS)
Montina, Alberto
2011-01-01
Recently we have presented a hidden-variable model of measurements for a qubit where the hidden-variable state-space dimension is one-half the quantum-state manifold dimension. The absence of a short memory (Markov) dynamics is the price paid for this dimensional reduction. The conflict between having the Markov property and achieving the dimensional reduction was proved by Montina [A. Montina, Phys. Rev. A 77, 022104 (2008)] using an additional hypothesis of trajectory relaxation. Here we analyze in more detail this hypothesis introducing the concept of invertible process and report a proof that makes clearer the role played by the topology of the hidden-variable space. This is accomplished by requiring suitable properties of regularity of the conditional probability governing the dynamics. In the case of minimal dimension the set of continuous hidden variables is identified with an object living an N-dimensional Hilbert space whose dynamics is described by the Schroedinger equation. A method for generating the economical non-Markovian model for the qubit is also presented.
Thermodynamic fluctuations and the monopole density of the early Universe
International Nuclear Information System (INIS)
Diosi, L.; Lukacs, B.
1984-10-01
The probability of thermodynamic fluctuations is calculated by explicitly using the Riemannian structure of the thermodynamic state space. By means of this probability distribution, a correlation volume can be defined. Identifying this volume with one domain in the GUT continuum at the symmetry breaking phase transition in the early Universe, a prediction can be obtained for the primordial monopole density. (author)
International Nuclear Information System (INIS)
Dubovitskii, V.A.; Pavlov, G.A.; Krasnikov, Yu.G.
1996-01-01
Thermodynamic analysis of media with strong interparticle (Coulomb) interaction is presented. A method for constructing isotherms is proposed for a medium described by a closed multicomponent thermodynamic model. The method is based on choosing an appropriate nondegenerate frame of reference in the extended space of thermodynamic variables and provides efficient thermodynamic calculations in a wide range of parameters, for an investigation of phase transitions of the first kind, and for determining both the number of phases and coexistence curves. A number of approximate thermodynamic models of hydrogen plasma are discussed. The approximation corresponding to the n5/2 law, in which the effects of particle attraction and repulsion are taken into account qualitatively, is studied. This approximation allows studies of thermodynamic properties of a substance for a wide range of parameters. In this approximation, for hydrogen at a constant temperature, various properties of the degree of ionization are revealed. In addition, the parameters of the second critical point are found under conditions corresponding to the Jovian interior
Thermodynamic and experimental studies of the CVD of A-15 superconductors. I
International Nuclear Information System (INIS)
Madar, R.; Weiss, F.; Fruchart, R.; Bernard, C.
1978-01-01
This paper deals with the experimental and thermodynamic study of the chemical vapor deposition (CVD) synthesis of Nb 3 Ga layers on various metallic and insulating substrates using the coreduction of mixed halides by hydrogen. Thermodynamic equilibrium in the seven-component system Nb-Ga-H-Cl-Si-O-Ar has been calculated using the method of minimization of the system Gibbs free energy as a function of the variables directly available in the CVD system. The chosen variables were the chloride ratio, the reduction and dilution parameters and the temperature of the deposition zone. The equilibrium compositions were calculated for the two composition limits of the A-15 phase: NbGasub(0.15) and Nb 3 Ga. They are presented in the form of CVD phase diagrams. A CVD reactor has been set up and more than one hundred measurements have been made in order to check the validity of the equilibrium calculations. The comparisons between equilibrium and experimental results show a good agreement and lead to a better understanding of the chemistry and thermodynamics of the system. (Auth.)
Partition Function and Configurational Entropy in Non-Equilibrium States: A New Theoretical Model
Directory of Open Access Journals (Sweden)
Akira Takada
2018-03-01
Full Text Available A new model of non-equilibrium thermodynamic states has been investigated on the basis of the fact that all thermodynamic variables can be derived from partition functions. We have thus attempted to define partition functions for non-equilibrium conditions by introducing the concept of pseudo-temperature distributions. These pseudo-temperatures are configurational in origin and distinct from kinetic (phonon temperatures because they refer to the particular fragments of the system with specific energies. This definition allows thermodynamic states to be described either for equilibrium or non-equilibrium conditions. In addition; a new formulation of an extended canonical partition function; internal energy and entropy are derived from this new temperature definition. With this new model; computational experiments are performed on simple non-interacting systems to investigate cooling and two distinct relaxational effects in terms of the time profiles of the partition function; internal energy and configurational entropy.
Universalities of thermodynamic signatures in topological phases
Kempkes, S. N.; Quelle, A.; de Morais Smith, C.
2016-01-01
Topological insulators (superconductors) are materials that host symmetry-protected metallic edge states in an insulating (superconducting) bulk. Although they are well understood, a thermodynamic description of these materials remained elusive, firstly because the edges yield a non-extensive
High-fidelity teleportation of continuous-variable quantum States using delocalized single photons
DEFF Research Database (Denmark)
Andersen, Ulrik L; Ralph, Timothy C
2013-01-01
Traditional continuous-variable teleportation can only approach unit fidelity in the limit of an infinite (and unphysical) amount of squeezing. We describe a new method for continuous-variable teleportation that approaches unit fidelity with finite resources. The protocol is not based on squeezed...... states as in traditional teleportation but on an ensemble of single photon entangled states. We characterize the teleportation scheme with coherent states, mesoscopic superposition states, and two-mode squeezed states and we find several situations in which near-unity teleportation fidelity can...
Thermodynamical quantum information sharing
International Nuclear Information System (INIS)
Wiesniak, M.; Vedral, V.; Brukner, C.
2005-01-01
Full text: Thermodynamical properties fully originate from classical physics and can be easily measured for macroscopic systems. On the other hand, entanglement is a widely spoken feature of quantum physics, which allows to perform certain task with efficiency unavailable with any classical resource. Therefore an interesting question is whether we can witness entanglement in a state of a macroscopic sample. We show, that some macroscopic properties, in particular magnetic susceptibility, can serve as an entanglement witnesses. We also study a mutual relation between magnetic susceptibility and magnetisation. Such a complementarity exhibits quantum information sharing between these two thermodynamical quantities. Magnetization expresses properties of individual spins, while susceptibility might reveal non-classical correlations as a witness. Therefore, a rapid change of one of these two quantities may mean a phase transition also in terms of entanglement. The complementarity relation is demonstrated by an analytical solution of an exemplary model. (author)
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
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...
Thermodynamics, kinetics and process control of nitriding
DEFF Research Database (Denmark)
Mittemeijer, Eric J.; Somers, Marcel A. J.
1999-01-01
As a prerequisite for predictability of properties obtained by a nitriding treatment of iron-based workpieces, the relation between the process parameters and the composition and structure of the surface layer produced must be known. At present (even) the description of thermodynamic equilibrium...... of pure iron-nitrogen phases has not been achieved fully. It has been shown that taking into account ordering of nitrogen in the epsilon and gamma' iron-nitride phases, leads to an improved understanding of the Fe-N phase diagram. Although thermodynamics indicate the state the system strives for......, the nitriding result is determined largely by the kinetics of the process. The nitriding kinetics have been shown to be characterised by the occurring local near-equilibria and stationary states at surfaces and interfaces, and the diffusion coefficient of nitrogen in the various phases, for which new data have...
Are the Laws of Thermodynamics Consequences of a Fractal Properties of Universe?
Kobelev, L. Ya.
2000-01-01
Why in our Universe the laws of thermodynamics are valid? In the paper is demonstrated the reason of it: if the time and the space are multifractal and the Universe is in an equilibrium state the laws of the thermodynamics are consequences of it's multifractal structure.
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
Energy Technology Data Exchange (ETDEWEB)
Mingarro, E.
1965-07-01
In order to get a classification of the uranium deposits, the geological processes have been ordered in thermodynamic systems according to the independent parameters that define their equilibrium state. Also, to apply the phase rule, we suppose that the ore forming elements are always ideally mobile components; that is, in the geological systems, these components are defined by their chemical potentials. In this paper, we show that in random conditions, i. e.; for any possible value of the factors of equilibrium or state the stable mineralizations are formed only in metasomatic regimes; so that the mineralogical sequence is a function both of the Helmholtz's free energy and the crystallisation pressure of the minerals. (Author) 7 refs.
Energy Technology Data Exchange (ETDEWEB)
Mingarro, E
1965-07-01
In order to get a classification of the uranium deposits, the geological processes have been ordered in thermodynamic systems according to the independent parameters that define their equilibrium state. Also, to apply the phase rule, we suppose that the ore forming elements are always ideally mobile components; that is, in the geological systems, these components are defined by their chemical potentials. In this paper, we show that in random conditions, i. e.; for any possible value of the factors of equilibrium or state the stable mineralizations are formed only in metasomatic regimes; so that the mineralogical sequence is a function both of the Helmholtz's free energy and the crystallisation pressure of the minerals. (Author) 7 refs.
Thermodynamics of random reaction networks.
Fischer, Jakob; Kleidon, Axel; Dittrich, Peter
2015-01-01
Reaction networks are useful for analyzing reaction systems occurring in chemistry, systems biology, or Earth system science. Despite the importance of thermodynamic disequilibrium for many of those systems, the general thermodynamic properties of reaction networks are poorly understood. To circumvent the problem of sparse thermodynamic data, we generate artificial reaction networks and investigate their non-equilibrium steady state for various boundary fluxes. We generate linear and nonlinear networks using four different complex network models (Erdős-Rényi, Barabási-Albert, Watts-Strogatz, Pan-Sinha) and compare their topological properties with real reaction networks. For similar boundary conditions the steady state flow through the linear networks is about one order of magnitude higher than the flow through comparable nonlinear networks. In all networks, the flow decreases with the distance between the inflow and outflow boundary species, with Watts-Strogatz networks showing a significantly smaller slope compared to the three other network types. The distribution of entropy production of the individual reactions inside the network follows a power law in the intermediate region with an exponent of circa -1.5 for linear and -1.66 for nonlinear networks. An elevated entropy production rate is found in reactions associated with weakly connected species. This effect is stronger in nonlinear networks than in the linear ones. Increasing the flow through the nonlinear networks also increases the number of cycles and leads to a narrower distribution of chemical potentials. We conclude that the relation between distribution of dissipation, network topology and strength of disequilibrium is nontrivial and can be studied systematically by artificial reaction networks.
Description of quantum coherence in thermodynamic processes requires constraints beyond free energy
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
On the Correct Formulation of the First Law of Thermodynamics
Kalanov, Temur Z.
2006-04-01
The critical analysis of the generally accepted formulation of the first law of thermodynamics is proposed. The purpose of the analysis is to prove that the standard formulation contains a mathematical error and to offer the correct formulation. The correct formulation is based on the concepts of function and differential of function. Really, if internal energy Uof a system is a function of two independent variables Q=Q(t) (describing of the thermal form of energy) and R=R(t) (describing non-thermal form of energy), then the correct formulation of the first law of thermodynamics is: dU(Q,R)dt=( UQ )RdQdt+( UR )QdRdt, where t and -( UR )Q / ( UR )Q ( UQ ) . - ( UQ )R are time and measure of mutual transformation of forms of energy, correspondingly. General conclusion: standard thermodynamics is incorrect.
Small Systems and Limitations on the Use of Chemical Thermodynamics
Tovbin, Yu. K.
2018-01-01
Limitations on using chemical thermodynamics to describe small systems are formulated. These limitations follow from statistical mechanics for equilibrium and nonequilibrium processes and reflect (1) differences between characteristic relaxation times in momentum, energy, and mass transfer in different aggregate states of investigated systems; (2) achievements of statistical mechanics that allow us to determine criteria for the size of smallest region in which thermodynamics can be applied and the scale of the emergence of a new phase, along with criteria for the conditions of violating a local equilibrium. Based on this analysis, the main thermodynamic results are clarified: the phase rule for distorted interfaces, the sense and area of applicability of Gibbs's concept of passive forces, and the artificiality of Kelvin's equation as a result of limitations on the thermodynamic approach to considering small bodies. The wrongness of introducing molecular parameters into thermodynamic derivations, and the activity coefficient for an activated complex into the expression for a reaction rate constant, is demonstrated.
The zeroth law in quasi-homogeneous thermodynamics and black holes
Directory of Open Access Journals (Sweden)
Alessandro Bravetti
2017-11-01
Full Text Available Motivated by black holes thermodynamics, we consider the zeroth law of thermodynamics for systems whose entropy is a quasi-homogeneous function of the extensive variables. We show that the generalized Gibbs–Duhem identity and the Maxwell construction for phase coexistence based on the standard zeroth law are incompatible in this case. We argue that the generalized Gibbs–Duhem identity suggests a revision of the zeroth law which in turns permits to reconsider Maxwell's construction in analogy with the standard case. The physical feasibility of our proposal is considered in the particular case of black holes.
Thermodynamic analysis of regulation in metabolic networks using constraint-based modeling
Directory of Open Access Journals (Sweden)
Mahadevan Radhakrishnan
2010-05-01
Full Text Available Abstract Background Geobacter sulfurreducens is a member of the Geobacter species, which are capable of oxidation of organic waste coupled to the reduction of heavy metals and electrode with applications in bioremediation and bioenergy generation. While the metabolism of this organism has been studied through the development of a stoichiometry based genome-scale metabolic model, the associated regulatory network has not yet been well studied. In this manuscript, we report on the implementation of a thermodynamics based metabolic flux model for Geobacter sulfurreducens. We use this updated model to identify reactions that are subject to regulatory control in the metabolic network of G. sulfurreducens using thermodynamic variability analysis. Findings As a first step, we have validated the regulatory sites and bottleneck reactions predicted by the thermodynamic flux analysis in E. coli by evaluating the expression ranges of the corresponding genes. We then identified ten reactions in the metabolic network of G. sulfurreducens that are predicted to be candidates for regulation. We then compared the free energy ranges for these reactions with the corresponding gene expression fold changes under conditions of different environmental and genetic perturbations and show that the model predictions of regulation are consistent with data. In addition, we also identify reactions that operate close to equilibrium and show that the experimentally determined exchange coefficient (a measure of reversibility is significant for these reactions. Conclusions Application of the thermodynamic constraints resulted in identification of potential bottleneck reactions not only from the central metabolism but also from the nucleotide and amino acid subsystems, thereby showing the highly coupled nature of the thermodynamic constraints. In addition, thermodynamic variability analysis serves as a valuable tool in estimating the ranges of ΔrG' of every reaction in the model
An introduction to equilibrium thermodynamics
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.
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
Thermodynamic control-oriented modeling of cycle-to-cycle exhaust gas temperature in an HCCI engine
International Nuclear Information System (INIS)
Dehghani Firoozabadi, M.; Shahbakhti, M.; Koch, C.R.; Jazayeri, S.A.
2013-01-01
Highlights: • First thermodynamic model in the literature to predict exhaust temperature in HCCI engines. • The model can be used for integrated control of HCCI combustion and exhaust temperature. • The model is experimentally validated at over 300 steady state and transient conditions. • Results show a good agreement between predicted and measured exhaust temperatures. • Sensitivity of exhaust gas temperature to variation of engine variables is shown. - Abstract: Model-based control of Homogenous Charge Compression Ignition (HCCI) engine exhaust temperature is a viable solution to optimize efficiency of both engine and the exhaust aftertreatment system. Low exhaust temperature in HCCI engines can limit the abatement of hydrocarbon (HC) and carbon monoxide (CO) emissions in an exhaust aftertreatment system. A physical–empirical model is described for control of exhaust temperature in HCCI engines. This model captures cycle-to-cycle dynamics affecting exhaust temperature and is based on thermodynamic relations and semi-empirical correlations. It incorporates intake and exhaust gas flow dynamics, residual gas mixing, and fuel burn rate and is validated with experimental data from a single cylinder engine at over 300 steady state and transient conditions. The validation results indicate a good agreement between predicted and measured exhaust gas temperature
International Nuclear Information System (INIS)
Peretrukhin, V.F.; Spitsyn, V.I.
1982-01-01
The oxidation potentials of neptunium, plutonium, and americium in the valance states from (III) to (VII) have been determined experimentally in 0.1-15 M NaOH. Heptavalent plutonium and americium are thermodynamically able to oxidize water with the evolution of oxygen in 0.1-15 M NaOH, neptunium(VII) in 0.1-7 M NaOH. All valance states of plutonium resist disproportionation in alkaline solutions; in the case of neptunium and americium only one disproportionation reaction is possible; of the hexavalent state in to penta- and heptavalent states. The degree of completion of the reaction can be calculated accurately from the oxidation potentials determined
Thermodynamic analysis on an anisotropically superhydrophobic surface with a hierarchical structure
Energy Technology Data Exchange (ETDEWEB)
Zhao, Jieliang [Division of Intelligent and Biomechanical Systems, State Key Laboratory of Tribology, Tsinghua University, Room 3407, Building 9003, 100084 Beijing (China); Su, Zhengliang [Division of Intelligent and Biomechanical Systems, State Key Laboratory of Tribology, Tsinghua University, Room 3407, Building 9003, 100084 Beijing (China); Department of Automotive Engineering, Tsinghua University, Beijing 100084 (China); Yan, Shaoze, E-mail: yansz@mail.tsinghua.edu.cn [Division of Intelligent and Biomechanical Systems, State Key Laboratory of Tribology, Tsinghua University, Room 3407, Building 9003, 100084 Beijing (China)
2015-12-01
Graphical abstract: - Highlights: • We model the superhydrophobic surface with anisotropic and hierarchical structure. • Anisotropic wetting only shows in noncomposite state (not in composite state). • Transition from noncomposite to composite state on dual-scale structure is hard. • Droplets tend to roll in the particular direction. • Droplets tend to stably remain in one preferred thermodynamic state. - Abstract: Superhydrophobic surfaces, which refer to the surfaces with contact angle higher than 150° and hysteresis less than 10°, have been reported in various studies. However, studies on the superhydrophobicity of anisotropic, hierarchical surfaces are limited and the corresponding thermodynamic mechanisms could not be explained thoroughly. Here we propose a simplified surface model of anisotropic patterned surface with dual scale roughness. Based on the thermodynamic method, we calculate the equilibrium contact angle (ECA) and the contact angle hysteresis (CAH) on the given surface. We show here that the hierarchical structure has much better anisotropic wetting properties than the single-scale one, and the results shed light on the potential application in controllable micro-/nano-fluidic systems. Our studies can be potentially applied for the fabrication of anisotropically superhydrophobic surfaces.
Thermodynamic analysis on an anisotropically superhydrophobic surface with a hierarchical structure
International Nuclear Information System (INIS)
Zhao, Jieliang; Su, Zhengliang; Yan, Shaoze
2015-01-01
Graphical abstract: - Highlights: • We model the superhydrophobic surface with anisotropic and hierarchical structure. • Anisotropic wetting only shows in noncomposite state (not in composite state). • Transition from noncomposite to composite state on dual-scale structure is hard. • Droplets tend to roll in the particular direction. • Droplets tend to stably remain in one preferred thermodynamic state. - Abstract: Superhydrophobic surfaces, which refer to the surfaces with contact angle higher than 150° and hysteresis less than 10°, have been reported in various studies. However, studies on the superhydrophobicity of anisotropic, hierarchical surfaces are limited and the corresponding thermodynamic mechanisms could not be explained thoroughly. Here we propose a simplified surface model of anisotropic patterned surface with dual scale roughness. Based on the thermodynamic method, we calculate the equilibrium contact angle (ECA) and the contact angle hysteresis (CAH) on the given surface. We show here that the hierarchical structure has much better anisotropic wetting properties than the single-scale one, and the results shed light on the potential application in controllable micro-/nano-fluidic systems. Our studies can be potentially applied for the fabrication of anisotropically superhydrophobic surfaces.
Thermodynamics-based Metabolite Sensitivity Analysis in metabolic networks.
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
Thermodynamics of Radiation Modes
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…
Understanding the edge effect in wetting: a thermodynamic approach.
Fang, Guoping; Amirfazli, A
2012-06-26
Edge effect is known to hinder spreading of a sessile drop. However, the underlying thermodynamic mechanisms responsible for the edge effect still is not well-understood. In this study, a free energy model has been developed to investigate the energetic state of drops on a single pillar (from upright frustum to inverted frustum geometries). An analysis of drop free energy levels before and after crossing the edge allows us to understand the thermodynamic origin of the edge effect. In particular, four wetting cases for a drop on a single pillar with different edge angles have been determined by understanding the characteristics of FE plots. A wetting map describing the four wetting cases is given in terms of edge angle and intrinsic contact angle. The results show that the free energy barrier observed near the edge plays an important role in determining the drop states, i.e., (1) stable or metastable drop states at the pillar's edge, and (2) drop collapse by liquid spilling over the edge completely or staying at an intermediate sidewall position of the pillar. This thermodynamic model presents an energetic framework to describe the functioning of the so-called "re-entrant" structures. Results show good consistency with the literature and expand the current understanding of Gibbs' inequality condition.
A New Perspective on Thermodynamics
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...
The thermodynamic cost of quantum operations
International Nuclear Information System (INIS)
Bedingham, D J; Maroney, O J E
2016-01-01
The amount of heat generated by computers is rapidly becoming one of the main problems for developing new generations of information technology. The thermodynamics of computation sets the ultimate physical bounds on heat generation. A lower bound is set by the Landauer limit, at which computation becomes thermodynamically reversible. For classical computation there is no physical principle which prevents this limit being reached, and approaches to it are already being experimentally tested. In this paper we show that for quantum computation with a set of signal states satisfying given conditions, there is an unavoidable excess heat generation that renders it inherently thermodynamically irreversible. The Landauer limit cannot, in general, be reached by quantum computers. We show the existence of a lower bound to the heat generated by quantum computing that exceeds that given by the Landauer limit, give the special conditions where this excess cost may be avoided, and provide a protocol for achieving the limiting heat cost when these conditions are met. We also show how classical computing falls within the special conditions. (paper)
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
Pineda, Evan Jorge; Waas, Anthony M.
2013-01-01
A thermodynamically-based work potential theory for modeling progressive damage and failure in fiber-reinforced laminates is presented. The current, multiple-internal state variable (ISV) formulation, referred to as enhanced Schapery theory (EST), utilizes separate ISVs for modeling the effects of damage and failure. Consistent characteristic lengths are introduced into the formulation to govern the evolution of the failure ISVs. Using the stationarity of the total work potential with respect to each ISV, a set of thermodynamically consistent evolution equations for the ISVs are derived. The theory is implemented into a commercial finite element code. The model is verified against experimental results from two laminated, T800/3900-2 panels containing a central notch and different fiber-orientation stacking sequences. Global load versus displacement, global load versus local strain gage data, and macroscopic failure paths obtained from the models are compared against the experimental results.
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
Can De Sitter spacetime be a final state of the contracting universe
International Nuclear Information System (INIS)
Berezin, V.A.
1984-01-01
This chapter attempts to phenomenologically describe the final stage of the Universe contraction. A model equation of state is used to demonstrate that during a cosmological contraction a de Sitter spacetime may be produced. It is shown that a equilibrium thermodynamic description of the matter in cosmological models leads to the absence of particle creation. It is proposed that these nonequilibrium processes be taken into account by introducing a new additional thermodynamic variable showing the explicit time dependence of all thermodynamic potentials into the thermodynamic relations. The spacetime is assumed to be homogeneous and isotropic, and the energy momentum tensor includes not only the energy density and pressure for the matter and radiation, but it also includes contributions due to vacuum polarization by correspondent fields. It is demonstrated that it is possible to reach in principle the de Sitter spacetime as the limit of the contraction
Thermodynamics, kinetics and process control of nitriding
DEFF Research Database (Denmark)
Mittemeijer, Eric J.; Somers, Marcel A. J.
1997-01-01
As a prerequisite for the predictability of properties obtained by a nitriding treatment of iron based workpieces, the relation between the process parameters and the composition and structure of the surface layer produced must be known. At present, even the description of thermodynamic equilibrium...... of pure Fe-N phases has not been fully achieved. It is shown that taking into account the ordering of nitrogen in the epsilon and gamma' iron nitride phases leads to an improved understanding of the Fe-N phase diagram. Although consideration of thermodynamics indicates the state the system strives for...... for process control of gaseous nitriding by monitoring the partial pressure of oxygen in the furnace using a solid state electrolyte is provided. At the time the work was carried out the authors were in the Laboratory of Materials Science, Delft University of Technology, Rotterdamseweg 137, 2628 AL Delft...
A thermodynamic approach to obtain materials properties for engineering applications
Chang, Y. Austin
1993-01-01
With the ever increases in the capabilities of computers for numerical computations, we are on the verge of using these tools to model manufacturing processes for improving the efficiency of these processes as well as the quality of the products. One such process is casting for the production of metals. However, in order to model metal casting processes in a meaningful way it is essential to have the basic properties of these materials in their molten state, solid state as well as in the mixed state of solid and liquid. Some of the properties needed may be considered as intrinsic such as the density, heat capacity or enthalpy of freezing of a pure metal, while others are not. For instance, the enthalpy of solidification of an alloy is not a defined thermodynamic quantity. Its value depends on the micro-segregation of the phases during the course of solidification. The objective of the present study is to present a thermodynamic approach to obtain some of the intrinsic properties and combining thermodynamics with kinetic models to estimate such quantities as the enthalpy of solidification of an alloy.
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...
Introduction to applied thermodynamics
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
Mass-independent area (or entropy) and thermodynamic volume products in conformal gravity
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.
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
Thermodynamics, diffusion and the Kirkendall effect in solids
Paul, Aloke; Vuorinen, Vesa; Divinski, Sergiy V
2014-01-01
Covering both basic and advanced thermodynamic and phase principles, as well as providing stability diagrams relevant for diffusion studies, Thermodynamics, Diffusion and the Kirkendall Effect in Solids maximizes reader insights into Fick’s laws of diffusion, atomic mechanisms, interdiffusion, intrinsic diffusion, tracer diffusion and the Kirkendall effect. Recent advances in the area of interdiffusion will be introduced, while the many practical examples and large number of illustrations given will serve to aid researches working in this area in learning the practical evaluation of various diffusion parameters from experimental results. With a unique approach to the two main focal points in solid state transformations, energetics (thermodynamics) and kinetics (interdiffusion) are extensively studied and their combined use in practise is discussed. Recent developments in the area of Kirkendall effect, grain boundary diffusion and multicomponent diffusion are also covered extensively. This book will appe...
Thermodynamics of random reaction networks.
Directory of Open Access Journals (Sweden)
Jakob Fischer
Full Text Available Reaction networks are useful for analyzing reaction systems occurring in chemistry, systems biology, or Earth system science. Despite the importance of thermodynamic disequilibrium for many of those systems, the general thermodynamic properties of reaction networks are poorly understood. To circumvent the problem of sparse thermodynamic data, we generate artificial reaction networks and investigate their non-equilibrium steady state for various boundary fluxes. We generate linear and nonlinear networks using four different complex network models (Erdős-Rényi, Barabási-Albert, Watts-Strogatz, Pan-Sinha and compare their topological properties with real reaction networks. For similar boundary conditions the steady state flow through the linear networks is about one order of magnitude higher than the flow through comparable nonlinear networks. In all networks, the flow decreases with the distance between the inflow and outflow boundary species, with Watts-Strogatz networks showing a significantly smaller slope compared to the three other network types. The distribution of entropy production of the individual reactions inside the network follows a power law in the intermediate region with an exponent of circa -1.5 for linear and -1.66 for nonlinear networks. An elevated entropy production rate is found in reactions associated with weakly connected species. This effect is stronger in nonlinear networks than in the linear ones. Increasing the flow through the nonlinear networks also increases the number of cycles and leads to a narrower distribution of chemical potentials. We conclude that the relation between distribution of dissipation, network topology and strength of disequilibrium is nontrivial and can be studied systematically by artificial reaction networks.
International Nuclear Information System (INIS)
Gurvich, L.V.; Bergman, G.A.; Gorokhov, L.N.; Iorish, V.S.; Leonidov, V.Y.; Yungman, V.S.
1997-01-01
The data on thermodynamic and molecular properties of the potassium, rubidium and cesium hydroxides have been collected, critically reviewed, analyzed, and evaluated. Tables of the thermodynamic properties [C p circ , Φ=-(G -H(0)/T, S, H -H(0), Δ f H, Δ f G)] of these hydroxides in the condensed and gaseous states have been calculated using the results of the analysis and some estimated values. The recommendations are compared with earlier evaluations given in the JANAF Thermochemical Tables and Thermodynamic Properties of Individual Substances. The properties considered are: the temperature and enthalpy of phase transitions and fusion, heat capacities, spectroscopic data, structures, bond energies, and enthalpies of formation at 298.15 K. The thermodynamic functions in solid, liquid, and gaseous states are calculated from T=0 to 2000 K for substances in condensed phase and up to 6000 K for gases. copyright 1997 American Institute of Physics and American Chemical Society
Fluctuating Thermodynamics for Biological Processes
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.
Chiral thermodynamics of nuclear matter
International Nuclear Information System (INIS)
Fiorilla, Salvatore
2012-01-01
The equation of state of nuclear matter is calculated at finite temperature in the framework of in-medium chiral perturbation theory up to three-loop order. The dependence of its thermodynamic properties on the isospin-asymmetry is investigated. The chiral quark condensate is evaluated for symmetric nuclear matter. Its behaviour as a function of density and temperature sets important nuclear physics constraints for the QCD phase diagram.
Chiral thermodynamics of nuclear matter
Energy Technology Data Exchange (ETDEWEB)
Fiorilla, Salvatore
2012-10-23
The equation of state of nuclear matter is calculated at finite temperature in the framework of in-medium chiral perturbation theory up to three-loop order. The dependence of its thermodynamic properties on the isospin-asymmetry is investigated. The chiral quark condensate is evaluated for symmetric nuclear matter. Its behaviour as a function of density and temperature sets important nuclear physics constraints for the QCD phase diagram.
Thermodynamic model of a solid with RKKY interaction and magnetoelastic coupling
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.
Genuine tripartite entangled states with a local hidden-variable model
International Nuclear Information System (INIS)
Toth, Geza; Acin, Antonio
2006-01-01
We present a family of three-qubit quantum states with a basic local hidden-variable model. Any von Neumann measurement can be described by a local model for these states. We show that some of these states are genuine three-partite entangled and also distillable. The generalization for larger dimensions or higher number of parties is also discussed. As a by-product, we present symmetric extensions of two-qubit Werner states
Thermodynamic properties of poly(phenylene-pyridyl) dendrons of the second and the third generations
International Nuclear Information System (INIS)
Smirnova, Natalia N.; Samosudova, Yanina S.; Markin, Alexey V.; Serkova, Elena S.; Kuchkina, Nina V.; Shifrina, Zinaida B.
2017-01-01
Highlights: • We report thermodynamic properties for poly(phenylene-pyridyl) dendrons of the second and the third generations. • The thermodynamic quantities of devitrification and fusion have been determined. • Thermodynamic functions for the temperature range from T → 0 to 520 K for different physical states were calculated. • The dependences of thermodynamic properties of the dendrons on their composition and structure have been obtained. - Abstract: The temperature dependence of the heat capacity of poly(phenylene-pyridyl) dendrons of the second and the third generations have been measured by the method of adiabatic vacuum and differential scanning calorimetry over the range from 6 K to (500–520) K in the present research. Phase transformations have been detected and their thermodynamic characteristics have been estimated and analysed in the above temperature range. The standard thermodynamic functions, namely, the heat capacity C p 0 (T), enthalpy H°(T) − H°(0), entropy S°(T) − S°(0) and potential Φ m °, for the range from T → 0 K to (500–520) K and the standard entropy of formation of the dendrons in different physical states at T = 298.15 K have been calculated based on the experimental results. The thermodynamic characteristics of the samples under study and investigated earlier, poly(phenylene-pyridyl) dendrons decorated with dodecyl groups of the same generations have been compared and discussed.
A thermodynamic-like approach for the study of probabilistic systems
Campos, Diógenes
2011-01-01
This paper starts by considering an arbitrary system for which the probability distribution P:={P1,P2,…,PN} of a measurable property, with N possible independent results, is known. By using the Hartley information (pseudo-energy), the escort probabilities of P and its Shannon entropy, a thermodynamic-like formalism is developed, including the deduction of the fundamental equation for the mean value of the pseudo-energies. Thus, the method allows a macrodescription of the system that is based on a purely mathematical procedure and involves thermodynamic-like variables. As a specific example we consider a bank that measures customer satisfaction by doing a statistical survey (satisfied or unsatisfied customers).
State variable theories based on Hart's formulation
Energy Technology Data Exchange (ETDEWEB)
Korhonen, M.A.; Hannula, S.P.; Li, C.Y.
1985-01-01
In this paper a review of the development of a state variable theory for nonelastic deformation is given. The physical and phenomenological basis of the theory and the constitutive equations describing macroplastic, microplastic, anelastic and grain boundary sliding enhanced deformation are presented. The experimental and analytical evaluation of different parameters in the constitutive equations are described in detail followed by a review of the extensive experimental work on different materials. The technological aspects of the state variable approach are highlighted by examples of the simulative and predictive capabilities of the theory. Finally, a discussion of general capabilities, limitations and future developments of the theory and particularly the possible extensions to cover an even wider range of deformation or deformation-related phenomena is presented.
Possible generalization of Yang variables for the study of many particle final states
International Nuclear Information System (INIS)
Becker, L.; Schiller, H.
1976-01-01
Starting from a discussion of constraints on invariant variables a generalization of the so called Yang-variables is discussed for the case of 5 and 6 particles in the final states. The obtained Lorentz-invariant variables are ''quasi permutation invariant'' with respect to the final state particles. The influence of Gram determinants is discussed in the context of the application of a cluster algorithm. (author)
Thermodynamics of nuclear materials
International Nuclear Information System (INIS)
1979-01-01
Full text: The science of chemical thermodynamics has substantially contributed to the understanding of the many problems encountered in nuclear and reactor technology. These problems include reaction of materials with their surroundings and chemical and physical changes of fuels. Modern reactor technology, by its very nature, has offered new fields of investigations for the scientists and engineers concerned with the design of nuclear fuel elements. Moreover, thermodynamics has been vital in predicting the behaviour of new materials for fission as well as fusion reactors. In this regard, the Symposium was organized to provide a mechanism for review and discussion of recent thermodynamic investigations of nuclear materials. The Symposium was held in the Juelich Nuclear Research Centre, at the invitation of the Government of the Federal Republic of Germany. The International Atomic Energy Agency has given much attention to the thermodynamics of nuclear materials, as is evidenced by its sponsorship of four international symposia in 1962, 1965, 1967, and 1974. The first three meetings were primarily concerned with the fundamental thermodynamics of nuclear materials; as with the 1974 meeting, this last Symposium was primarily aimed at the thermodynamic behaviour of nuclear materials in actual practice, i.e., applied thermodynamics. Many advances have been made since the 1974 meeting, both in fundamental and applied thermodynamics of nuclear materials, and this meeting provided opportunities for an exchange of new information on this topic. The Symposium dealt in part with the thermodynamic analysis of nuclear materials under conditions of high temperatures and a severe radiation environment. Several sessions were devoted to the thermodynamic studies of nuclear fuels and fission and fusion reactor materials under adverse conditions. These papers and ensuing discussions provided a better understanding of the chemical behaviour of fuels and materials under these
THERMODYNAMIC MODEL AND VISCOSITY OF SELECTED ZIRCONIA CONTAINING SILICATE GLASSES
Directory of Open Access Journals (Sweden)
MÁRIA CHROMČÍKOVÁ
2013-03-01
Full Text Available The compositional dependence of viscosity, and viscous flow activation energy of glasses with composition xNa2O∙(15-x K2O∙yCaO∙(10-yZnO∙zZrO2∙(75-zSiO2 (x = 0, 7.5, 15; y = 0, 5, 10; z = 0, 1, 3, 5, 7 was analyzed. The studied glasses were described by the thermodynamic model of Shakhmatkin and Vedishcheva considering the glass as an equilibrium ideal solution of species with stoichiometry given by the composition of stable crystalline phases of respective glass forming system. Viscosity-composition relationships were described by the regression approach considering the viscous flow activation energy and the particular isokome temperature as multilinear function of equilibrium molar amounts of system components. The classical approach where the mole fractions of individual oxides are considered as independent variables was compared with the thermodynamic model. On the basis of statistical analysis there was proved that the thermodynamic model is able to describe the composition property relationships with higher reliability. Moreover, due its better physical justification, thermodynamic model can be even used for predictive purposes.
Equilibrium and out-of-equilibrium thermodynamics in supercooled liquids and glasses
International Nuclear Information System (INIS)
Mossa, S; Nave, E La; Tartaglia, P; Sciortino, F
2003-01-01
We review the inherent structure thermodynamical formalism and the formulation of an equation of state (EOS) for liquids in equilibrium based on the (volume) derivatives of the statistical properties of the potential energy surface. We also show that, under the hypothesis that during ageing the system explores states associated with equilibrium configurations, it is possible to generalize the proposed EOS to out-of-equilibrium (OOE) conditions. The proposed formulation is based on the introduction of one additional parameter which, in the chosen thermodynamic formalism, can be chosen as the local minimum where the slowly relaxing OOE liquid is trapped
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...
International Nuclear Information System (INIS)
Liebenberg, D.H.; Mills, R.L.; Bronson, J.C.
1977-01-01
Hydrogen isotopes play an important role in energy technologies, in particular, the compression to high densities for initiation of controlled thermonuclear fusion energy. At high densities the properties of the compressed hydrogen isotopes depart drastically from ideal thermodynamic predictions. The measurement of accurate data including the author's own recent measurements of n-H 2 and n-D 2 in the range 75 to 300 K and 0.2 to 2.0 GPa (2 to 20 kbar) is reviewed. An equation-of-state of the Benedict type is fit to these data with a double-process least-squares computer program. The results are reviewed and compared with existing data and with a variety of theoretical work reported for fluid hydrogens. A new heuristic correlation is presented for simplicity in predicting volumes and sound velocity at high pressures. 9 figures, 1 table
Thermodynamic aspects of the glass-rubber transition
Staverman, A.J.
1966-01-01
In 1933 Ehren/est defined transitions in which not only the thermodynamical potential but also the specific volume and entropy of the two states are equal. For these transitions he derived three relations, between the differences of the coefficients of dilatation and of compressibility and the
A Thermodynamic Mixed-Solid Asphaltene Precipitation Model
DEFF Research Database (Denmark)
Lindeloff, Niels; Heidemann, R.A.; Andersen, Simon Ivar
1998-01-01
A simple model for the prediction of asphaltene precipitation is proposed. The model is based on an equation of state and uses standard thermodynamics, thus assuming that the precipitation phenomenon is a reversible process. The solid phase is treated as an ideal multicomponent mixture. An activity...
The critical roles of information and nonequilibrium thermodynamics in evolution of living systems.
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.
International Nuclear Information System (INIS)
Mazumder, Nairwita; Chakraborty, Subenoy
2009-01-01
In this work we examine the validity of the generalized second law of thermodynamics of the universe with the event horizon as the boundary assuming the first law of thermodynamics. We consider a homogeneous and isotropic model of the universe, filled with perfect fluid having an arbitrary equation of state. We study the validity of the generalized second law both in Einstein and Einstein-Gauss-Bonnet (EGB) gravity.
Tarnacka, M; Madejczyk, O; Adrjanowicz, K; Pionteck, J; Kaminska, E; Kamiński, K; Paluch, M
2015-06-14
Pressure-Volume-Temperature (PVT) measurements and broadband dielectric spectroscopy were carried out to investigate molecular dynamics and to test the validity of thermodynamic scaling of two homologous compounds of pharmaceutical activity: itraconazole and ketoconazole in the wide range of thermodynamic conditions. The pressure coefficients of the glass transition temperature (dT(g)/dp) for itraconazole and ketoconazole were determined to be equal to 183 and 228 K/GPa, respectively. However, for itraconazole, the additional transition to the nematic phase was observed and characterized by the pressure coefficient dT(n)/dp = 258 K/GPa. From PVT and dielectric data, we obtained that the liquid-nematic phase transition is governed by the relaxation time since it occurred at constant τ(α) = 10(-5) s. Furthermore, we plotted the obtained relaxation times as a function of T(-1)v(-γ), which has revealed that the validity of thermodynamic scaling with the γ exponent equals to 3.69 ± 0.04 and 3.64 ± 0.03 for itraconazole and ketoconazole, respectively. Further analysis of the scaling parameter in itraconazole revealed that it unexpectedly decreases with increasing relaxation time, which resulted in dramatic change of the shape of the thermodynamic scaling master curve. While in the case of ketoconazole, it remained the same within entire range of data (within experimental uncertainty). We suppose that in case of itraconazole, this peculiar behavior is related to the liquid crystals' properties of itraconazole molecule.
Energy Technology Data Exchange (ETDEWEB)
Tarnacka, M., E-mail: mtarnacka@us.edu.pl; Madejczyk, O.; Kamiński, K.; Paluch, M. [Institute of Physics, University of Silesia, ul. Uniwersytecka 4, 40-007 Katowice (Poland); Silesian Center of Education and Interdisciplinary Research, University of Silesia, ul. 75 Pulku Piechoty 1A, 41-500 Chorzow (Poland); Adrjanowicz, K. [NanoBioMedical Centre, ul. Umultowska 85, 61-614 Poznan (Poland); Pionteck, J. [Leibniz Institute of Polymer Research Dresden, Hohe Strasse 6, D-01069 Dresden (Germany); Kaminska, E. [Department of Pharmacognosy and Phytochemistry, School of Pharmacy and Division of Laboratory Medicine in Sosnowiec, Medical University of Silesia, ul. Jagiellonska 4, 41-200 Sosnowiec (Poland)
2015-06-14
Pressure-Volume-Temperature (PVT) measurements and broadband dielectric spectroscopy were carried out to investigate molecular dynamics and to test the validity of thermodynamic scaling of two homologous compounds of pharmaceutical activity: itraconazole and ketoconazole in the wide range of thermodynamic conditions. The pressure coefficients of the glass transition temperature (dT{sub g}/dp) for itraconazole and ketoconazole were determined to be equal to 183 and 228 K/GPa, respectively. However, for itraconazole, the additional transition to the nematic phase was observed and characterized by the pressure coefficient dT{sub n}/dp = 258 K/GPa. From PVT and dielectric data, we obtained that the liquid-nematic phase transition is governed by the relaxation time since it occurred at constant τ {sub α} = 10{sup −5} s. Furthermore, we plotted the obtained relaxation times as a function of T{sup −1}v{sup −γ}, which has revealed that the validity of thermodynamic scaling with the γ exponent equals to 3.69 ± 0.04 and 3.64 ± 0.03 for itraconazole and ketoconazole, respectively. Further analysis of the scaling parameter in itraconazole revealed that it unexpectedly decreases with increasing relaxation time, which resulted in dramatic change of the shape of the thermodynamic scaling master curve. While in the case of ketoconazole, it remained the same within entire range of data (within experimental uncertainty). We suppose that in case of itraconazole, this peculiar behavior is related to the liquid crystals’ properties of itraconazole molecule.
Specific features of the thermodynamics of superionic conductors
International Nuclear Information System (INIS)
Gurevich, Yu.Ya.; Kharkats, Yu.I.
1982-01-01
A review of theoretical and experimental investigations devoted to a study of thermodynamic aspects of the superionic conductivity phenomena for the recent decade is presented. A relation between a superionic conductivity and the disordering of one of the crystal sublattices, the phase transitions of the disordering caused by the point defects interaction, the mechanism of polymorphic transitions conjugated with a partial disordering are considered. The effect of an abrupt change of the ionic conductivity induced by electric field, the thermodynamics of the domain states in superionic conductors and the influence of pressure on phase transitions and ionic conductivity are analyzed
Thermodynamics of phase-separating nanoalloys: Single particles and particle assemblies
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.
An Equation of State for the Thermodynamic Properties of Cyclohexane
Energy Technology Data Exchange (ETDEWEB)
Zhou, Yong, E-mail: Yong.Zhou2@honeywell.com; Liu, Jun [Honeywell Integrated Technology China Co. Ltd., 430 Li Bing Road, Zhangjiang Hi-Tech Park, Shanghai 201203 (China); Penoncello, Steven G. [Center for Applied Thermodynamic Studies, College of Engineering, University of Idaho, Moscow, Idaho 83844 (United States); Lemmon, Eric W. [Applied Chemicals and Materials Division, National Institute of Standards and Technology, 325 Broadway, Boulder, Colorado 80305 (United States)
2014-12-15
An equation of state for cyclohexane has been developed using the Helmholtz energy as the fundamental property with independent variables of density and temperature. Multi-property fitting technology was used to fit the equation of state to data for pρT, heat capacities, sound speeds, virial coefficients, vapor pressures, and saturated densities. The equation of state was developed to conform to the Maxwell criteria for two-phase vapor-liquid equilibrium states, and is valid from the triple-point temperature to 700 K, with pressures up to 250 MPa and densities up to 10.3 mol dm{sup −3}. In general, the uncertainties (k = 2, indicating a level of confidence of 95%) in density for the equation of state are 0.1% (liquid and vapor) up to 500 K, and 0.2% above 500 K, with higher uncertainties within the critical region. Between 283 and 473 K with pressures lower than 30 MPa, the uncertainty is as low as 0.03% in density in the liquid phase. The uncertainties in the speed of sound are 0.2% between 283 and 323 K in the liquid, and 1% elsewhere. Other uncertainties are 0.05% in vapor pressure and 2% in heat capacities. The behavior of the equation of state is reasonable within the region of validity and at higher and lower temperatures and pressures. A detailed analysis has been performed in this article.
Thermodynamics of two component gaseous and solid state plasmas at any degeneracy
International Nuclear Information System (INIS)
Kraeft, W.D.; Stolzmann, W.; Fromhold-Treu, I.; Rother, T.
1988-10-01
We give the results of thermodynamical calculations for two component plasmas which are of interest for dense hydrogen, noble gas and alkali plasmas and for electron hole plasmas in optically excited semiconductors as well. 25 refs, 4 figs
Gravity as a thermodynamic phenomenon
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.
Equation of state in the presence of gravity
Kim, Hyeong-Chan; Kang, Gungwon
2016-11-01
We investigate how an equation of state for matter is affected when a gravity is present. For this purpose, we consider a box of ideal gas in the presence of Newtonian gravity. In addition to the ordinary thermodynamic quantities, a characteristic variable that represents a weight per unit area relative to the average pressure is required in order to describe a macroscopic state of the gas. Although the density and the pressure are not uniform due to the presence of gravity, the ideal gas law itself is satisfied for the thermodynamic quantities when averaged over the system. Assuming that the system follows an adiabatic process further, we obtain a new relation between the averaged pressure and density, which differs from the conventional equation of state for the ideal gas in the absence of gravity. Applying our results to a small volume in a Newtonian star, however, we find that the conventional one is reliable for most astrophysical situations when the characteristic scale is small. On the other hand, gravity effects become significant near the surface of a Newtonian star.
Thermodynamic matchers for the construction of the cuckoo RNA family.
Reinkensmeier, Jan; Giegerich, Robert
2015-01-01
RNA family models describe classes of functionally related, non-coding RNAs based on sequence and structure conservation. The most important method for modeling RNA families is the use of covariance models, which are stochastic models that serve in the discovery of yet unknown, homologous RNAs. However, the performance of covariance models in finding remote homologs is poor for RNA families with high sequence conservation, while for families with high structure but low sequence conservation, these models are difficult to built in the first place. A complementary approach to RNA family modeling involves the use of thermodynamic matchers. Thermodynamic matchers are RNA folding programs, based on the established thermodynamic model, but tailored to a specific structural motif. As thermodynamic matchers focus on structure and folding energy, they unfold their potential in discovering homologs, when high structure conservation is paired with low sequence conservation. In contrast to covariance models, construction of thermodynamic matchers does not require an input alignment, but requires human design decisions and experimentation, and hence, model construction is more laborious. Here we report a case study on an RNA family that was constructed by means of thermodynamic matchers. It starts from a set of known but structurally different members of the same RNA family. The consensus secondary structure of this family consists of 2 to 4 adjacent hairpins. Each hairpin loop carries the same motif, CCUCCUCCC, while the stems show high variability in their nucleotide content. The present study describes (1) a novel approach for the integration of the structurally varying family into a single RNA family model by means of the thermodynamic matcher methodology, and (2) provides the results of homology searches that were conducted with this model in a wide spectrum of bacterial species.
Association theories for complex thermodynamics
DEFF Research Database (Denmark)
Kontogeorgis, Georgios; Rafiqul Gani
2013-01-01
of this review is two-fold: first to illustrate some of the significant capabilities of these association theories and why indeed they have already been extensively used and are expected to find even more applications in the future. The second and most important aspect of this review is to outline many...... applications. While specialized models can handle different cases, even complex ones, with the advent of powerful theories and computers there is the hope that a single or a few models could be suitable for a general modeling of complex thermodynamics. After more than 100 years with active use of thermodynamic...... models, we have now come to the understanding that simple one-fluid theories like the cubic equations of state or the various forms of local composition models will never be able to model a wide range of complex systems with sufficient accuracy. While various modern approaches have appeared, one very...
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
Pathway Thermodynamics Highlights Kinetic Obstacles in Central Metabolism
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
Automatic Welding Control Using a State Variable Model.
1979-06-01
A-A10 610 NAVEAL POSTGRADUATE SCH4O.M CEAY CA0/ 13/ SAUTOMATIC WELDING CONTROL USING A STATE VARIABLE MODEL.W()JUN 79 W V "my UNCLASSIFIED...taverse Drive Unit // Jbint Path /Fixed Track 34 (servomotor positioning). Additional controls of heave (vertical), roll (angular rotation about the
Introduction to the thermodynamic Bethe ansatz
van Tongeren, Stijn J.
2016-08-01
We give a pedagogical introduction to the thermodynamic Bethe ansatz, a method that allows us to describe the thermodynamics of integrable models whose spectrum is found via the (asymptotic) Bethe ansatz. We set the stage by deriving the Fermi-Dirac distribution and associated free energy of free electrons, and then in a similar though technically more complicated fashion treat the thermodynamics of integrable models, focusing first on the one-dimensional Bose gas with delta function interaction as a clean pedagogical example, secondly the XXX spin chain as an elementary (lattice) model with prototypical complicating features in the form of bound states, and finally the {SU}(2) chiral Gross-Neveu model as a field theory example. Throughout this discussion we emphasize the central role of particle and hole densities, whose relations determine the model under consideration. We then discuss tricks that allow us to use the same methods to describe the exact spectra of integrable field theories on a circle, in particular the chiral Gross-Neveu model. We moreover discuss the simplification of TBA equations to Y systems, including the transition back to integral equations given sufficient analyticity data, in simple examples.
On Thermodynamic Interpretation of Transfer Entropy
Directory of Open Access Journals (Sweden)
Don C. Price
2013-02-01
Full Text Available We propose a thermodynamic interpretation of transfer entropy near equilibrium, using a specialised Boltzmann’s principle. The approach relates conditional probabilities to the probabilities of the corresponding state transitions. This in turn characterises transfer entropy as a difference of two entropy rates: the rate for a resultant transition and another rate for a possibly irreversible transition within the system affected by an additional source. We then show that this difference, the local transfer entropy, is proportional to the external entropy production, possibly due to irreversibility. Near equilibrium, transfer entropy is also interpreted as the difference in equilibrium stabilities with respect to two scenarios: a default case and the case with an additional source. Finally, we demonstrated that such a thermodynamic treatment is not applicable to information flow, a measure of causal effect.
Clarifying the link between von Neumann and thermodynamic entropies
Deville, Alain; Deville, Yannick
2013-01-01
The state of a quantum system being described by a density operator ρ, quantum statistical mechanics calls the quantity - kTr( ρln ρ), introduced by von Neumann, its von Neumann or statistical entropy. A 1999 Shenker's paper initiated a debate about its link with the entropy of phenomenological thermodynamics. Referring to Gibbs's and von Neumann's founding texts, we replace von Neumann's 1932 contribution in its historical context, after Gibbs's 1902 treatise and before the creation of the information entropy concept, which places boundaries into the debate. Reexamining von Neumann's reasoning, we stress that the part of his reasoning implied in the debate mainly uses thermodynamics, not quantum mechanics, and identify two implicit postulates. We thoroughly examine Shenker's and ensuing papers, insisting upon the presence of open thermodynamical subsystems, imposing us the use of the chemical potential concept. We briefly mention Landau's approach to the quantum entropy. On the whole, it is shown that von Neumann's viewpoint is right, and why Shenker's claim that von Neumann entropy "is not the quantum-mechanical correlate of thermodynamic entropy" can't be retained.
Relation between the psychological and thermodynamic arrows of time
Mlodinow, Leonard; Brun, Todd A.
2014-05-01
In this paper we lay out an argument that generically the psychological arrow of time should align with the thermodynamic arrow of time where that arrow is well defined. This argument applies to any physical system that can act as a memory, in the sense of preserving a record of the state of some other system. This result follows from two principles: the robustness of the thermodynamic arrow of time to small perturbations in the state, and the principle that a memory should not have to be fine-tuned to match the state of the system being recorded. This argument applies even if the memory system itself is completely reversible and nondissipative. We make the argument with a paradigmatic system, and then formulate it more broadly for any system that can be considered a memory. We illustrate these principles for a few other example systems and compare our criteria to earlier treatments of this problem.
Simulation of styrene polymerization reactors: kinetic and thermodynamic modeling
Directory of Open Access Journals (Sweden)
A. S. Almeida
2008-06-01
Full Text Available A mathematical model for the free radical polymerization of styrene is developed to predict the steady-state and dynamic behavior of a continuous process. Special emphasis is given for the kinetic and thermodynamic models, where the most sensitive parameters were estimated using data from an industrial plant. The thermodynamic model is based on a cubic equation of state and a mixing rule applied to the low-pressure vapor-liquid equilibrium of polymeric solutions, suitable for modeling the auto-refrigerated polymerization reactors, which use the vaporization rate to remove the reaction heat from the exothermic reactions. The simulation results show the high predictive capability of the proposed model when compared with plant data for conversion, average molecular weights, polydispersity, melt flow index, and thermal properties for different polymer grades.
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.
Generating entangled states of continuous variables via cross-Kerr nonlinearity
Energy Technology Data Exchange (ETDEWEB)
Zhang Zhiming [Center for Quantum Physics, COMSATS Institute of Information Technology, Islamabad (Pakistan); Khosa, Ashfaq H [Center for Quantum Physics, COMSATS Institute of Information Technology, Islamabad (Pakistan); Ikram, Manzoor [Center for Quantum Physics, COMSATS Institute of Information Technology, Islamabad (Pakistan); Zubairy, M Suhail [Center for Quantum Physics, COMSATS Institute of Information Technology, Islamabad (Pakistan)
2007-05-28
We propose a scheme for generating entanglement of quantum states with continuous variables (coherent states and squeezed vacuum states) of electromagnetical fields. The scheme involves cross-Kerr nonlinearity. It was shown that the cross-Kerr nonlinearity required for generating the superposition and entanglement of squeezed vacuum states is smaller than that required for coherent states. It was also found that the fidelity monotonously decreases with both the increase of the amplitude of the input coherent field and the increase of the deviation of the nonlinear phase shift from {pi}.
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
Quantum Rényi relative entropies affirm universality of thermodynamics.
Misra, Avijit; Singh, Uttam; Bera, Manabendra Nath; Rajagopal, A K
2015-10-01
We formulate a complete theory of quantum thermodynamics in the Rényi entropic formalism exploiting the Rényi relative entropies, starting from the maximum entropy principle. In establishing the first and second laws of quantum thermodynamics, we have correctly identified accessible work and heat exchange in both equilibrium and nonequilibrium cases. The free energy (internal energy minus temperature times entropy) remains unaltered, when all the entities entering this relation are suitably defined. Exploiting Rényi relative entropies we have shown that this "form invariance" holds even beyond equilibrium and has profound operational significance in isothermal process. These results reduce to the Gibbs-von Neumann results when the Rényi entropic parameter α approaches 1. Moreover, it is shown that the universality of the Carnot statement of the second law is the consequence of the form invariance of the free energy, which is in turn the consequence of maximum entropy principle. Further, the Clausius inequality, which is the precursor to the Carnot statement, is also shown to hold based on the data processing inequalities for the traditional and sandwiched Rényi relative entropies. Thus, we find that the thermodynamics of nonequilibrium state and its deviation from equilibrium together determine the thermodynamic laws. This is another important manifestation of the concepts of information theory in thermodynamics when they are extended to the quantum realm. Our work is a substantial step towards formulating a complete theory of quantum thermodynamics and corresponding resource theory.
Bipartite entanglement in continuous variable cluster states
Energy Technology Data Exchange (ETDEWEB)
Cable, Hugo; Browne, Daniel E, E-mail: cqthvc@nus.edu.s, E-mail: d.browne@ucl.ac.u [Centre for Quantum Technologies, National University of Singapore, 3 Science Drive 2, Singapore 117543 (Singapore)
2010-11-15
A study of the entanglement properties of Gaussian cluster states, proposed as a universal resource for continuous variable (CV) quantum computing is presented in this paper. The central aim is to compare mathematically idealized cluster states defined using quadrature eigenstates, which have infinite squeezing and cannot exist in nature, with Gaussian approximations that are experimentally accessible. Adopting widely used definitions, we first review the key concepts, by analysing a process of teleportation along a CV quantum wire in the language of matrix product states. Next we consider the bipartite entanglement properties of the wire, providing analytic results. We proceed to grid cluster states, which are universal for the qubit case. To extend our analysis of the bipartite entanglement, we adopt the entropic-entanglement width, a specialized entanglement measure introduced recently by Van den Nest et al (2006 Phys. Rev. Lett. 97 150504), adapting their definition to the CV context. Finally, we consider the effects of photonic loss, extending our arguments to mixed states. Cumulatively our results point to key differences in the properties of idealized and Gaussian cluster states. Even modest loss rates are found to strongly limit the amount of entanglement. We discuss the implications for the potential of CV analogues for measurement-based quantum computation.
Jacobs, Michael H G; Schmid-Fetzer, Rainer; van den Berg, Arie P.
2017-01-01
In a previous paper, we showed a technique that simplifies Kieffer’s lattice vibrational method by representing the vibrational density of states with multiple Einstein frequencies. Here, we show that this technique can be applied to construct a thermodynamic database that accurately represents
Van der Waals equation of state revisited: importance of the dispersion correction.
de Visser, Sam P
2011-04-28
One of the most basic equations of state describing nonideal gases and liquids is the van der Waals equation of state, and as a consequence, it is generally taught in most first year undergraduate chemistry courses. In this work, we show that the constants a and b in the van der Waals equation of state are linearly proportional to the polarizability volume of the molecules in a gas or liquid. Using this information, a new thermodynamic one-parameter equation of state is derived that contains experimentally measurable variables and physics constants only. This is the first equation of state apart from the Ideal Gas Law that contains experimentally measurable variables and physics constants only, and as such, it may be a very useful and practical equation for the description of dilute gases and liquids. The modified van der Waals equation of state describes pV as the sum of repulsive and attractive intermolecular interaction energies that are represented by an exponential repulsion function between the electron clouds of the molecules and a London dispersion component, respectively. The newly derived equation of state is tested against experimental data for several gas and liquid examples, and the agreement is satisfactory. The description of the equation of state as a one-parameter function also has implications on other thermodynamic functions, such as critical parameters, virial coefficients, and isothermal compressibilities. Using our modified van der Waals equation of state, we show that all of these properties are a function of the molecular polarizability volume. Correlations of experimental data confirm the derived proportionalities.
Thermodynamics as a Foundation for Density Functional Theory
International Nuclear Information System (INIS)
Argaman, Nathan
2014-01-01
Density Functional Theory (DFT) is the method of choice for an ever increasing number of electronic structure computations (recently reaching 30,000 publications per year). It was founded in the sixties on the basis of the Hohenberg-Kohn theorem and the Kohn-Sham equations, which were originally proved and derived for electronic ground states. Alternatively, one may use thermodynamics to derive DFT for finite-temperature ensembles, with the ground-state theory recovered in the zero temperature limit. Specifically, the transformation from chemical potential µ to electron number N as a free variable may be directly generalized to clarify how DFT uses the density distribution n(r), rather than the external potential v(r), to specify a particular inhomogeneous electronic system. Relating interacting and non-interacting systems with the same n(r) distribution, one recovers not only the Kohn-Sham formulation, but also the so-called adiabatic connection theorem, which gives an explicit expression for the exchange-correlation energy in terms of the 'exchangecorrelation hole.' This derivation has the advantage of being constructive, rather than being based on a reductio ad absurdum argument. It thus serves as an excellent basis for a discussion of the approximations which are inevitably introduced, including the Local Density Approximation (LDA) and the Generalized Gradient Approximation (GGA)
Nonequilibrium thermodynamics and information theory: basic concepts and relaxing dynamics
Altaner, Bernhard
2017-11-01
Thermodynamics is based on the notions of energy and entropy. While energy is the elementary quantity governing physical dynamics, entropy is the fundamental concept in information theory. In this work, starting from first principles, we give a detailed didactic account on the relations between energy and entropy and thus physics and information theory. We show that thermodynamic process inequalities, like the second law, are equivalent to the requirement that an effective description for physical dynamics is strongly relaxing. From the perspective of information theory, strongly relaxing dynamics govern the irreversible convergence of a statistical ensemble towards the maximally non-commital probability distribution that is compatible with thermodynamic equilibrium parameters. In particular, Markov processes that converge to a thermodynamic equilibrium state are strongly relaxing. Our framework generalizes previous results to arbitrary open and driven systems, yielding novel thermodynamic bounds for idealized and real processes. , which features invited work from the best early-career researchers working within the scope of J. Phys. A. This project is part of the Journal of Physics series’ 50th anniversary celebrations in 2017. Bernhard Altaner was selected by the Editorial Board of J. Phys. A as an Emerging Talent.
Quantum corrections to the stress-energy tensor in thermodynamic equilibrium with acceleration
Becattini, F.; Grossi, E.
2015-08-01
We show that the stress-energy tensor has additional terms with respect to the ideal form in states of global thermodynamic equilibrium in flat spacetime with nonvanishing acceleration and vorticity. These corrections are of quantum origin and their leading terms are second order in the gradients of the thermodynamic fields. Their relevant coefficients can be expressed in terms of correlators of the stress-energy tensor operator and the generators of the Lorentz group. With respect to previous assessments, we find that there are more second-order coefficients and that all thermodynamic functions including energy density receive acceleration and vorticity dependent corrections. Notably, also the relation between ρ and p , that is, the equation of state, is affected by acceleration and vorticity. We have calculated the corrections for a free real scalar field—both massive and massless—and we have found that they increase, particularly for a massive field, at very high acceleration and vorticity and very low temperature. Finally, these nonideal terms depend on the explicit form of the stress-energy operator, implying that different stress-energy tensors of the scalar field—canonical or improved—are thermodynamically inequivalent.
Uncovering state-dependent relationships in shallow lakes using Bayesian latent variable regression.
Vitense, Kelsey; Hanson, Mark A; Herwig, Brian R; Zimmer, Kyle D; Fieberg, John
2018-03-01
Ecosystems sometimes undergo dramatic shifts between contrasting regimes. Shallow lakes, for instance, can transition between two alternative stable states: a clear state dominated by submerged aquatic vegetation and a turbid state dominated by phytoplankton. Theoretical models suggest that critical nutrient thresholds differentiate three lake types: highly resilient clear lakes, lakes that may switch between clear and turbid states following perturbations, and highly resilient turbid lakes. For effective and efficient management of shallow lakes and other systems, managers need tools to identify critical thresholds and state-dependent relationships between driving variables and key system features. Using shallow lakes as a model system for which alternative stable states have been demonstrated, we developed an integrated framework using Bayesian latent variable regression (BLR) to classify lake states, identify critical total phosphorus (TP) thresholds, and estimate steady state relationships between TP and chlorophyll a (chl a) using cross-sectional data. We evaluated the method using data simulated from a stochastic differential equation model and compared its performance to k-means clustering with regression (KMR). We also applied the framework to data comprising 130 shallow lakes. For simulated data sets, BLR had high state classification rates (median/mean accuracy >97%) and accurately estimated TP thresholds and state-dependent TP-chl a relationships. Classification and estimation improved with increasing sample size and decreasing noise levels. Compared to KMR, BLR had higher classification rates and better approximated the TP-chl a steady state relationships and TP thresholds. We fit the BLR model to three different years of empirical shallow lake data, and managers can use the estimated bifurcation diagrams to prioritize lakes for management according to their proximity to thresholds and chance of successful rehabilitation. Our model improves upon
International Nuclear Information System (INIS)
Cai Qi; Shang Yanlong; Chen Lisheng; Zhao Yuguang
2013-01-01
Vector-universal generating function was presented to analyze the availability of thermodynamic system with multiple performance parameters. Vector-universal generating function of component's performance was defined, the arithmetic model based on vector-universal generating function was derived for the thermodynamic system, and the calculation method was given for state probability of multi-state component. With the stochastic simulation of the degeneration trend of the multiple factors, the system availability with multiple performance parameters was obtained under composite factors. It is shown by an example that the results of the availability obtained by the binary availability analysis method are somewhat conservative, and the results considering parameter failure based on vector-universal generating function reflect the operation characteristics of the thermodynamic system better. (authors)
Kleidon, Axel
2009-06-01
The Earth system is maintained in a unique state far from thermodynamic equilibrium, as, for instance, reflected in the high concentration of reactive oxygen in the atmosphere. The myriad of processes that transform energy, that result in the motion of mass in the atmosphere, in oceans, and on land, processes that drive the global water, carbon, and other biogeochemical cycles, all have in common that they are irreversible in their nature. Entropy production is a general consequence of these processes and measures their degree of irreversibility. The proposed principle of maximum entropy production (MEP) states that systems are driven to steady states in which they produce entropy at the maximum possible rate given the prevailing constraints. In this review, the basics of nonequilibrium thermodynamics are described, as well as how these apply to Earth system processes. Applications of the MEP principle are discussed, ranging from the strength of the atmospheric circulation, the hydrological cycle, and biogeochemical cycles to the role that life plays in these processes. Nonequilibrium thermodynamics and the MEP principle have potentially wide-ranging implications for our understanding of Earth system functioning, how it has evolved in the past, and why it is habitable. Entropy production allows us to quantify an objective direction of Earth system change (closer to vs further away from thermodynamic equilibrium, or, equivalently, towards a state of MEP). When a maximum in entropy production is reached, MEP implies that the Earth system reacts to perturbations primarily with negative feedbacks. In conclusion, this nonequilibrium thermodynamic view of the Earth system shows great promise to establish a holistic description of the Earth as one system. This perspective is likely to allow us to better understand and predict its function as one entity, how it has evolved in the past, and how it is modified by human activities in the future.
Thermodynamic properties of gaseous propane from model ...
African Journals Online (AJOL)
A fourth-order virial equation of state was combined with isotropic model potentials to predict accurate volumetric and caloric thermodynamic properties of propane in the gas phase. The parameters in the model were determined in a fit to speed-of-sound data alone; no other data were used. The approximation employed for ...
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 of a liquid crystal carbosilane dendrimer
Samosudova, Ya. S.; Markin, A. V.; Smirnova, N. N.; Ogurtsov, T. G.; Boiko, N. I.; Shibaev, V. P.
2016-11-01
The temperature dependence of the heat capacity of a first-generation liquid crystal carbosilane dendrimer with methoxyphenyl benzoate end groups is studied for the first time in the region of 6-370 K by means of precision adiabatic vacuum calorimetry. Physical transformations are observed in this interval of temperatures, and their standard thermodynamic characteristics are determined and discussed. Standard thermodynamic functions C p ° ( T), H°( T) - H°(0), S°( T) - S°(0), and G°( T) - H°(0) are calculated from the obtained experimental data for the region of T → 0 to 370 K. The standard entropy of formation of the dendrimer in the partially crystalline state at T = 298.15 K is calculated, and the standard entropy of the hypothetic reaction of its synthesis at this temperature is estimated. The thermodynamic properties of the studied dendrimer are compared to those of second- and fourth-generation liquid crystal carbosilane dendrimers with the same end groups studied earlier.
Thermodynamic curvature of soft-sphere fluids and solids
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.
Gravitational entropy and thermodynamics away from the horizon
Energy Technology Data Exchange (ETDEWEB)
Brustein, Ram, E-mail: ramyb@bgu.ac.il [Department of Physics, Ben-Gurion University, Beer-Sheva 84105 (Israel); CAS, Ludwig-Maximilians-Universitaet Muenchen, 80333 Muenchen (Germany); Medved, A.J.M., E-mail: j.medved@ru.ac.za [Department of Physics and Electronics, Rhodes University, Grahamstown 6140 (South Africa)
2012-08-29
We define, by an integral of geometric quantities over a spherical shell of arbitrary radius, an invariant gravitational entropy. This definition relies on defining a gravitational energy and pressure, and it reduces at the horizon of both black branes and black holes to Wald's Noether charge entropy. We support the thermodynamic interpretation of the proposed entropy by showing that, for some cases, the field theory duals of the entropy, energy and pressure are the same as the corresponding quantities in the field theory. In this context, the Einstein equations are equivalent to the field theory thermodynamic relation TdS=dE+PdV supplemented by an equation of state.
Thermodynamics and kinetics of the glass transition: A generic geometric approach
International Nuclear Information System (INIS)
Gutzow, I.; Ilieva, D.; Babalievski, F.; Yamakov, V.
2000-01-01
A generic phenomenological theory of the glass transition is developed in the framework of a quasilinear formulation of the thermodynamics of irreversible processes. Starting from one of the basic principles of this science in its approximate form given by de Donder's equation, after a change of variables the temperature dependence of the structural parameter ξ(T), the thermodynamic potentials ΔG(tilde sign)(T), the thermodynamic functions and the time of molecular relaxation τ of vitrifying systems is constructed. In doing so, a new effect in the ΔG(tilde sign)(T) course is observed. The analysis of the higher derivatives of the thermodynamic potential, and especially the nullification of the second derivative of the configurational specific heats ΔC(tilde sign) p (T) of the vitrifying liquid defines glass transition temperature T(tilde sign) g and leads directly to the basic dependence of glass transition kinetics: the Frenkel-Kobeko-Reiner equation. The conditions guaranteeing the fulfillment of this equation specify the temperature dependence of the activation energy U(T,ξ(tilde sign)) for viscous flow and give a natural differentiation of glass formers into fragile and strong liquids. The effect of thermal prehistory on the temperature dependence of both thermodynamic functions and kinetic coefficients is established by an appropriate separation of de Donder's equation. (c) 2000 American Institute of Physics
VALUE OF HEART RATE VARIABILITY ANALYSIS IN DIAGNOSTICS OF THE EMOTIONAL STATE
Directory of Open Access Journals (Sweden)
І. Chaykovskyi
2012-11-01
Full Text Available The is presented the development of method for evaluation of emotional state of man, what suitable for use at the workplace based on analysis of heart rate (HR variability. 28 healthy volunteers were examined. 3 audiovisual clips were consistently presented on the display of the personal computer for each of them. One clip contained information originating the positive emotions, the second one – negative emotions, the third one – neutral. All possible pairs of the emotional states were analysed with help of one- and multi-dimensional linear discriminant analysis based on HR variability. Showing the emotional video-clips (of both signs causes reliable slowing of HR frequency and also some decreasing of HR variability. In addition, negative emotions cause regularizing and simplification of structural organization of heart rhythm. Accuracy of discrimination for pair “emotional – neutral” video clips was 98 %, for pair “rest – neutral” was 74 %, for pair “positive – negative” was 91 %. Analysis of HR variability enables to determine the emotional state of observed person at the workplace with high reliability.
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)
Thermodynamic data for biomass conversion and waste incineration
Energy Technology Data Exchange (ETDEWEB)
Domalski, E.S.; Jobe, T.L. Jr; Milne, T.A.
1986-09-01
The general purpose of this collection of thermodynamic data of selected materials is to make property information available to the engineering community on chemical mixtures, polymers, composite materials, solid wastes, biomass, and materials not easily identifiable by a single stoichiometric formula. More than 700 materials have been compiled covering properties such as specific heat, gross heat of combustion, heat of fusion, heat of vaporization, and vapor pressure. The information was obtained from the master files of the NBS Chemical Thermodynamics Data Center, the annual issues of the Bulletin of Chemical Thermodynamics, intermittent examinations of the Chemical Abstracts subject indexes, individual articles by various authors, and other general reference sources. The compilation is organized into several broad categories; materials are listed alphabetically within each category. For each material, the physical state, information as to the composition or character of the material, the kind of thermodynamic property reported, the specific property values for the material, and citations to the reference list are given. In addition, appendix A gives an empirical formula that allows heats of combustion of carbonaceous materials to be predicted with surprising accuracy when the elemental composition is known. A spread sheet illustrates this predictability with examples from this report and elsewhere. Appendix B lists some reports containing heats of combustion not included in this publication. Appendix C contains symbols, units, conversion factors, and atomic weights used in evaluating and compiling the thermodynamic data.
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
Modern Thermodynamics with Statistical Mechanics
Helrich, Carl S
2009-01-01
With the aim of presenting thermodynamics in as simple and as unified a form as possible, this textbook starts with an introduction to the first and second laws and then promptly addresses the complete set of the potentials in a subsequent chapter and as a central theme throughout. Before discussing modern laboratory measurements, the book shows that the fundamental quantities sought in the laboratory are those which are required for determining the potentials. Since the subjects of thermodynamics and statistical mechanics are a seamless whole, statistical mechanics is treated as integral part of the text. Other key topics such as irreversibility, the ideas of Ilya Prigogine, chemical reaction rates, equilibrium of heterogeneous systems, and transition-state theory serve to round out this modern treatment. An additional chapter covers quantum statistical mechanics due to active current research in Bose-Einstein condensation. End-of-chapter exercises, chapter summaries, and an appendix reviewing fundamental pr...
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)
Non-equilibrium thermodynamics
De Groot, Sybren Ruurds
1984-01-01
The study of thermodynamics is especially timely today, as its concepts are being applied to problems in biology, biochemistry, electrochemistry, and engineering. This book treats irreversible processes and phenomena - non-equilibrium thermodynamics.S. R. de Groot and P. Mazur, Professors of Theoretical Physics, present a comprehensive and insightful survey of the foundations of the field, providing the only complete discussion of the fluctuating linear theory of irreversible thermodynamics. The application covers a wide range of topics: the theory of diffusion and heat conduction, fluid dyn
Advanced thermodynamics engineering
Annamalai, Kalyan; Jog, Milind A
2011-01-01
Thermolab Excel-Based Software for Thermodynamic Properties and Flame Temperatures of Fuels IntroductionImportance, Significance and LimitationsReview of ThermodynamicsMathematical BackgroundOverview of Microscopic/NanothermodynamicsSummaryAppendix: Stokes and Gauss Theorems First Law of ThermodynamicsZeroth LawFirst Law for a Closed SystemQuasi Equilibrium (QE) and Nonquasi-equilibrium (NQE) ProcessesEnthalpy and First LawAdiabatic Reversible Process for Ideal Gas with Constant Specific HeatsFirst Law for an Open SystemApplications of First Law for an Open SystemIntegral and Differential Form
Modern engineering thermodynamics
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
Jacobsen, R. T.; Stewart, R. B.; Crain, R. W., Jr.; Rose, G. L.; Myers, A. F.
1976-01-01
A method was developed for establishing a rational choice of the terms to be included in an equation of state with a large number of adjustable coefficients. The methods presented were developed for use in the determination of an equation of state for oxygen and nitrogen. However, a general application of the methods is possible in studies involving the determination of an optimum polynomial equation for fitting a large number of data points. The data considered in the least squares problem are experimental thermodynamic pressure-density-temperature data. Attention is given to a description of stepwise multiple regression and the use of stepwise regression in the determination of an equation of state for oxygen and nitrogen.
Thermodynamic performance optimization of a combined power/cooling cycle
International Nuclear Information System (INIS)
Pouraghaie, M.; Atashkari, K.; Besarati, S.M.; Nariman-zadeh, N.
2010-01-01
A combined thermal power and cooling cycle has already been proposed in which thermal energy is used to produce work and to generate a sub-ambient temperature stream that is suitable for cooling applications. The cycle uses ammonia-water mixture as working fluid and is a combination of a Rankine cycle and absorption cycle. The very high ammonia vapor concentration, exiting turbine under certain operating conditions, can provide power output as well as refrigeration. In this paper, the goal is to employ multi-objective algorithms for Pareto approach optimization of thermodynamic performance of the cycle. It has been carried out by varying the selected design variables, namely, turbine inlet pressure (P h ), superheater temperature (T superheat ) and condenser temperature (T condensor ). The important conflicting thermodynamic objective functions that have been considered in this study are turbine work (w T ), cooling capacity (q cool ) and thermal efficiency (η th ) of the cycle. It is shown that some interesting and important relationships among optimal objective functions and decision variables involved in the combined cycle can be discovered consequently. Such important relationships as useful optimal design principles would have not been obtained without the use of a multi-objective optimization approach.
Rajesh Kumar; S.C. Kaushik; Raj Kumar; Ranjana Hans
2016-01-01
Brayton heat engine model is developed in MATLAB simulink environment and thermodynamic optimization based on finite time thermodynamic analysis along with multiple criteria is implemented. The proposed work investigates optimal values of various decision variables that simultaneously optimize power output, thermal efficiency and ecological function using evolutionary algorithm based on NSGA-II. Pareto optimal frontier between triple and dual objectives is obtained and best optimal value is s...
International Nuclear Information System (INIS)
Du, Jianping; Zhao, Ruihua; Xue, Yongqiang
2012-01-01
Highlights: ► There is an obvious influence of the size on thermodynamic properties for the reaction referring nano-reactants. ► Gibbs function, enthalpy, entropy and equilibrium constant are dependent on the reactant size. ► There is an approximate linear relation between them. - Abstract: The theoretical relations of thermodynamic properties, the equilibrium constant and reactant size in nanosystem are described. The effects of size on thermodynamic properties and the equilibrium constant were studied using nanosize zinc oxide and sodium bisulfate solution as a reaction system. The experimental results indicated that the molar Gibbs free energy, the molar enthalpy and the molar entropy of the reaction decrease, but the equilibrium constant increases with decreasing reactant size. Linear trends were observed between the reciprocal of size for nano-reactant and thermodynamic variable, which are consistent with the theoretical relations.
Thermodynamically self-consistent integral equations and the structure of liquid metals
International Nuclear Information System (INIS)
Pastore, G.; Kahl, G.
1987-01-01
We discuss the application of the new thermodynamically self-consistent integral equations for the determination of the structural properties of liquid metals. We present a detailed comparison of the structure (S(q) and g(r)) for models of liquid alkali metals as obtained from two thermodynamically self-consistent integral equations and some published exact computer simulation results; the range of states extends from the triple point to the expanded metal. The theories which only impose thermodynamic self-consistency without any fitting of external data show an excellent agreement with the simulation results, thus demonstrating that this new type of integral equation is definitely superior to the conventional ones (hypernetted chain, Percus-Yevick, mean spherical approximation, etc). (author)
MMA-EoS: A Computational Framework for Mineralogical Thermodynamics
Chust, T. C.; Steinle-Neumann, G.; Dolejš, D.; Schuberth, B. S. A.; Bunge, H.-P.
2017-12-01
We present a newly developed software framework, MMA-EoS, that evaluates phase equilibria and thermodynamic properties of multicomponent systems by Gibbs energy minimization, with application to mantle petrology. The code is versatile in terms of the equation-of-state and mixing properties and allows for the computation of properties of single phases, solution phases, and multiphase aggregates. Currently, the open program distribution contains equation-of-state formulations widely used, that is, Caloric-Murnaghan, Caloric-Modified-Tait, and Birch-Murnaghan-Mie-Grüneisen-Debye models, with published databases included. Through its modular design and easily scripted database, MMA-EoS can readily be extended with new formulations of equations-of-state and changes or extensions to thermodynamic data sets. We demonstrate the application of the program by reproducing and comparing physical properties of mantle phases and assemblages with previously published work and experimental data, successively increasing complexity, up to computing phase equilibria of six-component compositions. Chemically complex systems allow us to trace the budget of minor chemical components in order to explore whether they lead to the formation of new phases or extend stability fields of existing ones. Self-consistently computed thermophysical properties for a homogeneous mantle and a mechanical mixture of slab lithologies show no discernible differences that require a heterogeneous mantle structure as has been suggested previously. Such examples illustrate how thermodynamics of mantle mineralogy can advance the study of Earth's interior.
Condensation: Passenger Not Driver in Atmospheric Thermodynamics
Directory of Open Access Journals (Sweden)
Jack Denur
2016-11-01
Full Text Available The second law of thermodynamics states that processes yielding work or at least capable of yielding work are thermodynamically spontaneous, and that those costing work are thermodynamically nonspontaneous. Whether a process yields or costs heat is irrelevant. Condensation of water vapor yields work and hence is thermodynamically spontaneous only in a supersaturated atmosphere; in an unsaturated atmosphere it costs work and hence is thermodynamically nonspontaneous. Far more of Earth’s atmosphere is unsaturated than supersaturated; based on this alone evaporation is far more often work-yielding and hence thermodynamically spontaneous than condensation in Earth’s atmosphere—despite condensation always yielding heat and evaporation always costing heat. Furthermore, establishment of the unstable or at best metastable condition of supersaturation, and its maintenance in the face of condensation that would wipe it out, is always work-costing and hence thermodynamically nonspontaneous in Earth’s atmosphere or anywhere else. The work required to enable supersaturation is most usually provided at the expense of temperature differences that enable cooling to below the dew point. In the case of most interest to us, convective weather systems and storms, it is provided at the expense of vertical temperature gradients exceeding the moist adiabatic. Thus, ultimately, condensation is a work-costing and hence thermodynamically nonspontaneous process even in supersaturated regions of Earth’s or any other atmosphere. While heat engines in general can in principle extract all of the work represented by any temperature difference until it is totally neutralized to isothermality, convective weather systems and storms in particular cannot. They can extract only the work represented by partial neutralization of super-moist-adiabatic lapse rates to moist-adiabaticity. Super-moist-adiabatic lapse rates are required to enable convection of saturated air
Stochastic thermodynamics, fluctuation theorems and molecular machines
International Nuclear Information System (INIS)
Seifert, Udo
2012-01-01
Stochastic thermodynamics as reviewed here systematically provides a framework for extending the notions of classical thermodynamics such as work, heat and entropy production to the level of individual trajectories of well-defined non-equilibrium ensembles. It applies whenever a non-equilibrium process is still coupled to one (or several) heat bath(s) of constant temperature. Paradigmatic systems are single colloidal particles in time-dependent laser traps, polymers in external flow, enzymes and molecular motors in single molecule assays, small biochemical networks and thermoelectric devices involving single electron transport. For such systems, a first-law like energy balance can be identified along fluctuating trajectories. For a basic Markovian dynamics implemented either on the continuum level with Langevin equations or on a discrete set of states as a master equation, thermodynamic consistency imposes a local-detailed balance constraint on noise and rates, respectively. Various integral and detailed fluctuation theorems, which are derived here in a unifying approach from one master theorem, constrain the probability distributions for work, heat and entropy production depending on the nature of the system and the choice of non-equilibrium conditions. For non-equilibrium steady states, particularly strong results hold like a generalized fluctuation–dissipation theorem involving entropy production. Ramifications and applications of these concepts include optimal driving between specified states in finite time, the role of measurement-based feedback processes and the relation between dissipation and irreversibility. Efficiency and, in particular, efficiency at maximum power can be discussed systematically beyond the linear response regime for two classes of molecular machines, isothermal ones such as molecular motors, and heat engines such as thermoelectric devices, using a common framework based on a cycle decomposition of entropy production. (review article)
Thermodynamics and kinetics of binary nucleation in ideal-gas mixtures.
Alekseechkin, Nikolay V
2015-08-07
The nonisothermal single-component theory of droplet nucleation [N. V. Alekseechkin, Physica A 412, 186 (2014)] is extended to binary case; the droplet volume V, composition x, and temperature T are the variables of the theory. An approach based on macroscopic kinetics (in contrast to the standard microscopic model of nucleation operating with the probabilities of monomer attachment and detachment) is developed for the droplet evolution and results in the derived droplet motion equations in the space (V, x, T)—equations for V̇≡dV/dt, ẋ, and Ṫ. The work W(V, x, T) of the droplet formation is obtained in the vicinity of the saddle point as a quadratic form with diagonal matrix. Also, the problem of generalizing the single-component Kelvin equation for the equilibrium vapor pressure to binary case is solved; it is presented here as a problem of integrability of a Pfaffian equation. The equation for Ṫ is shown to be the first law of thermodynamics for the droplet, which is a consequence of Onsager's reciprocal relations and the linked-fluxes concept. As an example of ideal solution for demonstrative numerical calculations, the o-xylene-m-xylene system is employed. Both nonisothermal and enrichment effects are shown to exist; the mean steady-state overheat of droplets and their mean steady-state enrichment are calculated with the help of the 3D distribution function. Some qualitative peculiarities of the nucleation thermodynamics and kinetics in the water-sulfuric acid system are considered in the model of regular solution. It is shown that there is a small kinetic parameter in the theory due to the small amount of the acid in the vapor and, as a consequence, the nucleation process is isothermal.
Squeezed states and Hermite polynomials in a complex variable
International Nuclear Information System (INIS)
Ali, S. Twareque; Górska, K.; Horzela, A.; Szafraniec, F. H.
2014-01-01
Following the lines of the recent paper of J.-P. Gazeau and F. H. Szafraniec [J. Phys. A: Math. Theor. 44, 495201 (2011)], we construct here three types of coherent states, related to the Hermite polynomials in a complex variable which are orthogonal with respect to a non-rotationally invariant measure. We investigate relations between these coherent states and obtain the relationship between them and the squeezed states of quantum optics. We also obtain a second realization of the canonical coherent states in the Bargmann space of analytic functions, in terms of a squeezed basis. All this is done in the flavor of the classical approach of V. Bargmann [Commun. Pure Appl. Math. 14, 187 (1961)
Energy Technology Data Exchange (ETDEWEB)
Mahendra P, Verma [Instituto de Investigaciones Electricas, Cuernavaca, Morelos (Mexico)
2005-07-01
In this paper are presented, the thermodynamic inconsistencies in formulation IAPWS-95 as well as the limitations in the experimental data of the thermodynamic properties of the water. In addition, a new methodology was developed: Verma procedure for the measurement of the calorific capacity of water. Thus, a procedure is presented to calculate other thermodynamic properties of liquids such as water. In the transformation processes of the planet Earth, water is an essential component. Nevertheless, the knowledge about its properties is still very limited. Recently, Verma developed a new program: SteamTablesIIE, to calculate the properties of water as a function of two independent variables between temperatures (T), pressure (P), volume (V), internal energy (U), enthalpy (H), Gibas energy (G) and entropy (S). Yet, thermodynamic inconsistencies were found in the formulation, same that are the limiting factors for the operation of the SteamTablesIIE in all the ranks of the independent variables. [Spanish] En este trabajo se presentan, tanto las inconsistencias termodinamicas en la formulacion IAPWS-95 como las limitaciones en los datos experimentales de las propiedades termodinamicas del agua. Ademas, se desarrollo una nueva metodologia: Procedimiento Verma para la medicion de la capacidad calorifica del agua. Asi, se presenta un procedimiento para calcular otras propiedades termodinamicas de liquidos tales como el agua. En los procesos de transformacion del planeta tierra, el agua es un componente esencial. Sin embargo, el conocimiento acerca de sus propiedades es todavia muy limitado. Recientemente, Verma desarrollo un nuevo programa: SteamTablesIIE, para calcular las propiedades del agua como una funcion de dos variables independientes entre temperaturas (T), presion (P), volumen (V), energia interna (U), entalpia (H), energia Gibas (G) y entropia (S). Con todo, se encontraron inconsistencias termodinamicas en la formulacion, mismas que son las limitantes para el
Variability of Photovoltaic Power in the State of Gujarat Using High Resolution Solar Data
Energy Technology Data Exchange (ETDEWEB)
Hummon, M. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Cochran, J. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Weekley, A. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Lopez, A. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Zhang, J. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Stoltenberg, B. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Parsons, B. [Evergreen Renewable Consulting, CO (United States); Batra, P. [Central Electricity Authority, New Delhi (India); Mehta, B. [Gujarat Energy Transmission Corporation Ltd., Vadodara (India); Patel, D. [Gujarat Energy Transmission Corporation Ltd., Vadodara (India)
2014-03-01
India has ambitious goals for high utilization of variable renewable power from wind and solar, and deployment has been proceeding at a rapid pace. The western state of Gujarat currently has the largest amount of solar generation of any Indian state, with over 855 Megawatts direct current (MWDC). Combined with over 3,240 MW of wind, variable generation renewables comprise nearly 18% of the electric-generating capacity in the state. A new historic 10-kilometer (km) gridded solar radiation data set capturing hourly insolation values for 2002-2011 is available for India. We apply an established method for downscaling hourly irradiance data to one-minute irradiance data at potential PV power production locations for one year, 2006. The objective of this report is to characterize the intra-hour variability of existing and planned photovoltaic solar power generation in the state of Gujarat (a total of 1.9 gigawatts direct current (GWDC)), and of five possible expansion scenarios of solar generation that reflect a range of geographic diversity (each scenario totals 500-1,000 MW of additional solar capacity). The report statistically analyzes one year's worth of power variability data, applied to both the baseline and expansion scenarios, to evaluate diurnal and seasonal power fluctuations, different timescales of variability (e.g., from one to 15 minutes), the magnitude of variability (both total megawatts and relative to installed solar capacity), and the extent to which the variability can be anticipated in advance. The paper also examines how Gujarat Energy Transmission Corporation (GETCO) and the Gujarat State Load Dispatch Centre (SLDC) could make use of the solar variability profiles in grid operations and planning.
Thermodynamics Far from the Thermodynamic Limit.
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.
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...
Thompson, D. R.; Kahn, B. H.; Green, R. O.; Chien, S.; Middleton, E.; Tran, D. Q.
2017-12-01
Clouds' variable ice and liquid content significantly influences their optical properties, evolution, and radiative forcing potential (Tan and Storelvmo, J. Atmos. Sci, 73, 2016). However, most remote measurements of thermodynamic phase have spatial resolutions of 1 km or more and are insensitive to mixed phases. This under-constrains important processes, such as spatial partitioning within mixed phase clouds, that carry outsize radiative forcing impacts. These uncertainties could shift Global Climate Model (GCM) predictions of future warming by over 1 degree Celsius (Tan et al., Science 352:6282, 2016). Imaging spectroscopy of reflected solar energy from the 1.4 - 1.8 μm shortwave infrared (SWIR) spectral range can address this observational gap. These observations can distinguish ice and water absorption, providing a robust and sensitive measurement of cloud top thermodynamic phase including mixed phases. Imaging spectrometers can resolve variations at scales of tens to hundreds of meters (Thompson et al., JGR-Atmospheres 121, 2016). We report the first such global high spatial resolution (30 m) survey, based on data from 2005-2015 acquired by the Hyperion imaging spectrometer onboard NASA's EO-1 spacecraft (Pearlman et al., Proc. SPIE 4135, 2001). Estimated seasonal and latitudinal distributions of cloud thermodynamic phase generally agree with observations made by other satellites such as the Atmospheric Infrared Sounder (AIRS). Variogram analyses reveal variability at different spatial scales. Our results corroborate previously observed zonal distributions, while adding insight into the spatial scales of processes governing cloud top thermodynamic phase. Figure: Thermodynamic phase retrievals. Top: Example of a cloud top thermodynamic phase map from the EO-1/Hyperion. Bottom: Latitudinal distributions of pure and mixed phase clouds, 2005-2015, showing Liquid Thickness Fraction (LTF). LTF=0 corresponds to pure ice absorption, while LTF=1 is pure liquid. The
Physicochemical properties and thermal stability of quercetin hydrates in the solid state
Energy Technology Data Exchange (ETDEWEB)
Borghetti, G.S., E-mail: greicefarm@yahoo.com.br [Programa de Pos-Graduacao em Ciencias Farmaceuticas, Faculdade de Farmacia, Universidade Federal do Rio Grande do Sul, Av. Ipiranga 2752, CEP 90.610-000, Porto Alegre, RS (Brazil); Carini, J.P. [Programa de Pos-Graduacao em Ciencias Farmaceuticas, Faculdade de Farmacia, Universidade Federal do Rio Grande do Sul, Av. Ipiranga 2752, CEP 90.610-000, Porto Alegre, RS (Brazil); Honorato, S.B.; Ayala, A.P. [Departamento de Fisica, Universidade Federal do Ceara, Caixa Postal 6030, CEP 60.455-970, Fortaleza, CE (Brazil); Moreira, J.C.F. [Departamento de Bioquimica, Instituto de Ciencias Basicas da Saude, Universidade Federal do Rio Grande do Sul, Rua Ramiro Barcelos 2600, CEP 90035-003, Porto Alegre, RS (Brazil); Bassani, V.L. [Programa de Pos-Graduacao em Ciencias Farmaceuticas, Faculdade de Farmacia, Universidade Federal do Rio Grande do Sul, Av. Ipiranga 2752, CEP 90.610-000, Porto Alegre, RS (Brazil)
2012-07-10
Highlights: Black-Right-Pointing-Pointer Quercetin raw materials may present different degree of hydration. Black-Right-Pointing-Pointer Thermal stability of quercetin in the solid state depends on its degree of hydration. Black-Right-Pointing-Pointer Quercetin dehydrate is thermodynamically more stable than the other crystal forms. - Abstract: In the present work three samples of quercetin raw materials (QCTa, QCTb and QCTc), purchased from different Brazilian suppliers, were characterized employing scanning electron microscopy, Raman spectroscopy, simultaneous thermogravimetry and infrared spectroscopy, differential scanning calorimetry, and variable temperature-powder X-ray diffraction, in order to know their physicochemical properties, specially the thermal stability in solid state. The results demonstrated that the raw materials of quercetin analyzed present distinct crystalline structures, ascribed to the different degree of hydration of their crystal lattice. The thermal stability of these quercetin raw materials in the solid state was highly dependent on their degree of hydration, where QCTa (quercetin dihydrate) was thermodynamically more stable than the other two samples.
Statistical Thermodynamics and Microscale Thermophysics
Carey, Van P.
1999-08-01
Many exciting new developments in microscale engineering are based on the application of traditional principles of statistical thermodynamics. In this text Van Carey offers a modern view of thermodynamics, interweaving classical and statistical thermodynamic principles and applying them to current engineering systems. He begins with coverage of microscale energy storage mechanisms from a quantum mechanics perspective and then develops the fundamental elements of classical and statistical thermodynamics. Subsequent chapters discuss applications of equilibrium statistical thermodynamics to solid, liquid, and gas phase systems. The remainder of the book is devoted to nonequilibrium thermodynamics of transport phenomena and to nonequilibrium effects and noncontinuum behavior at the microscale. Although the text emphasizes mathematical development, Carey includes many examples and exercises to illustrate how the theoretical concepts are applied to systems of scientific and engineering interest. In the process he offers a fresh view of statistical thermodynamics for advanced undergraduate and graduate students, as well as practitioners, in mechanical, chemical, and materials engineering.
Thermodynamic properties and equation of state of liquid lead and lead bismuth eutectic
Sobolev, V. P.; Schuurmans, P.; Benamati, G.
2008-06-01
Since the 1950s, liquid lead (Pb) and lead-bismuth eutectic (Pb-Bi) have been studied in the USA, Canada and in the former-USSR as potential coolants for nuclear installations due to their very attractive thermophysical and neutronic properties. However, experimental data on the thermal properties of these coolants in the temperature range of interest are still incomplete and often contradictory. This makes it very difficult to perform design calculations and to analyse the normal and abnormal behaviour of nuclear installations where these coolants are expected to be used. Recently, a compilation of heavy liquid metal (HLM) properties along with recommendations for its use was prepared by the OECD/NEA Working Party on Fuel Cycle (WPFC) Expert Group on Lead-Bismuth Eutectic Technology. A brief review of this compilation and some new data are presented in this article. A set of correlations for the temperature dependence of the main thermodynamic properties of Pb and Pb-Bi(e) at normal pressure, and a set of simplified thermal and caloric equations of state for the liquid phase are proposed.
Directory of Open Access Journals (Sweden)
Ying Jiang
2017-02-01
Full Text Available This paper presents a theoretical formalism for describing systems of semiflexible polymers, which can have density variations due to finite compressibility and exhibit an isotropic-nematic transition. The molecular architecture of the semiflexible polymers is described by a continuum wormlike-chain model. The non-bonded interactions are described through a functional of two collective variables, the local density and local segmental orientation tensor. In particular, the functional depends quadratically on local density-variations and includes a Maier–Saupe-type term to deal with the orientational ordering. The specified density-dependence stems from a free energy expansion, where the free energy of an isotropic and homogeneous homopolymer melt at some fixed density serves as a reference state. Using this framework, a self-consistent field theory is developed, which produces a Helmholtz free energy that can be used for the calculation of the thermodynamics of the system. The thermodynamic properties are analysed as functions of the compressibility of the model, for values of the compressibility realizable in mesoscopic simulations with soft interactions and in actual polymeric materials.
Álvarez-Rúa, Carmen; Borge, Javier
2016-01-01
Thermodynamic processes are complex phenomena that can be understood as a set of successive stages. When treating processes, classical thermodynamics (and most particularly, the Gibbsian formulation, predominantly used in chemistry) only pays attention to initial and final states. However, reintroducing the notion of process is absolutely…
Analytical thermodynamics of a strongly attractive three-component Fermi gas in one dimension
International Nuclear Information System (INIS)
He Peng; Yin Xiangguo; Wang Yupeng; Guan Xiwen; Batchelor, Murray T.
2010-01-01
Ultracold three-component atomic Fermi gases in one dimension are expected to exhibit rich physics due to the presence of trions and different pairing states. Quantum phase transitions from the trion state into a paired phase and a normal Fermi liquid occur at zero temperature. We derive the analytical thermodynamics of strongly attractive three-component one-dimensional fermions with SU(3) symmetry via the thermodynamic Bethe ansatz method in unequal Zeeman splitting fields H 1 and H 2 . We find explicitly that for low temperature the system acts like either a two-component or a three-component Tomonaga-Luttinger liquid dependent on the system parameters. The phase diagrams for the chemical potential and specific heat are presented for illustrative values of the Zeeman splitting. We also demonstrate that crossover between different Tomonaga-Luttinger-liquid phases exhibit singular behavior in specific heat and entropy as the temperature tends to zero. Beyond Tomonaga-Luttinger-liquid physics, we obtain the equation of state which provides a precise description of universal thermodynamics and quantum criticality in three-component, strongly attractive Fermi gases.
Bounded energy exchange as an alternative to the third law of thermodynamics
Energy Technology Data Exchange (ETDEWEB)
Heidrich, Matthias, E-mail: Heidrich_Matthias@web.de
2016-10-15
This paper introduces a postulate explicitly forbidding the extraction of an infinite amount of energy from a thermodynamic system. It also introduces the assumption that no measuring equipment is capable of detecting arbitrarily small energy exchanges. The Kelvin formulation of the second law is reinterpreted accordingly. Then statements related to both the unattainability version and the entropic version of the third law are derived. The value of any common thermodynamic potential of a one-component system at absolute zero of temperature is ascertained if some assumptions with regard to the state space can be made. The point of view is the phenomenological, macroscopic and non-statistical one of classical thermodynamics.
Bounded energy exchange as an alternative to the third law of thermodynamics
International Nuclear Information System (INIS)
Heidrich, Matthias
2016-01-01
This paper introduces a postulate explicitly forbidding the extraction of an infinite amount of energy from a thermodynamic system. It also introduces the assumption that no measuring equipment is capable of detecting arbitrarily small energy exchanges. The Kelvin formulation of the second law is reinterpreted accordingly. Then statements related to both the unattainability version and the entropic version of the third law are derived. The value of any common thermodynamic potential of a one-component system at absolute zero of temperature is ascertained if some assumptions with regard to the state space can be made. The point of view is the phenomenological, macroscopic and non-statistical one of classical thermodynamics.
Thermodynamics of the Schwarzschild and the Reissner–Nordström black holes with quintessence
Directory of Open Access Journals (Sweden)
K. Ghaderi
2016-02-01
Full Text Available In this paper, we study the thermodynamics of the Schwarzschild and the Reissner–Nordström black holes surrounded by quintessence. By using the thermodynamical laws of the black holes, we derive the thermodynamic properties of these black holes and we compare the results with each other. We investigate the mass, temperature and heat capacity as functions of entropy for these black holes. We also discuss the equation of state of the Schwarzschild and the Reissner–Nordström black holes surrounded by quintessence.
Thermodynamics of open, nonisothermal chemical systems far from equilibrium
International Nuclear Information System (INIS)
Yoshida, Nobuo
1992-01-01
The thermodynamic behavior of kinetic models based on a continuously stirred tank reactor (CSTR) is studied in an attempt to seek general trends in the thermodynamic properties of open nonlinear systems. The models consist of two reversible reactions, A + nB rightleftharpoons (n + 1) B (n = 0,1,or 2) and B rightleftharpoons C, taking place in an adiabatic CSTR. The heat of reaction is incorporated, and the rate constants are assumed to follow an Arrhenius temperature dependence. The models give rise to multiple stationary states and sustained oscillations (limit cycles). The entropy difference between stationary or oscillatory states and equilibrium and the rate of entropy production in the these states are calculated as a function of the residence time in the reactor. The entropy difference and entropy production may be taken, to some extent, as indicative of the influence of irreversible processes, which disappears at equilibrium. The results of the calculations reveal the following systematic trends: (I) The entropy difference or entropy production for stable states or both always increase as the residence time is shortened, namely, as the system is displaced further from equilibrium. (II) If stable and unstable states (stationary or oscillatory) coexist under identical conditions, then the stable state invariably has a smaller value of the entropy difference or entropy production or both than the corresponding unstable state. 26 refs., 3 figs
A thermodynamic counterpart of the Axelrod model of social influence: The one-dimensional case
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.
Thermodynamic properties of the DUPIC fuel and its performance
Energy Technology Data Exchange (ETDEWEB)
Park, Kwang Heon; Kim, Hee Moon [Kyung Hee Univ., Seoul (Korea, Republic of)
1997-07-01
This study describes thermodynamic properties of DUPIC fuel and performance. In initial state, DUPIC fuel which contains fissile materials is different from general nuclear fuel. So this study analyzed oxygen potential, thermal conductivity and specific heat of the DUPIC fuel.
A combined thermodynamic cycle used for waste heat recovery of internal combustion engine
International Nuclear Information System (INIS)
He, Maogang; Zhang, Xinxin; Zeng, Ke; Gao, Ke
2011-01-01
In this paper, we present a steady-state experiment, energy balance and exergy analysis of exhaust gas in order to improve the recovery of the waste heat of an internal combustion engine (ICE). Considering the different characteristics of the waste heat of exhaust gas, cooling water, and lubricant, a combined thermodynamic cycle for waste heat recovery of ICE is proposed. This combined thermodynamic cycle consists of two cycles: the organic Rankine cycle (ORC), for recovering the waste heat of lubricant and high-temperature exhaust gas, and the Kalina cycle, for recovering the waste heat of low-temperature cooling water. Based on Peng–Robinson (PR) equation of state (EOS), the thermodynamic parameters in the high-temperature ORC were calculated and determined via an in-house computer program. Suitable working fluids used in high-temperature ORC are proposed and the performance of this combined thermodynamic cycle is analyzed. Compared with the traditional cycle configuration, more waste heat can be recovered by the combined cycle introduced in this paper. -- Highlights: ► We study the energy balance of fuel in internal combustion engine. ► Heat recovery effect of exhaust gas is good when ICE is at a high-load condition. ► We propose a new combined thermodynamic cycle for waste heat of ICE. ► The combined cycle has a higher recovery efficiency than previous configurations.
Stochastic Independence as a Resource for Small-Scale Thermodynamics
Lostaglio, Matteo; Mueller, Markus P.; Pastena, Michele
It is well-known in thermodynamics that the creation of correlations costs work. It seems then a truism that if a thermodynamic transformation A --> B is impossible, so will be any transformation that in sending A to B also correlates among them some auxiliary systems C. Surprisingly, we show that this is not the case for non-equilibrium thermodynamics of microscopic systems. On the contrary, the creation of correlations greatly extends the set of accessible states, to the point that we can perform on individual systems and in a single shot any transformation that would otherwise be possible only if the number of systems involved was very large. We also show that one only ever needs to create a vanishingly small amount of correlations (as measured by mutual information) among a small number of auxiliary systems (never more than three). The many, severe constraints of microscopic thermodynamics are reduced to the sole requirement that the non-equilibrium free energy decreases in the transformation. This shows that, in principle, reliable extraction of work equal to the free energy of a system can be performed by microscopic engines.
Stochastic Independence as a Resource in Small-Scale Thermodynamics
Lostaglio, Matteo; Müller, Markus P.; Pastena, Michele
2015-10-01
It is well known in thermodynamics that the creation of correlations costs work. It seems then a truism that if a thermodynamic transformation A →B is impossible, so will be any transformation that in sending A to B also correlates among them some auxiliary systems C . Surprisingly, we show that this is not the case for nonequilibrium thermodynamics of microscopic systems. On the contrary, the creation of correlations greatly extends the set of accessible states, to the point that we can perform on individual systems and in a single shot any transformation that would otherwise be possible only if the number of systems involved was very large. We also show that one only ever needs to create a vanishingly small amount of correlations (as measured by mutual information) among a small number of auxiliary systems (never more than three). The many, severe constraints of microscopic thermodynamics are reduced to the sole requirement that the nonequilibrium free energy decreases in the transformation. This shows that, in principle, reliable extraction of work equal to the free energy of a system can be performed by microscopic engines.
Thermodynamic and Mechanical Analysis of a Thermomagnetic Rotary Engine
International Nuclear Information System (INIS)
Fajar, D M; Khotimah, S N; Khairurrijal
2016-01-01
A heat engine in magnetic system had three thermodynamic coordinates: magnetic intensity ℋ, total magnetization ℳ, and temperature T, where the first two of them are respectively analogous to that of gaseous system: pressure P and volume V. Consequently, Carnot cycle that constitutes the principle of a heat engine in gaseous system is also valid on that in magnetic system. A thermomagnetic rotary engine is one model of it that was designed in the form of a ferromagnetic wheel that can rotates because of magnetization change at Curie temperature. The study is aimed to describe the thermodynamic and mechanical analysis of a thermomagnetic rotary engine and calculate the efficiencies. In thermodynamic view, the ideal processes are isothermal demagnetization, adiabatic demagnetization, isothermal magnetization, and adiabatic magnetization. The values of thermodynamic efficiency depend on temperature difference between hot and cold reservoir. In mechanical view, a rotational work is determined through calculation of moment of inertia and average angular speed. The value of mechanical efficiency is calculated from ratio between rotational work and heat received by system. The study also obtains exergetic efficiency that states the performance quality of the engine. (paper)
Thermodynamic and Mechanical Analysis of a Thermomagnetic Rotary Engine
Fajar, D. M.; Khotimah, S. N.; Khairurrijal
2016-08-01
A heat engine in magnetic system had three thermodynamic coordinates: magnetic intensity ℋ, total magnetization ℳ, and temperature T, where the first two of them are respectively analogous to that of gaseous system: pressure P and volume V. Consequently, Carnot cycle that constitutes the principle of a heat engine in gaseous system is also valid on that in magnetic system. A thermomagnetic rotary engine is one model of it that was designed in the form of a ferromagnetic wheel that can rotates because of magnetization change at Curie temperature. The study is aimed to describe the thermodynamic and mechanical analysis of a thermomagnetic rotary engine and calculate the efficiencies. In thermodynamic view, the ideal processes are isothermal demagnetization, adiabatic demagnetization, isothermal magnetization, and adiabatic magnetization. The values of thermodynamic efficiency depend on temperature difference between hot and cold reservoir. In mechanical view, a rotational work is determined through calculation of moment of inertia and average angular speed. The value of mechanical efficiency is calculated from ratio between rotational work and heat received by system. The study also obtains exergetic efficiency that states the performance quality of the engine.
Hrubý Jan; Duška Michal
2014-01-01
We present a system of analytical equations for computation of all thermodynamic properties of dry steam and liquid water (undesaturated, saturated and metastable supersaturated) and properties of the liquid-vapor phase interface. The form of the equations is such that it enables computation of all thermodynamic properties for independent variables directly related to the balanced quantities - total mass, liquid mass, energy, momenta. This makes it suitable for the solvers of fluid dynamics e...
Thermodynamics an engineering approach
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...
International Nuclear Information System (INIS)
Adesso, Gerardo; Illuminati, Fabrizio
2006-01-01
For continuous-variable (CV) systems, we introduce a measure of entanglement, the CV tangle (contangle), with the purpose of quantifying the distributed (shared) entanglement in multimode, multipartite Gaussian states. This is achieved by a proper convex-roof extension of the squared logarithmic negativity. We prove that the contangle satisfies the Coffman-Kundu-Wootters monogamy inequality in all three-mode Gaussian states, and in all fully symmetric N-mode Gaussian states, for arbitrary N. For three-mode pure states, we prove that the residual entanglement is a genuine tripartite entanglement monotone under Gaussian local operations and classical communication. We show that pure, symmetric three-mode Gaussian states allow a promiscuous entanglement sharing, having both maximum tripartite residual entanglement and maximum couplewise entanglement between any pair of modes. These states are thus simultaneous CV analogues of both the GHZ and the W states of three qubits: in CV systems monogamy does not prevent promiscuity, and the inequivalence between different classes of maximally entangled states, holding for systems of three or more qubits, is removed
Energy Technology Data Exchange (ETDEWEB)
Adesso, Gerardo; Illuminati, Fabrizio [Dipartimento di Fisica ' E R Caianiello' , Universita degli Studi di Salerno (Italy); CNISM and CNR-Coherentia, Gruppo di Salerno (Italy); and INFN Sezione di Napoli-Gruppo Collegato di Salerno (Italy); Via S Allende, 84081 Baronissi, SA (Italy)
2006-01-15
For continuous-variable (CV) systems, we introduce a measure of entanglement, the CV tangle (contangle), with the purpose of quantifying the distributed (shared) entanglement in multimode, multipartite Gaussian states. This is achieved by a proper convex-roof extension of the squared logarithmic negativity. We prove that the contangle satisfies the Coffman-Kundu-Wootters monogamy inequality in all three-mode Gaussian states, and in all fully symmetric N-mode Gaussian states, for arbitrary N. For three-mode pure states, we prove that the residual entanglement is a genuine tripartite entanglement monotone under Gaussian local operations and classical communication. We show that pure, symmetric three-mode Gaussian states allow a promiscuous entanglement sharing, having both maximum tripartite residual entanglement and maximum couplewise entanglement between any pair of modes. These states are thus simultaneous CV analogues of both the GHZ and the W states of three qubits: in CV systems monogamy does not prevent promiscuity, and the inequivalence between different classes of maximally entangled states, holding for systems of three or more qubits, is removed.
International Nuclear Information System (INIS)
Roskosch, Dennis; Atakan, Burak
2015-01-01
Fluid selection for thermodynamic cycles like refrigeration cycles, heat pumps or organic Rankine cycles remains an actual topic. Generally the search for a working fluid is based on experimental approaches or on a not very systematic trial and error approach, far from being elegant. An alternative method may be a theory based reverse engineering approach, proposed and investigated here: The design process should start with an optimal process and with (abstract) properties of the fluid needed to fit into this optimal process, best described by some general equation of state and the corresponding fluid-describing parameters. These should be analyzed and optimized with respect to the defined model process, which also has to be optimized simultaneously. From this information real fluids can be selected or even synthesized which have fluid defining properties in the optimum regime like critical temperature or ideal gas capacities of heat, allowing to find new working fluids, not considered so far. The number and kind of the fluid-defining parameters is mainly based on the choice of the used EOS (equation of state). The property model used in the present work is based on the cubic Peng–Robinson equation, chosen due to its moderate numerical expense, sufficient accuracy as well as a general availability of the fluid-defining parameters for many compounds. The considered model-process works between the temperature levels of 273.15 and 333.15 K and can be used as heat pump for supplying buildings with heat, typically. The objective functions are the COP (coefficient of performance) and the VHC (volumetric heating capacity) as a function of critical pressure, critical temperature, acentric factor and two coefficients for the temperature-dependent isobaric ideal gas heat capacity. Also, the steam quality at the compressor entrance has to be regarded as a problem variable. The results give clear hints regarding optimal fluid parameters of the analyzed process and deepen
Estimation of kinetic and thermodynamic ligand-binding parameters using computational strategies.
Deganutti, Giuseppe; Moro, Stefano
2017-04-01
Kinetic and thermodynamic ligand-protein binding parameters are gaining growing importance as key information to consider in drug discovery. The determination of the molecular structures, using particularly x-ray and NMR techniques, is crucial for understanding how a ligand recognizes its target in the final binding complex. However, for a better understanding of the recognition processes, experimental studies of ligand-protein interactions are needed. Even though several techniques can be used to investigate both thermodynamic and kinetic profiles for a ligand-protein complex, these procedures are very often laborious, time consuming and expensive. In the last 10 years, computational approaches have enormous potential in providing insights into each of the above effects and in parsing their contributions to the changes in both kinetic and thermodynamic binding parameters. The main purpose of this review is to summarize the state of the art of computational strategies for estimating the kinetic and thermodynamic parameters of a ligand-protein binding.
International Nuclear Information System (INIS)
Kim, Sangjo; Son, Changmin; Kim, Kuisoon
2017-01-01
Aim of this work is to provide evidence of the effectiveness of combined use of the variable guide vanes (VGVs) and bleed air on the thermodynamic performance of aircraft engine system. This paper performed the comparative study to evaluate the overall thermal performance of an aircraft engine with optimized VGVs and bleed air, separately or simultaneously. The low-bypass ratio turbofan engine has been modeled with a 0D/1D modeling approach. The genetic algorithm is employed to find the optimum schedule of VGVs and bleed air. There are four types of design variables: (1) the inlet guide vane (IGV) angle, (2) the IGV and 1st stator vane (SV) angles, (3) bleed air mass flow rate at the exit of the axial compressor, and (4) both type 2 and type 3. The optimization is conducted with surge margin constraints of more than 10% and 15% in the axial compressor. The results show that the additional use of the bleed air increases the efficiency of the compressors. Overall, the percentage reductions of the total fuel consumption for the engine with the IGV, 1st SV and bleed air schedule is 1.63% for 15% surge margin constraints when compared with the engine with the IGV schedule. - Highlights: • The effect of combined use of variable guide vanes and bleed air is evaluated. • The genetic algorithm is employed to find the optimum setting angle and bleed air. • A low bypass ratio mixed turbofan engine is analyzed for optimization. • Additional use of the bleed air shows improved overall performance of the engine.
Teleportation of a Kind of Three-Mode Entangled States of Continuous Variables
Institute of Scientific and Technical Information of China (English)
无
2005-01-01
A quantum teleportation scheme to teleport a kind of tripartite entangled states of continuous variables by using a quantum channel composed of three bipartite entangled states is proposed. The joint Bell measurement is feasible because the bipartite entangled states are complete and the squeezed state has a natural representation in the entangled state basis. The calculation is greatly simplified by using the Schmidt decomposition of the entangled states.
Quantum key distribution using continuous-variable non-Gaussian states
Borelli, L. F. M.; Aguiar, L. S.; Roversi, J. A.; Vidiella-Barranco, A.
2016-02-01
In this work, we present a quantum key distribution protocol using continuous-variable non-Gaussian states, homodyne detection and post-selection. The employed signal states are the photon added then subtracted coherent states (PASCS) in which one photon is added and subsequently one photon is subtracted from the field. We analyze the performance of our protocol, compared with a coherent state-based protocol, for two different attacks that could be carried out by the eavesdropper (Eve). We calculate the secret key rate transmission in a lossy line for a superior channel (beam-splitter) attack, and we show that we may increase the secret key generation rate by using the non-Gaussian PASCS rather than coherent states. We also consider the simultaneous quadrature measurement (intercept-resend) attack, and we show that the efficiency of Eve's attack is substantially reduced if PASCS are used as signal states.
Thermodynamic properties of 5-(1-adamantyl)tetrazole
Energy Technology Data Exchange (ETDEWEB)
Stepurko, Elena N.; Paulechka, Yauheni U.; Blokhin, Andrey V., E-mail: blokhin@bsu.by; Kabo, Gennady J.; Voitekhovich, Sergei V.; Lyakhov, Alexander S.; Kohut, Sviataslau V.; Kazarovets, Tatiana E.
2014-09-20
Highlights: • Heat capacity, enthalpy of formation, vapor pressure, and enthalpy of sublimation were measured for 5-(1-adamantyl)tetrazole. • Crystal structure of the compound was determined from the X-ray diffraction analysis. • Ideal-gas thermodynamic properties of 5-(1-adamantyl)tetrazole were calculated. - Abstract: Temperature dependence of the heat capacity of 5-(1-adamantyl)tetrazole was studied between (5 and 370) K in a vacuum adiabatic calorimeter. From obtained data the thermodynamic properties of the compound in the condensed state were evaluated over the range of (0–370) K. The crystal structure of 5-(1-adamantyl)tetrazole was determined from the X-ray diffraction analysis. The saturated vapor pressure for crystalline 5-(1-adamantyl)tetrazole in the temperature ranges from (394 to 419) K was measured by the Knudsen effusion method, and its enthalpy of sublimation was obtained using these results. The standard enthalpy of formation for crystalline 5-(1-adamantyl)tetrazole at 298.15 K was determined in a static bomb combustion calorimeter. From these data, the standard enthalpy of formation for gaseous 5-(1-adamantyl)tetrazole was evaluated. The enthalpy of formation calculated using quantum chemical methods is in an excellent agreement with the experimental value. The thermodynamic properties of 5-(1-adamantyl)tetrazole in the ideal-gas state were calculated in the temperature range from (0 to 1000) K. The calculated entropy of gaseous 5-(1-adamantyl)tetrazole is in a good agreement with the one obtained from the experimental data.
Thermodynamic properties of 5-(1-adamantyl)tetrazole
International Nuclear Information System (INIS)
Stepurko, Elena N.; Paulechka, Yauheni U.; Blokhin, Andrey V.; Kabo, Gennady J.; Voitekhovich, Sergei V.; Lyakhov, Alexander S.; Kohut, Sviataslau V.; Kazarovets, Tatiana E.
2014-01-01
Highlights: • Heat capacity, enthalpy of formation, vapor pressure, and enthalpy of sublimation were measured for 5-(1-adamantyl)tetrazole. • Crystal structure of the compound was determined from the X-ray diffraction analysis. • Ideal-gas thermodynamic properties of 5-(1-adamantyl)tetrazole were calculated. - Abstract: Temperature dependence of the heat capacity of 5-(1-adamantyl)tetrazole was studied between (5 and 370) K in a vacuum adiabatic calorimeter. From obtained data the thermodynamic properties of the compound in the condensed state were evaluated over the range of (0–370) K. The crystal structure of 5-(1-adamantyl)tetrazole was determined from the X-ray diffraction analysis. The saturated vapor pressure for crystalline 5-(1-adamantyl)tetrazole in the temperature ranges from (394 to 419) K was measured by the Knudsen effusion method, and its enthalpy of sublimation was obtained using these results. The standard enthalpy of formation for crystalline 5-(1-adamantyl)tetrazole at 298.15 K was determined in a static bomb combustion calorimeter. From these data, the standard enthalpy of formation for gaseous 5-(1-adamantyl)tetrazole was evaluated. The enthalpy of formation calculated using quantum chemical methods is in an excellent agreement with the experimental value. The thermodynamic properties of 5-(1-adamantyl)tetrazole in the ideal-gas state were calculated in the temperature range from (0 to 1000) K. The calculated entropy of gaseous 5-(1-adamantyl)tetrazole is in a good agreement with the one obtained from the experimental data
Teran, Alexander Andrew
Nanostructured block copolymer electrolytes containing an ion-conducting block and a modulus-strengthening block are of interest for applications in solid-state lithium metal batteries. These materials can self-assemble into well-defined microstructures, creating conducting channels that facilitate ion transport. The overall objective of this dissertation is to gain a better understanding of the behavior of salt-containing block copolymers, and evaluate their potential for use in solid-state lithium/sulfur batteries. Anionically synthesized polystyrene-b-poly(ethylene oxide) (SEO) copolymers doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt were used as a model system. This thesis investigates the model system on several levels: from fundamental thermodynamic studies to bulk characterization and finally device assembly and testing. First, the thermodynamics of neat and salt-containing block copolymers was studied. The addition of salt to these materials is necessary to make them conductive, however even small amounts of salt can have significant effects on their phase behavior, and consequently their iontransport and mechanical properties. As a result, the effect of salt addition on block copolymer thermodynamics has been the subject of significant interest over the last decade. A comprehensive study of the thermodynamics of block copolymer/salt mixtures over a wide range of molecular weights, compositions, salt concentrations and temperatures was conducted. Next, the effect of molecular weight on ion transport in both homopolymer and copolymer electrolytes were studied over a wide range of chain lengths. Homopolymer electrolytes show an inverse relationship between conductivity and chain length, with a plateau in the infinite molecular weight limit. This is due to the presence of two mechanisms of ion conduction in homopolymers; the first mechanism is a result of the segmental motion of the chains surrounding the salt ions, 2 creating a liquid
Energy Technology Data Exchange (ETDEWEB)
Jakse, Noel; Bretonnet, Jean-Louis [Laboratoire de Theorie de la Matiere Condensee, Universite de Metz, 1 Boulevard FD Arago, 57078 Metz Cedex 3 (France)
2003-12-08
Understanding the interatomic interactions in noble gases remains one of the fundamental problems not completely solved to date. From small-angle neutron scattering experiments it is well-known that three-body forces exist and cannot be neglected. On the theoretical side, semi-analytic and simulation methods have been used to reveal the nature of these many-body interactions. The purpose of the present work is to provide an overview of the different three-body contributions to the interactions and their relative importance in describing the structural and thermodynamic properties for noble gases by means of the integral equation theory and molecular dynamics simulations. We examine the relevance of the effective state-dependent pair potential in this framework, as well as the self-consistency problem that we are faced with in the integral equation theory.
International Nuclear Information System (INIS)
Shpil'rain, E.E.; Yakimovich, K.A.
1981-01-01
The paper reviews briefly experimental determinations of thermodynamic properties of the LiH-Li system. Relationships fitted to the experimental data are presented and discussed, with the aim of determining a consistent set of thermodynamic properties (enthalpy, heat capacity) for the systems Li-(LiH, LiD, LiT) in the solid state and in the melt. (author)
Equilibrium thermodynamics - Callen's postulational approach
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
Thermodynamics of geothermal fluids
Energy Technology Data Exchange (ETDEWEB)
Rogers, P.S.Z.
1981-03-01
A model to predict the thermodynamic properties of geothermal brines, based on a minimum amount of experimental data on a few key systems, is tested. Volumetric properties of aqueous sodium chloride, taken from the literature, are represented by a parametric equation over the range 0 to 300{sup 0}C and 1 bar to 1 kbar. Density measurements at 20 bar needed to complete the volumetric description also are presented. The pressure dependence of activity and thermal properties, derived from the volumetric equation, can be used to complete an equation of state for sodium chloride solutions. A flow calorimeter, used to obtain heat capacity data at high temperatures and pressures, is described. Heat capacity measurements, from 30 to 200{sup 0}C and 1 bar to 200 bar, are used to derive values for the activity coefficient and other thermodynamic properties of sodium sulfate solutions as a function of temperature. Literature data on the solubility of gypsum in mixed electrolyte solutions have been used to evaluate model parameters for calculating gypsum solubility in seawater and natural brines. Predictions of strontium and barium sulfate solubility in seawater also are given.
High energy lithium-oxygen batteries - Transport barriers and thermodynamics
Das, Shyamal K.
2012-01-01
We show that it is possible to achieve higher energy density lithium-oxygen batteries by simultaneously lowering the discharge overpotential and increasing the discharge capacity via thermodynamic variables alone. By assessing the relative effects of temperature and pressure on the cell discharge profiles, we characterize and diagnose the critical roles played by multiple dynamic processes that have hindered implementation of the lithium-oxygen battery. © 2012 The Royal Society of Chemistry.
Perspective: Structural fluctuation of protein and Anfinsen's thermodynamic hypothesis
Hirata, Fumio; Sugita, Masatake; Yoshida, Masasuke; Akasaka, Kazuyuki
2018-01-01
The thermodynamics hypothesis, casually referred to as "Anfinsen's dogma," is described theoretically in terms of a concept of the structural fluctuation of protein or the first moment (average structure) and the second moment (variance and covariance) of the structural distribution. The new theoretical concept views the unfolding and refolding processes of protein as a shift of the structural distribution induced by a thermodynamic perturbation, with the variance-covariance matrix varying. Based on the theoretical concept, a method to characterize the mechanism of folding (or unfolding) is proposed. The transition state, if any, between two stable states is interpreted as a gap in the distribution, which is created due to an extensive reorganization of hydrogen bonds among back-bone atoms of protein and with water molecules in the course of conformational change. Further perspective to applying the theory to the computer-aided drug design, and to the material science, is briefly discussed.
Thermodynamics of the multicomponent vapor-liquid equilibrium under capillary pressure difference
DEFF Research Database (Denmark)
Shapiro, Alexander; Stenby, Erling Halfdan
2001-01-01
We discuss the two-phase multicomponent equilibrium, provided that the phase pressures are different due to the action of capillary forces. We prove the two general properties of such an equilibrium, which have previously been known for a single-component case, however, to the best of our knowledge......, not for the multicomponent mixtures. The importance is emphasized on the space of the intensive variables P, T and mu (i), where the laws of capillary equilibrium have a simple geometrical interpretation. We formulate thermodynamic problems specific to such an equilibrium, and outline changes to be introduced to common...... algorithms of flash calculations in order to solve these problems. Sample calculations show large variation of the capillary properties of the mixture in the very neighborhood of the phase envelope and the restrictive role of the spinodal surface as a boundary for possible equilibrium states with different...
For effective thermodynamic calculation of turbines flow-through by gas and steam
Energy Technology Data Exchange (ETDEWEB)
Fischer, S; Hultsch, M
1982-03-01
A programme system for the medium and multiple section calculation of axial-flow turbines is explained. It allows calculations of turbine flow-through by gas and steam at designing and partial load states. The algorithms are independent upon the formulation of thermodynamic function, so that the programmes can be used for any means of production. The highest accuracy and efficiency can be guaranteed by the use of formulations of thermodynamic functions of water.
Thermodynamics for the practicing engineer
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.
International Nuclear Information System (INIS)
McHugh, Derek; Buzek, Vladimir; Ziman, Mario
2006-01-01
We present a class of non-Gaussian two-mode continuous-variable states for which the separability criterion for Gaussian states can be employed to detect whether they are separable or not. These states reduce to the two-mode Gaussian states as a special case
International Nuclear Information System (INIS)
Walder, V.
1984-01-01
The possibility is discussed of a quantitative approach to the evaluation of changes in Nb-stabilized low alloy steel due to the effect of liquid sodium. The numerical finite difference method was applied to diffusion processes using the variability of all thermodynamic values entering the calculation. At thermodynamic balance with existing carbides, it will be possible to take into account the temperature gradient, the effect of the size of carbides and the effect of applied strain. The fact that the diffusion coefficient of carbide-forming niobium is by seven orders lower than that of carbon led to the use of the model of quasi-steady state diffusion. The dissolution of carbides and the diffusion of both elements is studied and the activities are investigated of carbon and niobium. The dissolution of NbC is controlled by the diffusion of niobium; the diffusion of niobium and carbon is induced by the balancing of their activities at the steel/sodium boundary. The local activity of carbon is at any moment determined via the steady state constant from the activity of niobium considering the type of carbide. The Nb-stabilized steel is characterized by a great difference in carbide sizes. Small carbides are accompanied by high carbon and niobium activities. Spontaneous diffusion occurs from the near vicinity of the carbides and the carbides dissolve. Stress increases activity thereby accelerating the process of decarburization of the steel in sodium. (Pu)
Thermodynamic and transport properties of sodium liquid and vapor
International Nuclear Information System (INIS)
Fink, J.K.; Leibowitz, L.
1995-01-01
Data have been reviewed to obtain thermodynamically consistent equations for thermodynamic and transport properties of saturated sodium liquid and vapor. Recently published Russian recommendations and results of equation of state calculations on thermophysical properties of sodium have been included in this critical assessment. Thermodynamic properties of sodium liquid and vapor that have been assessed include: enthalpy, heat capacity at constant pressure, heat capacity at constant volume, vapor pressure, boiling point, enthalpy of vaporization, density, thermal expansion, adiabatic and isothermal compressibility, speed of sound, critical parameters, and surface tension. Transport properties of liquid sodium that have been assessed include: viscosity and thermal conductivity. For each property, recommended values and their uncertainties are graphed and tabulated as functions of temperature. Detailed discussions of the analyses and determinations of the recommended equations include comparisons with recommendations given in other assessments and explanations of consistency requirements. The rationale and methods used in determining the uncertainties in the recommended values are also discussed
International Nuclear Information System (INIS)
Hyldgaard, P
2012-01-01
The standard formulation of tunneling transport rests on an open-boundary modeling. There, conserving approximations to nonequilibrium Green function or quantum statistical mechanics provide consistent but computational costly approaches; alternatively, the use of density-dependent ballistic-transport calculations (e.g., Lang 1995 Phys. Rev. B 52 5335), here denoted ‘DBT’, provides computationally efficient (approximate) atomistic characterizations of the electron behavior but has until now lacked a formal justification. This paper presents an exact, variational nonequilibrium thermodynamic theory for fully interacting tunneling and provides a rigorous foundation for frozen-nuclei DBT calculations as a lowest-order approximation to an exact nonequilibrium thermodynamic density functional evaluation. The theory starts from the complete electron nonequilibrium quantum statistical mechanics and I identify the operator for the nonequilibrium Gibbs free energy which, generally, must be treated as an implicit solution of the fully interacting many-body dynamics. I demonstrate a minimal property of a functional for the nonequilibrium thermodynamic grand potential which thus uniquely identifies the solution as the exact nonequilibrium density matrix. I also show that the uniqueness-of-density proof from a closely related Lippmann-Schwinger collision density functional theory (Hyldgaard 2008 Phys. Rev. B 78 165109) makes it possible to express the variational nonequilibrium thermodynamic description as a single-particle formulation based on universal electron-density functionals; the full nonequilibrium single-particle formulation improves the DBT method, for example, by a more refined account of Gibbs free energy effects. I illustrate a formal evaluation of the zero-temperature thermodynamic grand potential value which I find is closely related to the variation in the scattering phase shifts and hence to Friedel density oscillations. This paper also discusses the
Thermodynamic implications of the gravitationally induced particle creation scenario
Energy Technology Data Exchange (ETDEWEB)
Saha, Subhajit [Indian Institute of Science Education and Research Kolkata, Department of Physical Sciences, Mohanpur, West Bengal (India); Mondal, Anindita [S N Bose National Centre for Basic Sciences, Department of Astrophysics and Cosmology, Kolkata, West Bengal (India)
2017-03-15
A rigorous thermodynamic analysis has been done as regards the apparent horizon of a spatially flat Friedmann-Lemaitre-Robertson-Walker universe for the gravitationally induced particle creation scenario with constant specific entropy and an arbitrary particle creation rate Γ. Assuming a perfect fluid equation of state p = (γ - 1)ρ with (2)/(3) ≤ γ ≤ 2, the first law, the generalized second law (GSL), and thermodynamic equilibrium have been studied, and an expression for the total entropy (i.e., horizon entropy plus fluid entropy) has been obtained which does not contain Γ explicitly. Moreover, a lower bound for the fluid temperature T{sub f} has also been found which is given by T{sub f} ≥ 8 (((3γ)/(2)-1)/((2)/(γ)-1)) H{sup 2}. It has been shown that the GSL is satisfied for (Γ)/(3H) ≤ 1. Further, when Γ is constant, thermodynamic equilibrium is always possible for (1)/(2) < (Γ)/(3H) < 1, while for (Γ)/(3H) ≤ min {(1)/(2), (2γ-2)/(3γ-2)} and (Γ)/(3H) ≥ 1, equilibrium can never be attained. Thermodynamic arguments also lead us to believe that during the radiation phase, Γ ≤ H. When Γ is not a constant, thermodynamic equilibrium holds if H ≥ (27)/(4) γ{sup 2}H{sup 3} (1-(Γ)/(3H)){sup 2}, however, such a condition is by no means necessary for the attainment of equilibrium. (orig.)
Thermodynamic implications of the gravitationally induced particle creation scenario
International Nuclear Information System (INIS)
Saha, Subhajit; Mondal, Anindita
2017-01-01
A rigorous thermodynamic analysis has been done as regards the apparent horizon of a spatially flat Friedmann-Lemaitre-Robertson-Walker universe for the gravitationally induced particle creation scenario with constant specific entropy and an arbitrary particle creation rate Γ. Assuming a perfect fluid equation of state p = (γ - 1)ρ with (2)/(3) ≤ γ ≤ 2, the first law, the generalized second law (GSL), and thermodynamic equilibrium have been studied, and an expression for the total entropy (i.e., horizon entropy plus fluid entropy) has been obtained which does not contain Γ explicitly. Moreover, a lower bound for the fluid temperature T f has also been found which is given by T f ≥ 8 (((3γ)/(2)-1)/((2)/(γ)-1)) H 2 . It has been shown that the GSL is satisfied for (Γ)/(3H) ≤ 1. Further, when Γ is constant, thermodynamic equilibrium is always possible for (1)/(2) < (Γ)/(3H) < 1, while for (Γ)/(3H) ≤ min {(1)/(2), (2γ-2)/(3γ-2)} and (Γ)/(3H) ≥ 1, equilibrium can never be attained. Thermodynamic arguments also lead us to believe that during the radiation phase, Γ ≤ H. When Γ is not a constant, thermodynamic equilibrium holds if H ≥ (27)/(4) γ 2 H 3 (1-(Γ)/(3H)) 2 , however, such a condition is by no means necessary for the attainment of equilibrium. (orig.)
Ab initio thermodynamic model for magnesium carbonates and hydrates.
Chaka, Anne M; Felmy, Andrew R
2014-09-04
An ab initio thermodynamic framework for predicting properties of hydrated magnesium carbonate minerals has been developed using density-functional theory linked to macroscopic thermodynamics through the experimental chemical potentials for MgO, water, and CO2. Including semiempirical dispersion via the Grimme method and small corrections to the generalized gradient approximation of Perdew, Burke, and Ernzerhof for the heat of formation yields a model with quantitative agreement for the benchmark minerals brucite, magnesite, nesquehonite, and hydromagnesite. The model shows how small differences in experimental conditions determine whether nesquehonite, hydromagnesite, or magnesite is the result of laboratory synthesis from carbonation of brucite, and what transformations are expected to occur on geological time scales. Because of the reliance on parameter-free first-principles methods, the model is reliably extensible to experimental conditions not readily accessible to experiment and to any mineral composition for which the structure is known or can be hypothesized, including structures containing defects, substitutions, or transitional structures during solid state transformations induced by temperature changes or processes such as water, CO2, or O2 diffusion. Demonstrated applications of the ab initio thermodynamic framework include an independent means to evaluate differences in thermodynamic data for lansfordite, predicting the properties of Mg analogues of Ca-based hydrated carbonates monohydrocalcite and ikaite, which have not been observed in nature, and an estimation of the thermodynamics of barringtonite from the stoichiometry and a single experimental observation.
A thermodynamically influenced control for potato storage | Ndiema ...
African Journals Online (AJOL)
The results obtained show that the modified control achieved reduced mass loss by about 5% while the fan energy input was reduced by up to 10%. It is therefore possible to achieve improved control of the potato storage condition by modifying the controls to operate on the basis of thermodynamic state diagrams.
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.
Chakraborty, Anutosh
2009-02-17
Thermodynamic property surfaces for a single-component adsorbent + adsorbate system are derived and developed from the viewpoint of classical thermodynamics, thermodynamic requirements of chemical equilibrium, Gibbs law, and Maxwell relations. They enable us to compute the entropy and enthalpy of the adsorbed phase, the isosteric heat of adsorption, specific heat capacity, and the adsorbed phase volume thoroughly. These equations are very simple and easy to handle for calculating the energetic performances of any adsorption system. We have shown here that the derived thermodynamic formulations fill up the information gap with respect to the state of adsorbed phase to dispel the confusion as to what is the actual state of the adsorbed phase. We have also discussed and established the temperature-entropy diagrams of (i) CaCl 2-in-silica gel + water system for cooling applications, and (ii) activated carbon (Maxsorb III) + methane system for gas storage. © Copyright 2009 American Chemical Society.
Thermodynamic properties and atomic structure of Ca-based liquid alloys
Poizeau, Sophie
To identify the most promising positive electrodes for Ca-based liquid metal batteries, the thermodynamic properties of diverse Ca-based liquid alloys were investigated. The thermodynamic properties of Ca-Sb alloys were determined by emf measurements. It was found that Sb as positive electrode would provide the highest voltage for Ca-based liquid metal batteries (1 V). The price of such a battery would be competitive for the grid-scale energy storage market. The impact of Pb, a natural impurity of Sb, was predicted successfully and confirmed via electrochemical measurements. It was shown that the impact on the open circuit voltage would be minor. Indeed, the interaction between Ca and Sb was demonstrated to be much stronger than between Ca and Pb using thermodynamic modeling, which explains why the partial thermodynamic properties of Ca would not vary much with the addition of Pb to Sb. However, the usage of the positive electrode would be reduced, which would limit the interest of a Pb-Sb positive electrode. Throughout this work, the molecular interaction volume model (MIVM) was used for the first time for alloys with thermodynamic properties showing strong negative deviation from ideality. This model showed that systems such as Ca-Sb have strong short-range order: Ca is most stable when its first nearest neighbors are Sb. This is consistent with what the more traditional thermodynamic model, the regular association model, would predict. The advantages of the MIVM are the absence of assumption regarding the composition of an associate, and the reduced number of fitting parameters (2 instead of 5). Based on the parameters derived from the thermodynamic modeling using the MIVM, a new potential of mixing for liquid alloys was defined to compare the strength of interaction in different Ca-based alloys. Comparing this trend with the strength of interaction in the solid state of these systems (assessed by the energy of formation of the intermetallics), the systems with
Directory of Open Access Journals (Sweden)
Giuseppe Guzzetta
2013-06-01
Full Text Available In order to treat deformation as one of the processes taking place in an irreversible thermodynamic transformation, two main conditions must be satisfied: (1 strain and stress should be defined in such a way that the modification of the symmetry of these tensorial quantities reflects that of the structure of the actual material of which the deforming ideal continuum is the counterpart; and (2 the unique decomposition of the above tensors into the algebraic sum of an isotropic and an anisotropic part with different physical meanings should be recognized. The first condition allows the distinction of the energy balance in irrotational and rotational deformations; the second allows the description of a thermodynamic transformation involving deformation as a function of both process quantities, whose values depend on the specific transition, or path, between two equilibrium states, and of state quantities, which describe equilibrium states of a system quantitatively. One of the main conclusions that can be drawn is that, dealing with deformable materials, the quantities that must appear in thermodynamic equations cannot be tensorial quantities, such as the stress tensor and the infinitesimal or finite strain tensor usually considered in continuum mechanics (or, even worse, their components. The appropriate quantities should be invariants involved by the strain and stress tensors here defined. Another important conclusion is that, from a thermodynamic point of view, the consideration of the measurable volume change occurring in an isothermal deformation does not itself give any meaningful information.
Horowitz, Jordan M
2015-07-28
The stochastic thermodynamics of a dilute, well-stirred mixture of chemically reacting species is built on the stochastic trajectories of reaction events obtained from the chemical master equation. However, when the molecular populations are large, the discrete chemical master equation can be approximated with a continuous diffusion process, like the chemical Langevin equation or low noise approximation. In this paper, we investigate to what extent these diffusion approximations inherit the stochastic thermodynamics of the chemical master equation. We find that a stochastic-thermodynamic description is only valid at a detailed-balanced, equilibrium steady state. Away from equilibrium, where there is no consistent stochastic thermodynamics, we show that one can still use the diffusive solutions to approximate the underlying thermodynamics of the chemical master equation.
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
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...
International Nuclear Information System (INIS)
Wu, Wei; Wang, Jin
2014-01-01
We have established a general non-equilibrium thermodynamic formalism consistently applicable to both spatially homogeneous and, more importantly, spatially inhomogeneous systems, governed by the Langevin and Fokker-Planck stochastic dynamics with multiple state transition mechanisms, using the potential-flux landscape framework as a bridge connecting stochastic dynamics with non-equilibrium thermodynamics. A set of non-equilibrium thermodynamic equations, quantifying the relations of the non-equilibrium entropy, entropy flow, entropy production, and other thermodynamic quantities, together with their specific expressions, is constructed from a set of dynamical decomposition equations associated with the potential-flux landscape framework. The flux velocity plays a pivotal role on both the dynamic and thermodynamic levels. On the dynamic level, it represents a dynamic force breaking detailed balance, entailing the dynamical decomposition equations. On the thermodynamic level, it represents a thermodynamic force generating entropy production, manifested in the non-equilibrium thermodynamic equations. The Ornstein-Uhlenbeck process and more specific examples, the spatial stochastic neuronal model, in particular, are studied to test and illustrate the general theory. This theoretical framework is particularly suitable to study the non-equilibrium (thermo)dynamics of spatially inhomogeneous systems abundant in nature. This paper is the second of a series
International Nuclear Information System (INIS)
Godoy, E.; Benz, S.J.; Scenna, N.J.
2011-01-01
Optimal combined cycle gas turbine power plants characterized by minimum specific annual cost values are here determined for wide ranges of market conditions as given by the relative weights of capital investment and operative costs, by means of a non-linear mathematical programming model. On the other hand, as the technical optimization allows identifying trends in the system behavior and unveiling optimization opportunities, selected functional relationships are obtained as the thermodynamic optimal values of the decision variables are systematically linked to the ratio between the total heat transfer area and the net power production (here named as specific transfer area). A strategy for simplifying the resolution of the rigorous economic optimization problem of power plants is proposed based on the economic optima distinctive characteristics which describe the behavior of the decision variables of the power plant on its optima. Such approach results in a novel mathematical formulation shaped as a system of non-linear equations and additional constraints that is able to easily provide accurate estimations of the optimal values of the power plant design and operative variables. Research highlights: → We achieve relationships between power plants' economic and thermodynamic optima. → We achieve functionalities among thermodynamic optimal values of decision variables. → The rigorous optimization problem is reduced to a non-linear equations system. → Accurate estimations of power plants' design and operative variables are obtained.
Variability of Power from Large-Scale Solar Photovoltaic Scenarios in the State of Gujarat: Preprint
Energy Technology Data Exchange (ETDEWEB)
Parsons, B.; Hummon, M.; Cochran, J.; Stoltenberg, B.; Batra, P.; Mehta, B.; Patel, D.
2014-04-01
India has ambitious goals for high utilization of variable renewable power from wind and solar, and deployment has been proceeding at a rapid pace. The western state of Gujarat currently has the largest amount of solar generation of any Indian state, with over 855 Megawatts direct current (MWDC). Combined with over 3,240 MW of wind, variable generation renewables comprise nearly 18% of the electric-generating capacity in the state. A new historic 10-kilometer (km) gridded solar radiation data set capturing hourly insolation values for 2002-2011 is available for India. We apply an established method for downscaling hourly irradiance data to one-minute irradiance data at potential PV power production locations for one year, 2006. The objective of this report is to characterize the intra-hour variability of existing and planned photovoltaic solar power generation in the state of Gujarat (a total of 1.9 gigawatts direct current (GWDC)), and of five possible expansion scenarios of solar generation that reflect a range of geographic diversity (each scenario totals 500-1,000 MW of additional solar capacity). The report statistically analyzes one year's worth of power variability data, applied to both the baseline and expansion scenarios, to evaluate diurnal and seasonal power fluctuations, different timescales of variability (e.g., from one to 15 minutes), the magnitude of variability (both total megawatts and relative to installed solar capacity), and the extent to which the variability can be anticipated in advance. The paper also examines how Gujarat Energy Transmission Corporation (GETCO) and the Gujarat State Load Dispatch Centre (SLDC) could make use of the solar variability profiles in grid operations and planning.
Thermodynamic simulation of ammonia-water absorption refrigeration system
Directory of Open Access Journals (Sweden)
Sathyabhama A.
2008-01-01
Full Text Available The ammonia-water absorption refrigeration system is attracting increasing research interests, since the system can be powered by waste thermal energy, thus reducing demand on electricity supply. The development of this technology demands reliable and effective system simulations. In this work, a thermodynamic simulation of the cycle is carried out to investigate the effects of different operating variables on the performance of the cycle. A computer program in C language is written for the performance analysis of the cycle.
International Nuclear Information System (INIS)
Hassan, H.Z.; Mohamad, A.A.
2013-01-01
Due to the intermittent nature of the solar radiation, the day-long continuous production of cold is a challenge for solar-driven adsorption cooling systems. In the present study, a developed solar-powered adsorption cooling system is introduced. The proposed system is able to produce cold continuously along the 24-h of the day. The theoretical thermodynamic operating cycle of the system is based on adsorption at constant temperature. Both the cooling system operating procedure as well as the theoretical thermodynamic cycle are described and explained. Moreover, a steady state differential thermodynamic analysis is performed for all components and processes of the introduced system. The analysis is based on the energy conservation principle and the equilibrium dynamics of the adsorption and desorption processes. The Dubinin–Astakhov adsorption equilibrium equation is used in this analysis. Furthermore, the thermodynamic properties of the refrigerant are calculated from its equation of state. The case studied represents a water chiller which uses activated carbon–methanol as the working pair. The chiller is found to produce a daily mass of 2.63 kg cold water at 0 °C from water at 25 °C per kg of adsorbent. Moreover, the proposed system attains a cooling coefficient of performance of 0.66. - Highlights: • A new continuous operation solar-driven adsorption refrigeration system is introduced. • The theoretical thermodynamic cycle is presented and explained. • A complete thermodynamic analysis is performed for all components and processes of the system. • Activated carbon–methanol is used as the working pair in the case study
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
State variable participation in the limit cycle of induction motor
Indian Academy of Sciences (India)
State variable participation in the limit cycle of induction ... 2National Institute of Technical Teachers' Training and Research, Kolkata 700 106, India ..... the phase plot shown in figure 10 would be very useful as it shows infinite loops, meaning.
Thermodynamic properties of indan: Experimental and computational results
International Nuclear Information System (INIS)
Chirico, Robert D.; Steele, William V.; Kazakov, Andrei F.
2016-01-01
Highlights: • Heat capacities were measured for the temperature range (5 to 445) K. • Vapor pressures were measured for the temperature range (338 to 495) K. • Densities at saturation pressure were measured from T = (323 to 523) K. • Computed and experimentally derived properties for ideal gas entropies are in excellent accord. • Thermodynamic consistency analysis revealed anomalous literature data. - Abstract: Measurements leading to the calculation of thermodynamic properties in the ideal-gas state for indan (Chemical Abstracts registry number [496-11-7], 2,3-dihydro-1H-indene) are reported. Experimental methods were adiabatic heat-capacity calorimetry, differential scanning calorimetry, comparative ebulliometry, and vibrating-tube densitometry. Molar thermodynamic functions (enthalpies, entropies, and Gibbs energies) for the condensed and ideal-gas states were derived from the experimental studies at selected temperatures. Statistical calculations were performed based on molecular geometry optimization and vibrational frequencies calculated at the B3LYP/6-31+G(d, p) level of theory. Computed ideal-gas properties derived with the rigid-rotor harmonic-oscillator approximation are shown to be in excellent accord with ideal-gas entropies derived from thermophysical property measurements of this research, as well as with experimental heat capacities for the ideal-gas state reported in the literature. Literature spectroscopic studies and ab initio calculations report a range of values for the barrier to ring puckering. Results of the present work are consistent with a large barrier that allows use of the rigid-rotor harmonic-oscillator approximation for ideal-gas entropy and heat-capacity calculations, even with the stringent uncertainty requirements imposed by the calorimetric and physical property measurements reported here. All experimental results are compared with property values reported in the literature.
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.
Molecular thermodynamics of nonideal fluids
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
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...
Hybridization thermodynamics of DNA bound to gold nanoparticles
International Nuclear Information System (INIS)
Lang, Brian
2010-01-01
Isothermal Titration Calorimetry (ITC) was used to study the thermodynamics of hybridization on DNA-functionalized colloidal gold nanoparticles. When compared to the thermodynamics of hybridization of DNA that is free in solution, the differences in the values of the Gibbs free energy of reaction, Δ r G o , the enthalpy, Δ r H o , and entropy, Δ r S o , were small. The change in Δ r G o between the free and bound states was always positive but with statistical significance outside the 95% confidence interval, implying the free DNA is slightly more stable than when in the bound state. Additionally, ITC was also able to reveal information about the binding stoichiometry of the hybridization reactions on the DNA-functionalized gold nanoparticles, and indicates that there is a significant fraction of the DNA on gold nanoparticle surface that is unavailable for DNA hybridization. Furthermore, the fraction of available DNA is dependent on the spacer group on the DNA that is used to span the gold surface from that to the probe DNA.
Thermodynamically efficient solar concentrators
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.