Thermodynamic behavior of glassy state of structurally related compounds.

Science.gov (United States)

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.

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)

Methods and systems for thermodynamic evaluation of battery state of health

Science.gov (United States)

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.

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

Correlation of dew- and bubble-point curves for binary refrigerant mixtures. [Correlation between dew-point pressure(saturated vapor state) and bubble-point pressure(saturated liquid state)]. Niseibunkei kongo reibai no roten oyobi futten kyokusen no sokan

Energy Technology Data Exchange (ETDEWEB)

Yada, N. (Kanagawa Institute of Technology, Kanagawa (Japan)); Watanabe, K. (Keio University, Tokyo (Japan). Faculty of Science and Technology)

1991-12-25

The paper makes a correlation expressing dew- and bubble-point curves using measured values for seven binary refrigerant freon-mixtures. In most binary systems at the same temperature, the pressure shows a different value between in a saturated vapor state (dew-point pressure) and in a saturated liquid state (bubble-point pressure). The target is such correlation as has as simple a function form as possible and is able to estimate even near the critical point where it used to be difficult to estimate. The pressure difference between measured values of the dew- and bubble-point pressure and values calculated from Raoult's law showing an ideal mixture of fluid is expressed by a simple function form of reduced temperature Tr and molar fraction. Tr is thermodynamic temperature/critical temperature. Reproducibility of this correlation is less than {plus minus}3% of the pressure deviation. Concerning also the arbitary composition range and near the critical point, the dew- and bubble-point pressure can be calculated accurately. 24 refs., 4 figs., 5 tabs.

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.

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

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.

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.

Thermodynamic Stability of Ice II and Its Hydrogen-Disordered Counterpart: Role of Zero-Point Energy.

Science.gov (United States)

Nakamura, Tatsuya; Matsumoto, Masakazu; Yagasaki, Takuma; Tanaka, Hideki

2016-03-03

We investigate why no hydrogen-disordered form of ice II has been found in nature despite the fact that most of hydrogen-ordered ices have hydrogen-disordered counterparts. The thermodynamic stability of a set of hydrogen-ordered ice II variants relative to ice II is evaluated theoretically. It is found that ice II is more stable than the disordered variants so generated as to satisfy the simple ice rule due to the lower zero-point energy as well as the pair interaction energy. The residual entropy of the disordered ice II phase gradually compensates the unfavorable free energy with increasing temperature. The crossover, however, occurs at a high temperature well above the melting point of ice III. Consequently, the hydrogen-disordered phase does not exist in nature. The thermodynamic stability of partially hydrogen-disordered ices is also scrutinized by examining the free-energy components of several variants obtained by systematic inversion of OH directions in ice II. The potential energy of one variant is lower than that of the ice II structure, but its Gibbs free energy is slightly higher than that of ice II due to the zero-point energy. The slight difference in the thermodynamic stability leaves the possibility of the partial hydrogen-disorder in real ice II.

Statistical thermodynamics -- A tool for understanding point defects in intermetallic compounds

International Nuclear Information System (INIS)

Ipser, H.; Krachler, R.

1996-01-01

The principles of the derivation of statistical-thermodynamic models to interpret the compositional variation of thermodynamic properties in non-stoichiometric intermetallic compounds are discussed. Two types of models are distinguished: the Bragg-Williams type, where the total energy of the crystal is taken as the sum of the interaction energies of all nearest-neighbor pairs of atoms, and the Wagner-Schottky type, where the internal energy, the volume, and the vibrational entropy of the crystal are assumed to be linear functions of the numbers of atoms or vacancies on the different sublattices. A Wagner-Schottky type model is used for the description of two examples with different crystal structures: for β'-FeAl (with B2-structure) defect concentrations and their variation with composition are derived from the results of measurements of the aluminum vapor pressure, the resulting values are compared with results of other independent experimental methods; for Rh 3 Te 4 (with an NiAs-derivative structure) the defect mechanism responsible for non-stoichiometry is worked out by application of a theoretical model to the results of tellurium vapor pressure measurements. In addition it is shown that the shape of the activity curve indicates a certain sequence of superstructures. In principle, there are no limitations to the application of statistical thermodynamics to experimental thermodynamic data as long as these are available with sufficient accuracy, and as long as it is ensured that the distribution of the point defects is truly random, i.e. that there are no aggregates of defects

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

A Modified Benedict-Webb-Rubin Equation of State for the Thermodynamic Properties of R152a (1,1-difluoroethane)

Science.gov (United States)

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.

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

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...

Experimental thermodynamics experimental thermodynamics of non-reacting fluids

CERN Document Server

Neindre, B Le

2013-01-01

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

One-point functions in AdS/dCFT from matrix product states

International Nuclear Information System (INIS)

Buhl-Mortensen, Isak; Leeuw, Marius de; Kristjansen, Charlotte; Zarembo, Konstantin

2016-01-01

One-point functions of certain non-protected scalar operators in the defect CFT dual to the D3-D5 probe brane system with k units of world volume flux can be expressed as overlaps between Bethe eigenstates of the Heisenberg spin chain and a matrix product state. We present a closed expression of determinant form for these one-point functions, valid for any value of k. The determinant formula factorizes into the k=2 result times a k-dependent pre-factor. Making use of the transfer matrix of the Heisenberg spin chain we recursively relate the matrix product state for higher even and odd k to the matrix product state for k=2 and k=3 respectively. We furthermore find evidence that the matrix product states for k=2 and k=3 are related via a ratio of Baxter’s Q-operators. The general k formula has an interesting thermodynamical limit involving a non-trivial scaling of k, which indicates that the match between string and field theory one-point functions found for chiral primaries might be tested for non-protected operators as well. We revisit the string computation for chiral primaries and discuss how it can be extended to non-protected operators.

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.

Thermodynamic Temperature of High-Temperature Fixed Points Traceable to Blackbody Radiation and Synchrotron Radiation

Science.gov (United States)

Wähmer, M.; Anhalt, K.; Hollandt, J.; Klein, R.; Taubert, R. D.; Thornagel, R.; Ulm, G.; Gavrilov, V.; Grigoryeva, I.; Khlevnoy, B.; Sapritsky, V.

2017-10-01

Absolute spectral radiometry is currently the only established primary thermometric method for the temperature range above 1300 K. Up to now, the ongoing improvements of high-temperature fixed points and their formal implementation into an improved temperature scale with the mise en pratique for the definition of the kelvin, rely solely on single-wavelength absolute radiometry traceable to the cryogenic radiometer. Two alternative primary thermometric methods, yielding comparable or possibly even smaller uncertainties, have been proposed in the literature. They use ratios of irradiances to determine the thermodynamic temperature traceable to blackbody radiation and synchrotron radiation. At PTB, a project has been established in cooperation with VNIIOFI to use, for the first time, all three methods simultaneously for the determination of the phase transition temperatures of high-temperature fixed points. For this, a dedicated four-wavelengths ratio filter radiometer was developed. With all three thermometric methods performed independently and in parallel, we aim to compare the potential and practical limitations of all three methods, disclose possibly undetected systematic effects of each method and thereby confirm or improve the previous measurements traceable to the cryogenic radiometer. This will give further and independent confidence in the thermodynamic temperature determination of the high-temperature fixed point's phase transitions.

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

Thermodynamic and Quantum Thermodynamic Analyses of Brownian Movement

OpenAIRE

Gyftopoulos, Elias P.

2006-01-01

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

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

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...

A Unification between Dynamical System Theory and Thermodynamics Involving an Energy, Mass, and Entropy State Space Formalism

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

KAUST Repository

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.

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

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

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

Thermodynamics of diffusion under pressure and stress: Relation to point defect mechanisms

International Nuclear Information System (INIS)

Aziz, M.J.

1997-01-01

A thermodynamic formalism is developed for illuminating the predominant point defect mechanism of self- and impurity diffusion in silicon and is used to provide a rigorous basis for point defect-based interpretation of diffusion experiments in biaxially strained epitaxial layers in the Si endash Ge system. A specific combination of the hydrostatic and biaxial stress dependences of the diffusivity is ±1 times the atomic volume, depending upon whether the predominant mechanism involves vacancies or interstitials. Experimental results for Sb diffusion in biaxially strained Si endash Ge films and ab initio calculations of the activation volume for Sb diffusion by a vacancy mechanism are in quantitative agreement with no free parameters. Key parameters are identified that must be measured or calculated for a quantitative test of interstitial-based mechanisms. copyright 1997 American Institute of Physics

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

Science.gov (United States)

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

2016-04-01

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

Noise temperature measurements for the determination of the thermodynamic temperature of the melting point of palladium

Energy Technology Data Exchange (ETDEWEB)

Edler, F.; Kuhne, M.; Tegeler, E. [Bundesanstalt Physikalisch-Technische, Berlin (Germany)

2004-02-01

The thermodynamic temperature of the melting point of palladium in air was measured by noise thermometric methods. The temperature measurement was based on noise comparison using a two-channel arrangement to eliminate parasitic noises of electronic components by cross correlation. Three miniature fixed points filled with pure palladium (purity: {approx}99.99%, mass: {approx}90 g) were used to realize the melts of the fixed point metal. The measured melting temperature of palladium in air amounted to 1552.95 deg C {+-} 0.21 K (k = 2). This temperature is 0.45 K lower than the temperature of the melting point of palladium measured by radiation thermometry. (authors)

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

Fundamental aspects of plasma chemical physics Thermodynamics

CERN Document Server

Capitelli, Mario; D'Angola, Antonio

2012-01-01

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

Integrated stoichiometric, thermodynamic and kinetic modelling of steady state metabolism.

Science.gov (United States)

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.

Twenty lectures on thermodynamics

CERN Document Server

Buchdahl, H A

2013-01-01

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

The quantitative analysis of data for magnetization of ferromagnet. Extended thermodynamic approach

International Nuclear Information System (INIS)

Bodryakov, V.Yu.; Bashkatov, A.N.

2005-01-01

A quantitative analysis of M(H,T) data on magnetization of a gadolinium single crystal in the vicinity of Curie point is accomplished within the frameworks of extended thermodynamic approach. It is established that actually observed behavior of temperature dependences of thermodynamic coefficients for gadolinium even near Curie point is sharply different from that in Landau theory. A discrepancy revealed leads to conclusion that traditional concepts should be revised. The solution of extended equation of a ferromagnet magnetic state is found and criteria of its stability are shown [ru

Thermodynamics of non-ionic surfactant Triton X-100-cationic surfactants mixtures at the cloud point

International Nuclear Information System (INIS)

Batigoec, Cigdem; Akbas, Halide; Boz, Mesut

2011-01-01

Highlights: → Non-ionic surfactants are used as emulsifier and solubilizate in such as textile, detergent and cosmetic. → Non-ionic surfactants occur phase separation at temperature as named the cloud point in solution. → Dimeric surfactants have attracted increasing attention due to their superior surface activity. → The positive values of ΔG cp 0 indicate that the process proceeds nonspontaneous. - Abstract: This study investigates the effects of gemini and conventional cationic surfactants on the cloud point (CP) of the non-ionic surfactant Triton X-100 (TX-100) in aqueous solutions. Instead of visual observation, a spectrophotometer was used for measurement of the cloud point temperatures. The thermodynamic parameters of these mixtures were calculated at different cationic surfactant concentrations. The gemini surfactants of the alkanediyl-α-ω-bis (alkyldimethylammonium) dibromide type, on the one hand, with different alkyl groups containing m carbon atoms and an ethanediyl spacer, referred to as 'm-2-m' (m = 10, 12, and 16) and, on the other hand, with -C 16 alkyl groups and different spacers containing s carbon atoms, referred to as '16-s-16' (s = 6 and 10) were synthesized, purified and characterized. Additions of the cationic surfactants to the TX-100 solution increased the cloud point temperature of the TX-100 solution. It was accepted that the solubility of non-ionic surfactant containing polyoxyethylene (POE) hydrophilic chain was a maximum at the cloud point so that the thermodynamic parameters were calculated at this temperature. The results showed that the standard Gibbs free energy (ΔG cp 0 ), the enthalpy (ΔH cp 0 ) and the entropy (ΔS cp 0 ) of the clouding phenomenon were found positive in all cases. The standard free energy (ΔG cp 0 ) increased with increasing hydrophobic alkyl chain for both gemini and conventional cationic surfactants; however, it decreased with increasing surfactant concentration.

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.)

Rational extended thermodynamics

CERN Document Server

Müller, Ingo

1998-01-01

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

Conductivity and thermodynamic characteristic of superionic transition in strontium chloride

International Nuclear Information System (INIS)

Voronin, B.M.; Prisyazhnyj, V.D.

1989-01-01

Electric conductivity of strontium polycrystalline chloride in the wide temperature range including melting point is measured. Reciprocally caused anomalous behaviour of kinetic and thermodynamic properties, which relates to peculiarities of salt transition to a superionic state is established in the region of high temperatures. Thermodynamic functions corresponding to crystal anion sublattice disordering are determined and characterized. Comparative analysis of data on strontium chloride and other structural-like salts testifies about step-by-step washing-out character of superionic transition, and the depth of transition (the degree of disordering) reached at melting points relates regularly to relative sizes of cations and anions in the fluorite lattice

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.

Illustration of the thermodynamical method of research into a critical state through the Rainford-Edwards model

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

Inflection points of microcanonical entropy: Monte Carlo simulation of q state Potts model on a finite square lattice

Energy Technology Data Exchange (ETDEWEB)

Praveen, E., E-mail: svmstaya@gmail.com; Satyanarayana, S. V. M., E-mail: svmstaya@gmail.com [Department of Physics, Pondicherry University, Puducherry-605014 (India)

2014-04-24

Traditional definition of phase transition involves an infinitely large system in thermodynamic limit. Finite systems such as biological proteins exhibit cooperative behavior similar to phase transitions. We employ recently discovered analysis of inflection points of microcanonical entropy to estimate the transition temperature of the phase transition in q state Potts model on a finite two dimensional square lattice for q=3 (second order) and q=8 (first order). The difference of energy density of states (DOS) Δ ln g(E) = ln g(E+ ΔE) −ln g(E) exhibits a point of inflexion at a value corresponding to inverse transition temperature. This feature is common to systems exhibiting both first as well as second order transitions. While the difference of DOS registers a monotonic variation around the point of inflexion for systems exhibiting second order transition, it has an S-shape with a minimum and maximum around the point of inflexion for the case of first order transition.

Inflection points of microcanonical entropy: Monte Carlo simulation of q state Potts model on a finite square lattice

International Nuclear Information System (INIS)

Praveen, E.; Satyanarayana, S. V. M.

2014-01-01

Traditional definition of phase transition involves an infinitely large system in thermodynamic limit. Finite systems such as biological proteins exhibit cooperative behavior similar to phase transitions. We employ recently discovered analysis of inflection points of microcanonical entropy to estimate the transition temperature of the phase transition in q state Potts model on a finite two dimensional square lattice for q=3 (second order) and q=8 (first order). The difference of energy density of states (DOS) Δ ln g(E) = ln g(E+ ΔE) −ln g(E) exhibits a point of inflexion at a value corresponding to inverse transition temperature. This feature is common to systems exhibiting both first as well as second order transitions. While the difference of DOS registers a monotonic variation around the point of inflexion for systems exhibiting second order transition, it has an S-shape with a minimum and maximum around the point of inflexion for the case of first order transition

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

Ground-state thermodynamics of bistable redox-active donor-acceptor mechanically interlocked molecules.

Science.gov (United States)

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 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

Geodetic Control Points - Multi-State Control Point Database

Data.gov (United States)

NSGIC State | GIS Inventory — The Multi-State Control Point Database (MCPD) is a database of geodetic and mapping control covering Idaho and Montana. The control were submitted by registered land...

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

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

Thermodynamic state updated of the volcanic caldera and geothermal reservoir of Los Humeros, Puebla, Mexico

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.

Energy field of thermodynamic syste'ms

International Nuclear Information System (INIS)

Volchenkova, R.A.

1984-01-01

To reveal the qualitative and quantitative rules, regulating the properties of macro- and microsystems consideration is being given to the dependence of system enthalpy on environmental conditions. It was concluded that the dependence of material system enthalpy on temperature represents the energy field, containing the energy boundaries of phase states, described by exponential functions, in which the elements are arranged monotonically in the sequence of change of interatomic bonds, correlated with their physicomechanical properties; energy boundaries of phase states at that emanate from a single point, which is a reference a single point, which a reference one for the whole material system and determining its energy state in initial position. The presented energy field of thermodynamic systems enables to consider the change of their physicomechanical properties and energy state in dynamic process, depending on environmental parameters. Energy characteristics of single-component systems (W, Re, Hf, Nb, Mo etc) are given

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-04-14

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

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

International Nuclear Information System (INIS)

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

2016-01-01

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

Chlorine international thermodynamic tables of the fluid state

CERN Document Server

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

Relationship between potency and boiling point of general anesthetics: a thermodynamic consideration.

Science.gov (United States)

Dastmalchi, S; Barzegar-Jalali, M

2000-07-20

The most important group of nonspecific drugs is that of the general anesthetics. These nonspecific compounds vary greatly in structure, from noble gases such as Ar or Xe to complex steroids. Since the development of clinical anesthesia over a century ago, there has been a vast amount of research and speculation concerning the mechanism of action of general anesthetics. Despite these efforts, the exact mechanism remains unknown. Many theories of narcosis do not explain how unconsciousness is produced at a molecular level, but instead relate some physicochemical property of anesthetic agents to their anesthetic potencies. In this paper, we address some of those physicochemical properties, with more emphasis on correlating the anesthetic potency of volatile anesthetics to their boiling points based on thermodynamic principles.

Thermodynamic-state and kinetic-process dependent dual ferromagnetic states in high-Si content FeMn(PSi) alloys

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

Thermodynamics, diffusion and the Kirkendall effect in solids

CERN Document Server

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 hairy black holes in Lovelock gravity

Science.gov (United States)

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

2017-02-01

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

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.

A method for the selection of a functional form for a thermodynamic equation of state using weighted linear least squares stepwise regression

Science.gov (United States)

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.

Mathematical foundations of thermodynamics

CERN Document Server

Giles, R; Stark, M; Ulam, S

2013-01-01

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

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...

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.

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)

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

International Nuclear Information System (INIS)

Chirico, Robert D.; Steele, William V.

2009-01-01

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

Braun-Le Chatelier principle in dissipative thermodynamics

OpenAIRE

Pavelka, Michal; Grmela, Miroslav

2016-01-01

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

Thermodynamics and equations of state of matter from ideal gas to quark-gluon plasma

CERN Document Server

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.

Formulation of thermodynamics for the glassy state : Configurational energy as a modest source of energy

NARCIS (Netherlands)

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

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

The vitreous state thermodynamics, structure, rheology, and crystallization

CERN Document Server

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...

Urea-temperature phase diagrams capture the thermodynamics of denatured state expansion that accompany protein unfolding

Science.gov (United States)

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

Multiple critical points and liquid-liquid equilibria from the van der Waals like equations of state

International Nuclear Information System (INIS)

Artemenko, Sergey; Lozovsky, Taras; Mazur, Victor

2008-01-01

The principal aim of this work is a comprehensive analysis of the phase diagram of water via the van der Waals like equations of state (EoSs) which are considered as superpositions of repulsive and attractive forces. We test more extensively the modified van der Waals EoS (MVDW) proposed by Skibinski et al (2004 Phys. Rev. E 69 061206) and refine this model by introducing instead of the classical van der Waals repulsive term a very accurate hard sphere EoS over the entire stable and metastable regions (Liu 2006 Preprint cond-mat/0605392). It was detected that the simplest form of MVDW EoS displays a complex phase behavior, including three critical points, and identifies four fluid phases (gas, low density liquid (LDL), high density liquid (HDL), and very high density liquid (VHDL)). Moreover the experimentally observed (Mallamace et al 2007 Proc. Natl Acad. Sci. USA 104 18387) anomalous behavior of the density of water in the deeply supercooled region (a density minimum) is reproduced by the MWDW EoS. An improvement of the repulsive part does not change the topological picture of the phase behavior of water in the wide range of thermodynamic variables. The new parameters set for second and third critical points are recognized by thorough analysis of experimental data for the loci of thermodynamic response function extrema

Thermodynamic properties by equation of state and from Ab initio molecular dynamics of liquid potassium under pressure

Science.gov (United States)

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

Science.gov (United States)

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

2009-09-29

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

Thermodynamic-behaviour model for air-cooled screw chillers with a variable set-point condensing temperature

International Nuclear Information System (INIS)

Chan, K.T.; Yu, F.W.

2006-01-01

This paper presents a thermodynamic model to evaluate the coefficient of performance (COP) of an air-cooled screw chiller under various operating conditions. The model accounts for the real process phenomena, including the capacity control of screw compressors and variations in the heat-transfer coefficients of an evaporator and a condenser at part load. It also contains an algorithm to determine how the condenser fans are staged in response to a set-point condensing temperature. The model parameters are identified, based on the performance data of chiller specifications. The chiller model is validated using a wide range of operating data of an air-cooled screw chiller. The difference between the measured and modelled COPs is within ±10% for 86% of the data points. The chiller's COP can increase by up to 115% when the set-point condensing temperature is adjusted, based on any given outdoor temperature. Having identified the variation in the chiller's COP, a suitable strategy is proposed for air-cooled screw chillers to operate at maximum efficiency as much as possible when they have to satisfy a building's cooling-load

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

Elementary statistical thermodynamics a problems approach

CERN Document Server

Smith, Norman O

1982-01-01

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

Unifying mechanical and thermodynamic descriptions across the thioredoxin protein family.

Science.gov (United States)

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

2009-05-15

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

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.

Stochastic thermodynamics of quantum maps with and without equilibrium.

Science.gov (United States)

Barra, Felipe; Lledó, Cristóbal

2017-11-01

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

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

Science.gov (United States)

Abramov, Yuriy A

2015-06-01

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

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

Extrinsic and intrinsic curvatures in thermodynamic geometry

Energy Technology Data Exchange (ETDEWEB)

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

2016-08-10

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

Extrinsic and intrinsic curvatures in thermodynamic geometry

International Nuclear Information System (INIS)

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

2016-01-01

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

Thermodynamics of Bioreactions.

Science.gov (United States)

Held, Christoph; Sadowski, Gabriele

2016-06-07

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

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

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

Science.gov (United States)

Latella, Ivan; Pérez-Madrid, Agustín

2013-10-01

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

Thermodynamics I essentials

CERN Document Server

REA, The Editors of

2012-01-01

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

Communication: Analytic continuation of the virial series through the critical point using parametric approximants

Energy Technology Data Exchange (ETDEWEB)

Barlow, Nathaniel S., E-mail: nsbsma@rit.edu [School of Mathematical Sciences, Rochester Institute of Technology, Rochester, New York 14623 (United States); Schultz, Andrew J., E-mail: ajs42@buffalo.edu; Kofke, David A., E-mail: kofke@buffalo.edu [Department of Chemical and Biological Engineering, University at Buffalo, State University of New York, Buffalo, New York 14260 (United States); Weinstein, Steven J., E-mail: sjweme@rit.edu [Department of Chemical Engineering, Rochester Institute of Technology, Rochester, New York 14623 (United States)

2015-08-21

The mathematical structure imposed by the thermodynamic critical point motivates an approximant that synthesizes two theoretically sound equations of state: the parametric and the virial. The former is constructed to describe the critical region, incorporating all scaling laws; the latter is an expansion about zero density, developed from molecular considerations. The approximant is shown to yield an equation of state capable of accurately describing properties over a large portion of the thermodynamic parameter space, far greater than that covered by each treatment alone.

Communication: Analytic continuation of the virial series through the critical point using parametric approximants.

Science.gov (United States)

Barlow, Nathaniel S; Schultz, Andrew J; Weinstein, Steven J; Kofke, David A

2015-08-21

The mathematical structure imposed by the thermodynamic critical point motivates an approximant that synthesizes two theoretically sound equations of state: the parametric and the virial. The former is constructed to describe the critical region, incorporating all scaling laws; the latter is an expansion about zero density, developed from molecular considerations. The approximant is shown to yield an equation of state capable of accurately describing properties over a large portion of the thermodynamic parameter space, far greater than that covered by each treatment alone.

A solution thermodynamics definition of the fiber saturation point and the derivation of a wood-water phase (state) diagram

Science.gov (United States)

Samuel L. Zelinka; Samuel V. Glass; Joseph E. Jakes; Donald S. Stone

2016-01-01

The fiber saturation point (FSP) is an important concept in wood– moisture relations that differentiates between the states of water in wood and has been discussed in the literature for over 100 years. Despite its importance and extensive study, the exact theoretical definition of the FSP and the operational definition (the correct way to measure the FSP) are still...

Relationship between the partial molar and molar quantity of a thermodynamic state function in a multicomponent mixture – revisited

International Nuclear Information System (INIS)

Näfe, H.

2013-01-01

As far as a multicomponent mixture is concerned, different versions exist in the literature for the relationship between the partial molar and molar quantity of a thermodynamic state function with the most prominent example of the two quantities being the activity coefficient of an arbitrary component and the excess Gibbs free energy of a mixture comprising this component. Since the relationships published so far have to a large degree been derived independently of each other and result from apparently conflicting approaches, they are still considered as separate subjects in the literature. It is demonstrated that despite this curious situation all relationships are equivalent to each other from a mathematical point of view

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

Formation, Physicochemical Characterization, and Thermodynamic Stability of the Amorphous State of Drugs and Excipients.

Science.gov (United States)

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.

Thermodynamic holography

Science.gov (United States)

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

2015-01-01

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

Quantum thermodynamics of general quantum processes.

Science.gov (United States)

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

2015-03-01

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

Design of thermodynamic experiments and analyses of thermodynamic relationships

International Nuclear Information System (INIS)

Oezer Arnas, A.

2009-01-01

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

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

Science.gov (United States)

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

2018-04-01

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

Thermodynamics and economics

International Nuclear Information System (INIS)

Mansson, B.A.

1990-01-01

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

Thermodynamics of hairy black holes in Lovelock gravity

Energy Technology Data Exchange (ETDEWEB)

Hennigar, Robie A. [Department of Physics and Astronomy, University of Waterloo, Waterloo, Ontario, Canada, N2L 3G1 (Canada); Tjoa, Erickson [Division of Physics and Applied Physics, School of Physical and Mathematical Sciences,Nanyang Technological University, Singapore, 637371 (Singapore); Department of Physics and Astronomy, University of Waterloo, Waterloo, Ontario, Canada, N2L 3G1 (Canada); Mann, Robert B. [Department of Physics and Astronomy, University of Waterloo, Waterloo, Ontario, Canada, N2L 3G1 (Canada)

2017-02-14

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

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

CERN Document Server

Tassios, Dimitrios P

1993-01-01

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

Solvation thermodynamics

CERN Document Server

Ben-Naim, Arieh

1987-01-01

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

Stochastic Independence as a Resource for Small-Scale Thermodynamics

Science.gov (United States)

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

Science.gov (United States)

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.

A parametric model for the global thermodynamic behavior of fluids in the critical region

International Nuclear Information System (INIS)

Luettmer-Strathmann, J.; Tang, S.; Sengers, J.V.

1992-01-01

The asymptotic thermodynamic behavior of fluids near the critical point is described by scaling laws with universal scaling functions that can be represented by parametric equations. In this paper, we derive a more general parametric model that incorporates the crossover from singular thermodynamic behavior near the critical point to regular classical thermodynamic behavior far away from the critical point. Using ethane as an example, we show that such a parametric crossover model yields an accurate representation of the thermodynamic properties of fluids in a large region around the critical point

Critical point anomalies include expansion shock waves

Energy Technology Data Exchange (ETDEWEB)

Nannan, N. R., E-mail: ryan.nannan@uvs.edu [Mechanical Engineering Discipline, Anton de Kom University of Suriname, Leysweg 86, PO Box 9212, Paramaribo, Suriname and Process and Energy Department, Delft University of Technology, Leeghwaterstraat 44, 2628 CA Delft (Netherlands); Guardone, A., E-mail: alberto.guardone@polimi.it [Department of Aerospace Science and Technology, Politecnico di Milano, Via La Masa 34, 20156 Milano (Italy); Colonna, P., E-mail: p.colonna@tudelft.nl [Propulsion and Power, Delft University of Technology, Kluyverweg 1, 2629 HS Delft (Netherlands)

2014-02-15

From first-principle fluid dynamics, complemented by a rigorous state equation accounting for critical anomalies, we discovered that expansion shock waves may occur in the vicinity of the liquid-vapor critical point in the two-phase region. Due to universality of near-critical thermodynamics, the result is valid for any common pure fluid in which molecular interactions are only short-range, namely, for so-called 3-dimensional Ising-like systems, and under the assumption of thermodynamic equilibrium. In addition to rarefaction shock waves, diverse non-classical effects are admissible, including composite compressive shock-fan-shock waves, due to the change of sign of the fundamental derivative of gasdynamics.

Thermodynamic properties of water in the critical region

International Nuclear Information System (INIS)

Veloso, Marcelo A.

2009-01-01

The supercritical-water-cooled reactor (SCWR) is one of the nuclear reactor technologies selected for research and development under the Generation IV program. SCWRs offer the potential for high thermal efficiencies and considerable plant simplifications for improved economics. One of the main characteristics of critical water is the strong variations of its thermal-physical properties in the vicinity of the critical point. These large variations may result in an unusual heat transfer behavior. The 1967 IFC Formulation for Industrial Use, which until 1998 formed the basis of steam tables used in many areas of steam power industry throughout the world since the late 1960's, has been now replaced with the IAPWS IF-97 Formulation for the Thermodynamic Properties of Water and Steam for Industrial Use, adopted by the International Association for the Properties of Water and Steam (IAPWS) in 1997. An IAPWS release points out that this new formulation has some unsatisfactory features in the immediate vicinity of the critical point. In order to investigate this singular aspect, which is crucial to better understand the heat transfer mechanism in a SCWR system, predictions by the IAPWS-IF97 formulation will be compared with thermodynamic properties values predicted by an alternative crossover equation of state as well as with experimental data found in literature. (author)

VALIDITY OF EXCESS ENTROPY PRODUCTION CRITERION OF THERMODYNAMIC STABILITY FOR NONEQUILIBRIUM STEADY STATES

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

NARCIS (Netherlands)

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

Thermodynamics of bread baking: A two-state model

Science.gov (United States)

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.

Ab-initio modelling of thermodynamics and kinetics of point defects in indium oxide

International Nuclear Information System (INIS)

Agoston, Peter; Klein, Andreas; Albe, Karsten; Erhart, Paul

2008-01-01

The electrical and optical properties of indium oxide films strongly vary with the processing parameters. Especially the oxygen partial pressure and temperature determine properties like electrical conductivity, composition and transparency. Since this material owes its remarkable properties like the intrinsic n-type conductivity to its defect chemistry, it is important to understand both, the equilibrium defect thermodynamics and kinetics of the intrinsic point defects. In this contribution we present a defect model based on DFT total energy calculations using the GGA+U method. Further, the nudged elastic band method is employed in order to obtain a set of migration barriers for each defect species. Due to the complicated crystal structure of indium oxide a Kinetic Monte-Carlo algorithm was implemented, which allows to determine diffusion coefficients. The bulk tracer diffusion constant is predicted as a function of oxygen partial pressure, Fermi level and temperature for the pure material

Stochastic thermodynamics

Science.gov (United States)

Eichhorn, Ralf; Aurell, Erik

2014-04-01

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

Strong Coupling Corrections in Quantum Thermodynamics

Science.gov (United States)

Perarnau-Llobet, M.; Wilming, H.; Riera, A.; Gallego, R.; Eisert, J.

2018-03-01

Quantum systems strongly coupled to many-body systems equilibrate to the reduced state of a global thermal state, deviating from the local thermal state of the system as it occurs in the weak-coupling limit. Taking this insight as a starting point, we study the thermodynamics of systems strongly coupled to thermal baths. First, we provide strong-coupling corrections to the second law applicable to general systems in three of its different readings: As a statement of maximal extractable work, on heat dissipation, and bound to the Carnot efficiency. These corrections become relevant for small quantum systems and vanish in first order in the interaction strength. We then move to the question of power of heat engines, obtaining a bound on the power enhancement due to strong coupling. Our results are exemplified on the paradigmatic non-Markovian quantum Brownian motion.

Systematic thermodynamic properties of actinide metal-oxygen systems at high temperatures: Emphasis on lower valence states

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.

Thermodynamics

International Nuclear Information System (INIS)

Zanchini, E.

1988-01-01

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

Black hole thermodynamics under the microscope

Science.gov (United States)

Falls, Kevin; Litim, Daniel F.

2014-04-01

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

On thermodynamic limits of entropy densities

NARCIS (Netherlands)

Moriya, H; Van Enter, A

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

Technical evaluation of thermodynamics processes; Avaliacao tecnica dos processos termodinamicos

Energy Technology Data Exchange (ETDEWEB)

Petracco, Fulvio Celso

1986-05-01

An evaluation of thermodynamic processes, energy losses the origin of energy losses on thermodynamic process, where are the points or sources of those losses and variation of process when compared in relation of thermodynamic performance are discussed. The concept of energy losses and its origin, energy and work capacity, performance rates and examples of thermodynamic efficiency are also debated 3 figs.

A Concise Equation of State for Aqueous Solutions of Electrolytes Incorporating Thermodynamic Laws and Entropy

Directory of Open Access Journals (Sweden)

Raji Heyrovská

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.

Absolute determination of the gelling point of gelatin under quasi-thermodynamic equilibrium.

Science.gov (United States)

Bellini, Franco; Alberini, Ivana; Ferreyra, María G; Rintoul, Ignacio

2015-05-01

Thermodynamic studies on phase transformation of biopolymers in solution are useful to understand their nature and to evaluate their technological potentials. Thermodynamic studies should be conducted avoiding time-related phenomena. This condition is not easily achieved in hydrophilic biopolymers. In this contribution, the simultaneous effects of pH, salt concentration, and cooling rate (Cr) on the folding from random coil to triple helical collagen-like structures of gelatin were systematically studied. The phase transformation temperature at the absolute invariant condition of Cr = 0 °C/min (T(T)Cr=0) ) is introduced as a conceptual parameter to study phase transformations in biopolymers under quasi-thermodynamic equilibrium and avoiding interferences coming from time-related phenomena. Experimental phase diagrams obtained at different Cr are presented. The T(T)(Cr=0) compared with pH and TT(Cr=0) compared with [NaCl] diagram allowed to explore the transformation process at Cr = 0 °C/min. The results were explained by electrostatic interactions between the biopolymers and its solvation milieu. © 2015 Institute of Food Technologists®

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)

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

Teaching Differentials in Thermodynamics Using Spatial Visualization

Science.gov (United States)

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…

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.)

Thermodynamic consistency test procedure using orthogonal collocation and the Peng-Robinson equation of state

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

Is the thermodynamic behavior of the noble fluids consistent with the principle of corresponding states?

NARCIS (Netherlands)

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

Calculation of melting points of oxides

International Nuclear Information System (INIS)

Bobkova, O.S.; Voskobojnikov, V.G.; Kozin, A.I.

1975-01-01

The correlation between the melting point and thermodynamic parameters characterizing the strength of oxides and compounds is given. Such thermodynamic paramters include the energy and antropy of atomization

State Wildlife Management Area Public Facilities - points

Data.gov (United States)

Minnesota Department of Natural Resources — This point theme contains facilities and features for WMAs that are best represented as points. WMAs are part of the Minnesota state recreation system created to...

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.

Limits of predictions in thermodynamic systems: a review

Science.gov (United States)

Marsland, Robert, III; England, Jeremy

2018-01-01

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

The second laws of quantum thermodynamics.

Science.gov (United States)

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.

Common intersection points in dense fluids via equations of state

International Nuclear Information System (INIS)

Parsafar, G. A.; Noorian, R.

2001-01-01

Some new of state which are derived for dense fluids in recent years, namely the linear isotherm regularity, the dense system equation of state, Ihm-Song-Mason equation of state, and a newly derived semi-empirical equation of state have used to investigate the common intersection point of isobaric expansivity (α p ) in dense fluids. We have shown that the accuracy of these equations of state in predicting such a common intersection point is reduced from the new semi-imperial equation of state, dense system equation of state, linear isotherm regularity, to Ihm-Song-Mason equation of state. respectively. Form physical point of view, the van der Waals equation of state is used to investigate such an intersection point. It is shown that the van der Waals repulsion forces and temperature dependency of the effective molecular diameter are important for existence of this common point. Finally, we have shown that the common intersection points of the isotherms of thermal pressure coefficient, the isotherms of heat capacity at constant volume, and the iso chores of internal pressure for a fluid are related to each other. Also, the common intersection points of the reduced bulk modulus and 1/(Tα p ) for isotherms of a fluid both appear at the same density

Relating Deformation and Thermodynamics: An Opportunity for Rethinking Basic Concepts of Continuum Mechanics

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.

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

Directory of Open Access Journals (Sweden)

B. Hussain

2018-02-01

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

Hadronic thermodynamics: Is there a limiting temperature

International Nuclear Information System (INIS)

Olive, K.E.

1984-01-01

The hadron mass spectrum continues to be a topic of theoretical interest and will remain so until there can be some experimental verification in future heavy ion collisions. There are a variety of models such as the bootstrap, dual, bag etc., which all predict an exponentially rising density of states approx.= exp(m/T 0 ), T 0 approx.=160 MeV. Once one assumes an exponential mass spectrum, one generally finds singularities in thermodynamic quantities and hence possibly a limiting temperature at T 0 . In this talk, I point out some possible ways out of this dilemma. (orig./HSI)

The use of an MHV-2 equation of state for modeling the thermodynamic properties of refrigerant mixtures

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

Thermodynamics of complexity

DEFF Research Database (Denmark)

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

1998-01-01

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

Thermodynamically Based Equation of State for Shock Wave Studies : Application to the Design of Experiments on Tin

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

Thermodynamic Analysis of a Supercritical Mercury Power Cycle

Energy Technology Data Exchange (ETDEWEB)

Roberts, Jr, A S

1969-04-15

An heat engine is considered which employs supercritical mercury as the working fluid and a magnetohydrodynamic (MHD) generator for thermal to electrical energy conversion. The main thrust of the paper is power cycle thermodynamics, where constraints are imposed by utilizing a MHD generator operating between supercritical, electrically conducting states of the working fluid; and, pump work is accomplished with liquid mercury. The temperature range is approximately 300 to 2200 K and system pressure is > 1,500 atm. Equilibrium and transport properties are carefully considered since these are known to vary radically in the vicinity of the critical point, which is found near the supercritical states of interest. A maximum gross plant efficiency is 20% with a regenerator effectiveness of 90% and greater, a cycle pressure ratio of two, and with highly efficient pump and generator. Certain specified cycle irreversibilities and others such as heat losses and heat exchanger pressure drops, which are not accounted for explicitly, reduce the gross plant efficiency to a few per cent. Experimental efforts aimed at practical application of the power cycle are discouraged by the marginal thermodynamic performance predicted by this study, unless such applications are insensitive to gross cycle efficiency.

Thermodynamic Analysis of a Supercritical Mercury Power Cycle

International Nuclear Information System (INIS)

Roberts, A.S. Jr.

1969-04-01

An heat engine is considered which employs supercritical mercury as the working fluid and a magnetohydrodynamic (MHD) generator for thermal to electrical energy conversion. The main thrust of the paper is power cycle thermodynamics, where constraints are imposed by utilizing a MHD generator operating between supercritical, electrically conducting states of the working fluid; and, pump work is accomplished with liquid mercury. The temperature range is approximately 300 to 2200 K and system pressure is > 1,500 atm. Equilibrium and transport properties are carefully considered since these are known to vary radically in the vicinity of the critical point, which is found near the supercritical states of interest. A maximum gross plant efficiency is 20% with a regenerator effectiveness of 90% and greater, a cycle pressure ratio of two, and with highly efficient pump and generator. Certain specified cycle irreversibilities and others such as heat losses and heat exchanger pressure drops, which are not accounted for explicitly, reduce the gross plant efficiency to a few per cent. Experimental efforts aimed at practical application of the power cycle are discouraged by the marginal thermodynamic performance predicted by this study, unless such applications are insensitive to gross cycle efficiency

Thermodynamic properties of titanates, zirconates and hafnates of alkaline earth metals

Energy Technology Data Exchange (ETDEWEB)

1978-02-01

The problems are considered arising in critical analysis and choosing recommended values of thermodynamic constants of the series of the most important perovskites-ferroelectrics-titanates, zirconates, and hafnates of alkaline-earth metals finding application in modern radioelectronics. Recommended values of standard thermodynamic values are given: heat capacity Csub(p,298) , enthalpy change H/sub 298/-H/sub 0/, entropy S/sub 298/, heat formation ..delta..Hsub(f,298 ), free energy formation ..delta..Gsub(f,298) , temperatures and heats of phase transitions with indication of errors for the adopted values. The effect of impurities on thermal constants of phase transitions is discussed. The relationships between thermodynamic characteristics of perovskites and crystal structure as well as the effect of orthorhombic distortions of ideal perovskite lattice on entropy of the compounds have been considered. Along with thermodynamic methods of investigation, a great attention is given to other physical methods which have been used for finding temperature regions of phase transitions, Curie points, and temperatures of transition from ferroelectric to paraelectric state. The importance of physical methods is emphasized in those cases when phase transitions are accompanied by small energy changes and are not fixed in measuring heat capacity.

Applied thermodynamics of the real gas with respect to the thermodynamic zeros of the entropy and internal energy

International Nuclear Information System (INIS)

Elsner, Albrecht

2012-01-01

Gibbs's work on the thermodynamic properties of substances presented a complete thermodynamic theory. The formulations of the entropy S and internal energy U as extensive quantities allow the zeros of the real gas to be given: S=0 at absolute zero (Nernst, Planck) and U=0 at the critical point. Consequently, every thermodynamic function is unique and absolutely specified. Interdependences among quantities such as temperature, vapor pressure, chemical potential, volume, entropy, internal energy, and heat capacity are likewise unique and numerically well defined. This is shown for the saturated fluid, water, in the region between absolute zero and the critical point. As a consequence of the calculation of the chemical potential, it follows that the free particle flow in an inhomogeneous system is essentially governed by the difference in chemical potential, and not through the difference in pressure, this effect being of importance for meteorology and oceanography.

Entropy production and thermodynamics of nonequilibrium stationary states: a point of view.

Science.gov (United States)

Gallavotti, Giovanni

2004-09-01

Entropy might be a not well defined concept if the system can undergo transformations involving stationary nonequilibria. It might be analogous to the heat content (once called "caloric") in transformations that are not isochoric (i.e., which involve mechanical work): it could be just a quantity that can be transferred or created, like heat in equilibrium. The text first reviews the philosophy behind a recently proposed definition of entropy production in nonequilibrium stationary systems. A detailed technical attempt at defining the entropy of a stationary states via their variational properties follows: the unsatisfactory aspects of the results add arguments in favor of the nonexistence of a function of state to be identified with entropy; at the same time new aspects and properties of the phase space contraction emerge. Copyright 2004 American Institute of Physics

Investigation on the pinch point position in heat exchangers

Science.gov (United States)

Pan, Lisheng; Shi, Weixiu

2016-06-01

The pinch point is important for analyzing heat transfer in thermodynamic cycles. With the aim to reveal the importance of determining the accurate pinch point, the research on the pinch point position is carried out by theoretical method. The results show that the pinch point position depends on the parameters of the heat transfer fluids and the major fluid properties. In most cases, the pinch point locates at the bubble point for the evaporator and the dew point for the condenser. However, the pinch point shifts to the supercooled liquid state in the near critical conditions for the evaporator. Similarly, it shifts to the superheated vapor state with the condensing temperature approaching the critical temperature for the condenser. It even can shift to the working fluid entrance of the evaporator or the supercritical heater when the heat source fluid temperature is very high compared with the absorbing heat temperature. A wrong position for the pinch point may generate serious mistake. In brief, the pinch point should be founded by the iterative method in all conditions rather than taking for granted.

Thermodynamical stability of the Bardeen black hole

Energy Technology Data Exchange (ETDEWEB)

Bretón, Nora [Dpto. de Física, Centro de Investigación y de Estudios Avanzados del I. P. N., Apdo. 14-740, D.F. (Mexico); Perez Bergliaffa, Santiago E. [Dpto. de Física, U. Estado do Rio de Janeiro (Brazil)

2014-01-14

We analyze the stability of the regular magnetic Bardeen black hole both thermodynamically and dynamically. For the thermodynamical analysis we consider a microcanonical ensemble and apply the turning point method. This method allows to decide a change in stability (or instability) of a system, requiring only the assumption of smoothness of the area functional. The dynamical stability is asserted using criteria based on the signs of the Lagrangian and its derivatives. It turns out from our analysis that the Bardeen black hole is both thermodynamically and dynamically stable.

Thermodynamic Temperatures of High-Temperature Fixed Points: Uncertainties Due to Temperature Drop and Emissivity

Science.gov (United States)

Castro, P.; Machin, G.; Bloembergen, P.; Lowe, D.; Whittam, A.

2014-07-01

This study forms part of the European Metrology Research Programme project implementing the New Kelvin to assign thermodynamic temperatures to a selected set of high-temperature fixed points (HTFPs), Cu, Co-C, Pt-C, and Re-C. A realistic thermal model of these HTFPs, developed in finite volume software ANSYS FLUENT, was constructed to quantify the uncertainty associated with the temperature drop across the back wall of the cell. In addition, the widely applied software package, STEEP3 was used to investigate the influence of cell emissivity. The temperature drop, , relates to the temperature difference due to the net loss of heat from the aperture of the cavity between the back wall of the cavity, viewed by the thermometer, defining the radiance temperature, and the solid-liquid interface of the alloy, defining the transition temperature of the HTFP. The actual value of can be used either as a correction (with associated uncertainty) to thermodynamic temperature evaluations of HTFPs, or as an uncertainty contribution to the overall estimated uncertainty. In addition, the effect of a range of furnace temperature profiles on the temperature drop was calculated and found to be negligible for Cu, Co-C, and Pt-C and small only for Re-C. The effective isothermal emissivity is calculated over the wavelength range from 450 nm to 850 nm for different assumed values of surface emissivity. Even when furnace temperature profiles are taken into account, the estimated emissivities change only slightly from the effective isothermal emissivity of the bare cell. These emissivity calculations are used to estimate the uncertainty in the temperature assignment due to the uncertainty in the emissivity of the blackbody.

Chemical Thermodynamics and Information Theory with Applications

CERN Document Server

Graham, Daniel J

2011-01-01

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

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)

Thermodynamic study of the native and phosphorylated regulatory domain of the CFTR

Energy Technology Data Exchange (ETDEWEB)

Marasini, Carlotta, E-mail: marasini@ge.ibf.cnr.it [Istituto di Biofisica, Consiglio Nazionale delle Ricerche, Via De Marini 6, 16149 Genova (Italy); Galeno, Lauretta; Moran, Oscar [Istituto di Biofisica, Consiglio Nazionale delle Ricerche, Via De Marini 6, 16149 Genova (Italy)

2012-07-06

Highlights: Black-Right-Pointing-Pointer CFTR mutations produce cystic fibrosis. Black-Right-Pointing-Pointer Chloride transport depends on the regulatory domain phosphorylation. Black-Right-Pointing-Pointer Regulatory domain is intrinsically disordered. Black-Right-Pointing-Pointer Secondary structure and protein stability change upon phosphorylation. -- Abstract: The regulatory domain (RD) of the cystic fibrosis transmembrane conductance regulator (CFTR), the defective protein in cystic fibrosis, is the region of the channel that regulates the CFTR activity with multiple phosphorylation sites. This domain is an intrinsically disordered protein, characterized by lack of stable or unique tertiary structure. The disordered character of a protein is directly correlated with its function. The flexibility of RD may be important for its regulatory role: the continuous conformational change may be necessary for the progressive phosphorylation, and thus activation, of the channel. However, the lack of a defined and stable structure results in a considerable limitation when trying to in build a unique molecular model for the RD. Moreover, several evidences indicate significant structural differences between the native, non-phosphorylated state, and the multiple phosphorylated state of the protein. The aim of our work is to provide data to describe the conformations and the thermodynamic properties in these two functional states of RD. We have done the circular dichroism (CD) spectra in samples with a different degree of phosphorylation, from the non-phosphorylated state to a bona fide completely phosphorylated state. Analysis of CD spectra showed that the random coil and {beta}-sheets secondary structure decreased with the polypeptide phosphorylation, at expenses of an increase of {alpha}-helix. This observation lead to interpret phosphorylation as a mechanism favoring a more structured state. We also studied the thermal denaturation curves of the protein in the two

Concise chemical thermodynamics

CERN Document Server

Peters, APH

2010-01-01

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

Modern thermodynamics

CERN Document Server

Ben-Naim, Arieh

2017-01-01

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

Covariant Thermodynamics of Quantum Systems: Passivity, Semipassivity, and the Unruh Effect

NARCIS (Netherlands)

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.

Science.gov (United States)

Sivak, David A; Crooks, Gavin E

2012-05-11

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

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

Science.gov (United States)

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

2017-04-01

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

Singularity-free interpretation of the thermodynamics of supercooled water

International Nuclear Information System (INIS)

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

1996-01-01

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

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.

Thermodynamically consistent simulation of nonisothermal diffuse-interface two-phase flow with Peng-Robinson equation of state

KAUST Repository

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.

Thermodynamically consistent simulation of nonisothermal diffuse-interface two-phase flow with Peng-Robinson equation of state

KAUST Repository

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.

Non-equilibrium thermodynamics, maximum entropy production and Earth-system evolution.

Science.gov (United States)

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

Science.gov (United States)

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

2017-01-01

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

Metallic magnets without inversion symmetry and antiferromagnetic quantum critical points

Energy Technology Data Exchange (ETDEWEB)

Fischer, I.A.

2006-07-01

This thesis focusses on two classes of systems that exhibit non-Fermi liquid behaviour in experiments: we investigated aspects of chiral ferromagnets and of antiferromagnetic metals close to a quantum critical point. In chiral ferromagnets, the absence of inversion symmetry makes spin-orbit coupling possible, which leads to a helical modulation of the ferromagnetically ordered state. We studied the motion of electrons in the magnetically ordered state of a metal without inversion symmetry by calculating their generic band-structure. We found that spin-orbit coupling, although weak, has a profound effect on the shape of the Fermi surface: On a large portion of the Fermi surface the electron motion parallel to the helix practically stops. Signatures of this effect can be expected to show up in measurements of the anomalous Hall effect. Recent neutron scattering experiments uncovered the existence of a peculiar kind of partial order in a region of the phase diagram adjacent to the ordered state of the chiral ferromagnet MnSi. Starting from the premise that this partially ordered state is a thermodynamically distinct phase, we investigated an extended Ginzburg-Landau theory for chiral ferromagnets. In a certain parameter regime of the Ginzburg-Landau theory we identified crystalline phases that are reminiscent of the so-called blue phases in liquid crystals. Many antiferromagnetic heavy-fermion systems can be tuned into a regime where they exhibit non-Fermi liquid exponents in the temperature dependence of thermodynamic quantities such as the specific heat capacity; this behaviour could be due to a quantum critical point. If the quantum critical behaviour is field-induced, the external field does not only suppress antiferromagnetism but also induces spin precession and thereby influences the dynamics of the order parameter. We investigated the quantum critical behavior of clean antiferromagnetic metals subject to a static, spatially uniform external magnetic field. We

Thermodynamics of the topological Kondo model

Directory of Open Access Journals (Sweden)

Francesco Buccheri

2015-07-01

Full Text Available Using the thermodynamic Bethe ansatz, we investigate the topological Kondo model, which describes a set of one-dimensional external wires, pertinently coupled to a central region hosting a set of Majorana bound states. After a short review of the Bethe ansatz solution, we study the system at finite temperature and derive its free energy for arbitrary (even and odd number of external wires. We then analyse the ground state energy as a function of the number of external wires and of their couplings to the Majorana bound states. Then, we compute, both for small and large temperatures, the entropy of the Majorana degrees of freedom localized within the central region and connected to the external wires. Our exact computation of the impurity entropy provides evidence of the importance of fermion parity symmetry in the realization of the topological Kondo model. Finally, we also obtain the low-temperature behaviour of the specific heat of the Majorana bound states, which provides a signature of the non-Fermi-liquid nature of the strongly coupled fixed point.

Thermodynamics of the topological Kondo model

Energy Technology Data Exchange (ETDEWEB)

Buccheri, Francesco, E-mail: buccheri@iip.ufrn.br [International Institute of Physics, Universidade Federal do Rio Grande do Norte, 59078-400 Natal, RN (Brazil); Babujian, Hrachya [International Institute of Physics, Universidade Federal do Rio Grande do Norte, 59078-400 Natal, RN (Brazil); Yerevan Physics Institute, Alikhanian Brothers 2, Yerevan, 375036 (Armenia); Korepin, Vladimir E. [International Institute of Physics, Universidade Federal do Rio Grande do Norte, 59078-400 Natal, RN (Brazil); C. N. Yang Institute for Theoretical Physics, Stony Brook University, NY 11794 (United States); Sodano, Pasquale [International Institute of Physics, Universidade Federal do Rio Grande do Norte, 59078-400 Natal, RN (Brazil); Departemento de Fisíca Teorica e Experimental, Universidade Federal do Rio Grande do Norte, 59072-970 Natal, RN (Brazil); Trombettoni, Andrea [CNR-IOM DEMOCRITOS Simulation Center, Via Bonomea 265, I-34136 Trieste (Italy); SISSA and INFN, Sezione di Trieste, Via Bonomea 265, I-34136 Trieste (Italy)

2015-07-15

Using the thermodynamic Bethe ansatz, we investigate the topological Kondo model, which describes a set of one-dimensional external wires, pertinently coupled to a central region hosting a set of Majorana bound states. After a short review of the Bethe ansatz solution, we study the system at finite temperature and derive its free energy for arbitrary (even and odd) number of external wires. We then analyse the ground state energy as a function of the number of external wires and of their couplings to the Majorana bound states. Then, we compute, both for small and large temperatures, the entropy of the Majorana degrees of freedom localized within the central region and connected to the external wires. Our exact computation of the impurity entropy provides evidence of the importance of fermion parity symmetry in the realization of the topological Kondo model. Finally, we also obtain the low-temperature behaviour of the specific heat of the Majorana bound states, which provides a signature of the non-Fermi-liquid nature of the strongly coupled fixed point.

Exact thermodynamic principles for dynamic order existence and evolution in chaos

International Nuclear Information System (INIS)

Mahulikar, Shripad P.; Herwig, Heinz

2009-01-01

The negentropy proposed first by Schroedinger is re-examined, and its conceptual and mathematical definitions are introduced. This re-definition of negentropy integrates Schroedinger's intention of its introduction, and the subsequent diverse notions in literature. This negentropy is further corroborated by its ability to state the two exact thermodynamic principles: negentropy principle for dynamic order existence and principle of maximum negentropy production (PMNEP) for dynamic order evolution. These principles are the counterparts of the existing entropy principle and the law of maximum entropy production, respectively. The PMNEP encompasses the basic concepts in the evolution postulates by Darwin and de Vries. Perspectives of dynamic order evolution in literature point to the validity of PMNEP as the law of evolution. These two additional principles now enable unified explanation of order creation, existence, evolution, and destruction; using thermodynamics.

Nuclear thermodynamics below particle threshold

International Nuclear Information System (INIS)

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

2005-01-01

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

Phase equilibria and thermodynamic functions for Ag-Hg and Cu-Hg binary systems

Energy Technology Data Exchange (ETDEWEB)

Liu, Yajun, E-mail: yajunliu@gatech.edu [School of Materials and Energy, Guangdong University of Technology, Guangzhou, Guangdong 510006 (China); Wang, Guan [School of Electromechanical Engineering, Guangdong University of Technology, Guangzhou, Guangdong 510006 (China); Wang, Jiang [School of Materials Science and Engineering, Guilin University of Electronic Technology, Guilin, Guangxi 541004 (China); Chen, Yang [Mining, Metallurgy and Materials Research Department, General Research Institute for Nonferrous Metals, Beijing 100088 (China); Long, Zhaohui [School of Mechanical Engineering, Xiangtan University, Xiangtan, Hunan 411105 (China)

2012-11-10

Highlights: Black-Right-Pointing-Pointer The thermodynamic properties of Ag-Hg and Cu-Hg are explored in order to facilitate dental materials design. Black-Right-Pointing-Pointer A self-consistent set of thermodynamic parameters is obtained. Black-Right-Pointing-Pointer The experimental information can be well reproduced by the optimized thermodynamic data. - Abstract: In order to facilitate the computational design of new amalgams for novel dental alloys, the phase equilibria, phase diagrams and thermodynamic functions for Ag-Hg and Cu-Hg binary systems are explored in this work, based on the CALPHAD framework and experimental characterizations. The Gibbs free energies of the solution phases as well as the stoichiometric phases are calculated, with the aid of enthalpies of mixing, activities, enthalpies of formation, and phase equilibrium data. The thermodynamic descriptions provided in this work enable the stabilities of each phase at various temperatures and compositions to be well described, which contribute to the establishment of a general database to design novel metallic dental materials.

Thermodynamic properties of cryogenic fluids

CERN Document Server

Leachman, Jacob; Lemmon, Eric; Penoncello, Steven

2017-01-01

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

Denatured states of yeast cytochrome c induced by heat and guanidinium chloride are structurally and thermodynamically different.

Science.gov (United States)

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.

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

Steepest-entropy-ascent quantum thermodynamic modeling of the relaxation process of isolated chemically reactive systems using density of states and the concept of hypoequilibrium state

Science.gov (United States)

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?

Science.gov (United States)

Atanasov, Atanas Todorov

2017-11-01

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

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

Science.gov (United States)

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

Some remarks about the thermodynamics of discrete finite Markov chains

Energy Technology Data Exchange (ETDEWEB)

Siboni, S. [Trento Univ. (Italy). Facolta` di Ingegneria, Dip. di Ingegneria dei Materiali

1998-08-01

The Author propose a simple way to define a Hamiltonian for aperiodic Markov chains and to apply these chains in a thermodynamical context. The basic thermodynamic functions are correspondingly calculated. A quite intriguing and nontrivial application to stochastic automata is also pointed out.

Using Rubber-Elastic Material-Ideal Gas Analogies To Teach Introductory Thermodynamics. Part I: Equations of State.

Science.gov (United States)

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.)…

From thermodynamics to the solutions in gravity theory

International Nuclear Information System (INIS)

Zhang, Hongsheng; Li, Xin-Zhou

2014-01-01

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

From thermodynamics to the solutions in gravity theory

Directory of Open Access Journals (Sweden)

Hongsheng Zhang

2014-10-01

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

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

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

Coherence and measurement in quantum thermodynamics.

Science.gov (United States)

Kammerlander, P; Anders, J

2016-02-26

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

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

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.

Entropy and energy quantization: Planck thermodynamic calculation

International Nuclear Information System (INIS)

Mota e Albuquerque, Ivone Freire da.

1988-01-01

This dissertation analyses the origins and development of the concept of entropy and its meaning of the second Law of thermodynamics, as well as the thermodynamics derivation of the energy quantization. The probabilistic interpretation of that law and its implication in physics theory are evidenciated. Based on Clausius work (which follows Carnot's work), we analyse and expose in a original way the entropy concept. Research upon Boltzmann's work and his probabilistic interpretation of the second Law of thermodynamics is made. The discuss between the atomistic and the energeticist points of view, which were actual at that time are also commented. (author). 38 refs., 3 figs

Mechanics and thermodynamics

CERN Document Server

Demtröder, Wolfgang

2017-01-01

This introduction to classical mechanics and thermodynamics provides an accessible and clear treatment of the fundamentals. Starting with particle mechanics and an early introduction to special relativity this textbooks enables the reader to understand the basics in mechanics. The text is written from the experimental physics point of view, giving numerous real life examples and applications of classical mechanics in technology. This highly motivating presentation deepens the knowledge in a very accessible way. The second part of the text gives a concise introduction to rotational motion, an expansion to rigid bodies, fluids and gases. Finally, an extensive chapter on thermodynamics and a short introduction to nonlinear dynamics with some instructive examples intensify the knowledge of more advanced topics. Numerous problems with detailed solutions are perfect for self study.

Understanding the Thermodynamics of Biological Order

Science.gov (United States)

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…

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

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

Friction Force: From Mechanics to Thermodynamics

Science.gov (United States)

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…

Thermodynamic geometry of black holes in f(R) gravity

International Nuclear Information System (INIS)

Soroushfar, Saheb; Saffari, Reza; Kamvar, Negin

2016-01-01

In this paper, we consider three types (static, static charged, and rotating charged) of black holes in f(R) gravity. We study the thermodynamical behavior, stability conditions, and phase transition of these black holes. It is shown that the number and type of phase transition points are related to different parameters, which shows the dependency of the stability conditions to these parameters. Also, we extend our study to different thermodynamic geometry methods (Ruppeiner, Weinhold, and GTD). Next, we investigate the compatibility of curvature scalar of geothermodynamic methods with phase transition points of the above black holes. In addition, we point out the effect of different values of the spacetime parameters on the stability conditions of mentioned black holes. (orig.)

Optimization of thermal systems based on finite-time thermodynamics and thermoeconomics

Energy Technology Data Exchange (ETDEWEB)

Durmayaz, A. [Istanbul Technical University (Turkey). Department of Mechanical Engineering; Sogut, O.S. [Istanbul Technical University, Maslak (Turkey). Department of Naval Architecture and Ocean Engineering; Sahin, B. [Yildiz Technical University, Besiktas, Istanbul (Turkey). Department of Naval Architecture; Yavuz, H. [Istanbul Technical University, Maslak (Turkey). Institute of Energy

2004-07-01

The irreversibilities originating from finite-time and finite-size constraints are important in the real thermal system optimization. Since classical thermodynamic analysis based on thermodynamic equilibrium do not consider these constraints directly, it is necessary to consider the energy transfer between the system and its surroundings in the rate form. Finite-time thermodynamics provides a fundamental starting point for the optimization of real thermal systems including the fundamental concepts of heat transfer and fluid mechanics to classical thermodynamics. In this study, optimization studies of thermal systems, that consider various objective functions, based on finite-time thermodynamics and thermoeconomics are reviewed. (author)

A new approach toward geometrical concept of black hole thermodynamics

Energy Technology Data Exchange (ETDEWEB)

Hendi, Seyed Hossein [Shiraz University, Physics Department and Biruni Observatory, College of Sciences, Shiraz (Iran, Islamic Republic of); Research Institute for Astronomy and Astrophysics of Maragha (RIAAM), Maragha (Iran, Islamic Republic of); Panahiyan, Shahram; Panah, Behzad Eslam; Momennia, Mehrab [Shiraz University, Physics Department and Biruni Observatory, College of Sciences, Shiraz (Iran, Islamic Republic of)

2015-10-15

Motivated by the energy representation of Riemannian metric, in this paper we study different approaches toward the geometrical concept of black hole thermodynamics. We investigate thermodynamical Ricci scalar of Weinhold, Ruppeiner and Quevedo metrics and show that their number and location of divergences do not coincide with phase transition points arisen from heat capacity. Next, we introduce a new metric to solve these problems. We show that the denominator of the Ricci scalar of the new metric contains terms which coincide with different types of phase transitions. We elaborate the effectiveness of the new metric and shortcomings of the previous metrics with some examples. Furthermore, we find a characteristic behavior of the new thermodynamical Ricci scalar which enables one to distinguish two types of phase transitions. In addition, we generalize the new metric for the cases of more than two extensive parameters and show that in these cases the divergencies of thermodynamical Ricci scalar coincide with phase transition points of the heat capacity. (orig.)

A new approach toward geometrical concept of black hole thermodynamics

International Nuclear Information System (INIS)

Hendi, Seyed Hossein; Panahiyan, Shahram; Panah, Behzad Eslam; Momennia, Mehrab

2015-01-01

Motivated by the energy representation of Riemannian metric, in this paper we study different approaches toward the geometrical concept of black hole thermodynamics. We investigate thermodynamical Ricci scalar of Weinhold, Ruppeiner and Quevedo metrics and show that their number and location of divergences do not coincide with phase transition points arisen from heat capacity. Next, we introduce a new metric to solve these problems. We show that the denominator of the Ricci scalar of the new metric contains terms which coincide with different types of phase transitions. We elaborate the effectiveness of the new metric and shortcomings of the previous metrics with some examples. Furthermore, we find a characteristic behavior of the new thermodynamical Ricci scalar which enables one to distinguish two types of phase transitions. In addition, we generalize the new metric for the cases of more than two extensive parameters and show that in these cases the divergencies of thermodynamical Ricci scalar coincide with phase transition points of the heat capacity. (orig.)

On black hole thermodynamics with a momentum relaxation

International Nuclear Information System (INIS)

Park, Chanyong

2016-01-01

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

Fragile Thermodynamic Order

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)

Improved Estimates of Thermodynamic Parameters

Science.gov (United States)

Lawson, D. D.

1982-01-01

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

Quantum corrections to thermodynamics of quasitopological black holes

Directory of Open Access Journals (Sweden)

Sudhaker Upadhyay

2017-12-01

Full Text Available Based on the modification to area-law due to thermal fluctuation at small horizon radius, we investigate the thermodynamics of charged quasitopological and charged rotating quasitopological black holes. In particular, we derive the leading-order corrections to the Gibbs free energy, charge and total mass densities. In order to analyze the behavior of the thermal fluctuations on the thermodynamics of small black holes, we draw a comparative analysis between the first-order corrected and original thermodynamical quantities. We also examine the stability and bound points of such black holes under effect of leading-order corrections.

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.

A thermodynamic perspective on technologies in the Anthropocene : analyzing environmental sustainability

NARCIS (Netherlands)

Liao, Wenjie

2012-01-01

Technologies and sustainable development are interrelated from a thermodynamic perspective, with industrial ecology (IE) as a major point of access for studying the relationship in the Anthropocene. To offer insights into the potential offered by thermodynamics in the environmental sustainability

Constructal theory through thermodynamics of irreversible processes framework

International Nuclear Information System (INIS)

Tescari, S.; Mazet, N.; Neveu, P.

2011-01-01

Highlights: → Point to area flow problem is solved through Thermodynamics of irreversible processes. → A new optimisation criterion is defined: the exergy or entropy impedance. → Optimisation is performed following two different routes, constructal or global. → Global optimisation is more efficient than constructal optimisation. → Global optimisation enhances the domain of construct benefits. - Abstract: Point to volume flow problem is revisited on a thermodynamics of irreversible processes (TIP) basis. The first step consists in evaluating the local entropy production of the system, and deducing from this expression the phenomenological laws. Then, the total entropy production can be simply evaluated. It is demonstrated that total entropy production can be written in a remarkable form: the product of the so-called entropy impedance with the square of the heat flux. As the heat flux is given, optimisation consists in minimising the entropy impedance. It is also shown that minimising entropy impedance minimises the maximum temperature difference. Applied to the elemental volume, this optimisation process leads to a shape factor close to the one already published. For the first construction, the equivalent system is defined as stated by Prigogine: when subjected to the same constraints, two systems are thermodynamically equivalent if their entropy production is equal. Two optimisation routes are then investigated: a global optimisation where all scales are taken into account and the constructal optimisation where the system is optimised scale by scale. In this second case, results are close to Ghodossi's work. When global optimisation is performed, it is demonstrated that conductive paths have to be spread uniformly in the active material (i.e. the number of elemental volumes must go to infinite). Comparing the two routes, global optimisation leads to better performance than constructal optimisation. Moreover, global optimisation enlarges the domain of

Assessment of thermodynamic parameters of plasma shock wave

International Nuclear Information System (INIS)

Vasileva, O V; Isaev, Yu N; Budko, A A; Filkov, A I

2014-01-01

The work is devoted to the solution of the one-dimensional equation of hydraulic gas dynamics for the coaxial magneto plasma accelerator by means of Lax-Wendroff modified algorithm with optimum choice of the regularization parameter artificial viscosity. Replacement of the differential equations containing private derivatives is made by finite difference method. Optimum parameter of regularization artificial viscosity is added using the exact known decision of Soda problem. The developed algorithm of thermodynamic parameter calculation in a braking point is proved. Thermodynamic parameters of a shock wave in front of the plasma piston of the coaxial magneto plasma accelerator are calculated on the basis of the offered algorithm. Unstable high-frequency fluctuations are smoothed using modeling and that allows narrowing the ambiguity area. Results of calculation of gas dynamic parameters in a point of braking coincide with literary data. The chart 3 shows the dynamics of change of speed and thermodynamic parameters of a shock wave such as pressure, density and temperature just before the plasma piston

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-05-07

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

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

Science.gov (United States)

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

2016-05-07

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

Thermodynamics of asymptotically safe theories

DEFF Research Database (Denmark)

Rischke, Dirk H.; Sannino, Francesco

2015-01-01

We investigate the thermodynamic properties of a novel class of gauge-Yukawa theories that have recently been shown to be completely asymptotically safe, because their short-distance behaviour is determined by the presence of an interacting fixed point. Not only do all the coupling constants freeze...

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

Statistical thermodynamics

International Nuclear Information System (INIS)

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

1987-01-01

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

LOW-TEMPERATURE EQUATION OF STATE OF SOLID METHANE

Directory of Open Access Journals (Sweden)

L. N. Yakub

2016-02-01

Full Text Available The theoretical equation of state for solid methane, developed within the framework of perturbation theory, with the crystal consisting of spherical molecules as zero-order approximation, and octupole – octupole interaction of methane molecules as a perturbation, is proposed. Thermodynamic functions are computed on the sublimation line up to the triple point. The contribution of the octupole – octupole interaction to the thermodynamic properties of solid methane is estimated.

Thermodynamics of the frustrated ferromagnetic spin-1/2 Heisenberg chain

International Nuclear Information System (INIS)

Richter, J; Haertel, M; Ihle, D; Drechsler, S-L

2009-01-01

We studied the thermodynamics of the one-dimensional J 1 -J 2 spin-1/2 Heisenberg chain for ferromagnetic nearest-neighbor bonds J 1 2 > 0 using full diagonalization of finite rings and a second-order Green-function formalism. Thereby we focus on J 2 1 |/4 where the ground state is still ferromagnetic, but the frustration influences the thermodynamic properties. We found that their critical indices are not changed by J 2 . The analysis of the low-temperature behavior of the susceptibility χ leads to the conclusion that this behavior changes from χ ∝ T -2 at J 2 1 |/4 to χ ∝ T -3/2 at the quantum-critical point J 2 = |J 1 |/4. Another effect of the frustration is the appearance of an extra low-T maximum in the specific heat C v (T) for J 2 and |J 1 |/8, indicating its strong influence on the low-energy spectrum.

High dilution calorimetric determination of the standard state thermodynamic differences between the properties of H+(aq) and Na+(aq) up to 598.15 K

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

Some aspects of equations of state

International Nuclear Information System (INIS)

Frisch, H.L.

1979-02-01

Some elementary properties of the equation of state of molecules repulsing each other as point centers of force are developed briefly. An inequality for the Lennard--Jones gas is presented. The scaled particle theory equation of state of hard spheres is also reviewed briefly. Means of possibly applying these concepts to represent thermodynamic data on model detonating gases are suggested

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.

Fluid phases of hydrogen-bound states and thermodynamical properties

International Nuclear Information System (INIS)

Ebeling, W.; Kraeft, W.D.

1985-08-01

The fluid phases of hydrogen and especially the existence of two critical points, the density dependence of the two - particle states and the effective interactions are discussed. An effective Schroedinger equation and a Saha equation are given. (author)

Black hole thermodynamical entropy

International Nuclear Information System (INIS)

Tsallis, Constantino; Cirto, Leonardo J.L.

2013-01-01

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

Point-Defect Nature of the Ultraviolet Absorption Band in AlN

Science.gov (United States)

Alden, D.; Harris, J. S.; Bryan, Z.; Baker, J. N.; Reddy, P.; Mita, S.; Callsen, G.; Hoffmann, A.; Irving, D. L.; Collazo, R.; Sitar, Z.

2018-05-01

We present an approach where point defects and defect complexes are identified using power-dependent photoluminescence excitation spectroscopy, impurity data from SIMS, and density-functional-theory (DFT)-based calculations accounting for the total charge balance in the crystal. Employing the capabilities of such an experimental computational approach, in this work, the ultraviolet-C absorption band at 4.7 eV, as well as the 2.7- and 3.9-eV luminescence bands in AlN single crystals grown via physical vapor transport (PVT) are studied in detail. Photoluminescence excitation spectroscopy measurements demonstrate the relationship between the defect luminescent bands centered at 3.9 and 2.7 eV to the commonly observed absorption band centered at 4.7 eV. Accordingly, the thermodynamic transition energy for the absorption band at 4.7 eV and the luminescence band at 3.9 eV is estimated at 4.2 eV, in agreement with the thermodynamic transition energy for the CN- point defect. Finally, the 2.7-eV PL band is the result of a donor-acceptor pair transition between the VN and CN point defects since nitrogen vacancies are predicted to be present in the crystal in concentrations similar to carbon-employing charge-balance-constrained DFT calculations. Power-dependent photoluminescence measurements reveal the presence of the deep donor state with a thermodynamic transition energy of 5.0 eV, which we hypothesize to be nitrogen vacancies in agreement with predictions based on theory. The charge state, concentration, and type of impurities in the crystal are calculated considering a fixed amount of impurities and using a DFT-based defect solver, which considers their respective formation energies and the total charge balance in the crystal. The presented results show that nitrogen vacancies are the most likely candidate for the deep donor state involved in the donor-acceptor pair transition with peak emission at 2.7 eV for the conditions relevant to PVT growth.

Thermodynamic theory of equilibrium fluctuations

International Nuclear Information System (INIS)

Mishin, Y.

2015-01-01

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

Thermodynamics of 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.)

Towards a thermodynamics of active matter.

Science.gov (United States)

Takatori, S C; Brady, J F

2015-03-01

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

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)

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.

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

Science.gov (United States)

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

2015-11-01

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

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

Tables of thermodynamic properties of helium magnet coolant

International Nuclear Information System (INIS)

McAshan, M.

1992-07-01

The most complete treatment of the thermodynamic properties of helium at the present time is the monograph by McCarty: ''Thermodynamic Properties of Helium 4 from 2 to 1500 K at Pressures to 10 8 Pa'', Robert D. McCarty, Journal of Physical and Chemical Reference Data, Vol. 2, page 923--1040 (1973). In this work the complete range of data on helium is examined and the P-V-T surface is described by an equation of state consisting of three functions P(r,T) covering different regions together with rules for making the transition from one region to another. From this thermodynamic compilation together with correlations of the transport properties of helium was published the well-known NBS Technical Note: ''Thermophysical Properties of Helium 4 from 2 to 1500 K with pressures to 1000 Atmospheres'', Robert D. McCarty, US Department of Commerce, National Bureau of Standards Technical Note 631 (1972). This is the standard reference for helium cryogenics. The NBS 631 tables cover a wide range of temperature and pressure, and as a consequence, the number of points tabulated in the region of the single phase coolant for the SSC magnets are relatively few. The present work sets out to cover the range of interest in more detail in a way that is consistent with NBS 631. This new table is essentially identical to the older one and can be used as an auxiliary to it

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.

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....

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

Assessing the Conceptual Understanding about Heat and Thermodynamics at Undergraduate Level

Science.gov (United States)

Kulkarni, Vasudeo Digambar; Tambade, Popat Savaleram

2013-01-01

In this study, a Thermodynamic Concept Test (TCT) was designed to assess student's conceptual understanding heat and thermodynamics at undergraduate level. The different statistical tests such as item difficulty index, item discrimination index, point biserial coefficient were used for assessing TCT. For each item of the test these indices were…

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

Point defects in solids

International Nuclear Information System (INIS)

Anon.

1978-01-01

The principal properties of point defects are studied: thermodynamics, electronic structure, interactions with etended defects, production by irradiation. Some measuring methods are presented: atomic diffusion, spectroscopic methods, diffuse scattering of neutron and X rays, positron annihilation, molecular dynamics. Then points defects in various materials are investigated: ionic crystals, oxides, semiconductor materials, metals, intermetallic compounds, carbides, nitrides [fr

Thermodynamics and elastic moduli of fluids with steeply repulsive potentials

Science.gov (United States)

Heyes, D. M.

1997-08-01

Analytic expressions for the thermodynamic properties and elastic moduli of molecular fluids interacting with steeply repulsive potentials are derived using Rowlinson's hard-sphere perturbation treatment which employs a softness parameter, λ specifying the deviation from the hard-sphere potential. Generic potentials of this form might be used to represent the interactions between near-hard-sphere stabilized colloids. Analytic expressions for the equivalent hard-sphere diameter of inverse power [ɛ(σ/r)n where ɛ sets the energy scale and σ the distance scale] exponential and logarithmic potential forms are derived using the Barker-Henderson formula. The internal energies in the hard-sphere limit are predicted essentially exactly by the perturbation approach when compared against molecular dynamics simulation data using the same potentials. The elastic moduli are similarly accurately predicted in the hard-sphere limit, as they are trivially related to the internal energy. The compressibility factors from the perturbation expansion do not compare as favorably with simulation data, and in this case the Carnahan-Starling equation of state prediction using the analytic effective hard-sphere diameter would appear to be a preferable route for this thermodynamic property. A more refined state point dependent definition for the effective hard-sphere diameter is probably required for this property.

Thermodynamic modelling of fast dopant diffusion in Si

Science.gov (United States)

Saltas, V.; Chroneos, A.; Vallianatos, F.

2018-04-01

In the present study, nickel and copper fast diffusion in silicon is investigated in the framework of the cBΩ thermodynamic model, which connects point defect parameters with the bulk elastic and expansion properties. All the calculated point defect thermodynamic properties (activation Gibbs free energy, activation enthalpy, activation entropy, and activation volume) exhibit temperature dependence due to the non-linear anharmonic behavior of the isothermal bulk modulus of Si. Calculated activation enthalpies (0.15-0.16 eV for Ni and 0.17-0.19 eV for Cu) are in agreement with the reported experimental results. Small values of calculated activation volumes for both dopants (˜4% of the mean atomic volume) are consistent with the interstitial diffusion of Ni and Cu in Si.

Thermodynamical description of stationary, asymptotically flat solutions with conical singularities

International Nuclear Information System (INIS)

Herdeiro, Carlos; Rebelo, Carmen; Radu, Eugen

2010-01-01

We examine the thermodynamical properties of a number of asymptotically flat, stationary (but not static) solutions having conical singularities, with both connected and nonconnected event horizons, using the thermodynamical description recently proposed in [C. Herdeiro, B. Kleihaus, J. Kunz, and E. Radu, Phys. Rev. D 81, 064013 (2010).]. The examples considered are the double-Kerr solution, the black ring rotating in either S 2 or S 1 , and the black Saturn, where the balance condition is not imposed for the latter two solutions. We show that not only the Bekenstein-Hawking area law is recovered from the thermodynamical description, but also the thermodynamical angular momentum is the Arnowitt-Deser-Misner angular momentum. We also analyze the thermodynamical stability and show that, for all these solutions, either the isothermal moment of inertia or the specific heat at constant angular momentum is negative, at any point in parameter space. Therefore, all these solutions are thermodynamically unstable in the grand canonical ensemble.

Thermodynamic properties of water solvating biomolecular surfaces

Science.gov (United States)

Heyden, Matthias

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

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.)

Thermodynamics

CERN Document Server

Fermi, Enrico

1956-01-01

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

Thermodynamic free energy methods to investigate shape transitions in bilayer membranes.

Science.gov (United States)

Ramakrishnan, N; Tourdot, Richard W; Radhakrishnan, Ravi

2016-06-01

The conformational free energy landscape of a system is a fundamental thermodynamic quantity of importance particularly in the study of soft matter and biological systems, in which the entropic contributions play a dominant role. While computational methods to delineate the free energy landscape are routinely used to analyze the relative stability of conformational states, to determine phase boundaries, and to compute ligand-receptor binding energies its use in problems involving the cell membrane is limited. Here, we present an overview of four different free energy methods to study morphological transitions in bilayer membranes, induced either by the action of curvature remodeling proteins or due to the application of external forces. Using a triangulated surface as a model for the cell membrane and using the framework of dynamical triangulation Monte Carlo, we have focused on the methods of Widom insertion, thermodynamic integration, Bennett acceptance scheme, and umbrella sampling and weighted histogram analysis. We have demonstrated how these methods can be employed in a variety of problems involving the cell membrane. Specifically, we have shown that the chemical potential, computed using Widom insertion, and the relative free energies, computed using thermodynamic integration and Bennett acceptance method, are excellent measures to study the transition from curvature sensing to curvature inducing behavior of membrane associated proteins. The umbrella sampling and WHAM analysis has been used to study the thermodynamics of tether formation in cell membranes and the quantitative predictions of the computational model are in excellent agreement with experimental measurements. Furthermore, we also present a method based on WHAM and thermodynamic integration to handle problems related to end-point-catastrophe that are common in most free energy methods.

Black holes thermodynamics, information, and firewalls

CERN Document Server

Mann, Robert B

2015-01-01

This book reflects the resurgence of interest in the quantum properties of black holes, culminating most recently in controversial discussions about firewalls. On the thermodynamic side, it describes how new developments allowed the inclusion of pressure/volume terms in the first law, leading to a new understanding of black holes as chemical systems, experiencing novel phenomena such as triple points and reentrant phase transitions. On the quantum-information side, the reader learns how basic arguments undergirding quantum complementarity have been shown to be flawed; and how this suggests that a black hole may surround itself with a firewall: a violent and chaotic region of highly excited states. In this thorough and pedagogical treatment, Robert Mann traces these new developments from their roots to our present-day understanding, highlighting their relationships and the challenges they present for quantum gravity.

Thermodynamic properties calculation of the flue gas based on its composition estimation for coal-fired power plants

International Nuclear Information System (INIS)

Xu, Liang; Yuan, Jingqi

2015-01-01

Thermodynamic properties of the working fluid and the flue gas play an important role in the thermodynamic calculation for the boiler design and the operational optimization in power plants. In this study, a generic approach to online calculate the thermodynamic properties of the flue gas is proposed based on its composition estimation. It covers the full operation scope of the flue gas, including the two-phase state when the temperature becomes lower than the dew point. The composition of the flue gas is online estimated based on the routinely offline assays of the coal samples and the online measured oxygen mole fraction in the flue gas. The relative error of the proposed approach is found less than 1% when the standard data set of the dry and humid air and the typical flue gas is used for validation. Also, the sensitivity analysis of the individual component and the influence of the measurement error of the oxygen mole fraction on the thermodynamic properties of the flue gas are presented. - Highlights: • Flue gas thermodynamic properties in coal-fired power plants are online calculated. • Flue gas composition is online estimated using the measured oxygen mole fraction. • The proposed approach covers full operation scope, including two-phase flue gas. • Component sensitivity to the thermodynamic properties of flue gas is presented.

Positive Nonlinear Dynamical Group Uniting Quantum Mechanics and Thermodynamics

OpenAIRE

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.

Science.gov (United States)

Tomé, Tânia; de Oliveira, Mário J

2015-04-01

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

Ecosystem thermodynamics

International Nuclear Information System (INIS)

Gomez Palacio, German Rau

1998-01-01

Ecology is no more a descriptive and self-sufficient science. Many viewpoints are needed simultaneously to give a full coverage of such complex systems: ecosystems. These viewpoints come from physics, chemistry, and nuclear physics, without a new far from equilibrium thermodynamics and without new mathematical tools such as catastrophe theory, fractal theory, cybernetics and network theory, the development of ecosystem science would never have reached the point of today. Some ideas are presented about the importance that concept such as energy, entropy, exergy information and none equilibrium have in the analysis of processes taking place in ecosystems

Statistical thermodynamics

International Nuclear Information System (INIS)

Lim, Gyeong Hui

2008-03-01

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

Thermodynamic modelling of shape memory behaviour: some examples

International Nuclear Information System (INIS)

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

1995-01-01

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

Rapid Computation of Thermodynamic Properties over Multidimensional Nonbonded Parameter Spaces Using Adaptive Multistate Reweighting.

Science.gov (United States)

Naden, Levi N; Shirts, Michael R

2016-04-12

We show how thermodynamic properties of molecular models can be computed over a large, multidimensional parameter space by combining multistate reweighting analysis with a linear basis function approach. This approach reduces the computational cost to estimate thermodynamic properties from molecular simulations for over 130,000 tested parameter combinations from over 1000 CPU years to tens of CPU days. This speed increase is achieved primarily by computing the potential energy as a linear combination of basis functions, computed from either modified simulation code or as the difference of energy between two reference states, which can be done without any simulation code modification. The thermodynamic properties are then estimated with the Multistate Bennett Acceptance Ratio (MBAR) as a function of multiple model parameters without the need to define a priori how the states are connected by a pathway. Instead, we adaptively sample a set of points in parameter space to create mutual configuration space overlap. The existence of regions of poor configuration space overlap are detected by analyzing the eigenvalues of the sampled states' overlap matrix. The configuration space overlap to sampled states is monitored alongside the mean and maximum uncertainty to determine convergence, as neither the uncertainty or the configuration space overlap alone is a sufficient metric of convergence. This adaptive sampling scheme is demonstrated by estimating with high precision the solvation free energies of charged particles of Lennard-Jones plus Coulomb functional form with charges between -2 and +2 and generally physical values of σij and ϵij in TIP3P water. We also compute entropy, enthalpy, and radial distribution functions of arbitrary unsampled parameter combinations using only the data from these sampled states and use the estimates of free energies over the entire space to examine the deviation of atomistic simulations from the Born approximation to the solvation free

Basic Thermodynamics

International Nuclear Information System (INIS)

Duthil, P

2014-01-01

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

Basic Thermodynamics

Energy Technology Data Exchange (ETDEWEB)

Duthil, P [Orsay, IPN (France)

2014-07-01

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

Considerations about the correct evaluation of sorption thermodynamic parameters from equilibrium isotherms

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

Theoretical Understanding the Relations of Melting-point Determination Methods from Gibbs Thermodynamic Surface and Applications on Melting Curves of Lower Mantle Minerals

Science.gov (United States)

Yin, K.; Belonoshko, A. B.; Zhou, H.; Lu, X.

2016-12-01

The melting temperatures of materials in the interior of the Earth has significant implications in many areas of geophysics. The direct calculations of the melting point by atomic simulations would face substantial hysteresis problem. To overcome the hysteresis encountered in the atomic simulations there are a few different melting-point determination methods available nowadays, which are founded independently, such as the free energy method, the two-phase or coexistence method, and the Z method, etc. In this study, we provide a theoretical understanding the relations of these methods from a geometrical perspective based on a quantitative construction of the volume-entropy-energy thermodynamic surface, a model first proposed by J. Willard Gibbs in 1873. Then combining with an experimental data and/or a previous melting-point determination method, we apply this model to derive the high-pressure melting curves for several lower mantle minerals with less computational efforts relative to using previous methods only. Through this way, some polyatomic minerals at extreme pressures which are almost unsolvable before are calculated fully from first principles now.

Understanding Mn-Based Intercalation Cathodes from Thermodynamics and Kinetics

Directory of Open Access Journals (Sweden)

Yin Xie

2017-07-01

Full Text Available A series of Mn-based intercalation compounds have been applied as the cathode materials of Li-ion batteries, such as LiMn2O4, LiNi1−x−yCoxMnyO2, etc. With open structures, intercalation compounds exhibit a wide variety of thermodynamic and kinetic properties depending on their crystal structures, host chemistries, etc. Understanding these materials from thermodynamic and kinetic points of view can facilitate the exploration of cathodes with better electrochemical performances. This article reviews the current available thermodynamic and kinetic knowledge on Mn-based intercalation compounds, including the thermal stability, structural intrinsic features, involved redox couples, phase transformations as well as the electrical and ionic conductivity.

The generalized second law of thermodynamics in the accelerating universe

International Nuclear Information System (INIS)

Zhou Jia; Wang Bin; Gong Yungui; Abdalla, Elcio

2007-01-01

We show that in the accelerating universe the generalized second law of thermodynamics holds only in the case where the enveloping surface is the apparent horizon, but not in the case of the event horizon. The present analysis relies on the most recent SNe Ia events, being model independent. Our study might suggest that event horizon is not a physical boundary from the point of view of thermodynamics

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

Determination of the protonation state of the Asp dyad: conventional molecular dynamics versus thermodynamic integration.

Science.gov (United States)

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.

Non-equilibrium thermodynamics of radiation-induced processes in solids

International Nuclear Information System (INIS)

Yurov, V.M.; Eshchanov, A.N.; Kuketaev, A.T.; Sidorenya, Yu.S.

2005-01-01

In the paper an item about a defect system response in solids on external action (temperature, pressure, light, etc.) from the point of view of non-equilibrium statistical thermodynamics is considered

Surface thermodynamics

International Nuclear Information System (INIS)

Garcia-Moliner, F.

1975-01-01

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

Black Hole Thermodynamics in an Undergraduate Thermodynamics Course.

Science.gov (United States)

Parker, Barry R.; McLeod, Robert J.

1980-01-01

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

Quantum Thermodynamics at Strong Coupling: Operator Thermodynamic Functions and Relations

Directory of Open Access Journals (Sweden)

Jen-Tsung Hsiang

2018-05-01

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

Thermodynamic tables to accompany Modern engineering thermodynamics

CERN Document Server

Balmer, Robert T

2011-01-01

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

A computational/directional solidification method to establish saddle points on the Mg-Al-Ca liquidus

International Nuclear Information System (INIS)

Cao Hongbo; Zhang Chuan; Zhu Jun; Cao Guoping; Kou Sindo; Schmid-Fetzer, Rainer; Chang, Y. Austin

2008-01-01

We established two saddle point maxima, L + α(Mg) + C14 and L + α(Mg) + C36, on the monovariant liquidus, calculated from a previously presented thermodynamic description, by characterizing the microstructures of several directionally solidified alloys in the near-solidification front zone, the mushy zone, and the steady-state zone using optical microscopy, scanning electron microscopy and transmission electron microscopy

Completely mixed state is a critical point for three-qubit entanglement

International Nuclear Information System (INIS)

Tamaryan, Sayatnova

2011-01-01

Pure three-qubit states have five algebraically independent and one algebraically dependent polynomial invariants under local unitary transformations and an arbitrary entanglement measure is a function of these six invariants. It is shown that if the reduced density operator of a some qubit is a multiple of the unit operator, than the geometric entanglement measure of the pure three-qubit state is absolutely independent of the polynomial invariants and is a constant for such tripartite states. Hence a one-particle completely mixed state is a critical point for the geometric measure of entanglement. -- Highlights: → Geometric measure of pure three-qubits is expressed in terms of polynomial invariants. → When one Bloch vector is zero the measure is independent of the remaining invariants. → Hence a one-particle completely mixed state is a critical point for the geometric measure. → The existence of the critical points is an inherent feature of the entanglement.

Completely mixed state is a critical point for three-qubit entanglement

Energy Technology Data Exchange (ETDEWEB)

Tamaryan, Sayatnova, E-mail: sayat@mail.yerphi.am [Department of Theoretical Physics, A. Alikhanyan National Laboratory, Yerevan (Armenia)

2011-06-06

Pure three-qubit states have five algebraically independent and one algebraically dependent polynomial invariants under local unitary transformations and an arbitrary entanglement measure is a function of these six invariants. It is shown that if the reduced density operator of a some qubit is a multiple of the unit operator, than the geometric entanglement measure of the pure three-qubit state is absolutely independent of the polynomial invariants and is a constant for such tripartite states. Hence a one-particle completely mixed state is a critical point for the geometric measure of entanglement. -- Highlights: → Geometric measure of pure three-qubits is expressed in terms of polynomial invariants. → When one Bloch vector is zero the measure is independent of the remaining invariants. → Hence a one-particle completely mixed state is a critical point for the geometric measure. → The existence of the critical points is an inherent feature of the entanglement.

Thermodynamical description of excited nuclei

International Nuclear Information System (INIS)

Bonche, P.

1989-01-01

In heavy ion collisions it has been possible to obtain composite systems at rather high excitation energies corresponding to temperatures of several MeV. The theoretical studies of these systems are based on concepts borrowed from thermodynamics or statistical physics, such as the temperature. In these lectures, we present the concepts of statistical physics which are involved in the physics of heavy ion as they are produced nowadays in the laboratory and also during the final stage of a supernova collapse. We do not attempt to describe the reaction mechanisms which yield such nuclear systems nor their decay by evaporation or fragmentation. We shall only study their static properties. The content of these lectures is organized in four main sections. The first one gives the basic features of statistical physics and thermodynamics necessary to understand quantum mechanics at finite temperature. In the second one, we present a study of the liquid-gas phase transition in nuclear physics. A phenomenological approach of the stability of hot nuclei follows. The microscopic point of view is proposed in the third part. Starting from the basic concepts derived in the first part, it provides a description of excited or hot nuclei which confirms the qualitative results of the second part. Furthermore it gives a full description of most properties of these nuclei as a function of temperature. Finally in the last part, a microscopic derivation of the equation of state of nuclear matter is proposed to study the collapse of a supernova core

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

A New Thermodynamics from Nuclei to Stars

Directory of Open Access Journals (Sweden)

Dieter H.E. Gross

2004-03-01

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

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

Science.gov (United States)

Glavatskiy, K S

2015-05-28

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

Thermodynamic properties of gaseous ruthenium species.

Science.gov (United States)

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

2015-05-21

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

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.

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.

Black-hole thermodynamics: Entropy, information and beyond

Indian Academy of Sciences (India)

We review some recent advances in black-hole thermodynamics including statistical mechanical origins of black-hole entropy and its leading order corrections from the view points of various quantum gravity theories. We then examine the problem of information loss and some possible approaches to its resolution. Finally ...

A commentary on thermodynamics

CERN Document Server

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 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

Thermodynamics of a periodically driven qubit

Science.gov (United States)

Donvil, Brecht

2018-04-01

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

Extended thermodynamics

CERN Document Server

Müller, Ingo

1993-01-01

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

A consistent model for the equilibrium thermodynamic functions of partially ionized flibe plasma with Coulomb corrections

International Nuclear Information System (INIS)

Zaghloul, Mofreh R.

2003-01-01

Flibe (2LiF-BeF2) is a molten salt that has been chosen as the coolant and breeding material in many design studies of the inertial confinement fusion (ICF) chamber. Flibe plasmas are to be generated in the ICF chamber in a wide range of temperatures and densities. These plasmas are more complex than the plasma of any single chemical species. Nevertheless, the composition and thermodynamic properties of the resulting flibe plasmas are needed for the gas dynamics calculations and the determination of other design parameters in the ICF chamber. In this paper, a simple consistent model for determining the detailed plasma composition and thermodynamic functions of high-temperature, fully dissociated and partially ionized flibe gas is presented and used to calculate different thermodynamic properties of interest to fusion applications. The computed properties include the average ionization state; kinetic pressure; internal energy; specific heats; adiabatic exponent, as well as the sound speed. The presented results are computed under the assumptions of local thermodynamic equilibrium (LTE) and electro-neutrality. A criterion for the validity of the LTE assumption is presented and applied to the computed results. Other attempts in the literature are assessed with their implied inaccuracies pointed out and discussed

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

Holographic free energy and thermodynamic geometry

Science.gov (United States)

Ghorai, Debabrata; Gangopadhyay, Sunandan

2016-12-01

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

Holographic free energy and thermodynamic geometry

International Nuclear Information System (INIS)

Ghorai, Debabrata; Gangopadhyay, Sunandan

2016-01-01

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

Holographic free energy and thermodynamic geometry

Energy Technology Data Exchange (ETDEWEB)

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

2016-12-15

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

Hamiltonian and Thermodynamic Modeling of Quantum Turbulence

Science.gov (United States)

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.

The Thermodynamics of General and Local Anesthesia

Science.gov (United States)

Græsbøll, Kaare; Sasse-Middelhoff, Henrike; Heimburg, Thomas

2014-05-01

General anesthetics are known to cause depression of the freezing point of transitions in biomembranes. This is a consequence of ideal mixing of the anesthetic drugs in the membrane fluid phase and exclusion from the solid phase. Such a generic law provides physical justification of the famous Meyer-Overton rule. We show here that general anesthetics, barbiturates and local anesthetics all display the same effect on melting transitions. Their effect is reversed by hydrostatic pressure. Thus, the thermodynamic behavior of local anesthetics is very similar to that of general anesthetics. We present a detailed thermodynamic analysis of heat capacity profiles of membranes in the presence of anesthetics. This analysis is able to describe experimentally observed calorimetric profiles and permits prediction of the anesthetic features of arbitrary molecules. In addition, we discuss the thermodynamic origin of the cutoff-effect of long-chain alcohols and the additivity of the effect of general and local anesthetics.

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

Monte Carlo simulations for thermodynamical properties calculations of plasmas at thermodynamical equilibrium. Applications to opacity and equation of state calculations; Apport d'un code de simulation Monte Carlo pour l'etude des proprietes thermodynamiques d'un plasma a l'equilibre et application au calcul de l'elargissement des profils de raies ioniques emises dans les plasmas denses, aux opacites spectrales et aux equations d'etat de systemes fluides

Energy Technology Data Exchange (ETDEWEB)

Gilles, D

2005-07-01

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)

THERMODYNAMIC PARAMETERS OF LEAD SULFIDE CRYSTALS IN THE CUBIC PHASE

Directory of Open Access Journals (Sweden)

T. O. Parashchuk

2016-07-01

Full Text Available Geometric and thermodynamic parameters of cubic PbS crystals were obtained using the computer calculations of the thermodynamic parameters within density functional theory method DFT. Cluster models for the calculation based on the analysis of the crystal and electronic structure. Temperature dependence of energy ΔE and enthalpy ΔH, Gibbs free energy ΔG, heat capacity at constant pressure CP and constant volume CV, entropy ΔS were determined on the basis of ab initio calculations of the crystal structure of molecular clusters. Analytical expressions of temperature dependences of thermodynamic parameters which were approximated with quantum-chemical calculation points have been presented. Experimental results compared with theoretically calculated data.

Leveraging Environmental Correlations: The Thermodynamics of Requisite Variety

Science.gov (United States)

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.

Thermodynamic performance evaluation of combustion gas turbine cogeneration system with reheat

International Nuclear Information System (INIS)

Khaliq, A.; Kaushik, S.C.

2004-01-01

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

Phase behaviour and thermodynamic modelling for the system (grape seed oil + carbon dioxide + ethanol) at high pressures

International Nuclear Information System (INIS)

Dalmolin, Irede; Rigo, Aline A.; Corazza, Marcos L.; Ndiaye, Papa M.; Meireles, M. Angela A.; Batista, Eduardo A.C.; Oliveira, J. Vladimir

2014-01-01

This short communication reports phase equilibrium data (cloud points), employing the synthetic static method, for the system {grape seed oil (GSO) + carbon dioxide (CO 2 ) + ethanol} up to T = 343.15 K and 22.53 MPa. Experimental results were modelled using the Peng-Robinson equation of state with the classical van der Waals quadratic mixing rule (PR-vdW2). It is shown that the thermodynamic model is able to represent satisfactorily the phase behaviour of the system investigated

Perturbative thermodynamic geometry of nonextensive ideal classical, Bose, and Fermi gases.

Science.gov (United States)

Mohammadzadeh, Hosein; Adli, Fereshteh; Nouri, Sahereh

2016-12-01

We investigate perturbative thermodynamic geometry of nonextensive ideal classical, Bose, and Fermi gases. We show that the intrinsic statistical interaction of nonextensive Bose (Fermi) gas is attractive (repulsive) similar to the extensive case but the value of thermodynamic curvature is changed by a nonextensive parameter. In contrary to the extensive ideal classical gas, the nonextensive one may be divided to two different regimes. According to the deviation parameter of the system to the nonextensive case, one can find a special value of fugacity, z^{*}, where the sign of thermodynamic curvature is changed. Therefore, we argue that the nonextensive parameter induces an attractive (repulsive) statistical interaction for zz^{*}) for an ideal classical gas. Also, according to the singular point of thermodynamic curvature, we consider the condensation of nonextensive Boson gas.

Prediction of the critical point and the dew- and bubble-point curves fo natural gases. Tennen gas no rinkaiten oyobi roten futten kyokusen no suisan

Energy Technology Data Exchange (ETDEWEB)

Endo, T. (Hitachi, Ltd., Tokyo (Japan)); Arai, D.; Uematsu, M. (Keio University, Tokyo (Japan). Faculty of Science and Technology)

1993-02-25

Related to the natural gas transport by pipeline, etc., the critical point, dew point and bubble point of natural gas were presumed by calculation through equation of state for determining the exact thermophysical values. The natural gas is multi-component mixed fluid which is represented by methane as a representative component. It considerably differs in composition by its place of origin. Because the conventional method was complicated in process for thermodynamically determining the most stable composition of phases, algorithm of phasic equilibrium was applied by the equation of state which used the discrimination method by Nitta, et al. for the therodynamic stability of phases. The method by Michelsen was applied to the flash calculation, and figuration of both dew point and bubble point curves, while that by Heidemann, et al. was done to the critical point calculation. Peng-Robinson's was applied to an equation of state. To start the calculation, the constant of seven two-component systems the main component of which was methane was determined as a function of temperature based on the actually measured gas/liquid equilibrium value. Then, possibility of calculatively presuming the thermophysical values was shown through comparison of the actually measured values with those obtained by applying the present method to the above systems. Finally, the presumption was made for the natural gas which differed in place of origin. 17 refs., 15 figs., 2 tabs.

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

A review of marine anthropogenic CO2 definitions: introducing a thermodynamic approach based on observations

International Nuclear Information System (INIS)

Friis, Karsten

2006-01-01

A review of existing methods that define anthropogenic CO 2 as deduced from total inorganic carbon is presented. A refined approach to define anthropogenic CO 2 is introduced that has a stronger thermodynamic orientation than current methods, and is based on a back-calculation technique by Chen and Millero and Poisson and Chen. Anthropogenic CO 2 results of the new technique are compared with results from the original technique as well as with results of the technique of Gruber et al. The new technique is furthermore applied to three time-separated data sets in the subpolar North Atlantic and shows consistent results with regard to available data quality and anthropogenic CO 2 quantities. The difference between the new thermodynamic approach and the anthropogenic CO 2 definition of Gruber et al., which is termed mechanistic, is discussed. Here likely changes in the CO 2 solubility pump are a thermodynamic property of this definition, whereas it is a separate phenomenon in the mechanistic definition. The thermodynamic approach is not without caveats, but points to improvements by the synergistic use of model results and those from observations. Future improvements are considered for the initial saturation state of oxygen and CO 2 , at the instant the surface water loses contact with the atmosphere and for variations in the Redfield ratio

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

Science.gov (United States)

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

1990-11-01

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

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.)

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...

Incomplete nonextensive statistics and the zeroth law of thermodynamics

International Nuclear Information System (INIS)

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

2013-01-01

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

Thermodynamic simulation and evaluation of sugar refinery evaporators using a steady state modelling approach

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.

Thermodynamic properties of potassium chloride aqueous solutions

Science.gov (United States)

Zezin, Denis; Driesner, Thomas

2017-04-01

Potassium chloride is a ubiquitous salt in natural fluids, being the second most abundant dissolved salt in many geological aqueous solutions after sodium chloride. It is a simple solute and strong electrolyte easily dissociating in water, however the thermodynamic properties of KCl aqueous solutions were never correlated with sufficient accuracy for a wide range of physicochemical conditions. In this communication we propose a set of parameters for a Pitzer-type model which allows calculation of all necessary thermodynamic properties of KCl solution, namely excess Gibbs free energy and derived activity coefficient, apparent molar enthalpy, heat capacity and volume, as well as osmotic coefficient and activity of water in solutions. The system KCl-water is one of the best studied aqueous systems containing electrolytes. Although extensive experimental data were collected for thermodynamic properties of these solutions over the years, the accurate volumetric data became available only recently, thus making possible a complete thermodynamic formulation including a pressure dependence of excess Gibbs free energy and derived properties of the KCl-water liquids. Our proposed model is intended for calculation of major thermodynamic properties of KCl aqueous solutions at temperatures ranging from freezing point of a solution to 623 K, pressures ranging from saturated water vapor up to 150 MPa, and concentrations up to the salt saturation. This parameterized model will be further implemented in geochemical software packages and can facilitate the calculation of aqueous equilibrium for reactive transport codes.

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.

Microscopic dynamics in simple liquids: a clue to understanding the basic thermodynamics of the liquid state

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

Thermodynamic properties and equation of state of liquid di-isodecyl phthalate at temperature between (273 and 423) K and at pressures up to 140 MPa

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.

Thermodynamic properties and equation of state of liquid di-isodecyl phthalate at temperature between (273 and 423) K and at pressures up to 140 MPa

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.

Bifurcation and Stability Analysis of the Equilibrium States in Thermodynamic Systems in a Small Vicinity of the Equilibrium Values of Parameters

Science.gov (United States)

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.

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

OpenAIRE

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

2003-01-01

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

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

Science.gov (United States)

Zhou, Shiqi

2009-02-07

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

Thermodynamic properties of alkali borosilicate gasses and metaborates

International Nuclear Information System (INIS)

Asano, Mitsuru

1992-01-01

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

Nonequilibrium thermodynamics of dilute polymer solutions in flow.

Science.gov (United States)

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

CERN Document Server

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

Thermodynamic analysis of processes proceeding on (111) faces of diamond during chemical vapour deposition

International Nuclear Information System (INIS)

Piekarczyk, W.; Prawer, S.

1992-01-01

Chemically vapour deposited diamond is commonly synthesized from activated hydrogen-rich, carbon/hydrogen gas mixtures under conditions which should, from a thermodynamic equilibrium point of view, favour the production of graphite. Much remains to be understood about why diamond, and not graphite, forms under these conditions. However, it is well known that the presence of atomic hydrogen, is crucial to the success of diamond deposition. As part of an attempt to better understand the deposition process, a thermodynamic analysis of the process was performed on diamond (111) faces in hydrogen rich environments. It is shown that the key role of atomic hydrogen is to inhibit the reconstruction of the (111) face to an sp 2 -bonded structure, which would provide a template for graphite, rather than diamond formation. The model correctly predicts experimentally determined trends in growth rate and diamond film quality as a function of methane concentration in the stating gas mixture. 17 refs., 4 figs

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

ms 2: A molecular simulation tool for thermodynamic properties, release 3.0

Science.gov (United States)

Rutkai, Gábor; Köster, Andreas; Guevara-Carrion, Gabriela; Janzen, Tatjana; Schappals, Michael; Glass, Colin W.; Bernreuther, Martin; Wafai, Amer; Stephan, Simon; Kohns, Maximilian; Reiser, Steffen; Deublein, Stephan; Horsch, Martin; Hasse, Hans; Vrabec, Jadran

2017-12-01

A new version release (3.0) of the molecular simulation tool ms 2 (Deublein et al., 2011; Glass et al. 2014) is presented. Version 3.0 of ms 2 features two additional ensembles, i.e. microcanonical (NVE) and isobaric-isoenthalpic (NpH), various Helmholtz energy derivatives in the NVE ensemble, thermodynamic integration as a method for calculating the chemical potential, the osmotic pressure for calculating the activity of solvents, the six Maxwell-Stefan diffusion coefficients of quaternary mixtures, statistics for sampling hydrogen bonds, smooth-particle mesh Ewald summation as well as the ability to carry out molecular dynamics runs for an arbitrary number of state points in a single program execution.

Thermodynamics of Crystals

Science.gov (United States)

Navrotsky, Alexandra

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

A Simple Statistical Thermodynamics Experiment

Science.gov (United States)

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…

Thermodynamic Property Model of Wide-Fluid Phase Propane

Directory of Open Access Journals (Sweden)

I Made Astina

2007-05-01

Full Text Available A new thermodynamic property model for propane is expressed in form of the Helmholtz free energy function. It consists of eight terms of the ideal-gas part and eighteen terms of the residual part. Accurate experimental data of fluid properties and theoretical approach from the intermolecular potential were simultaneously considered in the development to insure accuracy and to improve reliability of the equation of state over wide range of pressures and temperatures. Based on the state range of experimental data used in the model development, the validity range is judged from the triple-point of 85.48 K to temperature of 450 K and pressure up to 60 MPa. The uncertainties with respect to different properties are estimated to be 0.03% in ideal-gas isobaric specific heat, 0.2% in liquid phase density, 0.3% in gaseous phase density 1% in specific heats, 0.1% in vapor-pressure except at very low temperatures, 0.05% in saturated-liquid density, 0.02% in speed of sound of the gaseous phase and 1% in speed of sound of the liquid phase.

A thermodynamic approach to model the caloric properties of semicrystalline polymers

Science.gov (United States)

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.

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

Science.gov (United States)

Ruppeiner, George

2005-07-01

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

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

CERN Document Server

Rizk, Hanna A

2016-01-01

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

Non-hard sphere thermodynamic perturbation theory.

Science.gov (United States)

Zhou, Shiqi

2011-08-21

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

Is thermodynamics of the universe bounded by event horizon a Bekenstein system?

International Nuclear Information System (INIS)

Chakraborty, Subenoy

2012-01-01

In this brief communication, we have studied the validity of the first law of thermodynamics for the universe bounded by event horizon with two examples. The key point is the appropriate choice of the temperature on the event horizon. Finally, we have concluded that universe bounded by the event horizon may be a Bekenstein system and Einstein's equations and the first law of thermodynamics on the event horizons are equivalent.

Is thermodynamics of the universe bounded by event horizon a Bekenstein system?

OpenAIRE

Chakraborty, Subenoy

2012-01-01

In this brief communication, we have studied the validity of the first law of thermodynamics for the universe bounded by event horizon with two examples. The key point is the appropriate choice of the temperature on the event horizon. Finally, we have concluded that universe bounded by the event horizon may be a Bekenstein system and the Einstein's equations and the first law of thermodynamics on the event horizons are equivalent.

Thermodynamic properties of donor-acceptor complexes of tertiary amine with aryl ketones in hexane medium

Energy Technology Data Exchange (ETDEWEB)

Kumar, R. [Department of Physics, The New College, Chennai 600 014 (India); Jayakumar, S. [Department of Physics, R.K.M. Vivekananda College, Chennai 600 004 (India); Kannappan, V., E-mail: vkannappan@hotmail.com [Department of Chemistry, Presidency College, Chennai 600 005 (India)

2012-05-20

Highlights: Black-Right-Pointing-Pointer Ultrasonic scan is carried out on ternary systems of aromatic tertiary amine and three aryl ketones. Black-Right-Pointing-Pointer Formation of CT complexes is found between tertiary amine with aryl ketones. Black-Right-Pointing-Pointer Stability constant values are computed by ultrasonic and spectral methods are compared. Black-Right-Pointing-Pointer The trend in the 'K' suggests that substituents in ketones influence the stabilities of these complexes. Black-Right-Pointing-Pointer The thermodynamic parameters suggest CT interaction is exothermic and the complexes are thermodynamically stable. - The thermodynamic stability of complexes formed between N,N-dimethylaniline (DMANI) and three ketones, namely, acetophenone (ACP), 4-chloroactophenone (ClACP) and 4-methylacetophenone (MACP) in n-hexane is extensively investigated by spectral and ultrasonic methods. The ultrasound scan was carried out in the temperature range 208.15-313.15 K and at atmospheric pressure on solutions containing equimolar concentrations of components ranging from 0.025 to 0.2 M. The existence of solute-solute interactions has also been confirmed through electronic absorption spectra analyzed with Benesi-Hildebrand theory at 303.15 K. The stability constants of the donor-acceptor complexes determined both by spectroscopic and ultrasonic methods are comparable and follow similar trends. The trend in the formation constants is discussed with structures of the components. The thermodynamic behavior of the systems was explained through the computed values of the free energy ({Delta}G), enthalpy ({Delta}H) and entropy ({Delta}S) changes for complex formation are computed and discussed.

Dynamics and thermodynamics of polymer glasses.

Science.gov (United States)

Cangialosi, D

2014-04-16

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

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

Thermodynamics, phase transition and quasinormal modes with Weyl corrections

Energy Technology Data Exchange (ETDEWEB)

Mahapatra, Subhash [The Institute of Mathematical Sciences,Chennai 600113 (India)

2016-04-21

We study charged black holes in D dimensional AdS space, in the presence of four derivative Weyl correction. We obtain the black hole solution perturbatively up to first as well as second order in the Weyl coupling, and show that first law of black hole thermodynamics is satisfied in all dimensions. We study its thermodynamic phase transition and then calculate the quasinormal frequencies of the massless scalar field perturbation. We find that, here too, the quasinormal frequencies capture the essence of black hole phase transition. Few subtleties near the second order critical point are discussed.

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

High-temperature of thermodynamic properties of sodium

Energy Technology Data Exchange (ETDEWEB)

Padilla, A. Jr.

1977-01-01

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

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

Science.gov (United States)

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.

Phase equilibria for mixtures containing very many components. development and application of continuous thermodynamics for chemical process design

International Nuclear Information System (INIS)

Cotterman, R.L.; Bender, R.; Prausnitz, J.M.

1984-01-01

For some multicomponent mixtures, where detailed chemical analysis is not feasible, the compositio of the mixture may be described by a continuous distribution function of some convenient macroscopic property suc as normal boiling point or molecular weight. To attain a quantitative description of phase equilibria for such mixtures, this work has developed thermodynamic procedures for continuous systems; that procedure is called continuous thermodynamics. To illustrate, continuous thermodynamics is used to calculate dew points for natural-gas mixtures, solvent loss in a high-pressure absorber, and liquid-liquid phase equilibria in a polymer fractionation process. Continuous thermodynamics provides a rational method for calculating phase equilibria for those mixtures where complete chemical analysis is not available but where composition can be given by some statistical description. While continuous thermodynamics is only the logical limit of the well-known pseudo-component method, it is more efficient than that method because it is less arbitrary and it often requires less computer time

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

Science.gov (United States)

Lostaglio, Matteo; Jennings, David; Rudolph, Terry

2015-03-01

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

Thermodynamic properties of a quasi-harmonic model for ferroelectric transitions

International Nuclear Information System (INIS)

Mkam Tchouobiap, S E; Mashiyama, H

2011-01-01

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

Thermodynamics of the CSCl-H2O system at low temperatures

International Nuclear Information System (INIS)

Monnin, C.; Dubois, M.

1999-01-01

The interpretation of fluid-inclusion data requires knowledge of phase diagrams at low (subfreezing) temperatures. From the example of the CsCl-H 2 O system, we here investigate the possibility to build such diagrams from thermodynamic models of aqueous solutions parameterized at higher temperatures. Holmes and Mesmer (1983) have built a model for the thermodynamic properties of CsCl(aq) based on Pitzer's equation fit to thermodynamic data mainly at temperatures above 0 C along with a few freezing-point-depression data down to -8 C. We show how this model can be used along with the published water-ice equilibrium constant and thermodynamic data at 25 C for Cs + (aq), Cl - (aq) and CsCl(s), to predict with confidence the ice-liquid-vapor (ILV) and the salt-liquid-vapor (SLV) curves down to the eutectic temperature for the CsCl-H 2 O system. (orig.)

Thermodynamic evaluation of the Kalina split-cycle concepts for waste heat recovery applications

International Nuclear Information System (INIS)

Nguyen, Tuong-Van; Knudsen, Thomas; Larsen, Ulrik; Haglind, Fredrik

2014-01-01

The Kalina split-cycle is a thermodynamic process for converting thermal energy into electrical power. It uses an ammonia–water mixture as a working fluid (like a conventional Kalina cycle) and has a varying ammonia concentration during the pre-heating and evaporation steps. This second feature results in an improved match between the heat source and working fluid temperature profiles, decreasing the entropy generation in the heat recovery system. The present work compares the thermodynamic performance of this power cycle with the conventional Kalina process, and investigates the impact of varying boundary conditions by conducting an exergy analysis. The design parameters of each configuration were determined by performing a multi-variable optimisation. The results indicate that the Kalina split-cycle with reheat presents an exergetic efficiency by 2.8% points higher than a reference Kalina cycle with reheat, and by 4.3% points without reheat. The cycle efficiency varies by 14% points for a variation of the exhaust gas temperature of 100 °C, and by 1% point for a cold water temperature variation of 30 °C. This analysis also pinpoints the large irreversibilities in the low-pressure turbine and condenser, and indicates a reduction of the exergy destruction by about 23% in the heat recovery system compared to the baseline cycle. - Highlights: • The thermodynamic performance of the Kalina split-cycle is assessed. • The Kalina split-cycle is compared to the Kalina cycle, with and without reheat. • An exergy analysis is performed to evaluate its thermodynamic performance. • The impact of varying boundary conditions is investigated. • The Kalina split-cycle displays high exergetic efficiency for low- and medium-temperature applications

THERMODYNAMIC PROPERTIES OF NONAQUEOUS SINGLE SALT SOLUTIONS USING THE Q-ELECTROLATTICE EQUATION OF STATE

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.

Mutually consistent thermodynamic potentials for fluid water, ice and seawater: a new standard for oceanography

Directory of Open Access Journals (Sweden)

R. Feistel

2008-12-01

Full Text Available A new seawater standard for oceanographic and engineering applications has been developed that consists of three independent thermodynamic potential functions, derived from extensive distinct sets of very accurate experimental data. The results have been formulated as Releases of the International Association for the Properties of Water and Steam, IAPWS (1996, 2006, 2008 and are expected to be adopted internationally by other organizations in subsequent years. In order to successfully perform computations such as phase equilibria from combinations of these potential functions, mutual compatibility and consistency of these independent mathematical functions must be ensured. In this article, a brief review of their separate development and ranges of validity is given. We analyse background details on the conditions specified at their reference states, the triple point and the standard ocean state, to ensure the mutual consistency of the different formulations, and the necessity and possibility of numerically evaluating metastable states of liquid water. Computed from this formulation in quadruple precision (128-bit floating point numbers, tables of numerical reference values are provided as anchor points for the consistent incorporation of additional potential functions in the future, and as unambiguous benchmarks to be used in the determination of numerical uncertainty estimates of double-precision implementations on different platforms that may be customized for special purposes.

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)

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

Work extraction and thermodynamics for individual quantum systems

Science.gov (United States)

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.

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

Science.gov (United States)

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

2018-05-01

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

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)

Fractional charge and inter-Landau-level states at points of singular curvature.

Science.gov (United States)

Biswas, Rudro R; Son, Dam Thanh

2016-08-02

The quest for universal properties of topological phases is fundamentally important because these signatures are robust to variations in system-specific details. Aspects of the response of quantum Hall states to smooth spatial curvature are well-studied, but challenging to observe experimentally. Here we go beyond this prevailing paradigm and obtain general results for the response of quantum Hall states to points of singular curvature in real space; such points may be readily experimentally actualized. We find, using continuum analytical methods, that the point of curvature binds an excess fractional charge and sequences of quantum states split away, energetically, from the degenerate bulk Landau levels. Importantly, these inter-Landau-level states are bound to the topological singularity and have energies that are universal functions of bulk parameters and the curvature. Our exact diagonalization of lattice tight-binding models on closed manifolds demonstrates that these results continue to hold even when lattice effects are significant. An important technological implication of these results is that these inter-Landau-level states, being both energetically and spatially isolated quantum states, are promising candidates for constructing qubits for quantum computation.

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

Universalities of thermodynamic signatures in topological phases

NARCIS (Netherlands)

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

Investigation of two and three parameter equations of state for cryogenic fluids

International Nuclear Information System (INIS)

Jenkins, S.L.; Majumdar, A.K.; Hendricks, R.C.

1990-01-01

Two-phase flows are a common occurrence in cryogenic engines and an accurate evaluation of the heat-transfer coefficient in two-phase flow is of significant importance in their analysis and design. The thermodynamic equation of state plays a key role in calculating the heat transfer coefficient which is a function of thermodynamic and thermophysical properties. An investigation has been performed to study the performance of two- and three-parameter equations of state to calculate the compressibility factor of cryogenic fluids along the saturation loci. The two-parameter equations considered here are van der Waals and Redlich-Kwong equations of state. The three-parameter equation represented here is the generalized Benedict-Webb-Rubin (BWR) equation of Lee and Kesler. Results have been compared with the modified BWR equation of Bender and the extended BWR equations of Stewart. Seven cryogenic fluids have been tested; oxygen, hydrogen, helium, nitrogen, argon, neon, and air. The performance of the generalized BWR equation is poor for hydrogen and helium. The van der Waals equation is found to be inaccurate for air near the critical point. For helium, all three equations of state become inaccurate near the critical point. 13 refs

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)

Thermodynamics and heat power

CERN Document Server

Granet, Irving

2014-01-01

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

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?

OpenAIRE

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.

Parametric analysis of the thermodynamic properties for a medium with strong interaction between particles

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 equilibrium and heavy particles near a black hole

Energy Technology Data Exchange (ETDEWEB)

Zeldovich, Ya B [AN SSSR, Moscow

1976-02-23

The purpose of this letter is to point out, that thermodynamic equilibrium in general relativity corresponds to T(r)=Tsub(infinity)g/sub 00/sup(-1/2)=Tsub(infinity)..sqrt..(r/(r-rsub(g))). The last expression is written for a static non-rotating (Schwarzschild) black hole.

Heat and thermodynamics

CERN Document Server

Saxena, A K

2014-01-01

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

Some problems on the thermodynamic state of the metallogenetic systems; Consideraciones sobre la genesis de los yacimientos uraniferos

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.

Some problems on the thermodynamic state of the metallogenetic systems; Consideraciones sobre la genesis de los yacimientos uraniferos

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.

Early history of extended irreversible thermodynamics (1953-1983): An exploration beyond local equilibrium and classical transport theory

Science.gov (United States)

Lebon, G.; Jou, D.

2015-06-01

This paper gives a historical account of the early years (1953-1983) of extended irreversible thermodynamics (EIT). The salient features of this formalism are to upgrade the thermodynamic fluxes of mass, momentum, energy, and others, to the status of independent variables, and to explore the consistency between generalized transport equations and a generalized version of the second law of thermodynamics. This requires going beyond classical irreversible thermodynamics by redefining entropy and entropy flux. EIT provides deeper foundations, closer relations with microscopic formalisms, a wider spectrum of applications, and a more exciting conceptual appeal to non-equilibrium thermodynamics. We first recall the historical contributions by Maxwell, Cattaneo, and Grad on generalized transport equations. A thermodynamic theory wide enough to cope with such transport equations was independently proposed between 1953 and 1983 by several authors, each emphasizing different kinds of problems. In 1983, the first international meeting on this theory took place in Bellaterra (Barcelona). It provided the opportunity for the various authors to meet together for the first time and to discuss the common points and the specific differences of their previous formulations. From then on, a large amount of applications and theoretical confirmations have emerged. From the historical point of view, the emergence of EIT has been an opportunity to revisit the foundations and to open new avenues in thermodynamics, one of the most classical and well consolidated physical theories.

Thermodynamics of random reaction networks.

Science.gov (United States)

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

Science.gov (United States)

Lostaglio, Matteo; Jennings, David; Rudolph, Terry

2015-01-01

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

Thermodynamics of novel charged dilatonic BTZ black holes

Science.gov (United States)

Dehghani, M.

2017-10-01

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

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

Small Systems and Limitations on the Use of Chemical Thermodynamics

Science.gov (United States)

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.

Temporal trends in United States dew point temperatures

Science.gov (United States)

Robinson, Peter J.

2000-07-01

In this study, hourly data for the 1951-1990 period for 178 stations in the coterminous United States were used to establish temporal trends in dew point temperature. Although the data had been quality controlled previously (Robinson, 1998. Monthly variations of dew point temperatures in the coterminous United States. International Journal of Climatology 18: 1539-1556), comparisons of values between nearby stations suggested that instrumental changes, combined with locational changes, may have modified the results by as much as 1°C during the 40-year period. Nevertheless, seasonally averaged results indicated an increase over much of the area, of slightly over 1°C/100 years in spring and autumn, slightly less than this in summer. Winter displayed a drying of over 1°C/100 years. When only the 1961-1990 period was considered, the patterns were similar and trends increased by approximately 1-2°C/100 years, except in autumn, which displayed a slight drying. Analyses for specific stations indicated periods of both increasing and decreasing Td, the change between them varying with observation hour. No single change point was common over a wide area, although January commonly indicated maximum values early in the period in the east and west, and much later in the north-central portion. Rates of increase were generally higher in daytime than at night, especially in summer. Investigation of the inter-decadal differences in dew point, as a function of wind conditions, indicated that changes during calm conditions were commonly similar in magnitude to that of the overall average changes, suggesting an important role for the local hydrologic cycle in driving changes. Other inter-decadal changes could be attributed to the changes in the frequency and moisture content of invading air-streams. This was particularly clear for the changes in north-south flow in the interior.

Thermodynamic Curvature and Phase Transitions from Black Hole with a Coulomb-Like Field

International Nuclear Information System (INIS)

Han Yiwen; Hong Yun; Bao Zhiqing

2011-01-01

In this paper, we first investigate the thermodynamic features of the black hole with a coulomb-like field. Moreover, we obtain the geometric description of the black hole thermodynamics. We find that for the black hole with a coulomb-like field the Weinhold geometry is flat, whereas its Ruppeiner geometry is curved. For the heat capacity and curvature calculation shows the Ruppeiner geometry has a transition point. (general)

An International Standard Equation of State for Difluoromethane (R-32) for Temperatures from the Triple Point at 136.34 K to 435 K and Pressures up to 70 MPa

International Nuclear Information System (INIS)

Tillner-Roth, R.; Yokozeki, A.

1997-01-01

A fundamental equation of state for the Helmholtz free energy of R-32 (difluoromethane) is presented which is valid from the triple point at 136.34 K to 435 K and pressures up to 70 MPa. It is based on accurate measurements of pressure-density-temperature (p,ρ,T), speed of sound, heat capacity, and vapor pressure currently available. New values for the isobaric heat capacity c p circ of the ideal gas calculated from spectroscopic data taking into account also first order anharmonicity corrections are presented. The Helmholtz free energy equation of state has 19 coefficients and represents all selected experimental data within their estimated accuracy with the exception for heat capacities and speed of sound in the region close to the critical point. Typical uncertainties are ±0.05% for density, ±0.02% for the vapor pressure and ±0.5%endash 1% for the heat capacity. This equation of state has been compared to equations developed by other research groups by Annex 18 of the International Energy Agency and has been selected as an international standard formulation for the thermodynamic properties of R-32 by this group. copyright 1997 American Institute of Physics and American Chemical Society

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

Science.gov (United States)

Collell, Guillem; Fauquet, Jordi

2015-01-01

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

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

Science.gov (United States)

Collell, Guillem; Fauquet, Jordi

2015-01-01

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

Energy and thermodynamic considerations involving electromagnetic zero-point radiation

International Nuclear Information System (INIS)

Cole, Daniel C.

1999-01-01

There has been recent speculation and controversy regarding whether electromagnetic zero-point radiation might be the next candidate in the progression of plentiful energy sources, ranging, for example, from hydrodynamic, chemical, and nuclear energy sources. Certainly, however, extracting energy from the vacuum seems counter intuitive to most people. Here, these ideas are clarified, drawing on simple and common examples. Known properties of electromagnetic zero-point energy are qualitatively discussed. An outlook on the success of utilizing this energy source is then discussed

An introduction to equilibrium thermodynamics

CERN Document Server

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

1973-01-01

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

Thermodynamics for scientists and engineers

International Nuclear Information System (INIS)

Lim, Gyeong Hui

2011-02-01

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

Thermodynamic structure of the marine atmosphere over the region ...

Indian Academy of Sciences (India)

R. Narasimhan (Krishtel eMaging) 1461 1996 Oct 15 13:05:22

course of observations the ship moved from an open ... Marine boundary layer; thermodynamic structure; saturation point; Bay of Bengal Monsoon Experiment; .... when the low-pressure area is close to the ship the pressure is low and as the system moves away, the .... over oceanic regions to characterize the differences.

Methods of thermodynamics

CERN Document Server

Reiss, Howard

1997-01-01

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

Microfour-point probe for studying electronic transport through surface states

DEFF Research Database (Denmark)

Petersen, Christian Leth; Grey, Francois; Shiraki, I.

2000-01-01

Microfour-point probes integrated on silicon chips have been fabricated with probe spacings in the range 4-60 mum. They provide a simple robust device for electrical transport measurements at surfaces, bridging the gap between conventional macroscopic four-point probes and scanning tunneling...... transport through surface states, which is not observed on the macroscopic scale, presumably due to scattering at atomic steps. (C) 2000 American Institute of Physics....

Electrochemical determination of the oxidation potentials and the thermodynamic stability of the valence states of the transuranium elements in aqueous alkaline media

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 of strongly coupled repulsive Yukawa particles in ambient neutralizing plasma: Thermodynamic instability and the possibility of observation in fine particle plasmas

International Nuclear Information System (INIS)

Totsuji, Hiroo

2008-01-01

The thermodynamics is analyzed for a system composed of particles with hard cores, interacting via the repulsive Yukawa potential (Yukawa particulates), and neutralizing ambient (background) plasma. An approximate equation of state is given with proper account of the contribution of ambient plasma and it is shown that there exists a possibility for the total isothermal compressibility of Yukawa particulates and ambient plasma to diverge when the coupling between Yukawa particulates is sufficiently strong. In this case, the system undergoes a transition into separated phases with different densities and we have a critical point for this phase separation. Examples of approximate phase diagrams related to this transition are given. It is emphasized that the critical point can be in the solid phase and we have the possibility to observe a solid-solid phase separation. The applicability of these results to fine particle plasmas is investigated. It is shown that, though the values of the characteristic parameters are semiquantitative due to the effects not described by this model, these phenomena are expected to be observed in fine particle plasmas, when approximately isotropic bulk systems are realized with a very strong coupling between fine particles.

Thermodynamics of strongly coupled repulsive Yukawa particles in ambient neutralizing plasma: Thermodynamic instability and the possibility of observation in fine particle plasmas

Science.gov (United States)

Totsuji, Hiroo

2008-07-01

The thermodynamics is analyzed for a system composed of particles with hard cores, interacting via the repulsive Yukawa potential (Yukawa particulates), and neutralizing ambient (background) plasma. An approximate equation of state is given with proper account of the contribution of ambient plasma and it is shown that there exists a possibility for the total isothermal compressibility of Yukawa particulates and ambient plasma to diverge when the coupling between Yukawa particulates is sufficiently strong. In this case, the system undergoes a transition into separated phases with different densities and we have a critical point for this phase separation. Examples of approximate phase diagrams related to this transition are given. It is emphasized that the critical point can be in the solid phase and we have the possibility to observe a solid-solid phase separation. The applicability of these results to fine particle plasmas is investigated. It is shown that, though the values of the characteristic parameters are semiquantitative due to the effects not described by this model, these phenomena are expected to be observed in fine particle plasmas, when approximately isotropic bulk systems are realized with a very strong coupling between fine particles.

An analytical coarse-graining method which preserves the free energy, structural correlations, and thermodynamic state of polymer melts from the atomistic to the mesoscale.

Science.gov (United States)

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.

Thermodynamics-based Metabolite Sensitivity Analysis in metabolic networks.

Science.gov (United States)

Kiparissides, A; Hatzimanikatis, V

2017-01-01

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

Thermodynamical motivation of the Polish energy policy

Directory of Open Access Journals (Sweden)

Ziębik Andrzej

2013-02-01

Full Text Available Basing on the first and second law of thermodynamics the fundamental trends in the Polish energy policy are analysed, including the aspects of environmental protection. The thermodynamical improvement of real processes (reduction of exergy losses is the main way leading to an improvement of the effectivity of energy consumption. If the exergy loss is economically not justified, we have to do with an error from the viewpoint of the second law analysis. The paper contains a thermodynamical analysis of the ratio of final and primary energy, as well as the analysis of the thermo-ecological cost and index of sustainable development concerning primary energy. Analyses of thermo-ecological costs concerning electricity and centralized heat production have been also carried out. The effect of increasing the share of high-efficiency cogeneration has been analyzed, too. Attention has been paid to an improved efficiency of the transmission and distribution of electricity, which is of special importance from the viewpoint of the second law analysis. The improvement of the energy effectivity in industry was analyzed on the example of physical recuperation, being of special importance from the point of view of exergy analysis.

Thermodynamics of Radiation Modes

Science.gov (United States)

Pina, Eduardo; de la Selva, Sara Maria Teresa

2010-01-01

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

Understanding the edge effect in wetting: a thermodynamic approach.

Science.gov (United States)

Fang, Guoping; Amirfazli, A

2012-06-26

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

A New Perspective on Thermodynamics

CERN Document Server

Lavenda, Bernard H

2010-01-01

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

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

State Level Point-of-Sale Policy Priority as a Result of the FSPTCA.

Science.gov (United States)

Moreland-Russell, Sarah; Combs, Todd; Jones, Janice; Sorg, Amy A

2015-01-01

The Family Smoking Prevention and Tobacco Control Act (FSPTCA) give the U.S. Food and Drug Administration (FDA) unprecedented power to regulate tobacco products. One of the most significant provisions of the law allows state and local governments to adopt and enforce tobacco control legislation restricting the time, place, and manner (but not the content) of tobacco advertising. However, there is still reluctance among states and localities for mass adoption of laws due to challenges associated with legal feasibility and lack of U.S.-based evidence in effectiveness. The Center for Public Health Systems Science conducted interviews with key tobacco control contacts in 48 states at two time points (2012 and 2014) since the passage of the FSPTCA to assess the influence of the law on point-of-sale policy development in their state tobacco programs. Logistic regression results show that point-of-sale policy importance is growing post-FSPTCA, and that key influencers of this importance are states' tobacco control histories and environments, including that related to excise taxes and smoke free air policies. The adoption of smokefree and tax policies has become commonplace across the U.S., and the quality and extent of these laws and prevailing political will increasingly impact the ability of states to work in emerging tobacco control policy areas including those directed at the point of sale.

State level point-of-sale policy priority as a result of the FSPTCA

Directory of Open Access Journals (Sweden)

Sarah Moreland-Russell PhD MPH

2015-10-01

Full Text Available The Family Smoking Prevention and Tobacco Control Act (FSPTCA give the U.S. Food and Drug Administration (FDA unprecedented power to regulate tobacco products. One of the most significant provisions of the law allows state and local governments to adopt and enforce tobacco control legislation restricting the time, place, and manner (but not the content of tobacco advertising. However, there is still reluctance among states and localities for mass adoption of laws due to challenges associated with legal feasibility and lack of U.S.-based evidence in effectiveness. The Center for Public Health Systems Science conducted interviews with key tobacco control contacts in 48 states at two time points (2012 and 2014 since the passage of the FSPTCA to assess the influence of the law on point-of-sale policy development in their state tobacco programs. Logistic regression results show that point-of-sale policy importance is growing post-FSPTCA, and that key influencers of this importance are states' tobacco control histories and environments, including that related to excise taxes and smoke free air policies. The adoption of smokefree and tax policies has become commonplace across the U.S., and the quality and extent of these laws and prevailing political will increasingly impact the ability of states to work in emerging tobacco control policy areas including those directed at the point of sale.

Contact symmetries and Hamiltonian thermodynamics

International Nuclear Information System (INIS)

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

2015-01-01

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

Thermodynamics, 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...

Predicting acid dew point with a semi-empirical model

International Nuclear Information System (INIS)

Xiang, Baixiang; Tang, Bin; Wu, Yuxin; Yang, Hairui; Zhang, Man; Lu, Junfu

2016-01-01

Highlights: • The previous semi-empirical models are systematically studied. • An improved thermodynamic correlation is derived. • A semi-empirical prediction model is proposed. • The proposed semi-empirical model is validated. - Abstract: Decreasing the temperature of exhaust flue gas in boilers is one of the most effective ways to further improve the thermal efficiency, electrostatic precipitator efficiency and to decrease the water consumption of desulfurization tower, while, when this temperature is below the acid dew point, the fouling and corrosion will occur on the heating surfaces in the second pass of boilers. So, the knowledge on accurately predicting the acid dew point is essential. By investigating the previous models on acid dew point prediction, an improved thermodynamic correlation formula between the acid dew point and its influencing factors is derived first. And then, a semi-empirical prediction model is proposed, which is validated with the data both in field test and experiment, and comparing with the previous models.

A thermodynamic approach to obtain materials properties for engineering applications

Science.gov (United States)

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

Science.gov (United States)

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

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...

Optimum design of dual pressure heat recovery steam generator using non-dimensional parameters based on thermodynamic and thermoeconomic approaches

International Nuclear Information System (INIS)

Naemi, Sanaz; Saffar-Avval, Majid; Behboodi Kalhori, Sahand; Mansoori, Zohreh

2013-01-01

The thermodynamic and thermoeconomic analyses are investigated to achieve the optimum operating parameters of a dual pressure heat recovery steam generator (HRSG), coupled with a heavy duty gas turbine. In this regard, the thermodynamic objective function including the exergy waste and the exergy destruction, is defined in such a way to find the optimum pinch point, and consequently to minimize the objective function by using non-dimensional operating parameters. The results indicated that, the optimum pinch point from thermodynamic viewpoint is 2.5 °C and 2.1 °C for HRSGs with live steam at 75 bar and 90 bar respectively. Since thermodynamic analysis is not able to consider economic factors, another objective function including annualized installation cost and annual cost of irreversibilities is proposed. To find the irreversibility cost, electricity price and also fuel price are considered independently. The optimum pinch point from thermoeconomic viewpoint on basis of electricity price is 20.6 °C (75 bar) and 19.2 °C (90 bar), whereas according to the fuel price it is 25.4 °C and 23.7 °C. Finally, an extensive sensitivity analysis is performed to compare optimum pinch point for different electricity and fuel prices. -- Highlights: ► Presenting thermodynamic and thermoeconomic optimization of a heat recovery steam generator. ► Defining an objective function consists of exergy waste and exergy destruction. ► Defining an objective function including capital cost and cost of irreversibilities. ► Obtaining the optimized operating parameters of a dual pressure heat recovery boiler. ► Computing the optimum pinch point using non-dimensional operating parameters

Analysis of Multicomponent Adsorption Close to a Dew Point

DEFF Research Database (Denmark)

Shapiro, Alexander; Stenby, Erling Halfdan

1998-01-01

We develop the potential theory of multicomponent adsorption close to a dew point. The approach is based on an asymptotic adsorption equation (AAE) which is valid in a vicinity of the dew point. By this equation the thickness of the liquid film is expressed through thermodynamic characteristics...... and the direct calculations, even if the mixture is not close to a dew point.Key Words: adsorption; potential theory; multicomponent; dew point....

Introduction to applied thermodynamics

CERN Document Server

Helsdon, R M; Walker, G E

1965-01-01

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

Transitions in state public health law: comparative analysis of state public health law reform following the Turning Point Model State Public Health Act.

Science.gov (United States)

Meier, Benjamin Mason; Hodge, James G; Gebbie, Kristine M

2009-03-01

Given the public health importance of law modernization, we undertook a comparative analysis of policy efforts in 4 states (Alaska, South Carolina, Wisconsin, and Nebraska) that have considered public health law reform based on the Turning Point Model State Public Health Act. Through national legislative tracking and state case studies, we investigated how the Turning Point Act's model legal language has been considered for incorporation into state law and analyzed key facilitating and inhibiting factors for public health law reform. Our findings provide the practice community with a research base to facilitate further law reform and inform future scholarship on the role of law as a determinant of the public's health.

Thermodynamic properties of copper compounds with oxygen and hydrogen from first principles

Energy Technology Data Exchange (ETDEWEB)

Korzhavyi, P.A.; Johansson, B. (Applied Materials Physics, Dept. of Materials Science and Engineering, Royal Inst. of Technology, Stockholm (Sweden))

2010-02-15

We employ quantum-mechanical calculations (based on density functional theory and linear response theory) in order to test the mechanical and chemical stability of several solid-state configurations of Cu1+, Cu2+, O2-, H1-, and H1+ ions. We begin our analysis with cuprous oxide (Cu{sub 2}O, cuprite structure), cupric oxide (CuO, tenorite structure), and cuprous hydride (CuH, wurtzite and sphalerite structures) whose thermodynamic properties have been studied experimentally. In our calculations, all these compounds are found to be mechanically stable configurations. Their formation energies calculated at T = 0 K (including the energy of zero-point and thermal motion of the ions) and at room temperature are in good agreement with existing thermodynamic data. A search for other possible solid-state conformations of copper, hydrogen, and oxygen ions is then performed. Several candidate structures for solid phases of cuprous oxy-hydride (Cu{sub 4}H{sub 2}O) and cupric hydride (CuH{sub 2}) have been considered but found to be dynamically unstable. Cuprous oxy-hydride is found to be energetically unstable with respect to decomposition onto cuprous oxide and cuprous hydride. Metastability of cuprous hydroxide (CuOH) is established in our calculations. The free energy of CuOH is calculated to be some 50 kJ/mol higher than the average of the free energies of Cu{sub 2}O and water. Thus, cuprite Cu{sub 2}O is the most stable of the examined Cu(I) compounds

Thermodynamic properties of copper compounds with oxygen and hydrogen from first principles

International Nuclear Information System (INIS)

Korzhavyi, P.A.; Johansson, B.

2010-02-01

We employ quantum-mechanical calculations (based on density functional theory and linear response theory) in order to test the mechanical and chemical stability of several solid-state configurations of Cu 1+ , Cu 2+ , O 2- , H 1- , and H 1+ ions. We begin our analysis with cuprous oxide (Cu 2 O, cuprite structure), cupric oxide (CuO, tenorite structure), and cuprous hydride (CuH, wurtzite and sphalerite structures) whose thermodynamic properties have been studied experimentally. In our calculations, all these compounds are found to be mechanically stable configurations. Their formation energies calculated at T = 0 K (including the energy of zero-point and thermal motion of the ions) and at room temperature are in good agreement with existing thermodynamic data. A search for other possible solid-state conformations of copper, hydrogen, and oxygen ions is then performed. Several candidate structures for solid phases of cuprous oxy-hydride (Cu 4 H 2 O) and cupric hydride (CuH 2 ) have been considered but found to be dynamically unstable. Cuprous oxy-hydride is found to be energetically unstable with respect to decomposition onto cuprous oxide and cuprous hydride. Metastability of cuprous hydroxide (CuOH) is established in our calculations. The free energy of CuOH is calculated to be some 50 kJ/mol higher than the average of the free energies of Cu 2 O and water. Thus, cuprite Cu 2 O is the most stable of the examined Cu(I) compounds

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.

Thermodynamic analysis and phase equilibria investigation in Pb−Zn−Ag system

Directory of Open Access Journals (Sweden)

Mitovski Aleksandra M.

2010-01-01

Full Text Available Physico-chemical processes that take place during the refining process in the extractive metallurgy of lead, are connected with ternary Pb−Zn−Ag system, which is necessary to study from the theoretical practical and aspects. Such investigation is important from production point of view, because of the phenomena that occur during desilvering of lead which is one of the important stages during lead refining process. Process of lead desilvering binds to ternary system Pb−Zn−Ag, which was the reason for numerous investigations, both from thermodynamic point of view and in terms of testing and determining the phase diagram, bearing in mind the theoretical, and practical importance of knowledge about the processes which are going in investigated system. The paper presents the results of thermodynamic analysis and investigation of phase equilibria of the Pb−Zn−Ag ternary system using the method of thermodynamic predictions and phase diagrams calculations, respectively, and the experimental results of metalography obtained by optical microscopy. Phase diagram of the vertical section Pb−Zn80Ag20 is presented, obtained by CALPHAD calculation methodology, and using PANDAT thermodynamic software, compared to experimental results obtained by DTA analysis. The results show a pronounced break in solubility, which is characteristic for the whole ternary Pb−Zn−Ag system. Also, it can be noticed that the thermodynamic properties follow the behavior of this system, which is expressed through positive deviation of Raoult’s law, pointing to the lack of lead affinity compared to the other two components in the system. The optical microscopy results of the investigated system show the following: - Sample L1 (weight% Pb = 98: the structure of the observed section shows double eutectic (Pbsol+Zn−Agsol which lies in the base of the primary crystals of lead (Pbsol - Samples L2−L5: the structure consists of a dual eutectic (Pbsol+Zn−Agsol and

Thermodynamic criterions for heat exchanger networks design

Energy Technology Data Exchange (ETDEWEB)

Guiglion, C.; Farhat, S.; Pibouleau, L.; Domenech, S. (Ecole Nationale Superieure d' Ingenieurs de Genie Chimique, 31 - Toulouse (France))

1994-03-01

This problem under consideration consists in selecting a heat exchanger network able to carry out a given request in heatings and coolings, in steady-state behaviour with constant pressure, by using if necessary cold and hot utilities, and under the constraint [Delta] T [>=] e in order to restrict investment costs. The exchanged energy and the produced entropy are compared in terms of operating costs. According to the request to be satisfied and the constraints of utility consumption, it is shown that the goal to minimize the produced entropy more or less agrees with the goal to minimize the exchanged energy. In the last part, the case where the cost of utility use is assumed to be proportional to the flow rate, with a proportionality constant only depending on the input thermodynamic state, is studied thoroughly. Under this assumption, the minimization of operating costs is compatible with the minimization of exchanged energy, and can be obtained via the maximization of the difficulty of the request part, made without using utilities. This point is based on the notion of a request easier than another, which explicits the quite vague idea that a request is all the more easier because it involves less heatings at high temperatures and less coolings at low temperatures. (author). 5 refs., 1 fig.

Thermodynamic Properties of Alkali Metal Hydroxides. Part II. Potassium, Rubidium, and Cesium Hydroxides

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

Science.gov (United States)

Ham, Sihyun

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

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

Science.gov (United States)

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

2018-04-01

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

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.

Thermodynamic optimization for cryogenic systems with a finite number of heat intercepts

International Nuclear Information System (INIS)

Bisio, G.

1989-01-01

It has been already shown that in cryogenic plants it is very useful to apply thermodynamic optimization, either with a continuous variation of the heat transfer rate through the insulation or with the spatial positioning of discrete heat exchangers in the same insulation. The aim of this paper is to study the thermodynamic optimization by the variation of the heat transfer rate in a finite number of points through insulation for one-dimensional materials in series, whose equivalent conductivity is a function of temperature. For this purpose the results of some researches by the author, in the field of generalized thermodynamics, for the properties of some functions and in particular of the rate of entropy production, regarding one-dimensional heat transfer, are utilized

Energetics of intrinsic point defects in uranium dioxide from electronic-structure calculations

International Nuclear Information System (INIS)

Nerikar, Pankaj; Watanabe, Taku; Tulenko, James S.; Phillpot, Simon R.; Sinnott, Susan B.

2009-01-01

The stability range of intrinsic point defects in uranium dioxide is determined as a function of temperature, oxygen partial pressure, and non-stoichiometry. The computational approach integrates high accuracy ab initio electronic-structure calculations and thermodynamic analysis supported by experimental data. In particular, the density functional theory calculations are performed at the level of the spin polarized, generalized gradient approximation and includes the Hubbard U term; as a result they predict the correct anti-ferromagnetic insulating ground state of uranium oxide. The thermodynamic calculations enable the effects of system temperature and partial pressure of oxygen on defect formation energy to be determined. The predicted equilibrium properties and defect formation energies for neutral defect complexes match trends in the experimental literature quite well. In contrast, the predicted values for charged complexes are lower than the measured values. The calculations predict that the formation of oxygen interstitials becomes increasingly difficult as higher temperatures and reducing conditions are approached

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