Energy Technology Data Exchange (ETDEWEB)
NONE
1996-12-31
Some chlorofluorocarbons (CFCs) are well-adapted to coldness production by vapour compression and thus are widely used in the storage of agriculture-food products from the production to the domestic consumer but also in air-conditioning systems and heat pumps. Atmospheric impacts of the use of CFCs (`ozone hole`) led the international community to adopt remedial measures which aim to prohibit the production of CFCs. These constraints led the users of refrigerating fluids to use substitution fluids and to develop new techniques of energy recovery and heat/coldness production. This workshop takes stock of this situation and of the problems encountered by the various actors involved in the replacement of CFCs in thermodynamical systems: evolutions of regulation, point of view of refrigerating fluid producers and of compressors and heat exchangers manufacturers, research studies on substitution fluids, recovery of CFCs and other refrigerating fluids, revival in the use of natural fluids (like ammonia), and use of new thermodynamical systems like compression/absorption (water/ammonia) cycles. (J.S.)
Energy Technology Data Exchange (ETDEWEB)
Fleurance, M.
1996-12-31
Following the Montreal protocol and the withdrawal of the CFC-type refrigerating fluids, York France company has developed and adapted its equipments to new refrigerants. Each user will have to know how to define the best option for his installation: opting for or ignoring the withdrawal of CFCs, confining the installations, changing for new intermediate substitutes (HCFC-type), or changing or replacing with new long term substitutes (HFCs). (J.S.)
Energy Technology Data Exchange (ETDEWEB)
Leveque, P.
1995-02-01
The control system of the Tore-Supra is a wide and complex system that cannot be interrupted while running without significant consequences on the operating of the machine. Replacing the current system cannot be achieved in a global way without immobilisation and high costs. Therefore partial changes have been decided on. This work presents the detailed analysis of the arrangements and the operating of the system that will be replaced: the pro`s and con`s that have appeared through experience are related. The possibilities that the new apparatus offers are also examined. A method of step by step replacements had to be set up in order to assess the means, funds, term of achievement, performance and quality of the overall project. (TEC). 15 refs., 29 figs.
Electrochemical thermodynamic measurement system
Reynier, Yvan [Meylan, FR; Yazami, Rachid [Los Angeles, CA; Fultz, Brent T [Pasadena, CA
2009-09-29
The present invention provides systems and methods for accurately characterizing thermodynamic and materials properties of electrodes and electrochemical energy storage and conversion systems. Systems and methods of the present invention are configured for simultaneously collecting a suite of measurements characterizing a plurality of interconnected electrochemical and thermodynamic parameters relating to the electrode reaction state of advancement, voltage and temperature. Enhanced sensitivity provided by the present methods and systems combined with measurement conditions that reflect thermodynamically stabilized electrode conditions allow very accurate measurement of thermodynamic parameters, including state functions such as the Gibbs free energy, enthalpy and entropy of electrode/electrochemical cell reactions, that enable prediction of important performance attributes of electrode materials and electrochemical systems, such as the energy, power density, current rate and the cycle life of an electrochemical cell.
Statistical Thermodynamics of Disperse Systems
DEFF Research Database (Denmark)
Shapiro, Alexander
1996-01-01
Principles of statistical physics are applied for the description of thermodynamic equilibrium in disperse systems. The cells of disperse systems are shown to possess a number of non-standard thermodynamic parameters. A random distribution of these parameters in the system is determined....... On the basis of this distribution, it is established that the disperse system has an additional degree of freedom called the macro-entropy. A large set of bounded ideal disperse systems allows exact evaluation of thermodynamic characteristics. The theory developed is applied to the description of equilibrium...
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
Energy Technology Data Exchange (ETDEWEB)
NONE
2004-07-01
A group of thirteen houses in Plan-les-Ouates (southwestern Switzerland) constructed in 1985 was originally equipped with direct electric heaters. Their inhabitants complained about high electricity bills and bad thermal comfort due to uneven room temperatures and insufficient amounts of warm water. A group of specialists from the Swiss Federal Office of Energy, the energy service of the canton of Geneva and from an engineering company studied the case and suggested to replace the direct electric heating system by an air to water heat pump. Seven owners have decided for this modification and the retrofit has been made in autumn 2000. The paper presents the results of performance measurements, operating experience gained and economic considerations for the years 2001, 2002 and 2003 for six installations. The average coefficients of performance ranged from 2.3 to 2.9.
Thermodynamics of Dipolar Chain Systems
DEFF Research Database (Denmark)
R. Armstrong, J.; Zinner, Nikolaj Thomas; V. Fedorov, D.
2012-01-01
The thermodynamics of a quantum system of layers containing perpendicularly oriented dipolar molecules is studied within an oscillator approximation for both bosonic and fermionic species. The system is assumed to be built from chains with one molecule in each layer. We consider the effects...... numerically. Our findings indicate that thermodynamic observables, such as the heat capacity, can be used to probe the signatures of the intralayer interaction between chains. This should be relevant for near future experiments on polar molecules with strong dipole moments....
Statistical Thermodynamics of Economic Systems
Directory of Open Access Journals (Sweden)
Hernando Quevedo
2011-01-01
Full Text Available We formulate the thermodynamics of economic systems in terms of an arbitrary probability distribution for a conserved economic quantity. As in statistical physics, thermodynamic macroeconomic variables emerge as the mean value of microeconomic variables, and their determination is reduced to the computation of the partition function, starting from an arbitrary function. Explicit hypothetical examples are given which include linear and nonlinear economic systems as well as multiplicative systems such as those dominated by a Pareto law distribution. It is shown that the macroeconomic variables can be drastically changed by choosing the microeconomic variables in an appropriate manner. We propose to use the formalism of phase transitions to study severe changes of macroeconomic variables.
Thermodynamic modeling of complex systems
DEFF Research Database (Denmark)
Liang, Xiaodong
. Contrary to earlier theories, the oil is not only present on the surface, but also in great volumes both in the water column and on the seafloor, which indicates that we do not know enough about how oil behaves in water and interacts with it. Sonar detection is one of the most important and necessary...... after an oil spill. Engineering thermodynamics could be applied in the state-of-the-art sonar products through advanced artificial technology, if the speed of sound, solubility and density of oil-seawater systems could be satisfactorily modelled. The addition of methanol or glycols into unprocessed well...... streams during subsea pipelines is necessary to inhibit gas hydrate formation, and the offshore reservoirs often mean complicated temperature and pressure conditions. Accurate description of the phase behavior and thermalphysical properties of complex systems containing petroleum fluids and polar...
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 Calculations for Systems Biocatalysis
DEFF Research Database (Denmark)
Abu, Rohana; Gundersen, Maria T.; Woodley, John M.
2015-01-01
on the basis of kinetics. However, many of the most interesting non-natural chemical reactions which could potentially be catalysed by enzymes, are thermodynamically unfavourable and are thus limited by the equilibrium position of the reaction. A good example is the enzyme ω-transaminase, which catalyses...... the transamination of a pro-chiral ketone into a chiral amine (interesting in many pharmaceutical applications). Here, the products are often less energetically stable than the reactants, meaning that the reaction may be thermodynamically unfavourable. As in nature, such thermodynamically-challenged reactions can...... be altered by coupling with other reactions. For instance, in the case of ω-transaminase, such a coupling could be with alanine dehydrogenase. Herein, the aim of this work is to identify thermodynamic bottlenecks within a multi-enzyme process, using group contribution method to calculate the Gibbs free...
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.
Thermodynamic Optimality criteria for biological systems in linear irreversible thermodynamics
International Nuclear Information System (INIS)
Chimal, J C; Sánchez, N; Ramírez, PR
2017-01-01
In this paper the methodology of the so-called Linear Irreversible Thermodynamics (LIT) is applied; although traditionally used locally to study general systems in non-equilibrium states in which it is consider both internal and external contributions to the entropy increments in order to analyze the efficiency of two coupled processes with generalized fluxes J 1 , J 2 and their corresponding forces X 1 , X 2 . We extend the former analysis to takes into account two different operating regimes namely: Omega Function and Efficient Power criterion, respectively. Results show analogies in the optimal performance between and we can say that there exist a criteria of optimization which can be used specially for biological systems where a good design of the biological parameters made by nature at maximum efficient power conditions lead to more efficient engines than those at the maximum power conditions or ecological conditions. (paper)
International Nuclear Information System (INIS)
Zanchini, E.
1988-01-01
The definition of energy, in thermodynamics, is dependent by starting operative definitions of the basic concepts of physics on which it rests, such as those of isolated systems, ambient of a system, separable system and set of separable states. Then the definition of energy is rigorously extended to open systems. The extension gives a clear physical meaning to the concept of energy difference between two states with arbitrary different compositions
Thermodynamic cycles of adsorption desalination system
International Nuclear Information System (INIS)
Wu, Jun W.; Hu, Eric J.; Biggs, Mark J.
2012-01-01
Highlights: ► Thermodynamic cycles of adsorption desalination (AD) system have been identified all possible evaporator temperature scenarios. ► Temperature of evaporator determines the cycle. ► Higher evaporator temperature leads to higher water production if no cooling is required. -- Abstract: The potential to use waste heat to co-generate cooling and fresh water from saline water using adsorption on silica is attracting increasing attention. A variety of different thermodynamic cycles of such an adsorption desalination (AD) system arise as the temperature of the saline water evaporator is varied relative to temperature of the water used to cool the adsorbent as it adsorbs the evaporated water. In this paper, all these possible thermodynamic cycles are enumerated and analysed to determine their relative performances in terms of specific energy consumption and fresh water productivity.
Solutions de remplacement à la culture du tabac et aux activités ...
International Development Research Centre (IDRC) Digital Library (Canada)
Solutions de remplacement à la culture du tabac et aux activités connexes (Inde) ... L'Inde fait toutefois partie du groupe de travail sur les activités de remplacement de la culture du tabac économiquement viables de l'Organisation mondiale de la santé (OMS) et dispose de ... India, Central Asia, Far East Asia, South Asia ...
Consistent thermodynamic properties of lipids systems
DEFF Research Database (Denmark)
Cunico, Larissa; Ceriani, Roberta; Sarup, Bent
Physical and thermodynamic properties of pure components and their mixtures are the basic requirement for process design, simulation, and optimization. In the case of lipids, our previous works[1-3] have indicated a lack of experimental data for pure components and also for their mixtures...... different pressures, with azeotrope behavior observed. Available thermodynamic consistency tests for TPx data were applied before performing parameter regressions for Wilson, NRTL, UNIQUAC and original UNIFAC models. The relevance of enlarging experimental databank of lipids systems data in order to improve...... the performance of predictive thermodynamic models was confirmed in this work by analyzing the calculated values of original UNIFAC model. For solid-liquid equilibrium (SLE) data, new consistency tests have been developed [2]. Some of the developed tests were based in the quality tests proposed for VLE data...
Calorimetry and thermodynamics of living systems
Energy Technology Data Exchange (ETDEWEB)
Lamprecht, Ingolf
2003-10-14
Calorimetry of living systems and classical thermodynamics developed in parallel, from Lavoisier's early ice calorimeter experiments on guinea pigs, followed by Dubrunfaut's macrocalorimetric research of fermentation processes and Atwater-Rosa's whole-body calorimetry on humans and domestic animals, to the introduction of the famous Tian-Calvet instrument that found entrance into so many different fields of biology. In this work, six examples of living-system calorimetry and thermodynamics are presented. These are: (i) glycolytic oscillations far off the thermodynamic equilibrium; (ii) growth and energy balances in fermenting and respiring yeast cultures; (iii) direct and indirect calorimetric monitoring of electrically stimulated reptile metabolism; (iv) biologic and climatic factors influencing the temperature constancy and distribution in the mound of a wood ant colony as an example of a complex ecological system; (v) energetic considerations on the clustering of European honeybees in winter as a means to save energy and stored food as well as for their Japanese counterparts in defending against hornet predators; and (vi) energetic and evolutionary aspects of the mass specific entropy production rate, the so-called bound dissipation or psiu-function. The examples presented here are just a very personal selection of living systems from a broad spectrum at all levels of complexity. Common for all of them is that they were investigated calorimetrically on the background of classical and irreversible thermodynamics.
Calorimetry and thermodynamics of living systems
International Nuclear Information System (INIS)
Lamprecht, Ingolf
2003-01-01
Calorimetry of living systems and classical thermodynamics developed in parallel, from Lavoisier's early ice calorimeter experiments on guinea pigs, followed by Dubrunfaut's macrocalorimetric research of fermentation processes and Atwater-Rosa's whole-body calorimetry on humans and domestic animals, to the introduction of the famous Tian-Calvet instrument that found entrance into so many different fields of biology. In this work, six examples of living-system calorimetry and thermodynamics are presented. These are: (i) glycolytic oscillations far off the thermodynamic equilibrium; (ii) growth and energy balances in fermenting and respiring yeast cultures; (iii) direct and indirect calorimetric monitoring of electrically stimulated reptile metabolism; (iv) biologic and climatic factors influencing the temperature constancy and distribution in the mound of a wood ant colony as an example of a complex ecological system; (v) energetic considerations on the clustering of European honeybees in winter as a means to save energy and stored food as well as for their Japanese counterparts in defending against hornet predators; and (vi) energetic and evolutionary aspects of the mass specific entropy production rate, the so-called bound dissipation or psiu-function. The examples presented here are just a very personal selection of living systems from a broad spectrum at all levels of complexity. Common for all of them is that they were investigated calorimetrically on the background of classical and irreversible thermodynamics
Thermodynamic equilibrium in relativistic rotating systems
International Nuclear Information System (INIS)
Suen, W.M.; Washington Univ., St. Louis, MO; Young, K.
1988-01-01
The thermodynamic equilibrium configurations of relativistic rotating stars are studied using the maximum entropy principle. It is shown that the heuristic arguments for the equilibrium conditions can be developed into a maximum entropy principle in which the variations are carried out in a fixed background spacetime. This maximum principle with the fixed background assumption is technically simpler than, but has to be justified by, a maximum entropy principle without the assumption. Such a maximum entropy principle is formulated in this paper, showing that the general relativistic system can be treated on the same footing as other long-range force systems. (author)
Theoretical Studies of Small-System Thermodynamics in Energetic Materials
2016-01-06
molecular explosives and interfaces between explosive constituent materials. Exploring how the fundamental thermodynamic properties and energy...SECURITY CLASSIFICATION OF: This is a comprehensive theoretical research program to investigate the fundamental principles of small-system thermodynamics ...a.k.a. nanothermodynamics). The proposed work is motivated by our desire to better understand the fundamental dynamics and thermodynamics of
Alternatives to Anti-Personnel Landmines (Solutions de remplacement aux mines antipersonnel)
2003-05-01
remplacement ont un prix : elles sont plus pesantes sur le plan logistique et impliquent des risques opérationnels pour les forces de l’OTAN. En...très importante, de l’interopérabilité dans le transfert de secteurs qui ont été minés par un pays non-signataire de la Convention d’Ottawa. Le...SEINE CEDEX, FRANCE RTO TECHNICAL REPORT 40(I) Alternatives to Anti-Personnel Landmines (Solutions de remplacement aux mines antipersonnel) Military
Geometry and symmetry in non-equilibrium thermodynamic systems
Sonnino, Giorgio
2017-06-01
The ultimate aim of this series of works is to establish the closure equations, valid for thermodynamic systems out from the Onsager region, and to describe the geometry and symmetry in thermodynamic systems far from equilibrium. Geometry of a non-equilibrium thermodynamic system is constructed by taking into account the second law of thermodynamics and by imposing the validity of the Glansdorff-Prigogine Universal Criterion of Evolution. These two constraints allow introducing the metrics and the affine connection of the Space of the Thermodynamic Forces, respectively. The Lie group associated to the nonlinear Thermodynamic Coordinate Transformations (TCT) leaving invariant both the entropy production σ and the Glansdorff-Prigogine dissipative quantity P, is also described. The invariance under TCT leads to the formulation of the Thermodynamic Covariance Principle (TCP): The nonlinear closure equations, i.e. the flux-force relations, must be covariant under TCT. In other terms, the fundamental laws of thermodynamics should be manifestly covariant under transformations between the admissible thermodynamic forces (i.e. under TCT). The symmetry properties of a physical system are intimately related to the conservation laws characterizing the thermodynamic system. Noether's theorem gives a precise description of this relation. The macroscopic theory for closure relations, based on this geometrical description and subject to the TCP, is referred to as the Thermodynamic Field Theory (TFT). This theory ensures the validity of the fundamental theorems for systems far from equilibrium.
Thermodynamic inversion origin of living systems
Kompanichenko, Vladimir N
2017-01-01
This book discusses the theory, general principles, and energy source conditions allowing for the emergence of life in planetary systems. The author examines the material conditions found in natural hydrothermal sites, the appropriate analogs of prebiotic environments on early Earth. He provides an overview of current laboratory experiments in prebiotic materials chemistry and substantiation of a new direction for the experiments in the origin of life field. Describes thermodynamic inversion and how it relates to the living cell; Examines the current direction of experiments on prebiotic materials chemistry; Introduces and substantiates necessary conditions for the emergence of life.
Thermodynamics of hydrothermal systems with oxalate ion
Khodakovsky, I. L.; Devina, O. A.
2009-04-01
The geochemical and industrial significance of oxalates have led to great interest in the behavior of oxalate ion in hydrothermal systems. On the basis of a study by G.B. Naumov et al (1971) of gaseous-liquid inclusions it is shown that whewellite (CaC2O4•H2O) which was found in quartz-calcite-fluorite veins in the uranium ore deposit of the Eastern Transbaikal region was formed at temperatures about 150°C and pressure CO2 of 600-860 atm. The isotopic composition of carbon for these hydrothermal whewellite samples was determined by Galimov et al (1975): Delta13C from -1.56 to -2.22%. In a continuation of the study of organic-acid-water-rock interactions the thermodynamics of hydrothermal equilibriums for the systems Ox-H, Ox-H-Ca, Ox-H-Mg (where Ox = C2O42-), are described up to 200°C. The key network reactions and compounds related to the aqueous ion C2O42- are discussed and used to define the key values. The critical evaluation of thermodynamic properties for this ion is a part of the development of the new key values system for the joint thermodynamic database in the Internet. The evaluation involves the analysis of the enthalpy changes, Gibbs energy changes, and the entropy calculations for all key substances in the key network. A consistent set of thermodynamic property values is given for α-H2C2O4(cr), β-H2C2O4(cr), H2C2O4•H2O(cr), CaC2O4(cr), CaC2O4•H2O(cr,whewellite), NaC2O4(cr,natroxalate), MgC2O4•2H2O(cr,glushinskite) and aqueous species C2O42-, HC2O4-, H2C2O4°, CaC2O4°. This study was funded by Russian Foundation for Basic Research (project N 07-05-01108).
Quantum thermodynamics for driven dissipative bosonic systems
Ochoa, Maicol A.; Zimbovskaya, Natalya; Nitzan, Abraham
2018-02-01
We investigate two prototypical dissipative bosonic systems under slow driving and arbitrary system-bath coupling strength, recovering their dynamic evolution as well as the heat and work rates, and we verify that thermodynamic laws are respected. Specifically, we look at the damped harmonic oscillator and the damped two-level system. For the former, we study independently the slow time-dependent perturbation in the oscillator frequency and in the coupling strength. For the latter, we concentrate on the slow modulation of the energy gap between the two levels. Importantly, we are able to find the entropy production rates for each case without explicitly defining nonequilibrium extensions for the entropy functional. This analysis also permits the definition of phenomenological friction coefficients in terms of structural properties of the system-bath composite.
Thermodynamics of small systems two volumes bound as one
Hill, Terrel L
1994-01-01
This authoritative summary of the basics of small system, or nonmacroscopic, thermodynamics was written by the field's founder. Originally published in two volumes, the text remains essential reading in an area in which the practical aim is to derive equations that provide interconnections among various thermodynamic functions. Part I introduces the basics of small system thermodynamics, exploring environmental variables, noting throughout the ways in which small thermodynamic systems differ operationally from macroscopic systems. Part II explores binding on macromolecules and aggregation, completes the discussion of environmental variables, and includes brief summaries of certain special topics, including electric and magnetic fields, spherical drops and bubbles, and polydisperse systems.
Limits of predictions in thermodynamic systems: a review
Marsland, Robert, III; England, Jeremy
2018-01-01
The past twenty years have seen a resurgence of interest in nonequilibrium thermodynamics, thanks to advances in the theory of stochastic processes and in their thermodynamic interpretation. Fluctuation theorems provide fundamental constraints on the dynamics of systems arbitrarily far from thermal equilibrium. Thermodynamic uncertainty relations bound the dissipative cost of precision in a wide variety of processes. Concepts of excess work and excess heat provide the basis for a complete thermodynamics of nonequilibrium steady states, including generalized Clausius relations and thermodynamic potentials. But these general results carry their own limitations: fluctuation theorems involve exponential averages that can depend sensitively on unobservably rare trajectories; steady-state thermodynamics makes use of a dual dynamics that lacks any direct physical interpretation. This review aims to present these central results of contemporary nonequilibrium thermodynamics in such a way that the power of each claim for making physical predictions can be clearly assessed, using examples from current topics in soft matter and biophysics.
Nonequilibrium statistical mechanics and stochastic thermodynamics of small systems
International Nuclear Information System (INIS)
Tu Zhanchun
2014-01-01
Thermodynamics is an old subject. The research objects in conventional thermodynamics are macroscopic systems with huge number of particles. In recent 30 years, thermodynamics of small systems is a frontier topic in physics. Here we introduce nonequilibrium statistical mechanics and stochastic thermodynamics of small systems. As a case study, we construct a Canot-like cycle of a stochastic heat engine with a single particle controlled by a time-dependent harmonic potential. We find that the efficiency at maximum power is 1 - √T c /T h , where Tc and Th are the temperatures of cold bath and hot bath, respectively. (author)
Thermodynamics and vibrational modes of hard sphere colloidal systems
Zargar, R.
2014-01-01
The central question that we address in this thesis is the thermodynamics of colloidal glasses. The thermodynamics of colloidal hard sphere glasses are directly related to the entropy of the system, since the phase behavior of hard sphere systems is dictated only by entropic contributions, and also
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
Thermodynamic modeling of the Co-Fe-O system
DEFF Research Database (Denmark)
Zhang, Weiwei; Chen, Ming
2013-01-01
As a part of the research project aimed at developing a thermodynamic database of the La-Sr-Co-Fe-O system for applications in Solid Oxide Fuel Cells (SOFCs), the Co-Fe-O subsystem was thermodynamically re-modeled in the present work using the CALPHAD methodology. The solid phases were described...... using the Compound Energy Formalism (CEF) and the ionized liquid was modeled with the ionic two-sublattice model based on CEF. A set of self-consistent thermodynamic parameters was obtained eventually. Calculated phase diagrams and thermodynamic properties are presented and compared with experimental...
International Nuclear Information System (INIS)
Glavatskiy, K. S.
2015-01-01
Validity of local equilibrium has been questioned for non-equilibrium systems which are characterized by delayed response. In particular, for systems with non-zero thermodynamic inertia, the assumption of local equilibrium leads to negative values of the entropy production, which is in contradiction with the second law of thermodynamics. In this paper, we address this question by suggesting a variational formulation of irreversible evolution of a system with non-zero thermodynamic inertia. We introduce the Lagrangian, which depends on the properties of the normal and the so-called “mirror-image” systems. We show that the standard evolution equations, in particular, the Maxwell-Cattaneo-Vernotte equation, can be derived from the variational procedure without going beyond the assumption of local equilibrium. We also argue that the second law of thermodynamics in non-equilibrium should be understood as a consequence of the variational procedure and the property of local equilibrium. For systems with instantaneous response this leads to the standard requirement of the local instantaneous entropy production being always positive. However, if a system is characterized by delayed response, the formulation of the second law of thermodynamics should be altered. In particular, the quantity, which is always positive, is not the instantaneous entropy production, but the entropy production averaged over a proper time interval
Glavatskiy, K S
2015-10-28
Validity of local equilibrium has been questioned for non-equilibrium systems which are characterized by delayed response. In particular, for systems with non-zero thermodynamic inertia, the assumption of local equilibrium leads to negative values of the entropy production, which is in contradiction with the second law of thermodynamics. In this paper, we address this question by suggesting a variational formulation of irreversible evolution of a system with non-zero thermodynamic inertia. We introduce the Lagrangian, which depends on the properties of the normal and the so-called "mirror-image" systems. We show that the standard evolution equations, in particular, the Maxwell-Cattaneo-Vernotte equation, can be derived from the variational procedure without going beyond the assumption of local equilibrium. We also argue that the second law of thermodynamics in non-equilibrium should be understood as a consequence of the variational procedure and the property of local equilibrium. For systems with instantaneous response this leads to the standard requirement of the local instantaneous entropy production being always positive. However, if a system is characterized by delayed response, the formulation of the second law of thermodynamics should be altered. In particular, the quantity, which is always positive, is not the instantaneous entropy production, but the entropy production averaged over a proper time interval.
Thermodynamics of Nonequilibrium Systems with Feedback Control
Sagawa, Takahiro
2015-03-01
In modern nonequilibrium physics, ``Maxwell's demon'' has attracted renewed attentions in both terms of theory and experiment. The demon plays a key role to unify thermodynamics and information theory, which can extract the useful work from a heat bath by using the obtained information via feedback control. In this talk, I will talk about the recent development of thermodynamics of information. In particular, I will focus on the generalizations of the second law of thermodynamics and the Jarzynski equality in the presence of feedback control, where information contents and thermodynamic quantities are treated on an equal footing. I will also discuss recent experimental results that realized Maxwell's demon by colloidal particles and single electrons.
Thermodynamic optimization of the Cu-Nd system
International Nuclear Information System (INIS)
Wang Peisheng; Zhou Liangcai; Du Yong; Xu Honghui; Liu Shuhong; Chen Li; Ouyang Yifang
2011-01-01
Research highlights: → The enthalpies of formation of the compounds Cu 6 Nd, Cu 5 Nd, Cu 2 Nd and αCuNd were calculated using DFT. → The thermodynamic constraints to eliminate the artificial phase relations were imposed during the thermodynamic optimization procedure. → The Cu-Nd system was optimized under the thermodynamic constraints. - Abstract: The thermodynamic constraints to eliminate artificial phase relations were introduced with the Cu-Nd system as an example. The enthalpies of formation of the compounds Cu 6 Nd, Cu 5 Nd, Cu 2 Nd and αCuNd are calculated using density functional theory. Taking into account all the experimental data and the first-principles calculated enthalpies of formation of these compounds, the thermodynamic optimization of the Cu-Nd system was performed under the proposed thermodynamic constraints. It is demonstrated that the thermodynamic constraints are critical to obtain a set of thermodynamic parameters for the Cu-Nd system, which can avoid the appearance of all the artificial phase relations.
Thermodynamic calculations in ternary titanium–aluminium–manganese system
Directory of Open Access Journals (Sweden)
ANA I. KOSTOV
2008-04-01
Full Text Available Thermodynamic calculations in the ternary Ti–Al–Mn system are shown in this paper. The thermodynamic calculations were performed using the FactSage thermochemical software and database, with the aim of determining thermodynamic properties, such as activities, coefficient of activities, partial and integral values of the enthalpies and Gibbs energies of mixing and excess energies at two different temperatures: 2000 and 2100 K. Bearing in mind that no experimental data for the Ti–Al–Mn ternary system have been obtained or reported. The obtained results represent a good base for further thermodynamic analysis and may be useful as a comparison with some future critical experimental results and thermodynamic optimization of this system.
Thermodynamic modeling of the Hf-N system
Directory of Open Access Journals (Sweden)
Pang M.
2018-01-01
Full Text Available Hf-N based alloys have been widely used and studied in the fields of electronic devices and cutting tools industry. A thermodynamic description of this system is essential for further materials development. By means of CALPHAD method, a thermodynamic modeling of the Hf-N system was carried out based on the available phase diagram data as well as thermodynamic property data. The Fcc phase is modeled as (Hf, Va1(N, Va1 to cover the composition range since the solubility of nitrogen in Fcc phase is reported up to about 52 at.%. A set of self-consistent thermodynamic parameters for the Hf-N system has been obtained. The computed phase diagrams and thermodynamic quantities using the present parameters agree well with the experimental data.
HATCHES - a thermodynamic database and management system
International Nuclear Information System (INIS)
Cross, J.E.; Ewart, F.T.
1990-03-01
The Nirex Safety Assessment Research Programme has been compiling the thermodynamic data necessary to allow simulations of the aqueous behaviour of the elements important to radioactive waste disposal to be made. These data have been obtained from the literature, when available, and validated for the conditions of interest by experiment. In order to maintain these data in an accessible form and to satisfy quality assurance on all data used for assessments, a database has been constructed which resides on a personal computer operating under MS-DOS using the Ashton-Tate dBase III program. This database contains all the input data fields required by the PHREEQE program and, in addition, a body of text which describes the source of the data and the derivation of the PHREEQE input parameters from the source data. The HATCHES system consists of this database, a suite of programs to facilitate the searching and listing of data and a further suite of programs to convert the dBase III files to PHREEQE database format. (Author)
Dynamics and Thermodynamics of Many Particle Cold Atom Systems
2016-05-05
AFRL-AFOSR-VA-TR-2016-0219 Dynamics and Thermodynamics of Many Particle Cold Atom Systems Anatoli Polkovnikov TRUSTEES OF BOSTON UNIVERSITY Final...TITLE AND SUBTITLE Dynamics and Thermodynamics of Many Particle Cold Atom Systems 5a. CONTRACT NUMBER 5b. GRANT NUMBER FA9550-13-1-0039 5c. PROGRAM...largely to cold atoms . All goals stated in the proposal were addressed. In addition two conceptually new ideas have emerged (Floquet systems and
A thermodynamic evaluation of the Fe-Nb system
International Nuclear Information System (INIS)
Srikanth, S.; Petric, A.
1994-01-01
An optimised set of thermodynamic functions consistent with the phase diagram was derived for the Fe-Nb system from information on phase equilibria and thermodynamic data available in the literature. The thermodynamic properties of the intermediate ε (Fe 2 Nb) phase were described using the sublattice model. A Redlich-Kister equation was used to describe the excess thermodynamic functions of the liquid, bcc and fcc phases. For the μ phase, the enthalpy of formation was estimated from Miedema's model. The interaction coefficients were evaluated using an optimisation procedure employing a conjugate gradient method. The phase diagram and the thermodynamic functions calculated from the evaluated parameters are in good agreement with experimental data. (orig.)
Thermodynamic 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
GENERIC Integrators: Structure Preserving Time Integration for Thermodynamic Systems
Öttinger, Hans Christian
2018-04-01
Thermodynamically admissible evolution equations for non-equilibrium systems are known to possess a distinct mathematical structure. Within the GENERIC (general equation for the non-equilibrium reversible-irreversible coupling) framework of non-equilibrium thermodynamics, which is based on continuous time evolution, we investigate the possibility of preserving all the structural elements in time-discretized equations. Our approach, which follows Moser's [1] construction of symplectic integrators for Hamiltonian systems, is illustrated for the damped harmonic oscillator. Alternative approaches are sketched.
Thermodynamic Efficiency and Entropy Production in the Climate System
Lucarini, V.
2009-04-01
We present a succinct analysis of the thermodynamics of the climate system, studying some of its macroscopic properties in terms of the 1st law and the 2nd law of thermodynamics. We first review and clarify the notion of efficiency of the climate system treated formally as a thermal machine, and show how the Lorenz energy cycle can be framed in a macro-scale thermodynamic context. We then exploit a thermodynamic inequality to relate the Carnot efficiency of the climate system to the lower bound to the amount of entropy production. Since entropy production due to heat transport from hot to cold regions is basically the difference between the actual and the minimal entropy production, the controversial principle of maximum entropy production is given a rigorous interpretation.
Thermodynamic modeling of the Ti-Al-Cr ternary system
International Nuclear Information System (INIS)
Chen Leyi; Qiu Aitao; Liu Lanjie; Jiang Ming; Lu Xionggang; Li Chonghe
2011-01-01
Research highlights: → The full experimental results of the Ti-Al-Cr ternary system and its sub-binary systems are reviewed and analysed in detail. → Based on the latest thermodynamic assessments of the Ti-Al, Ti-Cr and Al-Cr systems and the ternary experimental data in literature, the thermodynamic parameters of the Ti-Al-Cr ternary system are fully assessed by the Calphad method. → The transformation of disorder to order (bcc a 2 to B2) and the new ternary compound L 12T i 25 Cr 8 Al 67 are considered in this work. - Abstract: The Ti-Al-Cr ternary system is one of the most important systems to studying the titanium alloys. Some experimental data of this ternary system are available and a few partial thermodynamic assessments are reported. However, no full thermodynamic descriptions were published. In this study, the previous work on the Ti-Al-Cr system and its related binary systems are reviewed. Based on the thermodynamic descriptions of the Ti-Al, Ti-Cr and Al-Cr systems and the ternary experimental data in literature, the Ti-Al-Cr ternary system is assessed by means of the Calphad method. Several isothermal sections from 1073 K to 1573 K and some invariant reactions are calculated, which are in good agreement with the most of the experimental results.
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.
Stochastic and Macroscopic Thermodynamics of Strongly Coupled Systems
Directory of Open Access Journals (Sweden)
Christopher Jarzynski
2017-01-01
Full Text Available We develop a thermodynamic framework that describes a classical system of interest S that is strongly coupled to its thermal environment E. Within this framework, seven key thermodynamic quantities—internal energy, entropy, volume, enthalpy, Gibbs free energy, heat, and work—are defined microscopically. These quantities obey thermodynamic relations including both the first and second law, and they satisfy nonequilibrium fluctuation theorems. We additionally impose a macroscopic consistency condition: When S is large, the quantities defined within our framework scale up to their macroscopic counterparts. By satisfying this condition, we demonstrate that a unifying framework can be developed, which encompasses both stochastic thermodynamics at one end, and macroscopic thermodynamics at the other. A central element in our approach is a thermodynamic definition of the volume of the system of interest, which converges to the usual geometric definition when S is large. We also sketch an alternative framework that satisfies the same consistency conditions. The dynamics of the system and environment are modeled using Hamilton’s equations in the full phase space.
Quality Systems. A Thermodynamics-Related Interpretive Model
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Stefano A. Lollai
2017-08-01
Full Text Available In the present paper, a Quality Systems Theory is presented. Certifiable Quality Systems are treated and interpreted in accordance with a Thermodynamics-based approach. Analysis is also conducted on the relationship between Quality Management Systems (QMSs and systems theories. A measure of entropy is proposed for QMSs, including a virtual document entropy and an entropy linked to processes and organisation. QMSs are also interpreted in light of Cybernetics, and interrelations between Information Theory and quality are also highlighted. A measure for the information content of quality documents is proposed. Such parameters can be used as adequacy indices for QMSs. From the discussed approach, suggestions for organising QMSs are also derived. Further interpretive thermodynamic-based criteria for QMSs are also proposed. The work represents the first attempt to treat quality organisational systems according to a thermodynamics-related approach. At this stage, no data are available to compare statements in the paper.
Thermodynamic assessment of the Bi-Sn-Zn system
Czech Academy of Sciences Publication Activity Database
Vízdal, J.; Braga, M.H.; Kroupa, Aleš; Richter, K. W.; Soares, D.; Malheiros, L.F.; Ferreira, J.
2007-01-01
Roč. 31, č. 4 (2007), s. 438-448 ISSN 0364-5916 R&D Projects: GA MŠk OC 531.002 Institutional research plan: CEZ:AV0Z20410507 Keywords : phase-equilibria * bismuth system * binary-systems Subject RIV: BJ - Thermodynamics Impact factor: 1.352, year: 2007
Representation invariant Geometrothermodynamics: Applications to ordinary thermodynamic systems
Bravetti, Alessandro; Lopez-Monsalvo, Cesar S.; Nettel, Francisco; Quevedo, Hernando
2014-07-01
In this work we employ a recently devised metric within the Geometrothermodynamics program to study ordinary thermodynamic systems. The new feature of this metric is that, in addition to Legendre symmetry, it exhibits invariance under a change of representation. This metric was derived in a previous work by the authors while addressing the problem of the conformal structure of the thermodynamic metrics for different representations. Here, we present a thorough analysis for the ideal gas, the van der Waals fluid, the one dimensional Ising model and some other systems of cosmological interest.
Thermodynamic database for the Co-Pr system
Directory of Open Access Journals (Sweden)
S.H. Zhou
2016-03-01
Full Text Available In this article, we describe data on (1 compositions for both as-cast and heat treated specimens were summarized in Table 1; (2 the determined enthalpy of mixing of liquid phase is listed in Table 2; (3 thermodynamic database of the Co-Pr system in TDB format for the research articled entitle Chemical partitioning for the Co-Pr system: First-principles, experiments and energetic calculations to investigate the hard magnetic phase W. Keywords: Thermodynamic database of Co-Pr, Solution calorimeter measurement, Phase diagram Co-Pr
Thermodynamic performance assessment of wind energy systems: An application
International Nuclear Information System (INIS)
Redha, Adel Mohammed; Dincer, Ibrahim; Gadalla, Mohamed
2011-01-01
In this paper, the performance of wind energy system is assessed thermodynamically, from resource and technology perspectives. The thermodynamic characteristics of wind through energy and exergy analyses are considered and both energetic and exergetic efficiencies are studied. Wind speed is affected by air temperature and pressure and has a subsequent effect on wind turbine performance based on wind reference temperature and Bernoulli's equation. VESTAS V52 wind turbine is selected for (Sharjah/UAE). Energy and exergy efficiency equations for wind energy systems are further developed for practical applications. The results show that there are noticeable differences between energy and exergy efficiencies and that exergetic efficiency reflects the right/actual performance. Finally, exergy analysis has been proven to be the right tool used in design, simulation, and performance evaluation of all renewable energy systems. -- Highlights: → In this research the performance of wind energy system is assessed thermodynamically, from resource and technology perspectives. → Energy and exergy equations for wind energy systems are further developed for practical applications. → Thermodynamic characteristics of wind turbine systems through energetic and exergetic efficiencies are evaluated from January till March 2010. → Exergy efficiency describes the system irreversibility and the minimum irreversibility exists when the wind speed reaches 11 m/s. → The power production during March was about 17% higher than the month of February and 66% higher than January.
Thermodynamic modeling of the Sr-Co-Fe-O system
DEFF Research Database (Denmark)
Zhang, Wei Wei; Povoden-Karadeniz, Erwin; Chen, Ming
2016-01-01
This paper reviews and assesses phase equilibria and thermodynamic properties of phases in the Sr-Co-Fe-O system, with a focus on oxides, especially the SrCo1 - xFexO3 - δ perovskite. In our work, the SrCo1 - xFexO3 - δ perovskite was modeled with a three-sublattice model, where the three...... sublattices correspond to the A, B and oxygen sites in an ABO3 perovskite, respectively. A number of other important ternary oxide phases in Sr-Co-O and Sr-Co-Fe-O were also considered. Available thermodynamic and phase diagram data were carefully assessed. A thermodynamic description of Sr-Co-O was derived...... using the CALPHAD approach and was further extrapolated to that of Sr-Co-Fe-O. The thermodynamic database of Sr-Co-Fe-O established in this work allows for calculating phase diagrams, thermodynamic properties, cation distribution and defect chemistry properties, and therefore enables material...
Thermodynamic assessment of the Pr-Zn binary system
International Nuclear Information System (INIS)
Huang, X.M.; Liu, L.B.; Zhang, L.G.; Jia, B.R.; Jin, Z.P.; Zheng, F.
2008-01-01
On the basis of available experimental data of phase diagram and thermodynamic properties, the Pr-Zn binary system has been optimized using the CALPHAD approach. The phases, including liquid and bcc A 2(βPr) were treated as substitutional solutions, while the intermetallic compounds, including PrZn, PrZn 2 , PrZn 3 , Pr 3 Zn 11 , Pr 13 Zn 58 , Pr 3 Zn 22 , Pr 2 Zn 17 and PrZn 11 were modeled as stoichiometric compounds. As the result of optimization, a set of self-consistent thermodynamic parameters has been obtained, which can be used to reproduce the reported experimental data
Thermodynamic data management system for nuclear waste disposal performance assessment
International Nuclear Information System (INIS)
Phillips, S.L.; Hale, F.V.; Siegel, M.D.
1988-04-01
Thermodynamic property values for use in assessing the performance of a nuclear waste repository are described. More emphasis is on a computerized data base management system which facilitates use of the thermodynamic data in sensitivity analysis and other studies which critically assess the performance of disposal sites. Examples are given of critical evaluation procedures; comparison of apparent equilibrium constants calculated from the data base, with other work; and of correlations useful in estimating missing values of both free energy and enthalpy of formation for aqueous species. 49 refs., 11 figs., 6 tabs
Thermodynamic assessment of the calcium-germanium system
Energy Technology Data Exchange (ETDEWEB)
Djaballah, Y., E-mail: ydjaballah@yahoo.f [Laboratoire d' etude Physico-Chimique des Materiaux, Departement de Physique, Faculte des Sciences, Universite de Batna, Rue Chahid Boukhlouf, 05000 Batna (Algeria); Pasturel, A. [Sciences et Ingenierie des Materiaux et Procedes, INP Grenoble, 1130 rue de la Piscine, BP 75, 38402 Saint-Martin d' Heres Cedex (France); Belgacem-Bouzida, A. [Laboratoire d' etude Physico-Chimique des Materiaux, Departement de Physique, Faculte des Sciences, Universite de Batna, Rue Chahid Boukhlouf, 05000 Batna (Algeria)
2010-05-14
Thermodynamic modeling of the Ca-Ge system was carried out by means of the CALPHAD (calculation of phase diagrams) method and new experimental phase diagram data. The liquid phase and the intermetallic compounds Ca{sub 2}Ge, Ca{sub 5}Ge{sub 3}, Ca{sub 7}Ge{sub 6} (new compound), CaGe and CaGe{sub 2} are taken into consideration in this optimization. The substitutional solution model was used to describe the liquid phase. The five compounds were treated as stoichiometric phases. A consistent set of thermodynamic parameters has been obtained. The optimized phase diagram and thermodynamic properties are presented and compared with other calculated and experimental data obtained from literature.
The system Ta–V–Si: Thermodynamic modeling
Czech Academy of Sciences Publication Activity Database
Brož, P.; Khan, A.U.; Niu, H.; Chen, X.-Q.; Li, D.; Vřešťál, J.; Buršík, Jiří; Rogl, P.
2013-01-01
Roč. 199, MAR (2013), s. 171-180 ISSN 0022-4596 R&D Projects: GA ČR(CZ) GAP108/10/1908 Institutional support: RVO:68081723 Keywords : ternary alloy system * phase diagram * DFT calculations Subject RIV: BJ - Thermodynamics Impact factor: 2.200, year: 2013
A non-extensive thermodynamic theory of ecological systems
Van Xuan, Le; Khac Ngoc, Nguyen; Lan, Nguyen Tri; Viet, Nguyen Ai
2017-06-01
After almost 30 years of development, it is not controversial issue that the so-called Tsallis entropy provides a useful approach to studying the complexity where the non-additivity of the systems under consideration is frequently met. Also, in the ecological research, Tsallis entropy, or in other words, q-entropy has been found itself as a generalized approach to define a range of diversity indices including Shannon-Wiener and Simpson indices. As a further stage of development in theoretical research, a thermodynamic theory based on Tsallis entropy or diversity indices in ecology has to be constructed for ecological systems to provide knowledge of ecological macroscopic behaviors. The standard method of theoretical physics is used in the manipulation and the equivalence between phenomenological thermodynamics and ecological aspects is the purpose of the ongoing research. The present work is in the line of the authors research to implement Tsallis non-extensivity approach to obtain the most important thermodynamic quantities of ecological systems such as internal energy Uq and temperature Tq based on a given modeled truncated Boltzmann distribution of the Whittaker plot for a dataset. These quantities have their own ecological meaning, especially the temperature Tq provides the insight of equilibrium condition among ecological systems as it is well-known in 0th law of thermodynamics.
Perform Thermodynamics Measurements on Fuel Cycle Case Study Systems
Energy Technology Data Exchange (ETDEWEB)
Martin, Leigh R. [Idaho National Lab. (INL), Idaho Falls, ID (United States)
2014-09-01
This document was prepared to meet FCR&D level 3 milestone M3FT-14IN0304022, “Perform Thermodynamics Measurements on Fuel Cycle Case Study Systems.” This work was carried out under the auspices of the Thermodynamics and Kinetics FCR&D work package. This document reports preliminary work in support of determining the thermodynamic parameters for the ALSEP process. The ALSEP process is a mixed extractant system comprised of a cation exchanger 2-ethylhexyl-phosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) and a neutral solvating extractant N,N,N’,N’-tetraoctyldiglycolamide (TODGA). The extractant combination produces complex organic phase chemistry that is challenging for traditional measurement techniques. To neutralize the complexity, temperature dependent solvent extraction experiments were conducted with neat TODGA and scaled down concentrations of the ALSEP formulation to determine the enthalpies of extraction for the two conditions. A full set of thermodynamic data for Eu, Am, and Cm extraction by TODGA from 3.0 M HNO3 is reported. These data are compared to previous extraction results from a 1.0 M HNO3 aqueous medium, and a short discussion of the mixed HEH[EHP]/TODGA system results is offered.
Thermodynamic modeling of the Fe-Mg-Si system
Directory of Open Access Journals (Sweden)
Du Y.
2007-01-01
Full Text Available A thermo dynamic modeling for the Fe-Mg-Si system is conducted. All of the experimental phase diagram and thermodynamic data available from the literature are critically reviewed and assessed using thermo dynamic models for the Gibbs energies of individual phases. The thermodynamic parameters for ternary liquid as well as binary phases αFeSi, (high-temperature form of FeSi2 and FeSi showing noticeable solubilities for Mg are evaluated in the optimization. Comparisons between the calculated and measured phase diagrams show that the measured isothermal six-lions at 1600°, 1454°, 727° and 710°C, the observed regions of primary phases are satisfactorily accounted for by the thermodynamic description. The limited thermodynamic data concerning the activity of Mg in liquid at 1350°C are found to be inconsistent with the well established phase relations. The liquidus projection and reaction scheme for the entire Fe-Mg-Si system are also presented. .
Thermodynamic Analysis of Closed Steady or Cyclic Systems
Directory of Open Access Journals (Sweden)
Jim McGovern
2015-09-01
Full Text Available Closed, steady or cyclic thermodynamic systems, which have temperature variations over their boundaries, can represent an extremely large range of plants, devices or natural objects, such as combined heating, cooling and power plants, computers and data centres, and planets. Energy transfer rates can occur across the boundary, which are characterized as heat or work. We focus on the finite time thermodynamics aspects, on energy-based performance parameters, on rational efficiency and on the environmental reference temperature. To do this, we examine the net work rate of a closed, steady or cyclic system bounded by thermal resistances linked to isothermal reservoirs in terms of the first and second laws of thermodynamics. Citing relevant references from the literature, we propose a methodology that can improve the thermodynamic analysis of an energy-transforming or an exergy-destroying plant. Through the reflections and analysis presented, we have found an explanation of the second law that clarifies the link between the Clausius integral of heat over temperature and the reference temperature of the Gouy–Stodola theorem. With this insight and approach, the specification of the environmental reference temperature in exergy analysis becomes more solid. We have explained the relationship between the Curzon Ahlborn heat engine and an irreversible Carnot heat engine. We have outlined the nature of subsystem rational efficiencies and have found Rant’s anergy to play an important role. We postulate that heat transfer through thermal resistance is the sole basis of irreversibility.
Fisher information and the thermodynamics of scale-invariant systems
Hernando, A.; Vesperinas, C.; Plastino, A.
2010-02-01
We present a thermodynamic formulation for scale-invariant systems based on the minimization with constraints of the Fisher information measure. In such a way a clear analogy between these systems’ thermal properties and those of gases and fluids is seen to emerge in a natural fashion. We focus our attention on the non-interacting scenario, speaking thus of scale-free ideal gases (SFIGs) and present some empirical evidences regarding such disparate systems as electoral results, city populations and total citations in Physics journals, that seem to indicate that SFIGs do exist. We also illustrate the way in which Zipf’s law can be understood in a thermodynamical context as the surface of a finite system. Finally, we derive an equivalent microscopic description of our systems which totally agrees with previous numerical simulations found in the literature.
Thermodynamic database for the Co-Pr system.
Zhou, S H; Kramer, M J; Meng, F Q; McCallum, R W; Ott, R T
2016-03-01
In this article, we describe data on (1) compositions for both as-cast and heat treated specimens were summarized in Table 1; (2) the determined enthalpy of mixing of liquid phase is listed in Table 2; (3) thermodynamic database of the Co-Pr system in TDB format for the research articled entitle Chemical partitioning for the Co-Pr system: First-principles, experiments and energetic calculations to investigate the hard magnetic phase W.
Thermodynamically consistent Bayesian analysis of closed biochemical reaction systems
Directory of Open Access Journals (Sweden)
Goutsias John
2010-11-01
Full Text Available Abstract Background Estimating the rate constants of a biochemical reaction system with known stoichiometry from noisy time series measurements of molecular concentrations is an important step for building predictive models of cellular function. Inference techniques currently available in the literature may produce rate constant values that defy necessary constraints imposed by the fundamental laws of thermodynamics. As a result, these techniques may lead to biochemical reaction systems whose concentration dynamics could not possibly occur in nature. Therefore, development of a thermodynamically consistent approach for estimating the rate constants of a biochemical reaction system is highly desirable. Results We introduce a Bayesian analysis approach for computing thermodynamically consistent estimates of the rate constants of a closed biochemical reaction system with known stoichiometry given experimental data. Our method employs an appropriately designed prior probability density function that effectively integrates fundamental biophysical and thermodynamic knowledge into the inference problem. Moreover, it takes into account experimental strategies for collecting informative observations of molecular concentrations through perturbations. The proposed method employs a maximization-expectation-maximization algorithm that provides thermodynamically feasible estimates of the rate constant values and computes appropriate measures of estimation accuracy. We demonstrate various aspects of the proposed method on synthetic data obtained by simulating a subset of a well-known model of the EGF/ERK signaling pathway, and examine its robustness under conditions that violate key assumptions. Software, coded in MATLAB®, which implements all Bayesian analysis techniques discussed in this paper, is available free of charge at http://www.cis.jhu.edu/~goutsias/CSS%20lab/software.html. Conclusions Our approach provides an attractive statistical methodology for
Entanglement and thermodynamics after a quantum quench in integrable systems
Alba, Vincenzo; Calabrese, Pasquale
2017-07-01
Entanglement and entropy are key concepts standing at the foundations of quantum and statistical mechanics. Recently, the study of quantum quenches revealed that these concepts are intricately intertwined. Although the unitary time evolution ensuing from a pure state maintains the system at zero entropy, local properties at long times are captured by a statistical ensemble with nonzero thermodynamic entropy, which is the entanglement accumulated during the dynamics. Therefore, understanding the entanglement evolution unveils how thermodynamics emerges in isolated systems. Alas, an exact computation of the entanglement dynamics was available so far only for noninteracting systems, whereas it was deemed unfeasible for interacting ones. Here, we show that the standard quasiparticle picture of the entanglement evolution, complemented with integrability-based knowledge of the steady state and its excitations, leads to a complete understanding of the entanglement dynamics in the space-time scaling limit. We thoroughly check our result for the paradigmatic Heisenberg chain.
International Nuclear Information System (INIS)
Lim, Gyeong Hui
2008-03-01
This book consists of 15 chapters, which are basic conception and meaning of statistical thermodynamics, Maxwell-Boltzmann's statistics, ensemble, thermodynamics function and fluctuation, statistical dynamics with independent particle system, ideal molecular system, chemical equilibrium and chemical reaction rate in ideal gas mixture, classical statistical thermodynamics, ideal lattice model, lattice statistics and nonideal lattice model, imperfect gas theory on liquid, theory on solution, statistical thermodynamics of interface, statistical thermodynamics of a high molecule system and quantum statistics
Thermodynamics of irreversible processes in rotating systems
Hooyman, G.J.; Holtan, H.; Mazur, P.; Groot, S.R. de
1953-01-01
The general entropy balance equation for a rotating system containing a mixture of (charged and uncharged) components is calculated and the influence of centrifugal force and Coriolis force on the entropy production is considered. From the general formalism the equations for mechanical
Thermodynamic assessment of the Al-Mo-V ternary system
Directory of Open Access Journals (Sweden)
Hu B.
2017-01-01
Full Text Available Thermodynamic assessment of the Al-Mo-V ternary system was performed by means of the CALPHAD (CALculation of PHAse Diagram approach based on the thermodynamic descriptions of three constitutive binary systems (Al-Mo, Al-V and Mo-V as well as the experimental phase equilibria data available in the literature. The solution phases, i.e. liquid, bcc (Mo, V and fcc (Al, were described using the substitutional solution models with the Redlich-Kister equation. The binary phases in the Al-Mo and Al-V systems with the solubilities of the third element were modeled using the sublattice models. An optimal set of thermodynamic parameters for the Al-Mo-V system was obtained. Six isothermal sections at 1200, 1000, 750, 715, 675 and 630°C and liquidus projection with isotherm were calculated. The reaction scheme for the entire Al-Mo-V system was also constructed. Comparisons between the calculated and measured phase diagrams indicated that almost all the reliable experimental information was satisfactorily accounted for by the present modeling.
Thermodynamics of Paint Related Systems with Engineering Models
DEFF Research Database (Denmark)
Lindvig, Thomas; Michelsen, Michael Locht; Kontogeorgis, Georgios
2001-01-01
to solid surfaces and drying. Many engineering models have been applied over the last decades for solutions with commoditity polymers. In this work the performance of some of these models is investigated for paint-related systems, focusing on those drying by the so-called " lacquer mechanism " (evaporation......Paints are complex materials composed of polymers (binders) dissolved in one or more solvents, pigments, and other additives. The thermodynamics of such systems is essential, for example, for selecting improved solvents and understanding a number of phenomena related especially! to adhesion...... that, despite the uncertainties involved, several models yield reasonably accurate activity coefficients, even at infinite dilution. Thus, engineering models may be useful for solvent selection via semiempirical rules of thumb, which are based on thermodynamic considerations....
Thermodynamic analysis of the Ga-Pb binary system
Directory of Open Access Journals (Sweden)
Manasijević Dragan
2003-01-01
Full Text Available Thermodynamic properties of binary Ga-Pb alloys were investigated experimentally and analytically. Quantitative differential thermal analysis was used for determination of integral mixing enthalpies for the gallium-reach alloys, at the constant temperature inside the liquid two-phase region. Calculation of gallium activities in the temperature range of 800-1000 K was done using Chou’s calculation model developed for binary systems with miscibility gap existence.
Thermodynamic comparison of three small-scale gas liquefaction systems
DEFF Research Database (Denmark)
Nguyen, Tuong-Van; Rothuizen, Erasmus Damgaard; Markussen, Wiebke Brix
2017-01-01
to be more efficient (1000-2000 kJ/kgLNG) than expander-based ones (2500-5000 kJ/kgLNG) over larger ranges of operating conditions, at the expense of a greater system complexity and higher thermal conductance (250-500kW/K against 80-160 kW/K). The results show that the use of different thermodynamic models...
The thermodynamic assessment of the Au–In–Ga system
Energy Technology Data Exchange (ETDEWEB)
Ghasemi, M., E-mail: masoomeh.ghasemi@ftf.lth.se [Solid State Physics, Lund University, Box 118, SE-22100 Lund (Sweden); Sundman, B., E-mail: bo.sundman@gmail.com [INSTN-CEA Saclay, 91191 Gif sur Yvette (France); Fries, S.G., E-mail: suzana.g.fries@ruhr-uni-bochum.de [ICAMS, Interdisciplinary Centre for Advanced Materials Simulation, Ruhr Universitaet Bochum 44801, Bochum (Germany); Johansson, J., E-mail: jonas.johansson@ftf.lth.se [Solid State Physics, Lund University, Box 118, SE-22100 Lund (Sweden)
2014-07-05
Highlights: • The first thermodynamic assessment of the Au–In–Ga system has been presented. • Based on recent experimental results, a self-consistent database has been obtained. • A diagram of monovariant lines was calculated and invariant reactions were defined. • An isothermal section at 280 °C and two isoplethal sections were calculated. • Good agreement between the calculations and experimental results was achieved. - Abstract: The Au–In–Ga ternary phase diagram is of importance for understanding the involved thermodynamic processes during the growth of Au-seeded III–V heterostructure nanowires containing In and Ga (e.g. Au-seeded InAs/GaAs nanowires). In this work the Au–In–Ga system has been thermodynamically modeled using the CALPHAD technique based on a recent experimental investigation of the phase equilibria in the system. As a result, a set of self-consistent interaction parameters have been optimized that can reproduce most of the experimental results.
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
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
Eberard, D.; Maschke, B.M.; Schaft, A.J. van der
2007-01-01
It is shown that the intrinsic geometry associated with equilibrium thermodynamics, namely the contact geometry, provides also a suitable framework in order to deal with irreversible thermodynamical processes. Therefore we introduce a class of dynamical systems on contact manifolds, called
Thermodynamic investigations in the system U-Mo-O
International Nuclear Information System (INIS)
Chattopadhyay, G.; Kerkar, A.S.; Tripathi, S.N.
1984-01-01
Thermodynamic data on materials are required to answer some practical questions regarding chemical equilibria and also for the ultimate purpose of quantifying the relative stabilities of all possible chemical species. The present work was undertaken to determine what role molybdenum, one of the most preponderant fission products, could play in determining the state of the chemical equilibrium in the fuel fission product complex in an oxide-based nuclear reactor or in the nuclear waste disposed in ceramic or glass forms. To understand and analyze such complex systems, it is necessary to know which are the possible phases and species that are to be considered and their thermodynamic properties. In the present work attention was given to the ternary oxides of uranium and molybdenum with regard to the equilibria among the various phases. This is a prerequisite for determining the thermodynamic properties of the relevant phases. Therefore, experiments were carried out to construct the phase diagram in the region UO 2 -MoO 2 -O in a more precise manner than hitherto and, hence, to determine the free energy of formation of UMoO 5
Thermodynamic optimization of the Al-Yb binary system
Energy Technology Data Exchange (ETDEWEB)
Meng, F.G.; Zhang, L.G.; Liu, H.S.; Liu, L.B. [School of Materials Sciecne and Engineering, Central South University, ChangSha, HuNan 410083 (China); Jin, Z.P. [School of Materials Sciecne and Engineering, Central South University, ChangSha, HuNan 410083 (China)], E-mail: jin@mail.csu.edu.cn
2008-03-20
A thermodynamic description of the Al-Yb binary system was developed based on critically evaluated experimental data by using CALculation of PHAse Diagram (CALPHAD) approach. Liquid ({gamma}Yb) and ({beta}Yb) were modeled as substitutional solution phases. Al{sub 2}Yb and Al{sub 3}Yb were treated as stoichiometric compounds. A set of self-consistent parameters for describing various phases in this system was obtained, with which most of the experimental data reported in the literatures were well reproduced.
Advanced thermodynamics metrics for sustainability assessments of open engineering systems
Directory of Open Access Journals (Sweden)
Sekulić Dušan P.
2006-01-01
Full Text Available This paper offers a verification of the following hypotheses. Advanced thermodynamics metrics based on entropy generation assessments indicate the level of sustainability of transient open systems, such as in manufacturing or process industries. The indicator of sustainability may be related to particular property uniformity during materials processing. In such a case the property uniformity would indicate systems’ distance from equilibrium i.e., from the sustainable energy utilization level. This idea is applied to a selected state-of-the-art manufacturing process. The system under consideration involves thermal processing of complex aluminum structures during controlled atmosphere brazing for a near-net-shape mass production of compact heat exchangers.
Thermodynamic optimization of geometry in engineering flow systems
Energy Technology Data Exchange (ETDEWEB)
Bejan, A.; Jones, J.A. [Duke Univ., Durham, NC (United States)
2000-07-01
This review draws attention to an emerging body of work that relies on global thermodynamic optimization in the pursuit of flow system architecture. Exergy analysis establishes the theoretical performance limit. Thermodynamic optimization (or entropy generation minimization) brings the design as closely as permissible to the theoretical limit. The design is destined to remain imperfect because of constraints (finite sizes, times, and costs). Improvements are registered by spreading the imperfection (e.g., flow resistances) through the system. Resistances compete against each other and must be optimized together. Optimal spreading means spatial distribution, geometric form, topology, and geography. System architecture springs out of constrained global optimization. The principle is illustrated by simple examples: the optimization of dimensions, spacings, and the distribution (allocation) of heat transfer surface to the two heat exchangers of a power plant. Similar opportunities for deducing flow architecture exist in more complex systems for power and refrigeration. Examples show that the complete structure of heat exchangers for environmental control systems of aircraft can be derived based on this principle. (authors)
Thermodynamic properties of some metal oxide-zirconia systems
Jacobson, Nathan S.
1989-01-01
Metal oxide-zirconia systems are a potential class of materials for use as structural materials at temperatures above 1900 K. These materials must have no destructive phase changes and low vapor pressures. Both alkaline earth oxide (MgO, CaO, SrO, and BaO)-zirconia and some rare earth oxide (Y2O3, Sc2O3, La2O3, CeO2, Sm2O3, Gd2O3, Yb2O3, Dy2O3, Ho2O3, and Er2O3)-zirconia system are examined. For each system, the phase diagram is discussed and the vapor pressure for each vapor species is calculated via a free energy minimization procedure. The available thermodynamic literature on each system is also surveyed. Some of the systems look promising for high temperature structural materials.
International Nuclear Information System (INIS)
Phan, Anh Thu; Paek, Min-Kyu; Kang, Youn-Bae
2014-01-01
In order to provide an efficient tool to design alloy chemistry and processing conditions for high-strength, lightweight steel, an investigation of the Fe–Al–C ternary system was carried out by experimental phase diagram measurement and a CALPHAD thermodynamic analysis. Discrepancies between previously available experimental results and thermodynamic calculations were identified. The Fe–Al sub-binary system was re-optimized in order to obtain an accurate description of the liquid phase, while Gibbs energies of solid phases were mainly taken from a previous thermodynamic modeling. Phase equilibria among face-centered cubic (fcc)/body-centered cubic (bcc)/graphite/κ-carbide/liquid phases in the Fe–Al–C system in the temperature range from 1000 to 1400 °C were obtained by chemical equilibration followed by quenching, and subsequent composition analysis using electron probe microanalysis/inductively coupled plasma spectroscopy. By merging the revised Fe–Al binary description with existing Fe–C and Al–C binary descriptions, a complete thermodynamic description of the Fe–Al–C system was obtained in the present study. The modified quasi-chemical model in the pair approximation was used to model the liquid phase, while solid solutions were modeled using compound energy formalism. A2/B2 order/disorder transition in the bcc phase was taken into account. Compared with previously known experiments/thermodynamic modeling, a better agreement was obtained in the present study, regarding the stable region of fcc and the solidification thermal peak of a ternary alloy near the liquidus temperature. The obtained thermodynamic description also reproduced various types of experimental data in the Fe–Al–C system such as isothermal sections, vertical sections, liquidus projection, etc. The solidification of various steel grades was predicted and discussed
Variational discretization of the nonequilibrium thermodynamics of simple systems
Gay-Balmaz, François; Yoshimura, Hiroaki
2018-04-01
In this paper, we develop variational integrators for the nonequilibrium thermodynamics of simple closed systems. These integrators are obtained by a discretization of the Lagrangian variational formulation of nonequilibrium thermodynamics developed in (Gay-Balmaz and Yoshimura 2017a J. Geom. Phys. part I 111 169–93 Gay-Balmaz and Yoshimura 2017b J. Geom. Phys. part II 111 194–212) and thus extend the variational integrators of Lagrangian mechanics, to include irreversible processes. In the continuous setting, we derive the structure preserving property of the flow of such systems. This property is an extension of the symplectic property of the flow of the Euler–Lagrange equations. In the discrete setting, we show that the discrete flow solution of our numerical scheme verifies a discrete version of this property. We also present the regularity conditions which ensure the existence of the discrete flow. We finally illustrate our discrete variational schemes with the implementation of an example of a simple and closed system.
Thermodynamic analysis of solar assisted multi-functional trigeneration system
Directory of Open Access Journals (Sweden)
Önder KIZILKAN
2016-02-01
Full Text Available In this study, modelling and thermodynamic analysis of solar assisted trigeneration system was carried out. The required thermal energy for gas and vapor cycles were supplied from solar tower which is a new concept for gas cycle applications. Additionally, an absorption refrigeration cycle, vapor production process, drying process and water heating process were integrated to the system. Energy and exergy efficiencies of the trigeneration system were determined by the application of first and second law analyses. The results showed that the gas cycle efficiency was found to be 31%, vapor cycle efficiency was found to be 28% and coefficient of performance (COP values of the refrigeration system was found to be 0.77. Also the highest exergy destruction rate was found to be 4154 kW in solar tower.Keywords: Solar tower, Trigeneration, Gas cycle, Vapor cycle, Energy, Exergy
Additional energy-information relations in thermodynamics of small systems.
Uzdin, Raam
2017-09-01
The Clausius inequality form of the second law of thermodynamics relates information changes (entropy) to changes in the first moment of the energy (heat and indirectly also work). Are there similar relations between other moments of the energy distribution, and other information measures, or is the Clausius inequality a one of a kind instance of the energy-information paradigm? If there are additional relations, can they be used to make predictions on measurable quantities? Changes in the energy distribution beyond the first moment (average heat or work) are especially important in small systems which are often very far from thermal equilibrium. The additional energy-information relations (AEIR's), here derived, provide positive answers to the two questions above and add another layer to the fundamental connection between energy and information. To illustrate the utility of the new AEIR's, we find scenarios where the AEIR's yield tighter constraints on performance (e.g., in thermal machines) compared to the second law. To obtain the AEIR's we use the Bregman divergence-a mathematical tool found to be highly suitable for energy-information studies. The quantum version of the AEIR's provides a thermodynamic meaning to various quantum coherence measures. It is intriguing to fully map the regime of validity of the AEIR's and extend the present results to more general scenarios including continuous systems and particles exchange with the baths.
Additional energy-information relations in thermodynamics of small systems
Uzdin, Raam
2017-09-01
The Clausius inequality form of the second law of thermodynamics relates information changes (entropy) to changes in the first moment of the energy (heat and indirectly also work). Are there similar relations between other moments of the energy distribution, and other information measures, or is the Clausius inequality a one of a kind instance of the energy-information paradigm? If there are additional relations, can they be used to make predictions on measurable quantities? Changes in the energy distribution beyond the first moment (average heat or work) are especially important in small systems which are often very far from thermal equilibrium. The additional energy-information relations (AEIR's), here derived, provide positive answers to the two questions above and add another layer to the fundamental connection between energy and information. To illustrate the utility of the new AEIR's, we find scenarios where the AEIR's yield tighter constraints on performance (e.g., in thermal machines) compared to the second law. To obtain the AEIR's we use the Bregman divergence—a mathematical tool found to be highly suitable for energy-information studies. The quantum version of the AEIR's provides a thermodynamic meaning to various quantum coherence measures. It is intriguing to fully map the regime of validity of the AEIR's and extend the present results to more general scenarios including continuous systems and particles exchange with the baths.
Novel Hydrogen Production Systems Operative at Thermodynamic Extremes
Energy Technology Data Exchange (ETDEWEB)
Gunsalus, Robert
2012-11-30
We have employed a suite of molecular, bioinformatics, and biochemical tools to interrogate the thermodynamically limiting steps of H{sub 2} production from fatty acids in syntrophic communities. We also developed a new microbial model system that generates high H{sub 2} concentrations (over 17% of the gas phase) with high H{sub 2} yields of over 3 moles H{sub 2} per mole glucose. Lastly, a systems-based study of biohydrogen production in model anaerobic consortia was performed to begin identifying key regulated steps as a precursor to modeling co-metabolism. The results of these studies significantly expand our ability to predict and model systems for H{sub 2} production in novel anaerobes that are currently very poorly documented or understood.
International Nuclear Information System (INIS)
Garcia-Moliner, F.
1975-01-01
Basic thermodynamics of a system consisting of two bulk phases with an interface. Solid surfaces: general. Discussion of experimental data on surface tension and related concepts. Adsorption thermodynamics in the Gibbsian scheme. Adsorption on inert solid adsorbents. Systems with electrical charges: chemistry and thermodynamics of imperfect crystals. Thermodynamics of charged surfaces. Simple models of charge transfer chemisorption. Adsorption heat and related concepts. Surface phase transitions
Thermodynamic modelling and in-situ neutron diffraction investigation of the (Nd + Mg + Zn) system
International Nuclear Information System (INIS)
Zhu, Zhijun; Gharghouri, Michael A.; Pelton, Arthur D.
2016-01-01
Highlights: • All phase diagram and thermodynamic data critically assessed for the (Nd + Mg + Zn) system. • All phases described by optimised thermodynamic models. • In-situ neutron diffraction performed to identify phases and transition temperatures. • Assessments of other (RE + Mg + Zn) systems have been carried out simultaneously. • The final product is a thermodynamic database for multicomponent (Mg + RE + Zn) systems. - Abstract: All available phase diagram data for the (Nd + Mg + Zn) system were critically assessed. In-situ neutron diffraction (ND) experiments were performed on selected samples to identify phases and transition temperatures. A critical thermodynamic evaluation and optimization of the (Nd + Mg + Zn) system was carried out and model parameters for the thermodynamic properties of all phases were obtained. The phase transformation behaviour of selected samples was well resolved from the ND experiments and experimental values were used to refine the thermodynamic model parameters.
Thermodynamic modelling and in-situ neutron diffraction investigation of the (Ce + Mg + Zn) system
International Nuclear Information System (INIS)
Zhu, Zhijun; Gharghouri, Michael A.; Medraj, Mamoun; Lee, Soo Yeol; Pelton, Arthur D.
2016-01-01
Highlights: • All phase diagram and thermodynamic data critically assessed for the (Ce + Mg + Zn) system. • All phases described by optimized thermodynamic models. • In-situ neutron diffraction performed to identify phases and transition temperatures. • Assessments of other (RE + Mg + Zn) systems have been carried out simultaneously. • The final product is a thermodynamic database for multicomponent (Mg + RE + Zn) systems. - Abstract: All available phase diagram data for the (Ce + Mg + Zn) system were critically assessed. In-situ neutron diffraction (ND) experiments were performed on selected samples to identify phases and transition temperatures. A critical thermodynamic evaluation and optimization of the (Ce + Mg + Zn) system were carried out and model parameters for the thermodynamic properties of all phases were obtained. The phase transformation behaviour of selected samples was well resolved from the ND experiments and experimental data were used to refine the thermodynamic model parameters.
Thermodynamic limits to information harvesting by sensory systems
International Nuclear Information System (INIS)
Bo, Stefano; Giudice, Marco Del; Celani, Antonio
2015-01-01
In view of the relation between information and thermodynamics we investigate how much information about an external protocol can be stored in the memory of a stochastic measurement device given an energy budget. We consider a layered device with a memory component storing information about the external environment by monitoring the history of a sensory part coupled to the environment. We derive an integral fluctuation theorem for the entropy production and a measure of the information accumulated in the memory device. Its most immediate consequence is that the amount of information is bounded by the average thermodynamic entropy produced by the process. At equilibrium no entropy is produced and therefore the memory device does not add any information about the environment to the sensory component. Consequently, if the system operates at equilibrium the addition of a memory component is superfluous. Such a device can be used to model the sensing process of a cell measuring the external concentration of a chemical compound and encoding the measurement in the amount of phosphorylated cytoplasmic proteins. (paper)
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
Thermodynamic properties for polycyclic systems by non-calorimetric methods
Energy Technology Data Exchange (ETDEWEB)
Steele, W.V.; Chirico, R.D.; Klots, T.D.
1993-03-01
A detailed vibrational spectroscopic study of furan, pyrrole, and thiophene has been completed. These compounds form part of the base of five-membered ring systems on which the rest of the research program will be built Several methyl-substituted derivatives were also studied. The results will be used to confirm the model for alkyl- substitution in the ring systems. Gas-phase spectra and fundamental- frequency assignments were completed for 2,3- and 2,5-dihydrofuran. Those compounds initiate work on ring-puckering within the research program. A paper describing the need for third virial estimation, when using the virial equation of state to derive thermodynamic properties at pressures greater than 1 bar was completed.
The Theory of Thermodynamics for Chemical Reactions in Dispersed Heterogeneous Systems
Yongqiang; Baojiao; Jianfeng
1997-07-01
In this paper, the expressions of Gibbs energy change, enthalpy change, entropy change, and equilibrium constant for chemical reactions in dispersed heterogeneous systems are derived using classical thermodynamics theory. The thermodynamical relations for the same reaction system between the dispersed and the block state are also derived. The effects of degree of dispersion on thermodynamical properties, reaction directions, and chemical equilibria are discussed. The results show that the present equation of thermodynamics for chemical reactions is only a special case of the above-mentioned formulas and that the effect of the dispersity of a heterogeneous system on the chemical reaction obeys the Le Chatelier principle of movement of equilibria.
Thermodynamics of Horizons from a Dual Quantum System
Directory of Open Access Journals (Sweden)
T. Padmanabhan
2007-08-01
Full Text Available It was shown recently that, in the case of Schwarschild black hole, one can obtainthe correct thermodynamic relations by studying a model quantum system and using a partic-ular duality transformation. We study this approach further for the case a general sphericallysymmetric horizon. We show that the idea works for a general case only if we define the en-tropy S as a congruence (Ã¢Â€ÂœobserverÃ¢Â€Â dependent quantity and the energy E as the integral overthe source of the gravitational acceleration for the congruence. In fact, in this case, one recov-ers the relation S = E/2T between entropy, energy and temperature previously proposed byone of us in gr-qc/0308070. This approach also enables us to calculate the quantum correc-tions of the Bekenstein-Hawking entropy formula for all spherically symmetric horizons.
Thermodynamic Modeling of Natural Gas Systems Containing Water
DEFF Research Database (Denmark)
Karakatsani, Eirini K.; Kontogeorgis, Georgios M.
2013-01-01
As the need for dew point specifications remains very urgent in the natural gas industry, the development of accurate thermodynamic models, which will match experimental data and will allow reliable extrapolations, is needed. Accurate predictions of the gas phase water content in equilibrium...... with a heavy phase were previously obtained using cubic plus association (CPA) coupled with a solid phase model in the case of hydrates, for the binary systems of water–methane and water–nitrogen and a few natural gas mixtures. In this work, CPA is being validated against new experimental data, both water...... content and phase equilibrium data, and solid model parameters are being estimated for four natural gas main components (methane, ethane, propane, and carbon dioxide). Different tests for the solid model parameters are reported, including vapor-hydrate-equilibria (VHE) and liquid-hydrate-equilibria (LHE...
Computation of thermodynamic equilibrium in systems under stress
Vrijmoed, Johannes C.; Podladchikov, Yuri Y.
2016-04-01
Metamorphic reactions may be partly controlled by the local stress distribution as suggested by observations of phase assemblages around garnet inclusions related to an amphibolite shear zone in granulite of the Bergen Arcs in Norway. A particular example presented in fig. 14 of Mukai et al. [1] is discussed here. A garnet crystal embedded in a plagioclase matrix is replaced on the left side by a high pressure intergrowth of kyanite and quartz and on the right side by chlorite-amphibole. This texture apparently represents disequilibrium. In this case, the minerals adapt to the low pressure ambient conditions only where fluids were present. Alternatively, here we compute that this particular low pressure and high pressure assemblage around a stressed rigid inclusion such as garnet can coexist in equilibrium. To do the computations we developed the Thermolab software package. The core of the software package consists of Matlab functions that generate Gibbs energy of minerals and melts from the Holland and Powell database [2] and aqueous species from the SUPCRT92 database [3]. Most up to date solid solutions are included in a general formulation. The user provides a Matlab script to do the desired calculations using the core functions. Gibbs energy of all minerals, solutions and species are benchmarked versus THERMOCALC, PerpleX [4] and SUPCRT92 and are reproduced within round off computer error. Multi-component phase diagrams have been calculated using Gibbs minimization to benchmark with THERMOCALC and Perple_X. The Matlab script to compute equilibrium in a stressed system needs only two modifications of the standard phase diagram script. Firstly, Gibbs energy of phases considered in the calculation is generated for multiple values of thermodynamic pressure. Secondly, for the Gibbs minimization the proportion of the system at each particular thermodynamic pressure needs to be constrained. The user decides which part of the stress tensor is input as thermodynamic
Thermodynamics as the driving principle behind the immune system.
Finger, Eduardo
2012-01-01
Over the last 120 years, few things contributed more to our understanding of immune system than the study of its behavior in the host/parasite relationship. Despite the advances though, a few questions remain, such as what drives the immune system? What are its guiding principles? If we ask these questions randomly, most will immediately answer "defend the body from external threats," but what exactly do we defend ourselves from? How do these threats harm us? What criteria define what constitutes a threat? On the other hand, if the immune system evolved to defend us against external threats, how does its action against "internal" processes, such as neoplasms, qualify? Why do we die from cancer? Or from infection? Or even, why do we die at all? These apparently obvious questions are nor simple neither trivial, and the difficulty answering them reveals the complex reality that the immune system handles. The objective of this article is to articulate for the reader something that he instinctively already knows: that the decisions of the immune system are thermodynamically driven. Additionally, we will discuss how this apparent change in paradigm alters concepts such as health, disease, and therapeutics.
Thermodynamic analysis of a liquid air energy storage system
International Nuclear Information System (INIS)
Guizzi, Giuseppe Leo; Manno, Michele; Tolomei, Ludovica Maria; Vitali, Ruggero Maria
2015-01-01
The rapid increase in the share of electricity generation from renewable energy sources is having a profound impact on the power sector; one of the most relevant effects of this trend is the increased importance of energy storage systems, which can be used to smooth out peaks and troughs of production from renewable energy sources. Besides their role in balancing the electric grid, energy storage systems may provide also several other useful services, such as price arbitrage, stabilizing conventional generation, etc.; therefore, it is not surprising that many research projects are under way in order to explore the potentials of new technologies for electric energy storage. This paper presents a thermodynamic analysis of a cryogenic energy storage system, based on air liquefaction and storage in an insulated vessel. This technology is attractive thanks to its independence from geographical constraints and because it can be scaled up easily to grid-scale ratings, but it is affected by a low round-trip efficiency due to the energy intensive process of air liquefaction. The present work aims to assess the efficiency of such a system and to identify if and how it can achieve an acceptable round-trip efficiency (in the order of 50–60%).
Thermodynamic modeling of the Pt-Zr system
International Nuclear Information System (INIS)
Gao Yongliang; Guo Cuiping; Li Changrong; Du Zhenmin
2010-01-01
By means of the CALPHAD (CALculation of PHAse Diagram) technique, the Pt-Zr system was critically assessed. The solution phases (liquid, bcc, fcc and hcp) are described with the substitutional model. The intermetallic compounds Pt 4 Zr, Pt 4 Zr 3 , αPtZr and Pt 3 Zr 5 are treated as the formula (Pt,Zr) m (Pt,Zr) n by a two-sublattice model with the elements Pt and Zr on the first and the second sublattices, respectively. A two-sublattice model (Pt,Zr) 0.5 (Pt,Zr) 0.5 is applied to describe the compound βPtZr with CsCl-type structure (B2) in order to cope with the order-disorder transition between bcc solution (A2) and βPtZr (B2). Another two-sublattice model (Pt,Zr) 0.75 (Pt,Zr) 0.25 with Ni 3 Ti-type structure (D0 24 ) is applied to describe the compound Pt 3 Zr in order to cope with the order-disorder transition between hexagonal close-packed (A3) and Pt 3 Zr (D0 24 ). The compound Pt 10 Zr 7 is treated as a stoichiometric compound. A set of self-consistent thermodynamic parameters of the Pt-Zr system was obtained. (orig.)
Methods and systems for thermodynamic evaluation of battery state of health
Yazami, Rachid; McMenamin, Joseph; Reynier, Yvan; Fultz, Brent T
2014-12-02
Described are systems and methods for accurately characterizing thermodynamic and materials properties of electrodes and battery systems and for characterizing the state of health of electrodes and battery systems. Measurement of physical attributes of electrodes and batteries corresponding to thermodynamically stabilized electrode conditions permit determination of thermodynamic parameters, including state functions such as the Gibbs free energy, enthalpy and entropy of electrode/electrochemical cell reactions, that enable prediction of important performance attributes of electrode materials and battery systems, such as energy, power density, current rate, cycle life and state of health. Also provided are systems and methods for charging a battery according to its state of health.
Weinhold'length in an isochoric thermodynamic system at constant heat capacity
Santoro, Manuel
2004-01-01
The purpose of this paper is to study thermodynamic length of an isochoric two dimensional thermodynamic system with constant heat capacity. We find that length is related to the heat flow into the substance. We give examples of Ideal gas and Van der Waals gas.
Critical evaluation and thermodynamic optimization of the U-Pb and U-Sb binary systems
International Nuclear Information System (INIS)
Wang, Jian; Jin, Liling; Chen, Chuchu; Rao, Weifeng; Wang, Cuiping; Liu, Xingjun
2016-01-01
A complete literature review, critical evaluation and thermodynamic optimization of the phase diagrams and thermodynamic properties of U-Pb and U-Sb binary systems are presented. The CALculation of PHAse Diagrams (CALPHAD) method was used for the thermodynamic optimization, the results of which can reproduce all available reliable experimental phase equilibria and thermodynamic data. The modified quasi-chemical model in the pair approximation (MQMPA) was used for modeling the liquid solution. The Gibbs energies of all terminal solid solutions and intermetallic compounds were described by the compound energy formalism (CEF) model. All reliable experimental data of the U-Pb and U-Sb systems have been reproduced. A self-consistent thermodynamic database has been constructed for these binary systems; this database can be used in liquid-metal fuel reactor (LMFR) research.
A brief review study of various thermodynamic cycles for high temperature power generation systems
International Nuclear Information System (INIS)
Yu, Si-Cong; Chen, Lin; Zhao, Yan; Li, Hong-Xu; Zhang, Xin-Rong
2015-01-01
Highlights: • Various high temperature power generation cycles for are reviewed and analyzed. • The operating temperature is higher than 700 K for high temperature power systems. • Thermodynamic cycle model study and working fluid choices are discussed. • Characteristics and future developments of high temperature cycles are presented and compared. - Abstract: This paper presents a review of the previous studies and papers about various thermodynamic cycles working for high temperature power generation procedures, in these cycles the highest temperature is not lower than 700 K. Thermodynamic cycles that working for power generation are divided into two broad categories, thermodynamic cycle model study and working fluid analysis. Thermodynamic cycle contains the simple cycle model and the complex cycle model, emphasis has been given on the complex thermodynamic cycles due to their high thermal efficiencies. Working fluids used for high temperature thermodynamic cycles is a dense gas rather than a liquid. A suitable thermodynamic cycle is crucial for effectively power generation especially under the condition of high temperature. The main purpose is to find out the characteristics of various thermodynamic cycles when they are working in the high temperature region for power generation. As this study shows, combined cycles with both renewable and nonrenewable energies as the heat source can show good performance
Thermodynamic framework for information in nanoscale systems with memory.
Arias-Gonzalez, J Ricardo
2017-11-28
Information is represented by linear strings of symbols with memory that carry errors as a result of their stochastic nature. Proofreading and edition are assumed to improve certainty although such processes may not be effective. Here, we develop a thermodynamic theory for material chains made up of nanoscopic subunits with symbolic meaning in the presence of memory. This framework is based on the characterization of single sequences of symbols constructed under a protocol and is used to derive the behavior of ensembles of sequences similarly constructed. We then analyze the role of proofreading and edition in the presence of memory finding conditions to make revision an effective process, namely, to decrease the entropy of the chain. Finally, we apply our formalism to DNA replication and RNA transcription finding that Watson and Crick hybridization energies with which nucleotides are branched to the template strand during the copying process are optimal to regulate the fidelity in proofreading. These results are important in applications of information theory to a variety of solid-state physical systems and other biomolecular processes.
Memory systems, computation, and the second law of thermodynamics
International Nuclear Information System (INIS)
Wolpert, D.H.
1992-01-01
A memory is a physical system for transferring information form one moment in time to another, where that information concerns something external to the system itself. This paper argues on information-theoretic and statistical mechanical grounds that useful memories must be of one of two types, exemplified by memory in abstract computer programs and by memory in photographs. Photograph-type memories work by exploring a collapse of state space flow to an attractor state. (This attractor state is the open-quotes initializedclose quotes state of the memory.) The central assumption of the theory of reversible computation tells us that in any such collapsing, regardless of whether the collapsing must increase in entropy of the system. In concert with the second law, this establishes the logical necessity of the empirical observation that photograph-type memories are temporally asymmetric (they can tell us about the past but not about the future). Under the assumption that human memory is a photograph-type memory, this result also explains why we humans can remember only our past and not our future. In contrast to photo-graph-type memories, computer-type memories do not require any initialization, and therefore are not directly affected by the second law. As a result, computer memories can be of the future as easily as of the past, even if the program running on the computer is logically irreversible. This is entirely in accord with the well-known temporal reversibility of the process of computation. This paper ends by arguing that the asymmetry of the psychological arrow of time is a direct consequence of the asymmetry of human memory. With the rest of this paper, this explains, explicitly and rigorously, why the psychological and thermodynamic arrows of time are correlated with one another. 24 refs
Thermodynamic and kinetic analysis of heterogeneous photocatalysis for semiconductor systems.
Liu, Baoshun; Zhao, Xiujian; Terashima, Chiaki; Fujishima, Akira; Nakata, Kazuya
2014-05-21
Since the report of the Honda-Fujishima effect, heterogeneous photocatalysis has attracted much attention around the world because of its potential energy and environmental applications. Although great progresses have been made in recent years, most were focused on preparing highly-active photocatalysts and investigating visible light utilization. In fact, we are still unclear on the thermodynamic and kinetic nature of photocatalysis to date, which sometimes leads to misunderstandings for experimental results. It is timely to give a review and discussion on the thermodynamics and kinetics of photocatalysis, so as to direct future researches. However, there is an absence of a detailed review on this topic until now. In this article, we tried to review and discuss the thermodynamics and kinetics of photocatalysis. We explained the thermodynamic driving force of photocatalysis, and distinguished the functions of light and heat in photocatalysis. The Langmuir-Hinshelwood kinetic model, the ˙OH oxidation mechanism, and the direct-indirect (D-I) kinetic model were reviewed and compared. Some applications of the D-I model to study photocatalytic kinetics were also discussed. The electron transport mode and its importance in photocatalysis were investigated. Finally, the intrinsic relation between the kinetics and the thermodynamics of photocatalytic reactions was discussed.
Energy systems a new approach to engineering thermodynamics
Gicquel, Renaud
2011-01-01
Forewords, About the Author, General introduction, Structure of the book, Objectives, A working tool on many levels, Mind Maps, List of Symbols, Conversion FactorsI First Steps in Engineering Thermodynamics1 A New Educational Paradigm1.1 Introduction1.2 General remarks on the evolution of training specifi cations1.3 Specifi cs of applied thermodynamics teaching1.4 A new educational paradigm1.5 Diapason modules1.6 A three-step progressive approach1.7 Main pedagogic innovations brought by Thermoptim1.8 Digital resources of the Thermoptim-UNIT portal1.9 Comparison with other tools with teaching p
Thermodynamic and Process Modelling of Gas Hydrate Systems in CO2 Capture Processes
DEFF Research Database (Denmark)
Herslund, Peter Jørgensen
in this work compares well with other data available in the literature for similar systems. It is shown experimentally that the addition of tetrahydrofuran to the ternary system of water-cyclopentane-carbon dioxide provides an enhanced thermodynamic promotion of the gas hydrate phase. Hydrate equilibrium...... and tetrahydrofuran as the two most efficient pressure reducing additives in classical hydrate forming systems. The thermodynamic promoting effects reported in the literature for the two classical sII hydrate formers, tetrahydrofuran and cyclopentane are experimentally confirmed in the present work. Data presented...... pressures are reduced by approximately 20 percent compared to the cyclopentane promoted system. The mixed promoter system thereby represents a new state-ofthe-art within thermodynamic promotion of gas hydrates in the framework of the classical hydrate structures. A thermodynamic model based on the Cubic...
The critical roles of information and nonequilibrium thermodynamics in evolution of living systems.
Gatenby, Robert A; Frieden, B Roy
2013-04-01
Living cells are spatially bounded, low entropy systems that, although far from thermodynamic equilibrium, have persisted for billions of years. Schrödinger, Prigogine, and others explored the physical principles of living systems primarily in terms of the thermodynamics of order, energy, and entropy. This provided valuable insights, but not a comprehensive model. We propose the first principles of living systems must include: (1) Information dynamics, which permits conversion of energy to order through synthesis of specific and reproducible, structurally-ordered components; and (2) Nonequilibrium thermodynamics, which generate Darwinian forces that optimize the system.Living systems are fundamentally unstable because they exist far from thermodynamic equilibrium, but this apparently precarious state allows critical response that includes: (1) Feedback so that loss of order due to environmental perturbations generate information that initiates a corresponding response to restore baseline state. (2) Death due to a return to thermodynamic equilibrium to rapidly eliminate systems that cannot maintain order in local conditions. (3) Mitosis that rewards very successful systems, even when they attain order that is too high to be sustainable by environmental energy, by dividing so that each daughter cell has a much smaller energy requirement. Thus, nonequilibrium thermodynamics are ultimately responsible for Darwinian forces that optimize system dynamics, conferring robustness sufficient to allow continuous existence of living systems over billions of years.
Thermodynamics of Organic Compound Alteration in Hydrothermal Systems
Shock, E. L.
2005-12-01
Organic compounds enter hydrothermal systems through infiltrating surface waters, zones of microbial productivity in the subsurface, extracts of organic matter in surrounding host rocks, and abiotic synthesis. Owing to variations in pH, oxidation state, composition, temperature, and pressure throughout the changing pathways of fluid migration over the duration of the system, organic compounds from all of these sources are introduced to conditions where their relative stabilities and reactivities can be dramatically transformed. If those transformations were predictable, then the extent to which organic alteration reactions have occurred could be used to reveal flowpaths and histories of hydrothermal systems. Speciation and mass transfer calculations permit some insight into the underlying thermodynamic driving forces that result in organic compound alteration. As an example, the speciation of many geochemist's canonical organic matter: CH2O depends strongly on oxidation state, temperature, and total concentration of dissolved organic matter. Calculations show that at oxidation states buffered by iron-bearing mineral assemblages, organic acids dominate the speciation of CH2O throughout hydrothermal systems, with acetic acid (itself equivalent to 2 CH2O by bulk composition) and propanoic acid generally the most abundant compounds. However, at more reduced conditions, which may prevail in organic-rich iron-poor sediments, the drive is to form ketones and especially alcohols at the expense of organic acids. The distribution of organic carbon among the various members of these compound classes is strongly dependent on the total concentration of dissolved organic matter. As an example, at a bulk concentration equivalent to average dissolved organic matter in seawater (45μm), the dominant alcohols at 100°C are small compounds like ethanol and 1-propanol. In contrast, at a higher bulk concentration of 500μm, there is a drive to shift large percentages of dissolved
Thermodynamics of the Si-O-H System
Jacobson, Nathan S.; Opila, Elizabeth J.; Myers, Dwight; Copland, Evan
2004-01-01
Thermodynamic functions for Si(OH)4(g) and SiO(OH)2(g) have been measured using the transpiration method. A second law enthalpy of formation and entropy and a third law enthalpy of formation has been calculated for Si(OH)4. The results are in very good agreement with previous experimental measurements, ab-initio calculations, and estimates.
Thermodynamics of Glassy Systems: Glasses, Spin Glasses and Optimization
Leuzzi, L.
2002-01-01
After a long, self-standing dominance of Newtonian reductionism, at the beginning of the nineteenth century, with the birth of thermodynamics, a new approach began to develop to the study of nature. Indeed, the prediction of the behaviour of a macroscopic material through the knowledge of all the
Thermodynamic modelling of phase equilibria in Al–Ga–P–As system
Indian Academy of Sciences (India)
Unknown
- perimental ... In the present investigation, therefore, a multiparameter function is adopted for interpretation of thermodynamic behaviour of the liquid alloys in the system. According ...... temperature than those derived based on the simple solu-.
Non-equilibrium thermodynamics, maximum entropy production and Earth-system evolution.
Kleidon, Axel
2010-01-13
The present-day atmosphere is in a unique state far from thermodynamic equilibrium. This uniqueness is for instance reflected in the high concentration of molecular oxygen and the low relative humidity in the atmosphere. Given that the concentration of atmospheric oxygen has likely increased throughout Earth-system history, we can ask whether this trend can be generalized to a trend of Earth-system evolution that is directed away from thermodynamic equilibrium, why we would expect such a trend to take place and what it would imply for Earth-system evolution as a whole. The justification for such a trend could be found in the proposed general principle of maximum entropy production (MEP), which states that non-equilibrium thermodynamic systems maintain steady states at which entropy production is maximized. Here, I justify and demonstrate this application of MEP to the Earth at the planetary scale. I first describe the non-equilibrium thermodynamic nature of Earth-system processes and distinguish processes that drive the system's state away from equilibrium from those that are directed towards equilibrium. I formulate the interactions among these processes from a thermodynamic perspective and then connect them to a holistic view of the planetary thermodynamic state of the Earth system. In conclusion, non-equilibrium thermodynamics and MEP have the potential to provide a simple and holistic theory of Earth-system functioning. This theory can be used to derive overall evolutionary trends of the Earth's past, identify the role that life plays in driving thermodynamic states far from equilibrium, identify habitability in other planetary environments and evaluate human impacts on Earth-system functioning. This journal is © 2010 The Royal Society
Demirel, Yasar
2014-01-01
Natural phenomena consist of simultaneously occurring transport processes and chemical reactions. These processes may interact with each other and may lead to self-organized structures, fluctuations, instabilities, and evolutionary systems. Nonequilibrium Thermodynamics, 3rd edition emphasizes the unifying role of thermodynamics in analyzing the natural phenomena. This third edition updates and expands on the first and second editions by focusing on the general balance equations for coupled processes of physical, chemical, and biological systems. The new edition contains a new chapte
Thermodynamic treatment of nonphysical systems: formalism and an example (single-lane traffic)
International Nuclear Information System (INIS)
Reiss, H.; Hammerich, A.D.; Montroll, E.W.
1986-01-01
An effort is made to introduce thermodynamic and statistical thermodynamic methods into the treatment of nonphysical (e.g., social, economic, etc.) systems. Emphasis is placed on the use of the entire thermodynamic framework, not merely entropy. Entropy arises naturally, related in a simple manner to other measurables, but does not occupy a primary position in the theory. However, the maximum entropy formalism is a convenient procedure for deriving the thermodynamic analog framework in which undetermined multipliers are thermodynamic-like variables which summarize the collective behavior of the system. The authors discuss the analysis of Levine and his coworkers showing that the maximum entropy formalism is the unique algorithm for achieving consistent inference of probabilities. The thermodynamic-like formalism for treating a single lane of vehicular traffic is developed and applied to traffic in which the interaction between cars is chosen to be a particular form of the ''follow-the-leader'' type. The equation of state of the traffic, the distributions of velocity and headway, and the various thermodynamic-like parameters, e.g., temperature (collective sensitivity), pressure, etc. are determined for the example of the Holland Tunnel. Nearest-neighbor and pair correlation functions for the vehicles are also determined. Interesting and suggestive results are obtained
Cantera Integration with the Toolbox for Modeling and Analysis of Thermodynamic Systems (T-MATS)
Lavelle, Thomas M.; Chapman, Jeffryes W.; May, Ryan D.; Litt, Jonathan S.; Guo, Ten-Huei
2014-01-01
NASA Glenn Research Center (GRC) has recently developed a software package for modeling generic thermodynamic systems called the Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS). T-MATS is a library of building blocks that can be assembled to represent any thermodynamic system in the Simulink (The MathWorks, Inc.) environment. These elements, along with a Newton Raphson solver (also provided as part of the T-MATS package), enable users to create models of a wide variety of systems. The current version of T-MATS (v1.0.1) uses tabular data for providing information about a specific mixture of air, water (humidity), and hydrocarbon fuel in calculations of thermodynamic properties. The capabilities of T-MATS can be expanded by integrating it with the Cantera thermodynamic package. Cantera is an object-oriented analysis package that calculates thermodynamic solutions for any mixture defined by the user. Integration of Cantera with T-MATS extends the range of systems that may be modeled using the toolbox. In addition, the library of elements released with Cantera were developed using MATLAB native M-files, allowing for quicker prototyping of elements. This paper discusses how the new Cantera-based elements are created and provides examples for using T-MATS integrated with Cantera.
International Nuclear Information System (INIS)
Kim, Junghwan; Jung, In-Ho
2012-01-01
Highlights: ► The Mn–RE (RE = La, Ce, Pr, Nd and Sm) systems have been critically reviewed. ► The thermodynamic optimization of the Mn–RE systems have been performed. ► Systematic changes in the phase diagrams and thermodynamic properties were found. ► The systematic approach resolved inconsistencies in the experimental data. - Abstract: Critical evaluation and optimization of all available phase diagram and thermodynamic data for the Mn–RE (RE = La, Ce, Pr, Nd and Sm) systems have been conducted to obtain reliable thermodynamic functions of all the phases in the system. In the thermodynamic modeling, it is found that the Mn–RE systems show systematic changes in the phase diagrams and thermodynamic properties such as enthalpy of mixing in liquid state in the order of periodic number in the lanthanide series. This systematic thermodynamic modeling approach for all light RE elements can allow to resolve inconsistencies in the experimental data.
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.)
Comparative study of entropy and information change in closed and open thermodynamic systems
Energy Technology Data Exchange (ETDEWEB)
Popovic, Marko, E-mail: popovic.pasa@gmail.com
2014-12-20
Highlights: • The information and entropy change of the system are discussed in the context of RNA synthesis. • During synthesis reactions in a closed thermodynamic system, its information content increases while its entropy decreases. • In degradation reactions information decreases while entropy increases. • In open thermodynamic systems performing synthesis reactions both entropy and information content increase. • In open systems performing decomposition processes both entropy and information content decrease. - Abstract: In this paper we discuss the entropy and information aspects of closed and open systems. The information and entropy change of the system are discussed in the context of RNA synthesis.
Experimental investigation and thermodynamic calculation of the Mg-Sr-Zr system
International Nuclear Information System (INIS)
Zhou, Hua; Chen, Chong; Du, Yong; Central South Univ., Hunan; Gong, Haoran
2016-01-01
Both experimental investigation and thermodynamic calculation were performed for the Mg-Sr-Zr system. Four decisive alloys were firstly selected and prepared using a powder metallurgy method to measure the isothermal section at 400 C via a combination of X-ray diffraction and electron probe microanalysis. No ternary compound has been observed for this ternary system. Four three-phase regions, (Mg) + (αZr) + Mg 17 Sr 2 , Mg 17 Sr 2 + (αZr) + Mg 38 Sr 9 , Mg 38 Sr 9 + (αZr) + Mg 23 Sr 6 , and Mg 23 Sr 6 + (αZr) + Mg 2 Sr, have been identified at 400 C. No appreciable ternary solubility has been detected in the binary Mg-Sr compounds. Phase transition temperatures of the Mg-Sr-Zr alloys were measured by means of differential scanning calorimetry. The thermodynamic calculations match well with the experimental data in the present work, indicating that no ternary thermodynamic parameters are needed for the thermodynamic description of this ternary system. In order to verify the reliability of the current thermodynamic calculations of the Mg-Sr-Zr system, eight as-cast alloys in the Mg-rich corner were also prepared. The calculated liquidus projection is consistent with the observed primary phase regions. The present thermodynamic calculations are reliable and can be used in the development of Mg alloys.
Thermodynamic analysis and characterization of alloys in Bi-Cu-Sb system
Directory of Open Access Journals (Sweden)
Živković D.
2010-01-01
Full Text Available The results of thermodynamic analysis and characterization of some alloys in Bi-Cu-Sb lead-free solder system are presented in this paper. Thermodynamic analysis was done using general solution model, while optic microscopy, hardness and electroconductivity measurements were used in order to determine structural, mechanic and electric characteristics of selected samples in section from bismuth corner with molar ratio Cu:Sb=3:7.
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.
Directory of Open Access Journals (Sweden)
Chellaboina Vijaysekhar
2005-01-01
Full Text Available We develop thermodynamic models for discrete-time large-scale dynamical systems. Specifically, using compartmental dynamical system theory, we develop energy flow models possessing energy conservation, energy equipartition, temperature equipartition, and entropy nonconservation principles for discrete-time, large-scale dynamical systems. Furthermore, we introduce a new and dual notion to entropy; namely, ectropy, as a measure of the tendency of a dynamical system to do useful work and grow more organized, and show that conservation of energy in an isolated thermodynamic system necessarily leads to nonconservation of ectropy and entropy. In addition, using the system ectropy as a Lyapunov function candidate, we show that our discrete-time, large-scale thermodynamic energy flow model has convergent trajectories to Lyapunov stable equilibria determined by the system initial subsystem energies.
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.
Thermodynamic assessment of the palladium-tellurium (Pd-Te) system
International Nuclear Information System (INIS)
Gosse, S.; Gueneau, C.
2011-01-01
Among the fission products formed in nuclear fuels, the platinum-group metal palladium and the chalcogen element tellurium exhibit strong interaction. It is therefore of interest to be able to predict the chemical equilibria involving the Pd and Te fission products. A thermodynamic assessment is carried out using the Calphad (Calculation of Phase Diagram) method to investigate the behaviour of Pd-Te alloy system in nuclear fuels under irradiation and under waste disposal conditions. The Pd-Te binary description was optimized using experimental data found in literature including thermodynamic properties and phase diagram data. To validate the calculated phase diagram and thermodynamic properties, the results are compared with data from the literature. Both calculated and experimental phase diagrams and thermodynamic properties are in good agreement in the whole Pd-Te composition range. (authors)
Liquid Methane Testing With a Large-Scale Spray Bar Thermodynamic Vent System
Hastings, L. J.; Bolshinskiy, L. G.; Hedayat, A.; Flachbart, R. H.; Sisco, J. D.; Schnell. A. R.
2014-01-01
NASA's Marshall Space Flight Center conducted liquid methane testing in November 2006 using the multipurpose hydrogen test bed outfitted with a spray bar thermodynamic vent system (TVS). The basic objective was to identify any unusual or unique thermodynamic characteristics associated with densified methane that should be considered in the design of space-based TVSs. Thirteen days of testing were performed with total tank heat loads ranging from 720 to 420 W at a fill level of approximately 90%. It was noted that as the fluid passed through the Joule-Thompson expansion, thermodynamic conditions consistent with the pervasive presence of metastability were indicated. This Technical Publication describes conditions that correspond with metastability and its detrimental effects on TVS performance. The observed conditions were primarily functions of methane densification and helium pressurization; therefore, assurance must be provided that metastable conditions have been circumvented in future applications of thermodynamic venting to in-space methane storage.
Mixed 2D molecular systems: Mechanic, thermodynamic and dielectric properties
Energy Technology Data Exchange (ETDEWEB)
Beno, Juraj [Department of Physics, Faculty of Electrical Engineering and Information Technology, Slovak University of Technology, Ilkovicova 3, 812 19-SK Bratislava (Slovakia); Weis, Martin [Department of Physics, Faculty of Electrical Engineering and Information Technology, Slovak University of Technology, Ilkovicova 3, 812 19-SK Bratislava (Slovakia)], E-mail: Martin.Weis@stuba.sk; Dobrocka, Edmund [Department of Physics, Faculty of Electrical Engineering and Information Technology, Slovak University of Technology, Ilkovicova 3, 812 19-SK Bratislava (Slovakia); Institute of Electrical Engineering, Slovak Academy of Sciences, Dubravska cesta 9, 841 04-SK Bratislava (Slovakia); Hasko, Daniel [International Laser Centre, Ilkovicova 3, 812 19-SK Bratislava (Slovakia)
2008-08-15
Study of Langmuir monolayers consisting of stearic acid (SA) and dipalmitoylphosphatidylcholine (DPPC) molecules was done by surface pressure-area isotherms ({pi}-A), the Maxwell displacement current (MDC) measurement, X-ray reflectivity (XRR) and atomic force microscopy (AFM) to investigate the selected mechanic, thermodynamic and dielectric properties based on orientational structure of monolayers. On the base of {pi}-A isotherms analysis we explain the creation of stable structures and found optimal monolayer composition. The dielectric properties represented by MDC generated monolayers were analyzed in terms of excess dipole moment, proposing the effect of dipole-dipole interaction. XRR and AFM results illustrate deposited film structure and molecular ordering.
Thermodynamic and dynamic behaviors of self-organizing polymeric systems
Zhao, Yiqiang
Two topics of self-organizing polymeric systems are explored in this work: thermodynamic and dynamic properties of liquid crystal polymers in solutions and rheological behaviors of self-organizing gels. For dilute nematic solutions of end-on side-chain liquid crystal polysiloxanes (SCLCP) dissolved in 5CB, the chain anisotropies R∥/R ⊥, obtained from electrorheological(ER) analysis based on the Brochard model, are consistent with independent measurements of Rg∥/R g⊥ via small-angle neutron scattering (SANS), which unambiguously demonstrating a slightly prolate SCLCP chain conformation. Dissolution of this prolate SCLCP in flow-aligning 5CB produces a tumbling flow, clearly indicating a discrepancy with the Brochard hydrodynamic theory which predicts such a transition only for oblate conformation. A numerical comparison using a modified version of the Brochard model leads to improved self-consistent agreement between SANS, ER and shear transient experiments. The molecular weight dependence of the chain conformational relaxation time it indicates an extended SCLCP chain conformation in 5CB. SANS analysis suggests that the SCLCP conformation is sensitive to the solvent interaction, i.e. a more extended conformation is observed in isotropic acetone-d6 than in nematic 5CB. A SANS conformational study of SCLCCs with methoxyphenylbenzoate mesogenic side group in CDC13 demonstrates that the form factor of a single comb-like SCLCP chain is well described by a wormlike chain model with finite cross-sectional thickness over the entire q range, taking into account the molecular weight polydispersity. Consistent with measurement of a large R g from low q analysis, the resulting persistence length lp is in the range 28˜32 A, substantially larger than that of unsubstituted polydimethylsiloxane (PDMS) chain (l p =5.8 A), which suggests a relatively rigid SCLCP chain due to the influence of densely attached mesogenic groups. For nematic mixtures of copolysiloxane SCLCP in
Dissipative open systems theory as a foundation for the thermodynamics of linear systems.
Delvenne, Jean-Charles; Sandberg, Henrik
2017-03-06
In this paper, we advocate the use of open dynamical systems, i.e. systems sharing input and output variables with their environment, and the dissipativity theory initiated by Jan Willems as models of thermodynamical systems, at the microscopic and macroscopic level alike. We take linear systems as a study case, where we show how to derive a global Lyapunov function to analyse networks of interconnected systems. We define a suitable notion of dynamic non-equilibrium temperature that allows us to derive a discrete Fourier law ruling the exchange of heat between lumped, discrete-space systems, enriched with the Maxwell-Cattaneo correction. We complete these results by a brief recall of the steps that allow complete derivation of the dissipation and fluctuation in macroscopic systems (i.e. at the level of probability distributions) from lossless and deterministic systems.This article is part of the themed issue 'Horizons of cybernetical physics'. © 2017 The Author(s).
Wei, Bo-Bo; Jiang, Zhan-Feng; Liu, Ren-Bao
2015-10-19
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.
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
International Nuclear Information System (INIS)
Hassan, H.Z.; Mohamad, A.A.
2013-01-01
Due to the intermittent nature of the solar radiation, the day-long continuous production of cold is a challenge for solar-driven adsorption cooling systems. In the present study, a developed solar-powered adsorption cooling system is introduced. The proposed system is able to produce cold continuously along the 24-h of the day. The theoretical thermodynamic operating cycle of the system is based on adsorption at constant temperature. Both the cooling system operating procedure as well as the theoretical thermodynamic cycle are described and explained. Moreover, a steady state differential thermodynamic analysis is performed for all components and processes of the introduced system. The analysis is based on the energy conservation principle and the equilibrium dynamics of the adsorption and desorption processes. The Dubinin–Astakhov adsorption equilibrium equation is used in this analysis. Furthermore, the thermodynamic properties of the refrigerant are calculated from its equation of state. The case studied represents a water chiller which uses activated carbon–methanol as the working pair. The chiller is found to produce a daily mass of 2.63 kg cold water at 0 °C from water at 25 °C per kg of adsorbent. Moreover, the proposed system attains a cooling coefficient of performance of 0.66. - Highlights: • A new continuous operation solar-driven adsorption refrigeration system is introduced. • The theoretical thermodynamic cycle is presented and explained. • A complete thermodynamic analysis is performed for all components and processes of the system. • Activated carbon–methanol is used as the working pair in the case study
Experimental investigation and thermodynamic re-assessment of the Al–Mo–Ni system
Energy Technology Data Exchange (ETDEWEB)
Peng, Jian, E-mail: jian.peng@kit.edu [Institute for Applied Materials – Applied Materials Physics, Karlsruhe Institute of Technology, Hermann-von-Helmholtz Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Franke, Peter [Institute for Applied Materials – Applied Materials Physics, Karlsruhe Institute of Technology, Hermann-von-Helmholtz Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Manara, Dario; Watkins, Tyson; Konings, Rudy J.M. [European Commission, Joint Research Centre, Institute for Transuranium Elements, P.O. Box 2340, 76125 Karlsruhe (Germany); Seifert, Hans J. [Institute for Applied Materials – Applied Materials Physics, Karlsruhe Institute of Technology, Hermann-von-Helmholtz Platz 1, 76344 Eggenstein-Leopoldshafen (Germany)
2016-07-25
NiAl-based alloys have been investigated, because they are promising alternative materials for high temperature structural applications. Recent advancements in directional solidification offer the opportunity to manufacture metal-matrix composites of NiAl strengthened by embedded fibers of refractory metals such as Mo. The mechanical properties of these composites can be considerably improved, compared to NiAl, at least in fiber direction. The Al–Mo–Ni system has been thermodynamically assessed by several authors. However, none of them can reproduce a satisfactory description along the section NiAl–Mo. In the present work, liquidus and solidus temperatures of the NiAl–Mo system were measured by a laser heating-fast pyrometry apparatus. The results agree well with literature data. The thermodynamic descriptions of the Al–Ni and Al–Mo systems from the literature were refined and a new thermodynamic dataset of the Al–Mo–Ni system was established. The ordered B2 phase and its disordered A2 (bcc) parent phase were described by a single Gibbs energy function. Very good agreement between the calculated phase diagram and the experimental data is obtained. The description of the section NiAl–Mo is considerably improved and we conclude that this section does not represent a quasi-binary phase diagram. - Highlights: • The liquidus and solidus temperatures of the NiAl–Mo system were measured. • The Gibbs energy of vacancies in the bcc phase was considered in the modeling. • The thermodynamic descriptions of the Al–Ni and Al–Mo systems were refined. • A new thermodynamic database of the Al–Mo–Ni system was established. • The thermodynamic description of the NiAl–Mo system was considerably improved.
Thermodynamic assessment of the Pd−Rh−Ru system using calphad and first-principles methods
Energy Technology Data Exchange (ETDEWEB)
Gossé, S., E-mail: stephane.gosse@cea.fr [DEN-Service de la Corrosion et du Comportement des Matériaux dans leur Environnement (SCCME), CEA, Université Paris-Saclay, F-91191, Gif-sur-Yvette (France); Dupin, N. [Calcul Thermodynamique, Rue de l' avenir, 63670, Orcet (France); Guéneau, C. [DEN-Service de la Corrosion et du Comportement des Matériaux dans leur Environnement (SCCME), CEA, Université Paris-Saclay, F-91191, Gif-sur-Yvette (France); Crivello, J.-C.; Joubert, J.-M. [Chimie Métallurgique des Terres Rares, Université Paris Est, ICMPE (UMR 7182), CNRS, UPEC, F-94320, Thiais (France)
2016-06-15
Palladium, rhodium and ruthenium are abundant fission products that form in oxide fuels in nuclear reactors. Under operating conditions, these Platinum-Group Metal (PGM) fission products accumulate in high concentration at the rim of the oxide fuel and mainly precipitate into metallic solid solutions. Their thermochemistry is of significant interest to predict the high temperature chemical interactions between the fuel and the cladding or the possible precipitation of PGM phases in high level nuclear waste glasses. To predict the thermodynamic properties of these PGM fission products, a thermodynamic modeling is being developed on the ternary Pd−Rh−Ru system using the Calphad method. Because experimental thermodynamic data are scarce, Special Quasirandom Structures coupled with Density Functional Theory methods were used to calculate mixing enthalpy data in the solid solutions. The resulting thermodynamic description based on only binary interaction parameters is in good agreement with the few data on the ternary system. - Highlights: • The mixing enthalpy of solid solutions in the Pd−Rh−Ru system was calculated using the DFT and SQS methods. • A thermodynamic assessment of the Pd−Rh−Ru ternary system was performed using the Calphad method. • The extrapolation based on only binary interaction parameters leads to a good agreement with the data on the ternary.
Experimental investigation and thermodynamic assessment of the Mn–In binary system
Energy Technology Data Exchange (ETDEWEB)
Wang, L.Y. [Guangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology, Guilin 541004 (China); School of Materials Science and Engineering, Guilin University of Electronic Technology, Guilin 541004 (China); Wang, J., E-mail: wangjiang158@163.com [Guangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology, Guilin 541004 (China); School of Materials Science and Engineering, Guilin University of Electronic Technology, Guilin 541004 (China); Zhu, C.F.; Cheng, G.; Tang, C.Y. [Guangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology, Guilin 541004 (China); School of Materials Science and Engineering, Guilin University of Electronic Technology, Guilin 541004 (China); Rao, G.H., E-mail: rgh@guet.edu.cn [Guangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology, Guilin 541004 (China); School of Materials Science and Engineering, Guilin University of Electronic Technology, Guilin 541004 (China); Zhou, H.Y. [Guangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology, Guilin 541004 (China); School of Materials Science and Engineering, Guilin University of Electronic Technology, Guilin 541004 (China)
2015-05-10
Highlights: • Three invariant reactions and liquidus were determined by thermal analysis. • The Mn–In binary system was assessed using CALPHAD method. • A set of self-consistent thermodynamic parameters was obtained. • The calculation results agree well with phase equilibria and thermodynamic data. - Abstract: In the present work, sixteen Mn–In alloys were investigated experimentally by means of thermal analysis and X-ray diffraction techniques. The temperatures of the invariant reactions and liquidus in the Mn–In binary system were determined. Based on the experimental results obtained in the present work and the critical review of the available experimental data from the published literature, the Mn–In binary system was assessed thermodynamically using the CALPHAD method. The solution phases including liquid, α-Mn, β-Mn, γ-Mn, δ-Mn and tetragonal-A6(In), are modeled by the substitutional solution model and their excess Gibbs energies are expressed with the Redlich–Kister polynomial. The intermetallic compound, InMn{sub 3}, is treated as a stoichiometric compound. A set of self-consistent thermodynamic parameters obtained finally to describe the Gibbs energies of various phases in the Mn–In binary system can be used to reproduce well the phase equilibria and thermodynamic data.
Thermodynamic equivalence between the Lennard-Jones and hard-core attractive Yukawa systems
International Nuclear Information System (INIS)
Kadiri, Y.; Albaki, R.; Bretonnet, J.L.
2008-01-01
The investigation of the thermodynamic properties of the Lennard-Jones (LJ) fluid is made by means of a system of particles interacting with a potential of hard-core plus attractive Yukawa tail (HCY). Due to the similarity between the LJ potential and the HCY potential in its overall form, it is worthwhile seeking to approximate the LJ potential in much the same way that the hard-sphere reference potential has been so used. The study consists in describing the thermodynamics of the LJ fluid in terms of the equivalent HCY system, whose the properties are known accurately, by means of mapping the thermodynamic quantities for the HCY potential parameters. The method is feasible owing to a convenient analytical expression of the Helmholtz free energy from the mean-spherical approximation expanded in power of the inverse temperature. Two different procedures are used to determine the parameters of the HCY potential as a function of the thermodynamic states: one is based on the simultaneous fits of pressure and internal energy of the LJ system and the other uses the concept of collision frequency. The reasonable homogeneity of the results in both procedures of mapping makes that the HCY potential is a very good reference system, whose the proposed theoretical expressions can be used confidently to predict the thermodynamic properties of more realistic potentials
Thermodynamic study of the binary system copper-indium. II
International Nuclear Information System (INIS)
Kang, T.; Kehiaian, H.V.; Castanet, R.
1977-01-01
The electrochemical cell with solid electrolytes -Mo/In(l),In 2 O 3 (s)/ZrO 2 , CaO/air, Pt/Pt, air/CaO, ZrO 2 /In-Cu(l), In 2 O 3 (s)/Mo+ was used to measure the activity of indium in liquid Cu-In alloys at nine concentrations in the temperature range from 1020 to 1389 K. The procedure was checked by determining the enthalpy of formation of indium oxide In 2 O 3 . Combining the present results with those obtained by direct calorimetry, thermodynamically consistent values were proposed for the free energy, entropy, enthalpy and heat capacity of liquid Cu-In alloys. (Auth.)
Boyd, Alexander B.; Crutchfield, James P.
2016-05-01
We introduce a deterministic chaotic system—the Szilard map—that encapsulates the measurement, control, and erasure protocol by which Maxwellian demons extract work from a heat reservoir. Implementing the demon's control function in a dynamical embodiment, our construction symmetrizes the demon and the thermodynamic system, allowing one to explore their functionality and recover the fundamental trade-off between the thermodynamic costs of dissipation due to measurement and those due to erasure. The map's degree of chaos—captured by the Kolmogorov-Sinai entropy—is the rate of energy extraction from the heat bath. Moreover, an engine's statistical complexity quantifies the minimum necessary system memory for it to function. In this way, dynamical instability in the control protocol plays an essential and constructive role in intelligent thermodynamic systems.
Thermodynamic analysis of an HCCI engine based system running on natural gas
International Nuclear Information System (INIS)
Djermouni, Mohamed; Ouadha, Ahmed
2014-01-01
Highlights: • A thermodynamic analysis of an HCCI based system has been carried out. • A thermodynamic model has been developed taking into account the gas composition resulting from the combustion process. • The specific heat of the working fluid is temperature dependent. - Abstract: This paper attempts to carry out a thermodynamic analysis of a system composed of a turbocharged HCCI engine, a mixer, a regenerator and a catalytic converter within the meaning of the first and the second law of thermodynamics. For this purpose, a thermodynamic model has been developed taking into account the gas composition resulting from the combustion process and the specific heat temperature dependency of the working fluid. The analysis aims in particular to examine the influence of the compressor pressure ratio, ambient temperature, equivalence ratio, engine speed and the compressor isentropic efficiency on the performance of the HCCI engine. Results show that thermal and exergetic efficiencies increase with increasing the compressor pressure ratio. However, the increase of the ambient temperature involves a decrease of the engine efficiencies. Furthermore, the variation of the equivalence ratio improves considerably both thermal and exergetic efficiencies. As expected, the increase of the engine speed enhances the engine performances. Finally, an exergy losses mapping of the system show that the maximum exergy losses occurs in the HCCI engine
International Nuclear Information System (INIS)
Sutton, S.B.; Stein, W.; Reitter, T.A.; Hindmarsh, A.C.
1983-01-01
A numerical model for calculating the thermodynamic behavior of the MFTF-B cryogenic cooling system is described. Nine component types are discussed with governing equations given. The algorithm for solving the coupled set of algebraic and ordinary differential equations is described. The model and its application to the MFTF-B cryogenic cooling system has not been possible due to lack of funding
Modeling of Energy Management Systems for Commercial Parks with Thermodynamic Equipment
Shanshan, Shi; Yu, Zhang; Liuyang, Fan; Tian, Luo
2017-05-01
Commercial park energy management systems (CPEMS) can reasonably plan appliances’ schedule of commercial tenants (CT) and lower their electricity purchasing cost. However, in the existing models, thermodynamic equipment like air conditioners and water heaters are not precise enough, failing to reflect the actual operating characteristics of the equipment. This paper presents an energy management system model including thermodynamic equipment. By coordinating the electricity consumption schedule of multiple CTs, CPEMS can reduce CTs’ electricity purchase costs. In the demonstration example, electricity purchase costs of CTs are reduced and operators of CPEMS gain profit, proving the feasibility of the model.
Shukla, Adarsh
In a thermodynamic system which contains several elements, the phase relationships among the components are usually very complex. Especially, systems containing oxides are generally very difficult to investigate owing to the very high experimental temperatures and corrosive action of slags. Due to such difficulties, large inconsistencies are often observed among the available experimental data. In order to investigate and understand the complex phase relationships effectively, it is very useful to develop thermodynamic databases containing optimized model parameters giving the thermodynamic properties of all phases as functions of temperature and composition. In a thermodynamic optimization, adjustable model parameters are calculated using, simultaneously, all available thermodynamic and phase-equilibrium data in order to obtain one set of model equations as functions of temperature and composition. Thermodynamic data, such as activities, can aid in the evaluation of the phase diagrams, and information on phase equilibria can be used to deduce thermodynamic properties. Thus, it is frequently possible to resolve discrepancies in the available data. From the model equations, all the thermodynamic properties and phase diagrams can be back-calculated, and interpolations and extrapolations can be made in a thermodynamically correct manner. The data are thereby rendered self-consistent and consistent with thermodynamic principles, and the available data are distilled into a small set of model parameters, ideal for computer storage. As part of a broader research project at the Centre de Recherche en Calcul Thermochimique (CRCT), Ecole Polytechnique to develop a thermodynamic database for multicomponent oxide systems, this thesis deals with the addition of components SrO and BaO to the existing multicomponent database of the SiO2-B2O3-Al2O 3-CaO-MgO system. Over the years, in collaboration with many industrial companies, a thermodynamic database for the SiO2-B2O 3-Al2O3-Ca
Thermodynamic assessment of the LiF-NaF-ThF4-UF4 system
International Nuclear Information System (INIS)
Benes, O.; Beilmann, M.; Konings, R.J.M.
2010-01-01
A thermodynamic assessment of the LiF-NaF-ThF 4 -UF 4 system is presented in this study. The binary phase diagrams are optimized based on the known experimental data and the excess Gibbs energies of liquid and solid solutions are described using a modified quasi chemical model and polynomial formalism respectively. The higher order systems are extrapolated according to asymmetric Toop mathematical formalism. Based on the developed thermodynamic database the fuel composition of the molten salt fast reactor is optimized. In total three different fuel compositions are identified. Properties of these fuel compositions such as melting point, vapour pressure and the boiling temperature are derived from the obtained thermodynamic assessment and are presented in this study.
Kleidon, Axel
2009-06-01
The Earth system is maintained in a unique state far from thermodynamic equilibrium, as, for instance, reflected in the high concentration of reactive oxygen in the atmosphere. The myriad of processes that transform energy, that result in the motion of mass in the atmosphere, in oceans, and on land, processes that drive the global water, carbon, and other biogeochemical cycles, all have in common that they are irreversible in their nature. Entropy production is a general consequence of these processes and measures their degree of irreversibility. The proposed principle of maximum entropy production (MEP) states that systems are driven to steady states in which they produce entropy at the maximum possible rate given the prevailing constraints. In this review, the basics of nonequilibrium thermodynamics are described, as well as how these apply to Earth system processes. Applications of the MEP principle are discussed, ranging from the strength of the atmospheric circulation, the hydrological cycle, and biogeochemical cycles to the role that life plays in these processes. Nonequilibrium thermodynamics and the MEP principle have potentially wide-ranging implications for our understanding of Earth system functioning, how it has evolved in the past, and why it is habitable. Entropy production allows us to quantify an objective direction of Earth system change (closer to vs further away from thermodynamic equilibrium, or, equivalently, towards a state of MEP). When a maximum in entropy production is reached, MEP implies that the Earth system reacts to perturbations primarily with negative feedbacks. In conclusion, this nonequilibrium thermodynamic view of the Earth system shows great promise to establish a holistic description of the Earth as one system. This perspective is likely to allow us to better understand and predict its function as one entity, how it has evolved in the past, and how it is modified by human activities in the future.
Energy Technology Data Exchange (ETDEWEB)
Hamm, L.L.; Van Brunt, V.
1982-08-01
A comparison of implicit Runge-Kutta and orthogonal collocation methods is made for the numerical solution to the ordinary differential equation which describes the high-pressure vapor-liquid equilibria of a binary system. The systems of interest are limited to binary solubility systems where one of the components is supercritical and exists as a noncondensable gas in the pure state. Of the two methods - implicit Runge-Kuta and orthogonal collocation - this paper attempts to present some preliminary but not necessarily conclusive results that the implicit Runge-Kutta method is superior for the solution to the ordinary differential equation utilized in the thermodynamic consistency testing of binary solubility systems. Due to the extreme nonlinearity of thermodynamic properties in the region near the critical locus, an extended cubic spline fitting technique is devised for correlating the P-x data. The least-squares criterion is employed in smoothing the experimental data. Even though the derivation is presented specifically for the correlation of P-x data, the technique could easily be applied to any thermodynamic data by changing the endpoint requirements. The volumetric behavior of the systems must be given or predicted in order to perform thermodynamic consistency tests. A general procedure is developed for predicting the volumetric behavior required and some indication as to the expected limit of accuracy is given.
International Nuclear Information System (INIS)
Hamm, L.L.; Van Brunt, V.
1982-08-01
A comparison of implicit Runge-Kutta and orthogonal collocation methods is made for the numerical solution to the ordinary differential equation which describes the high-pressure vapor-liquid equilibria of a binary system. The systems of interest are limited to binary solubility systems where one of the components is supercritical and exists as a noncondensable gas in the pure state. Of the two methods - implicit Runge-Kuta and orthogonal collocation - this paper attempts to present some preliminary but not necessarily conclusive results that the implicit Runge-Kutta method is superior for the solution to the ordinary differential equation utilized in the thermodynamic consistency testing of binary solubility systems. Due to the extreme nonlinearity of thermodynamic properties in the region near the critical locus, an extended cubic spline fitting technique is devised for correlating the P-x data. The least-squares criterion is employed in smoothing the experimental data. Even though the derivation is presented specifically for the correlation of P-x data, the technique could easily be applied to any thermodynamic data by changing the endpoint requirements. The volumetric behavior of the systems must be given or predicted in order to perform thermodynamic consistency tests. A general procedure is developed for predicting the volumetric behavior required and some indication as to the expected limit of accuracy is given
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.
Phase equilibria and thermodynamic functions for Ag–Hg and Cu–Hg binary systems
International Nuclear Information System (INIS)
Liu, Yajun; Wang, Guan; Wang, Jiang; Chen, Yang; Long, Zhaohui
2012-01-01
Highlights: ► The thermodynamic properties of Ag–Hg and Cu–Hg are explored in order to facilitate dental materials design. ► A self-consistent set of thermodynamic parameters is obtained. ► 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.
Iribarne, J V
1973-01-01
The thermodynamics of the atmosphere is the subject of several chapters in most textbooks on dynamic meteorology, but there is no work in English to give the subject a specific and more extensive treatment. In writing the present textbook, we have tried to fill this rather remarkable gap in the literature related to atmospheric sciences. Our aim has been to provide students of meteorology with a book that can playa role similar to the textbooks on chemical thermodynamics for the chemists. This implies a previous knowledge of general thermodynamics, such as students acquire in general physics courses; therefore, although the basic principles are reviewed (in the first four chapters), they are only briefly discussed, and emphasis is laid on those topics that will be useful in later chapters, through their application to atmospheric problems. No attempt has been made to introduce the thermodynamics of irreversible processes; on the other hand, consideration of heterogeneous and open homogeneous systems permits a...
Thermodynamic assessment of the CoOx-CrO1.5 system
DEFF Research Database (Denmark)
Östby, Jonas Allan; Chen, Ming
2009-01-01
By application of the CALPHAD method, a consistent set of thermodynamic model parameters is optimized for the oxide phases in the Co–Cr–O system. Cobalt chromium spinel is described as a normal spinel at room temperature and with cation redistribution at high temperature. All the solid oxide...... solution phases are described using the compound energy model, and the liquid phase is described using the two-sublattice model for ionic liquids. Calculated phase diagrams are presented, and values for the thermodynamic properties are compared with experimental data....
Contribution to the thermodynamic description of the corium - The U-Zr-O system
Quaini, A.; Guéneau, C.; Gossé, S.; Dupin, N.; Sundman, B.; Brackx, E.; Domenger, R.; Kurata, M.; Hodaj, F.
2018-04-01
In order to understand the stratification process that may occur in the late phase of the fuel degradation during a severe accident in a PWR, the thermodynamic knowledge of the U-Zr-O system is crucial. The presence of a miscibility gap in the U-Zr-O liquid phase may lead to a stratified configuration, which will impact the accidental scenario management. The aim of this work was to obtain new experimental data in the U-Zr-O liquid miscibility gap. New tie-line data were provided at 2567 ± 25 K. The related thermodynamic models were reassessed using present data and literature values. The reassessed model will be implemented in the TAF-ID international database. The composition and density of phases potentially formed during stratification will be predicted by coupling current thermodynamic model with thermal-hydraulics codes.
Thermodynamics and Kinetics of Advanced Separations Systems - FY 2010 Summary Report
International Nuclear Information System (INIS)
Martin, Leigh R.; Zalupski, Peter R.
2010-01-01
This report presents a summary of the work performed in the area of thermodynamics and kinetics of advanced separations systems under the Fuel Cycle Research and Development (FCR and D) program during FY 2010. Thermodynamic investigations into metal extraction dependencies on lactate and HDEHP have been performed. These metal distribution studies indicate a substantial deviation from the expected behavior at conditions that are typical of TALSPEAK process operational platform. These studies also identify that no thermodynamically stable mixed complexes exist in the aqueous solutions and increasing the complexity of the organic medium appears to influence the observed deviations. Following on from this, the first calorimetric measurement of the heat of extraction of americium across a liquid-liquid boundary was performed.
Thermodynamics and Kinetics of Advanced Separations Systems – FY 2010 Summary Report
Energy Technology Data Exchange (ETDEWEB)
Leigh R. Martin; Peter R. Zalupski
2010-09-01
This report presents a summary of the work performed in the area of thermodynamics and kinetics of advanced separations systems under the Fuel Cycle Research and Development (FCR&D) program during FY 2010. Thermodynamic investigations into metal extraction dependencies on lactate and HDEHP have been performed. These metal distribution studies indicate a substantial deviation from the expected behavior at conditions that are typical of TALSPEAK process operational platform. These studies also identify that no thermodynamically stable mixed complexes exist in the aqueous solutions and increasing the complexity of the organic medium appears to influence the observed deviations. Following on from this, the first calorimetric measurement of the heat of extraction of americium across a liquid-liquid boundary was performed.
Thermodynamic assessments of the Au–Th and As–U systems
International Nuclear Information System (INIS)
Wang, C.P.; Wang, G.C.; Lu, Y.; Wang, D.; Liu, X.J.
2013-01-01
The thermodynamic assessments of the Au–Th and As–U binary systems were carried out using the CALPHAD (CALculation of PHAse Diagram) method based on experimental data for phase equilibria and thermodynamic properties. The Gibbs free energies of the liquid, bcc, fcc, rhombohedral, (αU) and (βU) phases were described by the subregular solution model, and those of the intermetallic compounds (Au 51 Th 14 , Au 2 Th, Au 4 Th 3 , AuTh, Au 2 Th 3 AuTh 2 , AsU, As 4 U 3 and As 2 U) were described by the two-sublattice model. A set of thermodynamic parameters leading to reasonable agreement between the present calculated results and experimental data have been obtained
Mathematical foundations of thermodynamics
Giles, R; Stark, M; Ulam, S
2013-01-01
Mathematical Foundations of Thermodynamics details the core concepts of the mathematical principles employed in thermodynamics. The book discusses the topics in a way that physical meanings are assigned to the theoretical terms. The coverage of the text includes the mechanical systems and adiabatic processes; topological considerations; and equilibrium states and potentials. The book also covers Galilean thermodynamics; symmetry in thermodynamics; and special relativistic thermodynamics. The book will be of great interest to practitioners and researchers of disciplines that deal with thermodyn
Thermodynamic properties of citric acid and the system citric acid-water
Kruif, C.G. de; Miltenburg, J.C. van; Sprenkels, A.J.J.; Stevens, G.; Graaf, W. de; Wit, H.G.M. de
1982-01-01
The binary system citric acid-water has been investigated with static vapour pressure measurements, adiabatic calorimetry, solution calorimetry, solubility measurements and powder X-ray measurements. The data are correlated by thermodynamics and a large part of the phase diagram is given. Molar heat
International Nuclear Information System (INIS)
Frenkel, Michael
2007-01-01
This Hugh M. Huffman Memorial Award Lecture illustrates the power of phenomenological and statistical thermodynamics and the unique role of thermochemical data by a variety of studies in very diverse scientific and industrial fields ranging from conformational analysis to optimization of high-tech space and mass-scale chemical technologies and from data communications to data expert systems for chemical process design
Experimental investigation and thermodynamic description of the In-Sb-Sn ternary system
Czech Academy of Sciences Publication Activity Database
Manasijevič, D.; Vřešťál, J.; Minic, D.; Kroupa, Aleš; Zivkovic, D.; Zivkovic, Z.
2008-01-01
Roč. 450, 1-2 (2008), s. 193-199 ISSN 0925-8388 R&D Projects: GA MŠk(CZ) OC08053 Institutional research plan: CEZ:AV0Z20410507 Keywords : In-Sb-Sn system * phase diagram * CALPHAD Subject RIV: BJ - Thermodynamics Impact factor: 1.510, year: 2008
Thermodynamic assessment of the Na-O and Na-U-O systems : Margin to the safe operation of SFRs
Smith, A.L.; Guéneau, C; Flèche, J. L.; Chatain, S.; Beneš, O.; Konings, R.J.M.
2017-01-01
A thermodynamic model for the Na-O system was developed for the first time using the CALPHAD method after review of the structural, thermodynamic, and phase diagram data available on this system. Differential Scanning Calorimetry measurements were moreover performed to assess the phase equilibria
An introduction to equilibrium thermodynamics
Morrill, Bernard; Hartnett, James P; Hughes, William F
1973-01-01
An Introduction to Equilibrium Thermodynamics discusses classical thermodynamics and irreversible thermodynamics. It introduces the laws of thermodynamics and the connection between statistical concepts and observable macroscopic properties of a thermodynamic system. Chapter 1 discusses the first law of thermodynamics while Chapters 2 through 4 deal with statistical concepts. The succeeding chapters describe the link between entropy and the reversible heat process concept of entropy; the second law of thermodynamics; Legendre transformations and Jacobian algebra. Finally, Chapter 10 provides a
The thermodynamic meaning of local temperature of nonequilibrium open quantum systems
Ye, LvZhou; Zheng, Xiao; Yan, YiJing; Di Ventra, Massimiliano
2016-01-01
Measuring the local temperature of nanoscale systems out of equilibrium has emerged as a new tool to study local heating effects and other local thermal properties of systems driven by external fields. Although various experimental protocols and theoretical definitions have been proposed to determine the local temperature, the thermodynamic meaning of the measured or defined quantities remains unclear. By performing analytical and numerical analysis of bias-driven quantum dot systems both in ...
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...
Constraints of Compound Systems: Prerequisites for Thermodynamic Modeling Based on Shannon Entropy
Directory of Open Access Journals (Sweden)
Martin Pfleger
2014-05-01
Full Text Available Thermodynamic modeling of extensive systems usually implicitly assumes the additivity of entropy. Furthermore, if this modeling is based on the concept of Shannon entropy, additivity of the latter function must also be guaranteed. In this case, the constituents of a thermodynamic system are treated as subsystems of a compound system, and the Shannon entropy of the compound system must be subjected to constrained maximization. The scope of this paper is to clarify prerequisites for applying the concept of Shannon entropy and the maximum entropy principle to thermodynamic modeling of extensive systems. This is accomplished by investigating how the constraints of the compound system have to depend on mean values of the subsystems in order to ensure additivity. Two examples illustrate the basic ideas behind this approach, comprising the ideal gas model and condensed phase lattice systems as limiting cases of fluid phases. The paper is the first step towards developing a new approach for modeling interacting systems using the concept of Shannon entropy.
International Nuclear Information System (INIS)
Wang, Jiangjiang; Lu, Yanchao; Yang, Ying; Mao, Tianzhi
2016-01-01
This study aims to present a thermodynamic performance analysis and to optimize the configurations of a hybrid combined cooling, heating and power (CCHP) system incorporating solar energy and natural gas. A basic natural gas CCHP system containing a power generation unit, a heat recovery system, an absorption cooling system and a storage tank is integrated with solar photovoltaic (PV) panels and/or a heat collector. Based on thermodynamic modeling, the thermodynamic performance, including energy and exergy efficiencies, under variable work conditions, such as electric load factor, solar irradiance and installation ratio, of the solar PV panels and heat collector is investigated and analyzed. The results of the energy supply side analysis indicate that the integration of solar PV into the CCHP system more efficiently improves the exergy efficiency, whereas the integration of a solar heat collector improves the energy efficiency. To match the building loads, the optimization method combined with the operation strategy is employed to optimize the system configurations to maximize the integrated benefits of energy and economic costs. The optimization results of demand–supply matching demonstrate that the integration of a solar heat collector achieves a better integrated performance than the solar PV integration in the specific case study. - Highlights: • Design a CCHP system integrated with solar PV and heat collector. • Present the energy and exergy analyses under variable work conditions. • Propose an optimization method of CCHP system for demand-supply matching.
International Nuclear Information System (INIS)
Wu, Wei; Wang, Jin
2014-01-01
We have established a general non-equilibrium thermodynamic formalism consistently applicable to both spatially homogeneous and, more importantly, spatially inhomogeneous systems, governed by the Langevin and Fokker-Planck stochastic dynamics with multiple state transition mechanisms, using the potential-flux landscape framework as a bridge connecting stochastic dynamics with non-equilibrium thermodynamics. A set of non-equilibrium thermodynamic equations, quantifying the relations of the non-equilibrium entropy, entropy flow, entropy production, and other thermodynamic quantities, together with their specific expressions, is constructed from a set of dynamical decomposition equations associated with the potential-flux landscape framework. The flux velocity plays a pivotal role on both the dynamic and thermodynamic levels. On the dynamic level, it represents a dynamic force breaking detailed balance, entailing the dynamical decomposition equations. On the thermodynamic level, it represents a thermodynamic force generating entropy production, manifested in the non-equilibrium thermodynamic equations. The Ornstein-Uhlenbeck process and more specific examples, the spatial stochastic neuronal model, in particular, are studied to test and illustrate the general theory. This theoretical framework is particularly suitable to study the non-equilibrium (thermo)dynamics of spatially inhomogeneous systems abundant in nature. This paper is the second of a series
Thermodynamics of the CSCl-H{sub 2}O system at low temperatures
Energy Technology Data Exchange (ETDEWEB)
Monnin, C. [Centre National de la Recherche Scientifique (CNRS), 31 - Toulouse (France). Lab. de Geochimie; Dubois, M. [Centre National de la Recherche Scientifique (CNRS), 59 - Villeneuve d`Ascq (France). Lab. de Sedimentologie et Geodynamique
1999-05-01
The interpretation of fluid-inclusion data requires knowledge of phase diagrams at low (subfreezing) temperatures. From the example of the CsCl-H{sub 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{sup +}(aq), Cl{sup -}(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{sub 2}O system. (orig.)
Optimization of the thermodynamic properties and phase diagrams of P2O5-containing systems
Hudon, Pierre; Jung, In-Ho
2014-05-01
P2O5 is an important oxide component in the late stage products of numerous igneous rocks such as granites and pegmatites. Typically, P2O5 combines with CaO and crystallizes in the form of apatite, while in volatile-free conditions, Ca-whitlockite is formed. In spite of their interest, the thermodynamic properties and phase diagrams of P2O5-containg systems are not well known yet. In the case of the pure P2O5 for example, no experimental thermodynamic data are available for the liquid and the O and O' solid phases. As a result, we re-evaluated all the thermodynamic and phase diagram data of the P2O5 unary system [1]. Optimization of the thermodynamic properties and phase diagrams of the binary P2O5 systems was then performed including the Li2O-, Na2O-, MgO-, CaO-, BaO-, MnO-, FeO-, Fe2O3-, ZnO-, Al2O3-, and SiO2-P2O5 [2] systems. All available thermodynamic and phase equilibrium data were simultaneously reproduced in order to obtain a set of model equations for the Gibbs energies of all phases as functions of temperature and composition. In particular, the Gibbs energy of the liquid solution was described using the Modified Quasichemical Model [3-5] implemented in the FactSage software [6]. Thermodynamic modeling of the Li2O-Na2O-K2O-MgO-CaO-FeO-Fe2O3-Al2O3-SiO2 system, which include many granite-forming minerals such as nepheline, leucite, pyroxene, melilite, feldspar and spinel is currently in progress. [1] Jung, I.-H., Hudon, P. (2012) Thermodynamic assessment of P2O5. J. Am. Ceram. Soc., 95 (11), 3665-3672. [2] Rahman, M., Hudon, P. and Jung, I.-H. (2013) A coupled experimental study and thermodynamic modeling of the SiO2-P2O5 system. Metall. Mater. Trans. B, 44 (4), 837-852. [3] Pelton, A.D. and Blander, M. (1984) Computer-assisted analysis of the thermodynamic properties and phase diagrams of slags. Proc. AIME Symp. Metall. Slags Fluxes, TMS-AIME, 281-294. [4] Pelton, A.D. and Blander, M. (1986) Thermodynamic analysis of ordered liquid solutions by a modified
Urdiales, Álvaro; Jiménez Alvaro, Ángel; Sánchez Orgaz, Susana; González Fernández, M. Celina
2016-01-01
Chemical-looping hydrogen generation (CLHG) is a chemical-looping combustion variant that allows simultaneous production of power and hydrogen. A thermodynamic analysis from the exergy method point of view of an integrated syngas-fueled CLHG cycle is carried out with the aim of contributing to the conceptual understanding and development of CLHG systems. The cycle working point is optimized in a range of conditions. The proposed system shows a very interesting potential for power, hydrogen an...
Thermodynamic Assessment of the La-Cr-O System
DEFF Research Database (Denmark)
Povoden, E.; Chen, Ming; Grundy, A.N.
2009-01-01
The La-Cr and the La-Cr-O systems are assessed using the Calphad approach. The calculated La-Cr phase diagram as well as LaO1.5-CrO1.5 phase diagrams in pure oxygen, air, and under reducing conditions are presented. Phase equilibria of the La-Cr-O system are calculated at 1273 K as a function of ...
Thermodynamic framework for discrete optimal control in multiphase flow systems
Sieniutycz, Stanislaw
1999-08-01
Bellman's method of dynamic programming is used to synthesize diverse optimization approaches to active (work producing) and inactive (entropy generating) multiphase flow systems. Thermal machines, optimally controlled unit operations, nonlinear heat conduction, spontaneous relaxation processes, and self-propagating wave fronts are all shown to satisfy a discrete Hamilton-Jacobi-Bellman equation and a corresponding discrete optimization algorithm of Pontryagin's type, with the maximum principle for a Hamiltonian. The extremal structures are always canonical. A common unifying criterion is set for all considered systems, which is the criterion of a minimum generated entropy. It is shown that constraints can modify the entropy functionals in a different way for each group of the processes considered; thus the resulting structures of these functionals may differ significantly. Practical conclusions are formulated regarding the energy savings and energy policy in optimally controlled systems.
Control of Thermodynamical System with Input-Dependent State Delays
DEFF Research Database (Denmark)
Bendtsen, Jan Dimon; Krstic, Miroslav
2013-01-01
We consider control of a cooling system with several consumers that require cooling from a common source. The flow feeding coolant to the consumers can be controlled, but due to significant physical distances between the common source and the consumers, the coolant flow takes a non...
Distribution functions and thermodynamic functions of many particle systems
International Nuclear Information System (INIS)
Isihara, A.; Rosa Junior, S.G.
1976-01-01
A method is given of determining and upper bound of the entropy of a classical interacting system. A family of gaussian trial distribution functions is introduced for an electron gas. It was found that the ring diagram energy corresponds to the minimum free energy which the family produces. In contrast to the ring diagram method, the new approach is extremely simple and general [pt
Thermodynamic assessment of the La-Fe-O system
DEFF Research Database (Denmark)
Povoden-Karadeniz, E.; Grundy, A.N.; Chen, Ming
2009-01-01
The La-Fe and the La-Fe-O systems are assessed using the Calphad approach, and the Gibbs energy functions of ternary oxides are presented. Oxygen and mutual La and Fe solubilities in body-centered cubic (bcc) and face-centered cubic (fcc) structured metallic phases are considered in the modeling....
Thermodynamic Model for the Ammonia-Water System
DEFF Research Database (Denmark)
Thomsen, Kaj; Rasmussen, Peter
2000-01-01
The ammonia-water system is described by the Extended UNIQUAC model, which is an electrolyte model, formed by combining the original UNIQUAC model, the Debye-Hückel law and the Soave-Redlich-Kwong equation of state. The model is limited to temperatures below the critical temperature of ammonia. V...
Thermodynamics in Einstein's thought
International Nuclear Information System (INIS)
Klein, M.J.
1983-01-01
The role of the thermodynamical approach in the Einstein's scientific work is analyzed. The Einstein's development of a notion about statistical fluctuations of thermodynamical systems that leads him to discovery of corpuscular-wave dualism is retraced
Thermodynamic simulation of biomass gas steam reforming for a solid oxide fuel cell (SOFC system
Directory of Open Access Journals (Sweden)
A. Sordi
2009-12-01
Full Text Available This paper presents a methodology to simulate a small-scale fuel cell system for power generation using biomass gas as fuel. The methodology encompasses the thermodynamic and electrochemical aspects of a solid oxide fuel cell (SOFC, as well as solves the problem of chemical equilibrium in complex systems. In this case the complex system is the internal reforming of biomass gas to produce hydrogen. The fuel cell input variables are: operational voltage, cell power output, composition of the biomass gas reforming, thermodynamic efficiency, electrochemical efficiency, practical efficiency, the First and Second law efficiencies for the whole system. The chemical compositions, molar flows and temperatures are presented to each point of the system as well as the exergetic efficiency. For a molar water/carbon ratio of 2, the thermodynamic simulation of the biomass gas reforming indicates the maximum hydrogen production at a temperature of 1070 K, which can vary as a function of the biomass gas composition. The comparison with the efficiency of simple gas turbine cycle and regenerative gas turbine cycle shows the superiority of SOFC for the considered electrical power range.
Liquidus Projection and Thermodynamic Modeling of a Sn-Ag-Zn System
Chen, Sinn-wen; Chiu, Wan-ting; Gierlotka, Wojciech; Chang, Jui-shen; Wang, Chao-hong
2017-12-01
Sn-Ag-Zn alloys are promising Pb-free solders. In this study, the Sn-Ag-Zn liquidus projection was determined, and the Sn-Ag-Zn thermodynamic modeling was developed. Various Sn-Ag-Zn alloys were prepared. Their as-cast microstructures and primary solidification phases were examined. The invariant reaction temperatures of the ternary Sn-Ag-Zn system were determined. The liquidus projection of the Sn-Ag-Zn ternary system was constructed. It was found that the Sn-Ag-Zn ternary system has eight primary solidification phases: ɛ2-AgZn3, γ-Ag5Zn8, β-AgZn, ζ-Ag4Sn, (Ag), ɛ1-Ag3Sn, β-(Sn) and (Zn) phases. There are eight ternary invariant reactions, and the liquid + (Ag) = β-AgZn + ζ-Ag4Sn reaction is of the highest temperature at 935.5 K. Thermodynamic modeling of the ternary Sn-Ag-Zn system was also carried out in this study based on the thermodynamic models of the three constituent binary systems and the experimentally determined liquidus projection. The liquidus projection and the isothermal sections are calculated. The calculated and experimentally determined liquidus projections are in good agreement.
Slow Dynamics and Thermodynamics of Open Quantum Systems.
Cavina, Vasco; Mari, Andrea; Giovannetti, Vittorio
2017-08-04
We develop a perturbation theory of quantum (and classical) master equations with slowly varying parameters, applicable to systems which are externally controlled on a time scale much longer than their characteristic relaxation time. We apply this technique to the analysis of finite-time isothermal processes in which, differently from quasistatic transformations, the state of the system is not able to continuously relax to the equilibrium ensemble. Our approach allows one to formally evaluate perturbations up to arbitrary order to the work and heat exchange associated with an arbitrary process. Within first order in the perturbation expansion, we identify a general formula for the efficiency at maximum power of a finite-time Carnot engine. We also clarify under which assumptions and in which limit one can recover previous phenomenological results as, for example, the Curzon-Ahlborn efficiency.
Thermodynamics of organic mixtures containing amines. VIII. Systems with quinoline
Energy Technology Data Exchange (ETDEWEB)
Gonzalez, Juan Antonio [G.E.T.E.F., Grupo Especializado en Termodinamica de Equilibrio entre Fases, Departamento de Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, E-47071 Valladolid (Spain)], E-mail: jagl@termo.uva.es; Domanska, Urszula; Zawadzki, Maciej [Physical Chemistry Division, Faculty of Chemistry, Warsaw University of Technology, 00-664 Warsaw (Poland)
2008-08-15
(Solid + liquid) equilibrium temperatures for mixtures containing quinoline and 1-dodecanol, 1-hexadecanol, or 1-octadecanol have been measured using a dynamic method. (Quinoline + benzene, +alkane, or +1-alkanol) systems were investigated using DISQUAC. The corresponding interaction parameters are reported. The model yields a good representation of molar excess Gibbs free energies, G{sup E}, molar excess enthalpies, H{sup E}, and of the (solid + liquid) equilibria, SLE. Interactional and structural effects were analysed comparing H{sup E} and the molar excess internal energy at constant volume, U{sub V}{sup E}. It was encountered that structural effects are very important in systems involving alkanes or 1-alkanols. Interactions between amine molecules are stronger in mixtures with quinoline than in those containing pyridine, which was ascribed to the higher polarizability of quinoline.
Relative entropies in thermodynamics of complete fluid systems
Czech Academy of Sciences Publication Activity Database
Feireisl, Eduard
2012-01-01
Roč. 32, č. 9 (2012), s. 3059-3080 ISSN 1078-0947 R&D Projects: GA ČR GA201/09/0917 Institutional research plan: CEZ:AV0Z10190503 Keywords : relative entropy * Navier-Stokes-Fourier system * weak-strong uniqueness Subject RIV: BA - General Mathematics Impact factor: 1.005, year: 2012 http://www.aimsciences.org/journals/displayArticlesnew.jsp?paperID=7281
Hsiang, J.-T.; Chou, C. H.; Subaşı, Y.; Hu, B. L.
2018-01-01
In a series of papers, we intend to take the perspective of open quantum systems and examine from their nonequilibrium dynamics the conditions when the physical quantities, their relations, and the laws of thermodynamics become well defined and viable for quantum many-body systems. We first describe how an open-system nonequilibrium dynamics (ONEq) approach is different from the closed combined system + environment in a global thermal state (CGTs) setup. Only after the open system equilibrates will it be amenable to conventional thermodynamics descriptions, thus quantum thermodynamics (QTD) comes at the end rather than assumed in the beginning. The linkage between the two comes from the reduced density matrix of ONEq in that stage having the same form as that of the system in the CGTs. We see the open-system approach having the advantage of dealing with nonequilibrium processes as many experiments in the near future will call for. Because it spells out the conditions of QTD's existence, it can also aid us in addressing the basic issues in quantum thermodynamics from first principles in a systematic way. We then study one broad class of open quantum systems where the full nonequilibrium dynamics can be solved exactly, that of the quantum Brownian motion of N strongly coupled harmonic oscillators, interacting strongly with a scalar-field environment. In this paper, we focus on the internal energy, heat capacity, and the third law. We show for this class of physical models, amongst other findings, the extensive property of the internal energy, the positivity of the heat capacity, and the validity of the third law from the perspective of the behavior of the heat capacity toward zero temperature. These conclusions obtained from exact solutions and quantitative analysis clearly disprove claims of negative specific heat in such systems and dispel allegations that in such systems the validity of the third law of thermodynamics relies on quantum entanglement. They are
Ferroelectric-antiferroelectric mixed systems. Equation of state, thermodynamic functions
Directory of Open Access Journals (Sweden)
N.A.Korynevskii
2006-01-01
Full Text Available The problem of equation of state for ferroelectric-antiferroelectric mixed systems in the whole region of a concentration change (0≤n≤1 is discussed. The main peculiarity of the presented model turns out to be the possibility for the site dipole momentum to be oriented ferroelectrically in z-direction and antiferroelectrically in x-direction. Such a situation takes place in mixed compounds of KDP type. The different phases (ferro-, antiferro-, paraelectric, dipole glass and some combinations of them have been found and analyzed.
Experimental and thermodynamic investigation of Al-Cu-Nd ternary system
Energy Technology Data Exchange (ETDEWEB)
Bai, W.M. [School of Materials Science and Engineering, Central South University, Changsha, 410083 (China); Jiang, Y. [Hunan Sushi Guangbo Testing Techniques Co. LTD, Changsha (China); Guo, Z.Y.; Zeng, L.J.; Tan, M.Y. [School of Materials Science and Engineering, Central South University, Changsha, 410083 (China); Meggs, C. [School of Metallurgy and Materials, The University of Birmingham, Edgbaston, Birmingham, B15 2TT (United Kingdom); Zhang, L.G., E-mail: ligangzhang@csu.edu.cn [School of Materials Science and Engineering, Central South University, Changsha, 410083 (China); Liu, L.B., E-mail: pdc@csu.edu.cn [School of Materials Science and Engineering, Central South University, Changsha, 410083 (China); Jin, Z.P. [School of Materials Science and Engineering, Central South University, Changsha, 410083 (China)
2017-07-01
The phase relationships in the Al–Cu-Nd ternary system at 673 K have been investigated by X-ray powder diffraction (XRD) and scanning electron microscope (SEM) with energy disperse X-ray spectroscopy (EDS) in backscattered electron imaging (BSE) modes. The existence of six ternary Stoichiometric compounds, namely τ{sub 1}-Al{sub 8}Cu{sub 4}Nd, τ{sub 2}-Al{sub 9}Cu{sub 8}Nd{sub 2}, τ{sub 3}-Al{sub 6}Cu{sub 7}Nd, τ{sub 4}-Al{sub 2.4}Cu{sub 8.6}Nd, τ{sub 5}-Al{sub 3}CuNd, τ{sub 6}-AlCuNd, have been confirmed. A complete thermodynamic description of the Al–Cu-Nd ternary system coupled with the CALPHAD method is obtained based on experimental results and first-principles calculations. The calculated phase equilibria were in agreement with the available experimental data. - Highlights: • Phase relationships in the Al-Cu-Nd system has been systematically investigated. • 9 three-phase regions and 4 two-phase regions are confirmed. • A complete thermodynamic description of the Al-Cu-Nd system is obtained. • Results of first-principle calculation consist with thermodynamic calculation.
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
Heating without heat: Thermodynamics of passive energy filters between finite systems.
Muñoz-Tapia, R; Brito, R; Parrondo, J M R
2017-09-01
Passive filters allowing the exchange of particles in a narrow band of energy are currently used in microrefrigerators and energy transducers. In this Rapid Communication, we analyze their thermal properties using linear irreversible thermodynamics and kinetic theory, and discuss a striking phenomenon: the possibility of simultaneously increasing or decreasing the temperatures of two systems without any supply of energy. This occurs when the filter induces a flow of particles whose energy is between the average energies of the two systems. Here we show that this selective transfer of particles does not need the action of any sort of Maxwell demon and can be carried out by passive filters without compromising the second law of thermodynamics. This phenomenon allows us to design cycles between two reservoirs at temperatures T_{1}
A thermodynamic-like approach for the study of probabilistic systems
Campos, Diógenes
2011-01-01
This paper starts by considering an arbitrary system for which the probability distribution P:={P1,P2,…,PN} of a measurable property, with N possible independent results, is known. By using the Hartley information (pseudo-energy), the escort probabilities of P and its Shannon entropy, a thermodynamic-like formalism is developed, including the deduction of the fundamental equation for the mean value of the pseudo-energies. Thus, the method allows a macrodescription of the system that is based on a purely mathematical procedure and involves thermodynamic-like variables. As a specific example we consider a bank that measures customer satisfaction by doing a statistical survey (satisfied or unsatisfied customers).
Eichhorn, Ralf; Aurell, Erik
2014-04-01
'Stochastic thermodynamics as a conceptual framework combines the stochastic energetics approach introduced a decade ago by Sekimoto [1] with the idea that entropy can consistently be assigned to a single fluctuating trajectory [2]'. This quote, taken from Udo Seifert's [3] 2008 review, nicely summarizes the basic ideas behind stochastic thermodynamics: for small systems, driven by external forces and in contact with a heat bath at a well-defined temperature, stochastic energetics [4] defines the exchanged work and heat along a single fluctuating trajectory and connects them to changes in the internal (system) energy by an energy balance analogous to the first law of thermodynamics. Additionally, providing a consistent definition of trajectory-wise entropy production gives rise to second-law-like relations and forms the basis for a 'stochastic thermodynamics' along individual fluctuating trajectories. In order to construct meaningful concepts of work, heat and entropy production for single trajectories, their definitions are based on the stochastic equations of motion modeling the physical system of interest. Because of this, they are valid even for systems that are prevented from equilibrating with the thermal environment by external driving forces (or other sources of non-equilibrium). In that way, the central notions of equilibrium thermodynamics, such as heat, work and entropy, are consistently extended to the non-equilibrium realm. In the (non-equilibrium) ensemble, the trajectory-wise quantities acquire distributions. General statements derived within stochastic thermodynamics typically refer to properties of these distributions, and are valid in the non-equilibrium regime even beyond the linear response. The extension of statistical mechanics and of exact thermodynamic statements to the non-equilibrium realm has been discussed from the early days of statistical mechanics more than 100 years ago. This debate culminated in the development of linear response
Thermodynamic assessment of the rhodium-ruthenium-oxygen (Rh-Ru-O) system
Gossé, S.; Bordier, S.; Guéneau, C.; Brackx, E.; Domenger, R.; Rogez, J.
2018-03-01
Ruthenium (Ru) and rhodium (Rh) are abundant platinum-group metals formed during burn-up of nuclear fuels. Under normal operating conditions, Rh and Ru accumulate and predominantly form metallic precipitates with other fission products like Mo, Pd and Tc. In the framework of vitrification of high-level nuclear waste, these fission products are poorly soluble in molten glasses. They precipitate as metallic particles and oxide phases. Moreover, these Ru and Rh rich phases strongly depend on temperature and the oxygen fugacity of the glass melt. In case of severe accidental conditions with air ingress, oxidation of the Ru and Rh is possible. At low temperatures (T 1422 K for rhodium sesquioxide and T > 1815 K for ruthenium dioxide), they may decompose into (Rh)-FCC or (Ru)-HCP metallic phases and radiotoxic volatile gaseous species. A thermodynamic assessment of the Rh-Ru-O system will enable the prediction of: (1) the metallic and oxide phases that form during the vitrification of high-level nuclear wastes and (2) the release of volatile gaseous species during a severe accident. The Calphad method developed herein employs a thermodynamic approach in the investigation of the thermochemistry of rhodium and ruthenium at high temperatures. Current literature on the thermodynamic properties and phase diagram data enables preliminary thermodynamic assessments of the Rh-O and Ru-O systems. Additionally, select compositions in the ternary Rh-Ru-O system underwent experimental tests to complement data found in literature and to establish the phase equilibria in the ternary system.
2006-03-31
NUMBER. Wassim M. Haddad 5e. TASK NUMBER Quirino Baizano 5f. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING...2 2. Description of Work Accomplished 2 2.1. Thermodynamics and Large-Scale Nonlinear Dynamical Systems...control for operating room hypnosis and intefisive care unit sedation. 1.3. Goals of this Report The main goal of this report is to summarize the
Thermodynamic assessment of the Bi–Er and the Bi–Dy systems
International Nuclear Information System (INIS)
Wang, Jinsan; Li, Changrong; Guo, Cuiping; Du, Zhenmin; Wu, Bo
2013-01-01
Highlights: • The Bi–Er and Bi–Dy binary systems were optimized. • The first-principles method was used to calculate formation enthalpies of compounds. • A self-consistent set of thermodynamic parameters were obtained. • The experimental and calculated data were well reproduced by the optimized results. - Abstract: Based on the available experimental data, the Bi–Er and the Bi–Dy binary systems have been assessed thermodynamically using the CALPHAD (CALculaton of PHAse Diagram) technique. The formation enthalpies at 0 K of the compounds, Bi 3 Er 5 , BiEr, Bi 3 Dy 5 and BiDy, were calculated by the first-principles method and Birch–Murnaghan equation of state, and the calculated results were used in the present thermodynamic optimization. All these compounds in the Bi–Er and the Bi–Dy systems were treated as stoichiometric compounds. The liquid phase was modeled as a substitutional solution phase based on random mixing of the constituent atoms and the excess Gibbs energy was formulated with the Redlich–Kister polynomial. Good agreements were obtained between the calculated results and the experimental data for both the thermochemical properties and the phase equilibrium relations
Chloride corrosion in biomass-fired boilers – Fe-O-Cl system thermodynamic analysis
Directory of Open Access Journals (Sweden)
Kaczmarczyk Robert
2016-01-01
The paper presents a thermodynamic analysis of chloride-induced corrosion in the Fe-O-Cl system. The ranges of the metallic, oxide and chloride phase stability are determined within the temperature range T = 750-1000 K. Based on the parametric equations the equilibrium concentration of gaseous phase determined by Deacon reaction are presented. The effect of H2O concentration in the gaseous phase on high-temperature corrosion process and gaseous NaCl influence on NaFeO2 formation in the passive oxide scale layer (FeO/Fe3O4/Fe2O3 are discussed as well. The results are correlated with available in the literature laboratory experimental data and industrial corrosion process observations. Presented thermodynamic analysis is compared with assumptions of “active oxidation” model. The results may be used for experimental research prediction and a corrosion prevention in the industry.
1976-01-01
The entropy of a gas system with the number of particles subject to external control is maximized to derive relations between the thermodynamic variables that obtain at equilibrium. These relations are described in terms of the chemical potential, defined as equivalent partial derivatives of entropy, energy, enthalpy, free energy, or free enthalpy. At equilibrium, the change in total chemical potential must vanish. This fact is used to derive the equilibrium constants for chemical reactions in terms of the partition functions of the species involved in the reaction. Thus the equilibrium constants can be determined accurately, just as other thermodynamic properties, from a knowledge of the energy levels and degeneracies for the gas species involved. These equilibrium constants permit one to calculate the equilibrium concentrations or partial pressures of chemically reacting species that occur in gas mixtures at any given condition of pressure and temperature or volume and temperature.
Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria
Circone, S.; Kirby, S.H.; Stern, L.A.
2006-01-01
Using the Gibbs function of reaction, equilibrium pressure, temperature conditions for the formation of methane clathrate hydrate have been calculated from the thermodynamic properties of phases in the system CH4-H 2O. The thermodynamic model accurately reproduces the published phase-equilibria data to within ??2 K of the observed equilibrium boundaries in the range 0.08-117 MPa and 190-307 K. The model also provides an estimate of the third-law entropy of methane hydrate at 273.15 K, 0.1 MPa of 56.2 J mol-1 K-1 for 1/n CH4??H 2O, where n is the hydrate number. Agreement between the calculated and published phase-equilibria data is optimized when the hydrate composition is fixed and independent of the pressure and temperature for the conditions modeled. ?? 2006 American Chemical Society.
Thermodynamic analyses and the experimental validation of the Pulse Tube Expander system
Jia, Qiming; Gong, Linghui; Feng, Guochao; Zou, Longhui
2018-04-01
A Pulse Tube Expander (PTE) for small and medium capacity cryogenic refrigeration systems is described in this paper. An analysis of the Pulse Tube Expander is developed based on the thermodynamic analyses of the system. It is shown that the gas expansion is isentropic in the cold end of the pulse tube. The temperature variation at the outlet of Pulse Tube Expander is measured and the isentropic efficiency is calculated to be 0.455 at 2 Hz. The pressure oscillations in the pulse tube are obtained at different frequencies. The limitations and advantages of this system are also discussed.
Polylogs, thermodynamics and scaling functions of one-dimensional quantum many-body systems
International Nuclear Information System (INIS)
Guan, X-W; Batchelor, M T
2011-01-01
We demonstrate that the thermodynamics of one-dimensional Lieb-Liniger bosons can be accurately calculated in analytic fashion using the polylog function in the framework of the thermodynamic Bethe ansatz. The approach does away with the need to numerically solve the thermodynamic Bethe ansatz (Yang-Yang) equation. The expression for the equation of state allows the exploration of Tomonaga-Luttinger liquid physics and quantum criticality in an archetypical quantum system. In particular, the low-temperature phase diagram is obtained, along with the scaling functions for the density and compressibility. It has been shown recently by Guan and Ho (arXiv:1010.1301) that such scaling can be used to map out the criticality of ultracold fermionic atoms in experiments. We show here how to map out quantum criticality for Lieb-Liniger bosons. More generally, the polylog function formalism can be applied to a wide range of Bethe ansatz integrable quantum many-body systems which are currently of theoretical and experimental interest, such as strongly interacting multi-component fermions, spinor bosons and mixtures of bosons and fermions. (fast track communication)
Thermodynamic analysis of a new combined cooling and power system using ammonia–water mixture
International Nuclear Information System (INIS)
Wang, Jiangfeng; Wang, Jianyong; Zhao, Pan; Dai, Yiping
2016-01-01
Highlights: • A new combined cooling and power system is proposed. • Exergy destruction analysis is used to identify irreversibility of components in system. • Thermodynamic parameter analysis is performed for system. - Abstract: In order to achieve both power and cooling supply for users, a new combined cooling and power system using ammonia–water mixture is proposed to utilizing low grade heat sources, such as industrial waste heat, solar energy and geothermal energy. The proposed system combines a Kalina cycle and an ammonia–water absorption refrigeration cycle, in which the ammonia–water turbine exhaust is delivered to a separator to extract purer ammonia vapor. The purer ammonia vapor enters an evaporator to generate refrigeration output after being condensed and throttled. Mathematical models are established to simulate the combined system under steady-state conditions. Exergy destruction analysis is conducted to display the exergy destruction distribution in the system qualitatively and the results show that the major exergy destruction occurs in the heat exchangers. Finally a thermodynamic sensitivity analysis is performed and reveals that with an increase in the pressure of separator I or the ammonia mass fraction of basic solution, thermal efficiency and exergy efficiency of the system increase, whereas with an increase in the temperature of separator I, the ammonia–water turbine back pressure or the condenser II pressure, thermal efficiency and exergy efficiency of the system drop.
Thermodynamic analysis of a fuel cell power system for transportation applications
International Nuclear Information System (INIS)
Hussain, M.M.; Baschuk, J.J.; Li, X.; Dincer, I.
2004-01-01
This study deals with the thermodynamic modeling of a polymer electrolyte membrane (PEM) fuel cell power system for transportation applications. The PEM fuel cell performance model developed previously by two of the authors is incorporated into the present model. The analysis includes the operation of all the components in the system, which consists of two major modules: PEM fuel cell stack module and system module and a cooling pump. System module includes air compressor, heat exchanger, humidifier and a cooling loop. A parametric study is performed to examine the effect of varying operating conditions (e.g., temperature pressure and air stoichiometry) on the energy and exergy efficiencies of the system. Further, thermodynamic irreversibilities in each component of the system are determined. It is found that, with the increase of external load (current density), the difference between the gross stack power and net system power increases. The largest irreversibility rate occurs in the fuel cell stack. Thus, minimization of irreversibility rate in the fuel cell stack is essential to enhance the performance of the system, which in turn reduces the cost and helps in commercialization of fuel cell power system in transportation applications. (author)
Duan, W. J.; Li, P.; Lei, W.; Chen, W.; Yu, Q. B.; Wang, K.; Qin, Q.
2015-05-01
The blast furnace (BF) slag waste heat was recovered by an integrated system stage by stage, which combined a physical and chemical method. The water and coal gasification reactions were used to recover the heat in the system. Based on the first and second law of thermodynamics, the thermodynamic analysis of the system was carried out by the enthalpy-exergy diagram. The results showed that the concept of the "recovery-temperature countercurrent, energy cascade utilization" was realized by this system to recover and use the high-quality BF slag waste heat. In this system, the high-temperature waste heat was recovered by coal gasification and the relatively low-temperature waste heat was used to produce steam. The system's exergy and thermal recycling efficiency were 52.6% and 75.4%, respectively. The exergy loss of the integrated system was only 620.0 MJ/tslag. Compared with the traditional physical recycling method producing steam, the exergy and thermal efficiencies of the integrated system were improved significantly. Meanwhile, approximately 182.0 m3/tslag syngas was produced by coal gasification. The BF slag waste heat will be used integrally and efficiently by the integrated system. The results provide the theoretical reference for recycling and using the BF slag waste heat.
Thermodynamic characteristics of a novel supercritical compressed air energy storage system
International Nuclear Information System (INIS)
Guo, Huan; Xu, Yujie; Chen, Haisheng; Zhou, Xuezhi
2016-01-01
Highlights: • A novel supercritical compressed air energy storage system is proposed. • The energy density of SC-CAES is approximately 18 times larger than that of conventional CAES. • The characteristic of thermodynamics and exergy destruction is comprehensively analysed. • The corresponding optimum relationship between charging and discharging pressure is illustrated. • A turning point of efficiency is indicated because of the heat transfer of crossing the critical point. - Abstract: A novel supercritical compressed air energy storage (SC-CAES) system is proposed by our team to solve the problems of conventional CAES. The system eliminates the dependence on fossil fuel and large gas-storage cavern, as well as possesses the advantages of high efficiency by employing the special properties of supercritical air, which is significant for the development of electrical energy storage. The thermodynamic model of the SC-CAES system is built, and the thermodynamic characters are revealed. Through the exergy analysis of the system, the processes of the larger exergy destruction include compression, expansion, cold storage/heat exchange and throttle. Furthermore, sensitivity analysis shows that there is an optimal energy releasing pressure to make the system achieve the highest efficiency when energy storage pressure is constant. The efficiency of SC-CAES is expected to reach about 67.41% when energy storage pressure and energy releasing pressure are 120 bar and 95.01 bar, respectively. At the same time, the energy density is 18 times larger than that of conventional CAES. Sensitivity analysis also shows the change laws of system efficiency varying with other basic system parameters. The study provides support for the design and engineering of SC-CAES.
Kleidon, A
2010-05-12
The Earth system is remarkably different from its planetary neighbours in that it shows pronounced, strong global cycling of matter. These global cycles result in the maintenance of a unique thermodynamic state of the Earth's atmosphere which is far from thermodynamic equilibrium (TE). Here, I provide a simple introduction of the thermodynamic basis to understand why Earth system processes operate so far away from TE. I use a simple toy model to illustrate the application of non-equilibrium thermodynamics and to classify applications of the proposed principle of maximum entropy production (MEP) to such processes into three different cases of contrasting flexibility in the boundary conditions. I then provide a brief overview of the different processes within the Earth system that produce entropy, review actual examples of MEP in environmental and ecological systems, and discuss the role of interactions among dissipative processes in making boundary conditions more flexible. I close with a brief summary and conclusion.
Chakraborty, Anutosh; Saha, Bidyut Baran; Ng, Kim Choon; Koyama, Shigeru; Srinivasan, Kandadai
2009-02-17
Thermodynamic property surfaces for a single-component adsorbent+adsorbate system are derived and developed from the viewpoint of classical thermodynamics, thermodynamic requirements of chemical equilibrium, Gibbs law, and Maxwell relations. They enable us to compute the entropy and enthalpy of the adsorbed phase, the isosteric heat of adsorption, specific heat capacity, and the adsorbed phase volume thoroughly. These equations are very simple and easy to handle for calculating the energetic performances of any adsorption system. We have shown here that the derived thermodynamic formulations fill up the information gap with respect to the state of adsorbed phase to dispel the confusion as to what is the actual state of the adsorbed phase. We have also discussed and established the temperature-entropy diagrams of (i) CaCl2-in-silica gel+water system for cooling applications, and (ii) activated carbon (Maxsorb III)+methane system for gas storage.
Kleidon, A.
2010-01-01
The Earth system is remarkably different from its planetary neighbours in that it shows pronounced, strong global cycling of matter. These global cycles result in the maintenance of a unique thermodynamic state of the Earth's atmosphere which is far from thermodynamic equilibrium (TE). Here, I provide a simple introduction of the thermodynamic basis to understand why Earth system processes operate so far away from TE. I use a simple toy model to illustrate the application of non-equilibrium thermodynamics and to classify applications of the proposed principle of maximum entropy production (MEP) to such processes into three different cases of contrasting flexibility in the boundary conditions. I then provide a brief overview of the different processes within the Earth system that produce entropy, review actual examples of MEP in environmental and ecological systems, and discuss the role of interactions among dissipative processes in making boundary conditions more flexible. I close with a brief summary and conclusion. PMID:20368248
Chakraborty, Anutosh
2009-02-17
Thermodynamic property surfaces for a single-component adsorbent + adsorbate system are derived and developed from the viewpoint of classical thermodynamics, thermodynamic requirements of chemical equilibrium, Gibbs law, and Maxwell relations. They enable us to compute the entropy and enthalpy of the adsorbed phase, the isosteric heat of adsorption, specific heat capacity, and the adsorbed phase volume thoroughly. These equations are very simple and easy to handle for calculating the energetic performances of any adsorption system. We have shown here that the derived thermodynamic formulations fill up the information gap with respect to the state of adsorbed phase to dispel the confusion as to what is the actual state of the adsorbed phase. We have also discussed and established the temperature-entropy diagrams of (i) CaCl 2-in-silica gel + water system for cooling applications, and (ii) activated carbon (Maxsorb III) + methane system for gas storage. © Copyright 2009 American Chemical Society.
Tang, Hui-Yi; Wang, Jian-Hui; Ma, Yong-Li
2014-06-01
For a small system at a low temperature, thermal fluctuation and quantum effect play important roles in quantum thermodynamics. Starting from micro-canonical ensemble, we generalize the Boltzmann-Gibbs statistical factor from infinite to finite systems, no matter the interactions between particles are considered or not. This generalized factor, similar to Tsallis's q-form as a power-law distribution, has the restriction of finite energy spectrum and includes the nonextensivities of the small systems. We derive the exact expression for distribution of average particle numbers in the interacting classical and quantum nonextensive systems within a generalized canonical ensemble. This expression in the almost independent or elementary excitation quantum finite systems is similar to the corresponding ones obtained from the conventional grand-canonical ensemble. In the reconstruction for the statistical theory of the small systems, we present the entropy of the equilibrium systems and equation of total thermal energy. When we investigate the thermodynamics for the interacting nonextensive systems, we obtain the system-bath heat exchange and "uncompensated heat" which are in the thermodynamical level and independent on the detail of the system-bath coupling. For ideal finite systems, with different traps and boundary conditions, we calculate some thermodynamic quantities, such as the specific heat, entropy, and equation of state, etc. Particularly at low temperatures for the small systems, we predict some novel behaviors in the quantum thermodynamics, including internal entropy production, heat exchanges between the system and its surroundings and finite-size effects on the free energy.
Experimental and thermodynamic study of the Mg–Sn–In–Zn quaternary system
International Nuclear Information System (INIS)
Wang, Jian; Hudon, Pierre; Kevorkov, Dmytro; Chartrand, Patrice; Jung, In-Ho; Medraj, Mamoun
2014-01-01
Highlights: • Phase equilibria in the Mg-rich region of the Mg–Sn–In are determined. • Phase equilibria in the Mg-rich region of the Mg–Sn–Zn are determined. • Evaluation and thermodynamic optimization of the Mg–Sn–In–Zn quaternary system are developed. -- Abstract: Phase equilibria in the Mg-rich region of the Mg–Sn–In (at 415 °C and 330 °C), and Mg–Sn–Zn (at 300 °C) ternary systems were determined by quenching experiments, electron probe micro-analyzer (EPMA), and X-ray diffraction (XRD) techniques. The ternary isoplethal sections with constant 5 In and 10 Sn at.% of Mg–In–Sn system, and 10 Sn at.% of Mg–In–Zn system were determined by differential scanning calorimetry (DSC). No ternary compounds were found in the Mg–Sn–Zn and Mg–Sn–In isothermal sections. Critical evaluation and thermodynamic optimization of the Mg–Sn–In–Zn quaternary system were carried out using CALPHAD (Calculation of Phase Diagrams) technique. The Modified Quasichemical Model in the Pair Approximation (MQMPA) was used for modeling the liquid solution, which exhibits a high degree of short-range ordering behavior. The solid phases were modeled with the Compound Energy Formalism (CEF). All available and reliable experimental data were reproduced within experimental error limits. A self-consistent thermodynamic database was constructed for the Mg–Sn–In–Zn quaternary system, which can be used as a guide for Mg-based alloys development
Directory of Open Access Journals (Sweden)
Xuan L Liu
Full Text Available The phase relations and thermodynamic properties of the condensed Al-Co-Cr ternary alloy system are investigated using first-principles calculations based on density functional theory (DFT and phase-equilibria experiments that led to X-ray diffraction (XRD and electron probe micro-analysis (EPMA measurements. A thermodynamic description is developed by means of the calculations of phase diagrams (CALPHAD method using experimental and computational data from the present work and the literature. Emphasis is placed on modeling the bcc-A2, B2, fcc-γ, and tetragonal-σ phases in the temperature range of 1173 to 1623 K. Liquid, bcc-A2 and fcc-γ phases are modeled using substitutional solution descriptions. First-principles special quasirandom structures (SQS calculations predict a large bcc-A2 (disordered/B2 (ordered miscibility gap, in agreement with experiments. A partitioning model is then used for the A2/B2 phase to effectively describe the order-disorder transitions. The critically assessed thermodynamic description describes all phase equilibria data well. A2/B2 transitions are also shown to agree well with previous experimental findings.
Thermodynamic stability of hydrogen-bonded systems in polar and nonpolar environments.
Pasalić, Hasan; Aquino, Adélia J A; Tunega, Daniel; Haberhauer, Georg; Gerzabek, Martin H; Georg, Herbert C; Moraes, Tatiane F; Coutinho, Kaline; Canuto, Sylvio; Lischka, Hans
2010-07-30
The thermodynamic properties of a selected set of benchmark hydrogen-bonded systems (acetic acid dimer and the complexes of acetic acid with acetamide and methanol) was studied with the goal of obtaining detailed information on solvent effects on the hydrogen-bonded interactions using water, chloroform, and n-heptane as representatives for a wide range in the dielectric constant. Solvent effects were investigated using both explicit and implicit solvation models. For the explicit description of the solvent, molecular dynamics and Monte Carlo simulations in the isothermal-isobaric (NpT) ensemble combined with the free energy perturbation technique were performed to determine solvation free energies. Within the implicit solvation approach, the polarizable continuum model and the conductor-like screening model were applied. Combination of gas phase results with the results obtained from the different solvation models through an appropriate thermodynamic cycle allows estimation of complexation free energies, enthalpies, and the respective entropic contributions in solution. Owing to the strong solvation effects of water the cyclic acetic acid dimer is not stable in aqueous solution. In less polar solvents the double hydrogen bond structure of the acetic acid dimer remains stable. This finding is in agreement with previous theoretical and experimental results. A similar trend as for the acetic acid dimer is also observed for the acetamide complex. The methanol complex was found to be thermodynamically unstable in gas phase as well as in any of the three solvents. 2010 Wiley Periodicals, Inc.
Two-Phase Cryogenic Heat Exchanger for the Thermodynamic Vent System
Christie, Robert J.
2011-01-01
A two-phase cryogenic heat exchanger for a thermodynamic vent system was designed and analyzed, and the predicted performance was compared with test results. A method for determining the required size of the Joule-Thomson device was also developed. Numerous sensitivity studies were performed to show that the design was robust and possessed a comfortable capacity margin. The comparison with the test results showed very similar heat extraction performance for similar inlet conditions. It was also shown that estimates for Joule- Thomson device flow rates and exit quality can vary significantly and these need to be accommodated for with a robust system design.
DEFF Research Database (Denmark)
Alphinas, Robert A.; Hansen, Hans Henrik; Tambo, Torben
2017-01-01
Non-adaptive proportional controllers suffer from the ability to handle a system disturbance leading to a large steady-state error and undesired transient behavior. On the other hand, they are easy to implement and tune. This article examines whether an adaptive controller based on the MIT...... and Lyapunov principle leads to a more robust and accurate regulation. Both controllers have been tested on a thermodynamic system exposed to a disturbance. The experiment shows that the adaptive controller handles the disturbance faster and more accurate....
The Lanczos algorithm for extensive many-body systems in the thermodynamic limit
International Nuclear Information System (INIS)
Witte, N.S.; Bessis, D.
1999-01-01
We establish rigorously the scaling properties of the Lanczos process applied to an arbitrary extensive Many-Body System which is carried to convergence n → ∞ and the thermodynamic limit N → ∞ taken. In this limit the solution for the limiting Lanczos coefficients are found exactly and generally through two equivalent sets of equations, given initial knowledge of the exact cumulant generating function. The measure and the Orthogonal Polynomial System associated with the Lanczos process in this regime are also given explicitly. Some important representations of these Lanczos functions are provided, including Taylor series expansions, and the theorems controlling their general properties are proven. (authors)
International Nuclear Information System (INIS)
Nguyen, Tuong-Van; Elmegaard, Brian
2016-01-01
Highlights: • Six thermodynamic models used for evaluating gas liquefaction systems are compared. • Three gas liquefaction systems are modelled, assessed and optimised for each equation of state. • The predictions of thermophysical properties and energy flows are significantly different. • The GERG-2008 model is the only consistent one, while cubic, virial and statistical equations are unsatisfying. - Abstract: Natural gas liquefaction systems are based on refrigeration cycles – they consist of the same operations such as heat exchange, compression and expansion, but they have different layouts, components and working fluids. The design of these systems requires a preliminary simulation and evaluation of their performance. However, the thermodynamic models used for this purpose are characterised by different mathematical formulations, ranges of application and levels of accuracy. This may lead to inconsistent results when estimating hydrocarbon properties and assessing the efficiency of a given process. This paper presents a thorough comparison of six equations of state widely used in the academia and industry, including the GERG-2008 model, which has recently been adopted as an ISO standard for natural gases. These models are used to (i) estimate the thermophysical properties of a Danish natural gas, (ii) simulate, and (iii) optimise liquefaction systems. Three case studies are considered: a cascade layout with three pure refrigerants, a single mixed-refrigerant unit, and an expander-based configuration. Significant deviations are found between all property models, and in all case studies. The main discrepancies are related to the prediction of the energy flows (up to 7%) and to the heat exchanger conductances (up to 11%), and they are not systematic errors. The results illustrate the superiority of using the GERG-2008 model for designing gas processes in real applications, with the aim of reducing their energy use. They demonstrate as well that
Thurner, Stefan; Corominas-Murtra, Bernat; Hanel, Rudolf
2017-09-01
There are at least three distinct ways to conceptualize entropy: entropy as an extensive thermodynamic quantity of physical systems (Clausius, Boltzmann, Gibbs), entropy as a measure for information production of ergodic sources (Shannon), and entropy as a means for statistical inference on multinomial processes (Jaynes maximum entropy principle). Even though these notions represent fundamentally different concepts, the functional form of the entropy for thermodynamic systems in equilibrium, for ergodic sources in information theory, and for independent sampling processes in statistical systems, is degenerate, H(p)=-∑_{i}p_{i}logp_{i}. For many complex systems, which are typically history-dependent, nonergodic, and nonmultinomial, this is no longer the case. Here we show that for such processes, the three entropy concepts lead to different functional forms of entropy, which we will refer to as S_{EXT} for extensive entropy, S_{IT} for the source information rate in information theory, and S_{MEP} for the entropy functional that appears in the so-called maximum entropy principle, which characterizes the most likely observable distribution functions of a system. We explicitly compute these three entropy functionals for three concrete examples: for Pólya urn processes, which are simple self-reinforcing processes, for sample-space-reducing (SSR) processes, which are simple history dependent processes that are associated with power-law statistics, and finally for multinomial mixture processes.
Modelling non-equilibrium thermodynamic systems from the speed-gradient principle.
Khantuleva, Tatiana A; Shalymov, Dmitry S
2017-03-06
The application of the speed-gradient (SG) principle to the non-equilibrium distribution systems far away from thermodynamic equilibrium is investigated. The options for applying the SG principle to describe the non-equilibrium transport processes in real-world environments are discussed. Investigation of a non-equilibrium system's evolution at different scale levels via the SG principle allows for a fresh look at the thermodynamics problems associated with the behaviour of the system entropy. Generalized dynamic equations for finite and infinite number of constraints are proposed. It is shown that the stationary solution to the equations, resulting from the SG principle, entirely coincides with the locally equilibrium distribution function obtained by Zubarev. A new approach to describe time evolution of systems far from equilibrium is proposed based on application of the SG principle at the intermediate scale level of the system's internal structure. The problem of the high-rate shear flow of viscous fluid near the rigid plane plate is discussed. It is shown that the SG principle allows closed mathematical models of non-equilibrium processes to be constructed.This article is part of the themed issue 'Horizons of cybernetical physics'. © 2017 The Author(s).
Thurner, Stefan; Corominas-Murtra, Bernat; Hanel, Rudolf
2017-09-01
There are at least three distinct ways to conceptualize entropy: entropy as an extensive thermodynamic quantity of physical systems (Clausius, Boltzmann, Gibbs), entropy as a measure for information production of ergodic sources (Shannon), and entropy as a means for statistical inference on multinomial processes (Jaynes maximum entropy principle). Even though these notions represent fundamentally different concepts, the functional form of the entropy for thermodynamic systems in equilibrium, for ergodic sources in information theory, and for independent sampling processes in statistical systems, is degenerate, H (p ) =-∑ipilogpi . For many complex systems, which are typically history-dependent, nonergodic, and nonmultinomial, this is no longer the case. Here we show that for such processes, the three entropy concepts lead to different functional forms of entropy, which we will refer to as SEXT for extensive entropy, SIT for the source information rate in information theory, and SMEP for the entropy functional that appears in the so-called maximum entropy principle, which characterizes the most likely observable distribution functions of a system. We explicitly compute these three entropy functionals for three concrete examples: for Pólya urn processes, which are simple self-reinforcing processes, for sample-space-reducing (SSR) processes, which are simple history dependent processes that are associated with power-law statistics, and finally for multinomial mixture processes.
Equilibrium Statistical Thermodynamics of a Many-Particle System Coupled to an External Scalar Field
Salvino, R. E.
1990-01-01
The equilibrium thermodynamics of a many-particle assembly in the presence of an external scalar field is examined. Two types of scalar coupling are considered: an external field coupled to the particle density and an external scalar field coupled to the energy density. It is shown that the broken translational and rotational invariance of the system due to the external field is reflected in the macroscopic physics by loss of the usual extensivity property of the system and by means of anisotropy in the response of the system to changes in the system lengths or to the system shape. In addition, the assumptions used in local equilibrium analyses are shown to be incorrect in principle. Nonlocal effects due to the external field must be included in the determination of the equation of state. Simple model calculations for a system in an external gravitational field and an externally imposed temperature field are presented as illustrations.
Thermodynamic description of non-Markovian information flux of nonequilibrium open quantum systems
Chen, Hong-Bin; Chen, Guang-Yin; Chen, Yueh-Nan
2017-12-01
One of the fundamental issues in the field of open quantum systems is the classification and quantification of non-Markovianity. In the contest of quantity-based measures of non-Markovianity, the intuition of non-Markovianity in terms of information backflow is widely discussed. However, it is not easy to characterize the information flux for a given system state and show its connection to non-Markovianity. Here, by using the concepts from thermodynamics and information theory, we discuss a potential definition of information flux of an open quantum system, valid for static environments. We present a simple protocol to show how a system attempts to share information with its environment and how it builds up system-environment correlations. We also show that the information returned from the correlations characterizes the non-Markovianity and a hierarchy of indivisibility of the system dynamics.
International Nuclear Information System (INIS)
Ohno, M.; Kozlov, A.; Arroyave, R.; Liu, Z.K.; Schmid-Fetzer, R.
2006-01-01
The thermodynamic model of the Ca-Sn system was obtained, utilizing the first-principles total energies and heat capacities calculated from 0 K to the melting points of the major phases. Since the first-principles result for the formation energy of the dominating Ca 2 Sn intermetallic phase is drastically different from the reported experimental data, we performed two types of thermodynamic modeling: one based on the first-principles output and the other based on the experimental data. In the former modeling, the Gibbs energies of the intermetallic compounds were fully quantified from the first-principles finite temperature properties and the superiority of the former thermodynamic description is demonstrated. It is shown that it is the combination of finite temperature first-principle calculations and the Calphad modeling tool that provides a sound basis for identifying and deciding on conflicting key thermodynamic data in the Ca-Sn system
Maser, Adam Charles
More electric aircraft systems, high power avionics, and a reduction in heat sink capacity have placed a larger emphasis on correctly satisfying aircraft thermal management requirements during conceptual design. Thermal management systems must be capable of dealing with these rising heat loads, while simultaneously meeting mission performance. Since all subsystem power and cooling requirements are ultimately traced back to the engine, the growing interactions between the propulsion and thermal management systems are becoming more significant. As a result, it is necessary to consider their integrated performance during the conceptual design of the aircraft gas turbine engine cycle to ensure that thermal requirements are met. This can be accomplished by using thermodynamic subsystem modeling and simulation while conducting the necessary design trades to establish the engine cycle. However, this approach also poses technical challenges associated with the existence of elaborate aircraft subsystem interactions. This research addresses these challenges through the creation of a parsimonious, transparent thermodynamic model of propulsion and thermal management systems performance with a focus on capturing the physics that have the largest impact on propulsion design choices. This modeling environment, known as Cycle Refinement for Aircraft Thermodynamically Optimized Subsystems (CRATOS), is capable of operating in on-design (parametric) and off-design (performance) modes and includes a system-level solver to enforce design constraints. A key aspect of this approach is the incorporation of physics-based formulations involving the concurrent usage of the first and second laws of thermodynamics, which are necessary to achieve a clearer view of the component-level losses across the propulsion and thermal management systems. This is facilitated by the direct prediction of the exergy destruction distribution throughout the system and the resulting quantification of available
Thermodynamic exergy analysis for small modular reactor in nuclear hybrid energy system
Directory of Open Access Journals (Sweden)
Boldon Lauren
2016-01-01
Full Text Available Small modular reactors (SMRs provide a unique opportunity for future nuclear development with reduced financial risks, allowing the United States to meet growing energy demands through safe, reliable, clean air electricity generation while reducing greenhouse gas emissions and the reliance on unstable fossil fuel prices. A nuclear power plant is comprised of several complex subsystems which utilize materials from other subsystems and their surroundings. The economic utility of resources, or thermoeconomics, is extremely difficult to analyze, particularly when trying to optimize resources and costs among individual subsystems and determine prices for products. Economics and thermodynamics cannot provide this information individually. Thermoeconomics, however, provides a method of coupling the quality of energy available based on exergy and the value of this available energy – “exergetic costs”. For an SMR exergy analysis, both the physical and economic environments must be considered. The physical environment incorporates the energy, raw materials, and reference environment, where the reference environment refers to natural resources available without limit and without cost, such as air input to a boiler. The economic environment includes market influences and prices in addition to installation, operation, and maintenance costs required for production to occur. The exergetic cost or the required exergy for production may be determined by analyzing the physical environment alone. However, to optimize the system economics, this environment must be coupled with the economic environment. A balance exists between enhancing systems to improve efficiency and optimizing costs. Prior research into SMR thermodynamics has not detailed methods on improving exergetic costs for an SMR coupled with storage technologies and renewable energy such as wind or solar in a hybrid energy system. This process requires balancing technological efficiencies and
Entropy production in a fluid-solid system far from thermodynamic equilibrium.
Chung, Bong Jae; Ortega, Blas; Vaidya, Ashwin
2017-11-24
The terminal orientation of a rigid body in a moving fluid is an example of a dissipative system, out of thermodynamic equilibrium and therefore a perfect testing ground for the validity of the maximum entropy production principle (MaxEP). Thus far, dynamical equations alone have been employed in studying the equilibrium states in fluid-solid interactions, but these are far too complex and become analytically intractable when inertial effects come into play. At that stage, our only recourse is to rely on numerical techniques which can be computationally expensive. In our past work, we have shown that the MaxEP is a reliable tool to help predict orientational equilibrium states of highly symmetric bodies such as cylinders, spheroids and toroidal bodies. The MaxEP correctly helps choose the stable equilibrium in these cases when the system is slightly out of thermodynamic equilibrium. In the current paper, we expand our analysis to examine i) bodies with fewer symmetries than previously reported, for instance, a half-ellipse and ii) when the system is far from thermodynamic equilibrium. Using two-dimensional numerical studies at Reynolds numbers ranging between 0 and 14, we examine the validity of the MaxEP. Our analysis of flow past a half-ellipse shows that overall the MaxEP is a good predictor of the equilibrium states but, in the special case of the half-ellipse with aspect ratio much greater than unity, the MaxEP is replaced by the Min-MaxEP, at higher Reynolds numbers when inertial effects come into play. Experiments in sedimentation tanks and with hinged bodies in a flow tank confirm these calculations.
Directory of Open Access Journals (Sweden)
İbrahim ÜÇGÜL
2009-02-01
Full Text Available The refrigeration processes have been widely applied for especially in cold storages. In these plants, the systems working with compressed vapour cooling cycles have been used as a classical method. In general, electrical energy is used for compressing in these processes. Although, mainly the electricity itself has no pollution effect on the environment, the fossil fuels that are widely used to produce electricity in the most of the world, affect the nature terribly. In short, these refrigeration plants, because of the source of the electricity pollute the nature indirectly. However, for compression an ejector refrigeration system requires one of the important renewable energy sources with negligible pollution impact on the environment, namely solar energy from a thermal source. Thermodynamical, environmental and economical aspects of the ejector refrigeration system working with solar energy was investigated in this study. As a pilot case, apple cold storage plants widely used in ISPARTA city, which 1/5 th of apple production of TURKEY has been provided from, was chosen. Enviromental and economical advantages of solar ejector refrigeration system application for cold storage dictated by thermodynamic, economic and enviromental analyses in this research.
Thermodynamic assessment of the Ho–Te system supported by ab initio calculations
Energy Technology Data Exchange (ETDEWEB)
Ghamri, H.; Belgacem-Bouzida, A. [Laboratoire d’étude Physico-Chimique des Matériaux, Département de Physique, Faculté des Sciences, Université de Batna, Rue Chahid Boukhlouf, 05000 Batna (Algeria); Djaballah, Y., E-mail: ydjaballah@yahoo.fr [Laboratoire d’étude Physico-Chimique des Matériaux, Département de Physique, Faculté des Sciences, Université de Batna, Rue Chahid Boukhlouf, 05000 Batna (Algeria); Hidoussi, A. [Laboratoire d’étude Physico-Chimique des Matériaux, Département de Physique, Faculté des Sciences, Université de Batna, Rue Chahid Boukhlouf, 05000 Batna (Algeria)
2013-03-05
Highlights: ► We calculated enthalpies of formation of the HoTe and Ho{sub 2}Te{sub 5} compounds by using ab initio method. ► We modeled the Gibbs energy of the HoTe intermediate phase for the first time. ► The thermodynamic parameters of the all phases existing in the system were determined. ► The complete phase diagram of the system (Ho–Te) is calculated. -- Abstract: The phase diagram of the Ho–Te binary system has been assessed by using the CALPHAD (Calculation of Phase Diagrams) method on the basis of the experimental data of the phase equilibria and enthalpies of formation from ab initio electronic-structure calculations within the framework of density-functional theory. Reasonable models were constructed for all the phases of the system. The liquid phase was described as the substitutional solution model with excess energy expressed by Redlich–Kister polynomial. The compounds Ho{sub 2}Te{sub 5} and HoTe{sub 3} were expressed as stoichiometric phases. The (HoTe) phase was modeled by two-sublattices; (Ho,Va){sub 1}(Te){sub 1}. A consistent set of thermodynamic parameters has been derived, and calculated phase diagram was compared with the experimental data. A good agreement between the calculated results and experimental data was obtained.
Rational extended thermodynamics
Müller, Ingo
1998-01-01
Ordinary thermodynamics provides reliable results when the thermodynamic fields are smooth, in the sense that there are no steep gradients and no rapid changes. In fluids and gases this is the domain of the equations of Navier-Stokes and Fourier. Extended thermodynamics becomes relevant for rapidly varying and strongly inhomogeneous processes. Thus the propagation of high frequency waves, and the shape of shock waves, and the regression of small-scale fluctuation are governed by extended thermodynamics. The field equations of ordinary thermodynamics are parabolic while extended thermodynamics is governed by hyperbolic systems. The main ingredients of extended thermodynamics are • field equations of balance type, • constitutive quantities depending on the present local state and • entropy as a concave function of the state variables. This set of assumptions leads to first order quasi-linear symmetric hyperbolic systems of field equations; it guarantees the well-posedness of initial value problems and f...
Thermodynamic characteristics of a novel wind-solar-liquid air energy storage system
Ji, W.; Zhou, Y.; Sun, Y.; Zhang, W.; Pan, C. Z.; Wang, J. J.
2017-12-01
Due to the nature of fluctuation and intermittency, the utilization of wind and solar power will bring a huge impact to the power grid management. Therefore a novel hybrid wind-solar-liquid air energy storage (WS-LAES) system was proposed. In this system, wind and solar power are stored in the form of liquid air by cryogenic liquefaction technology and thermal energy by solar thermal collector, respectively. Owing to the high density of liquid air, the system has a large storage capacity and no geographic constraints. The WS-LAES system can store unstable wind and solar power for a stable output of electric energy and hot water. Moreover, a thermodynamic analysis was carried out to investigate the best system performance. The result shows that the increases of compressor adiabatic efficiency, turbine inlet pressure and inlet temperature all have a beneficial effect.
Thermodynamic Modeling of the SRS Evaporators: Part II. The 3H System
Energy Technology Data Exchange (ETDEWEB)
Jantzen, C.M.
2001-10-02
Accumulations of two solid phases have formed scale deposits in the Savannah River Site 2H Evaporator system since late 1996. The aluminosilicate scale deposits caused the evaporator pot to become inoperable in October 1999. Accumulations of the diuranate phase have caused criticality concerns in the SRS 2H Evaporator. In order to ensure that similar deposits are not and will not form in the SRS 3H Evaporator, thermodynamically derived activity diagrams specific to the feeds processed from Tanks 30 and 32 are evaluated in this report.
Thermodynamic reassessment of Nb-Ni-Ti system with order–disorder model
Energy Technology Data Exchange (ETDEWEB)
Santhy, K.; Hari Kumar, K.C.
2015-01-15
Highlights: • Thermodynamic re-assessment of Ni-Ti and Nb-Ni-Ti systems using CALPHAD with DFT. • Incorporation of order-disorder model in ternary and binaries. • Ternary solubility in the binary phases Ni{sub 3}Ti, NiTi, and NbNi{sub 3} are obtained by DFT. • Solubility of Ni{sub 3}Ti, NiTi, and NbNi{sub 3} in ternary are incorporated in modelling. • The calculated ternary Nb-Ni-Ti system compared with experimental data. - Abstract: A thermodynamic description of the Nb-Ni-Ti system is refined by combining results of first-principle total energy calculations with the CALPHAD approach. The lower order binary system Ni-Ti is reassessed with all available thermochemical and phase diagram data. Single Gibbs energy description is used for ordered and disordered bcc phase in this system. To make consistent extrapolation to ternary system, metastable B2 phase is introduced in both Nb-Ni and Nb-Ti systems. The enthalpy of formation of binary intermediate phases are calculated by first-principle method, which are compared with the experimental data. The energy of formation of hypothetical end-members in Ni-Ti binary system and the ternary solubility in the binary phases Ni{sub 3}Ti, NiTi, and NbNi{sub 3} are also calculated by first-principle method and incorporated in the modelling of those phases. Calculated phase diagram and thermochemical properties of Ni-Ti system is show good agreement with experimental data. The calculated ternary Nb-Ni-Ti system is summarily presented in the form of isothermal and isopleth sections, liquids projection and reaction scheme, with appropriate comparisons with available experimental data.
Manikandan, S.; Kaushik, S. C.
2015-04-01
Thermoelectric generator (TEG) operated thermoelectric cooler (TEC) is a highly compatible combination for low-cooling power application. The conventional TEG-TEC combined systems have low operating efficiency and low cooling power because maximum power output from the TEG is not fully utilized. This paper proposes and analyses the combined system with maximum power point tracking technique (MPPT) to maximize the cooling power and overall efficiency. This paper also presents the effect of TEG, TEC source temperature and the effect of heat transfer area in the performance of the combined system. The thermodynamic models of the combined system are developed in MATLAB simulink environment with temperature dependent material properties and analysed for variable operating temperatures. It has been found that, in the irreversible thermodynamic model of the combined system with MPPT, when the hot and cold side of TEG and TEC are kept at a temperature difference of 150 K and 10 K respectively, the power output of TEG increases from 20.49 W to 43.92 W, cooling power of TEC increases from 32.66 W to 46.51 W and the overall combined system efficiency increases from 2.606% to 4.375% respectively when compared with the irreversible combined system without MPPT. The characteristics improvements obtained by this practice in the combined system for the above mentioned operating conditions is also true for other range of operating temperatures. It is also been observed that the external irreversibilities decreases the cooling power and the overall system efficiency of the combined system by 36.49% and by 16.9% respectively.
Thermodynamics and statistical physics. 2. rev. ed.
International Nuclear Information System (INIS)
Schnakenberg, J.
2002-01-01
This textbook covers tthe following topics: Thermodynamic systems and equilibrium, irreversible thermodynamics, thermodynamic potentials, stability, thermodynamic processes, ideal systems, real gases and phase transformations, magnetic systems and Landau model, low temperature thermodynamics, canonical ensembles, statistical theory, quantum statistics, fermions and bosons, kinetic theory, Bose-Einstein condensation, photon gas
Thermodynamic design of hydrogen liquefaction systems with helium or neon Brayton refrigerator
Chang, Ho-Myung; Ryu, Ki Nam; Baik, Jong Hoon
2018-04-01
A thermodynamic study is carried out for the design of hydrogen liquefaction systems with helium (He) or neon (Ne) Brayton refrigerator. This effort is motivated by our immediate goal to develop a small-capacity (100 L/h) liquefier for domestic use in Korea. Eight different cycles are proposed and their thermodynamic performance is investigated in comparison with the existing liquefaction systems. The proposed cycles include the standard and modified versions of He Brayton refrigerators whose lowest temperature is below 20 K. The Brayton refrigerator is in direct thermal contact with the hydrogen flow at atmospheric pressure from ambient-temperature gas to cryogenic liquid. The Linde-Hampson system pre-cooled by a Ne Brayton refrigerator is also considered. Full cycle analysis is performed with the real properties of fluids to estimate the figure of merit (FOM) under an optimized operation condition. It is concluded that He Brayton refrigerators are feasible for this small-scale liquefaction, because a reasonably high efficiency can be achieved with simple and safe (low-pressure) operation. The complete cycles with He Brayton refrigerator are presented for the development of a prototype, including the ortho-to-para conversion.
Hastings, L. J.; Bolshinskiy, L. G.; Hedayat, A.; Schnell, A.
2011-01-01
NASA s Marshall Space Flight Center (MSFC) conducted liquid methane (LCH4) testing in November 2006 using the multipurpose hydrogen test bed (MHTB) outfitted with a spray-bar thermodynamic vent system (TVS). The basic objective was to identify any unusual or unique thermodynamic characteristics associated with subcooled LCH4 that should be considered in the design of space-based TVSs. Thirteen days of testing were performed with total tank heat loads ranging from 720 W to 420 W at a fill level of approximately 90%. During an updated evaluation of the data, it was noted that as the fluid passed through the Joule Thompson expansion, thermodynamic conditions consistent with the pervasive presence of metastability were indicated. This paper describes the observed thermodynamic conditions that correspond with metastability and effects on TVS performance.
International Nuclear Information System (INIS)
Kim, Junghwan; Jung, In-Ho
2015-01-01
Highlights: • The (Si-RE) (RE = Gd, Tb, Dy, Ho, Er, Tm, Lu and Y) systems have been reviewed. • The thermodynamic optimization of the (Si-RE) systems have been performed. • Systematic changes and similarities in the (Si-RE) systems were found. • The systematic approach resolved inconsistencies in the experimental data. • The systematic approach was used to assess the unexplored phase diagrams. - Abstract: A critical evaluation and optimisation of all available phase diagrams and thermodynamic data of the (Si-RE) (RE = Gd, Tb, Dy, Ho, Er, Tm, Lu and Y) systems was conducted to obtain reliable thermodynamic functions of all the phases in the system. In the thermodynamic modelling, a systematic analysis involving the similarity and periodicity observed in the lanthanide series was applied to resolve inconsistencies in the experimental data and to estimate the unknown thermodynamic properties and phase equilibria data. In particular, the phase diagrams and thermodynamic properties of (Si-Tm) and (Si-Lu) systems which are rarely investigated can be predicted from this approach. Systematic trends in thermodynamic properties of solid and liquid phases and phase diagram of the entire (Si-RE) systems were summarized
Thermodynamic assessment of integrated biogas-based micro-power generation system
International Nuclear Information System (INIS)
Hosseini, Seyed Ehsan; Barzegaravval, Hasan; Wahid, Mazlan Abdul; Ganjehkaviri, Abdolsaeid; Sies, Mohsin Mohd
2016-01-01
Highlights: • A thermodynamic modelling of an integrated biogas-based micro-power generation system is reported. • The impact of design parameters on the thermodynamic performance of the system is evaluated. • High turbine inlet temperatures lead the system to the higher energy and exergy efficiency and higher power generation. • Enhancement of GT isentropic efficiency incurs negative effects on the performance of air preheater and heat exchanger. • The rate of power generation increases by the enhancement of steam turbine pressure in ORC. - Abstract: In this paper, a thermodynamic modelling of an integrated biogas (60%CH 4 + 40%CO 2 ) micro-power generation system for electricity generation is reported. This system involves a gas turbine cycle and organic Rankine cycle (ORC) where the wasted heat of gas turbine cycle is recovered by closed ORC. The net output power of the micro-power generation system is fixed at 1.4 MW includes 1 MW power generated by GT and 0.4 MW by ORC. Energy and exergy assessments and related parametric studies are carried out, and parameters that influence on energy and exergy efficiency are evaluated. The performance of the system with respect to variation of design parameters such as combustion air inlet temperature, turbine inlet temperature, compressor pressure ratio, gas turbine isentropic efficiency and compressor isentropic efficiency (from the top cycle) and steam turbine inlet pressure, and condenser pressure (from bottoming cycle) is evaluated. The results reveal that by the increase of gas turbine isentropic efficiency, the outlet temperature of gas turbine decreases which incurs negative impacts on the performance of air preheater and heat exchanger, however the energy and exergy efficiency increases in the whole system. By the increase of air compressor pressure ratio, the energy and exergy of the combined cycle decreases. The exergy efficiency of ORC alters by the variation of gas turbine parameters which can be
Review of the thermodynamics of the U--C, Pu--C, and U--Pu--C systems
International Nuclear Information System (INIS)
Tetenbaum, M.; Sheth, A.; Olson, W.
1975-06-01
Thermodynamic properties such as enthalpy, heat capacity, entropy, heat and free energy of formation, and vaporization behavior are presented for the U--C, Pu--C, and U--Pu--C systems. These properties are of interest to scientists and engineers involved in the expanding field of advanced fuel LMFBR systems. The information on these systems has been derived largely from the discussions of the IAEA Panel on the assessment of thermodynamic properties of the U--C, Pu--C, and U--Pu--C systems. (U.S.)
Thermodynamic analysis of a solar-based multi-generation system with hydrogen production
International Nuclear Information System (INIS)
Ozturk, Murat; Dincer, Ibrahim
2013-01-01
Thermodynamic analysis of a renewable-based multi-generation energy production system which produces a number of outputs, such as power, heating, cooling, hot water, hydrogen and oxygen is conducted. This solar-based multi-generation system consists of four main sub-systems: Rankine cycle, organic Rankine cycle, absorption cooling and heating, and hydrogen production and utilization. Exergy destruction ratios and rates, power or heat transfer rates, energy and exergy efficiencies of the system components are carried out. Some parametric studies are performed in order to examine the effects of varying operating conditions (e.g., reference temperature, direct solar radiation and receiver temperature) on the exergy efficiencies of the sub-systems as well as the whole system. The solar-based multi-generation system which has an exergy efficiency of 57.35%, is obtained to be higher than using these sub-systems separately. The evaluation of the exergy efficiency and exergy destruction for the sub-systems and the overall system show that the parabolic dish collectors have the highest exergy destruction rate among constituent parts of the solar-based multi-generation system, due to high temperature difference between the working fluid and collector receivers. -- Highlights: ► Development of a new multi-generation system for solar-based hydrogen production. ► Investigation of exergy efficiencies and destructions in each process of the system. ► Evaluation of varying operating conditions on the exergy destruction and efficiency
Thermodynamics of Bi2O3-SiO2 system
Directory of Open Access Journals (Sweden)
Onderka B.
2017-01-01
Full Text Available Thermodynamic properties of the liquid Bi2O3-SiO2 solutions were determined from the results of the electrochemical measurements by use of the solid oxide galvanic cells with YSZ (Yttria-Stabilized-Zirconia electrolyte. Activities of Bi2O3 in the solutions were determined for 0.2, 0.3, 0.4, and 0.5 SiO2 mole fractions in the temperature range 1073-1293 K from measured electromotive force (e.m.f of the solid electrolyte galvanic cell: Bi, Bi2O3-SiO2 | YSZ | air (pO2 = 0.213 bar Additionally, heat capacity data obtained for two solid phases 6Bi2O3•SiO2 and 2Bi2O3•3SiO2 were included into optimization of thermodynamic properties of the system. Optimization procedure was supported by differential thermal analysis (DTA data obtained in this work as well as those accepted from the literature. Using the data obtained in this work, and the information about phase equilibria found in the literature, binary system Bi2O3-SiO2 was assessed with the ThermoCalc software.
Directory of Open Access Journals (Sweden)
Cheng Loong Ngan
2014-01-01
Full Text Available Fullerene nanoemulsions were formulated in palm kernel oil esters stabilized by low amount of mixed nonionic surfactants. Pseudoternary phase diagrams were established in the colloidal system of PKOEs/Tween 80 : Span 80/water incorporated with fullerene as antioxidant. Preformulation was subjected to combination of high and low energy emulsification methods and the physicochemical characteristics of fullerene nanoemulsions were analyzed using electroacoustic spectrometer. Oil-in-water (O/W nanoemulsions with particle sizes in the range of 70–160 nm were formed. The rheological characteristics of colloidal systems exhibited shear thinning behavior which fitted well into the power law model. The effect of xanthan gum (0.2–1.0%, w/w and beeswax (1–3%, w/w in the estimation of thermodynamics was further studied. From the energetic parameters calculated for the viscous flow, a moderate energy barrier for transport process was observed. Thermodynamic study showed that the enthalpy was positive in all xanthan gum and beeswax concentrations indicating that the formation of nanoemulsions could be endothermic in nature. Fullerene nanoemulsions with 0.6% or higher xanthan gum content were found to be stable against creaming and flocculation when exposed to extreme environmental conditions.
Basri, Mahiran; Tripathy, Minaketan; Abdul-Malek, Emilia
2014-01-01
Fullerene nanoemulsions were formulated in palm kernel oil esters stabilized by low amount of mixed nonionic surfactants. Pseudoternary phase diagrams were established in the colloidal system of PKOEs/Tween 80 : Span 80/water incorporated with fullerene as antioxidant. Preformulation was subjected to combination of high and low energy emulsification methods and the physicochemical characteristics of fullerene nanoemulsions were analyzed using electroacoustic spectrometer. Oil-in-water (O/W) nanoemulsions with particle sizes in the range of 70–160 nm were formed. The rheological characteristics of colloidal systems exhibited shear thinning behavior which fitted well into the power law model. The effect of xanthan gum (0.2–1.0%, w/w) and beeswax (1–3%, w/w) in the estimation of thermodynamics was further studied. From the energetic parameters calculated for the viscous flow, a moderate energy barrier for transport process was observed. Thermodynamic study showed that the enthalpy was positive in all xanthan gum and beeswax concentrations indicating that the formation of nanoemulsions could be endothermic in nature. Fullerene nanoemulsions with 0.6% or higher xanthan gum content were found to be stable against creaming and flocculation when exposed to extreme environmental conditions. PMID:25165736
Energy Technology Data Exchange (ETDEWEB)
Fuertauer, Siegfried; Beutl, Alexander; Flanorfer, Hans [Vienna Univ. (Austria). Dept. of Inorganic Chemistry - Functional Materials; Li, Dajian; Cupid, Damian [Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen (Germany). Inst. for Applied Materials - Applied Materials Physics (IAM-AWP); Henriques, David; Giel, Hans; Markus, Thorsten [Mannheim Univ. of Applied Sciences (Germany). Inst. for Thermo- and Fluiddynamics
2017-11-15
This article reports on two consecutive joint projects titled ''Experimental Thermodynamics and Phase Relations of New Electrode Materials for Lithium-Ion Batteries'', which were performed in the framework of the WenDeLIB 1473 priority program ''Materials with new Design for Lithium Ion Batteries''. Hundreds of samples were synthesized using experimental techniques specifically developed to deal with highly reactive lithium and lithium-containing compounds to generate electrochemical, phase diagram and crystal structure data in the Cu-Li, Li-Sn, Li-Sb, Cu-Li-Sn, Cu-Li-Sb and selected oxide systems. The thermochemical and phase diagram data were subsequently used to develop self-consistent thermodynamic descriptions of several binary systems. In the present contribution, the experimental techniques, working procedures, results and their relevance to the development of new electrode materials for lithium ion batteries are discussed and summarized. The collaboration between the three groups has resulted in more than fifteen (15) published articles during the six-year funding period.
Thermodynamic study of multi-effect thermal vapour-compression desalination systems
International Nuclear Information System (INIS)
Samaké, Oumar; Galanis, Nicolas; Sorin, Mikhail
2014-01-01
The parametric analysis of a multi-effect-evaporation (MEE) desalination system combined with a thermal-vapour-compression (TVC) process activated by a gaseous stream of specified flowrate and temperature was performed based on the principles of classical (1st and 2nd laws) and finite-size thermodynamics. The MEE subsystem was treated as a black box and therefore the results are valid for any combination of physical characteristics and internal operational conditions of this subsystem. They show the effects of four design variables (the motive fluid pressure and the compression ratio of the ejector, the condenser temperature pinch and the ratio of rejected to supplied seawater) on significant operating quantities and performance indicators such as: energy supplied by the heat source; motive fluid flowrate; flowrates of the supplied seawater and produced potable water; specific heat consumption; thermal conductance of the vapour generator and the condenser; exergy destruction by the MEE, the ejector and the vapour generator. Based on the obtained results recommendations are formulated for the optimal choice of values for the four design variables. - Highlights: • Model of a MEE-TVC desalination system independent of MEE characteristics. • Parametric study based on classical (1st and 2nd law) and finite-size thermodynamics. • Effect of 4 design parameters on operating conditions and performance indicators. • Recommended values for the design parameters
Thermal analysis of double-pipe heat exchanger in thermodynamic vent system
International Nuclear Information System (INIS)
Liu, Zhan; Li, Yanzhong; Zhou, Ke
2016-01-01
Highlights: • The thermodynamic analysis of TVS heat exchanger is investigated. • One quasi-steady state model is established to investigate the thermal performance of double-pipe heat exchanger. • The external natural convection, inner forced convection and the annular two-phase boiling are coupled. • The effect of the external natural convection should be given enough attention in the ground condition. • The influence of the pipe size is studied. - Abstract: Full use and effective management of cold capacity are significant for improving the performance of heat exchanger in the thermodynamic vent system (TVS). To understand the operation principle of TVS easily, the thermodynamic analysis, based on the ideal gas state equation and energy conservation equation, is detailed introduced. Some key operation parameters are optimized and suggested. As the low mass flow rate and low heat fluxes are involved in flow boiling of the annular pipe fluid, the Kandlikar’s boiling heat transfer correlation is selected to predict the flow boiling process, after validated with the related experimental results. One quasi-steady state model is established to investigate the heat transfer performance of double-pipe heat exchanger in normal gravity, with the bulk fluid natural convection, annular pipe two-phase boiling and inner pipe forced convection coupled from outside to inside. Determined by the local pressure and temperature, the fluid thermophysical properties are variable with the pipe length and time. With the variable fluid thermophysical properties, both the static analysis and the transient thermal performance of TVS heat exchanger are investigated respectively. Meanwhile, effects of the external natural convection and the pipe sizes on the thermal and flow performance of heat exchanger are detailed researched and analyzed. Some valuable conclusions are obtained and significant to optimize the TVS heat exchanger design.
Mikulecky, D C; Thellier, M
1993-12-01
As an example of the application of network thermodynamics to the treatment of complicated enzymatic systems, we have studied the transient kinetic behavior of a sequence of five enzymatic reactions, four with Michaelis-Menten kinetics and the final one with sigmoid kinetics. The object was to determine how the time-courses of the concentrations of all the intermediate substrates involved, depend on the effect of forward activation by the first substrate on the final enzymatic step. The case with forward activation exhibited an unexpected behavior with a reversal of the direction of the reaction before reaching equilibrium. The solution of the set of five non-linear differential equations was achieved using the student version of the simulation package PSPICE. The same approach can be utilized to study the behavior of any type of complex multienzymatic system (steady-states, transients, oscillations, chaos), or of combinations of enzymatic reactions with transmembrane transport in compartmental systems.
Thermodynamic description of the Al-Cu-Yb ternary system supported by first-principles calculations
Directory of Open Access Journals (Sweden)
Huang G.
2016-01-01
Full Text Available Phase relationships of the ternary Al-Cu-Yb system have been assessed using a combination of CALPHAD method and first principles calculations. A self-consistent thermodynamic parameter was established based on the experimental and theoretical information. Most of the binary intermetallic phases, except Al3Yb, Al2Yb, Cu2Yb and Cu5Yb, were assumed to be zero solubility in the ternary system. Based on the experimental data, eight ternary intermetallic compounds were taken into consideration in this system. Among them, three were treated as line compounds with large homogeneity ranges for Al and Cu. The others were treated as stoichiometric compounds. The calculated phase diagrams were in agreement with available experimental and theoretical data.
DEFF Research Database (Denmark)
Nguyen, Tuong-Van; Elmegaard, Brian
2016-01-01
Natural gas liquefaction systems are based on refrigeration cycles – they consist of the same operations such as heat exchange, compression and expansion, but they have different layouts, components and working fluids. The design of these systems requires a preliminary simulation and evaluation...... of their performance. However, the thermodynamic models used for this purpose are characterised by different mathematical formulations, ranges of application and levels of accuracy. This may lead to inconsistent results when estimating hydrocarbon properties and assessing the efficiency of a given process. This paper......, and (iii) optimise liquefaction systems. Three case studies are considered: a cascade layout with three pure refrigerants, a single mixed-refrigerant unit, and an expander-based configuration. Significant deviations are found between all property models, and in all case studies. The main discrepancies...
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...
Recondensation of chondritic material in the early solar system: Results of thermodynamic simulation
Dorofeyeva, V. A.; Makalkin, A. B.; Mironenko, M. V.; Vityazev, A. V.
1993-01-01
We have performed a thermodynamic simulation of the recondensation of evaporated meteoritic material. We suggest that evaporation and recondensation occurred in impact events during the intercollision of planetesimals during the early evolution of the solar system. The source materials adopted for our model are the chondrites CI Orgueil and H5 Richardton. These chondrites are representative examples of the two extremes regarding volatile content and oxidation state. We calculated equilibrium mineral compositions of the closed systems of the Orgueil's and Richardton's elemental composition at the P-T conditions characteristic of the explosion cloud formed at a planetesimal collision. The P-T conditions are as follows: 10(exp -4) bar, and 1500 and 2000 K. The results are presented.
Thermodynamics of the hexagonal close-packed iron-nitrogen system from first-principles
DEFF Research Database (Denmark)
Bakkedal, Morten Bjørn
expansion coefficient can be obtained at any temperature of interest. The thermal expansion predicted by the generalized quasiharmonic phonon model is in excellent agreement with experimental data. The model also allows calculation of the volume–pressure relationship at finite temperature, and good...... are described in the quasiharmonic phonon model and the linear response method is applied to determine force constants from first-principles calcula-tions. The hexagonal lattice poses a special challenge as two lattice parameters are required to describe the system. The quasiharmonic phonon model is generalized...... to hexagonal systems and a numerically tractable extended equation of state is developed to describe thermody-namic equilibrium properties at finite temperature.The model is applied to ε-Fe3N specifically. Through the versatility of the model, equi-librium lattice parameters, the bulk modulus, and the thermal...
FY-2011 Status Report for Thermodynamics and Kinetics of Advanced Separations Systems
Energy Technology Data Exchange (ETDEWEB)
Leigh R. Martin; Peter R. Zalupski; Travis S. Grimes
2011-09-01
This report presents a summary of the work performed in the area of thermodynamics and kinetics of advanced separations systems under the Fuel Cycle Research and Development (FCR&D) program during FY 2011 at the INL. On the thermodynamic front, investigations of liquid-liquid distribution of lanthanides at TALSPEAK-related conditions continued in FY11. It has been determined that a classical ion-exchanging phase transfer mechanism, where three HDEHP dimers solvate the metal ion in the organic phase, dominates metal extraction for systems that contain up to 0.1 M free lactate in solution. The correct graphical interpretation of the observed data in those regions relied on incorporating corrections for non-ideal behavior of HDEHP dimer in aliphatic diluents as well as sodium extraction equilibria. When aqueous conditions enter the complex regions of high lactate concentrations, slope analysis is no longer possible. When normalized metal distribution ratios were studied along the increasing concentration of free lactate, a slope of -1 was apparent. Such dependency either indicates aqueous complexing competition from lactate, or, a more likely scenario, a participation of lactate in the extracted metal complex. This finding agrees with our initial assessment of postulated changes in the extraction mechanism as a source of the lactate-mediated loss of extraction efficiency. The observed shape in the lanthanide distribution curve in our studies of TALSPEAK systems was the same for solutions containing no lactate or 2.3 M lactate. As such we may conclude that the mechanism of phase transfer is not altered dramatically and remains similarly sensitive to effective charge density of the metal ion. In addition to these thermodynamics studies, this report also summarizes the first calorimetric determination of heat of extraction of 248Cm in a bi-phasic system. The heat of extraction measured by isothermal titration calorimetry is compared to that determined using van
FY-2011 Status Report for Thermodynamics and Kinetics of Advanced Separations Systems
International Nuclear Information System (INIS)
Martin, Leigh R.; Zalupski, Peter R.; Grimes, Travis S.
2011-01-01
This report presents a summary of the work performed in the area of thermodynamics and kinetics of advanced separations systems under the Fuel Cycle Research and Development (FCR and D) program during FY 2011 at the INL. On the thermodynamic front, investigations of liquid-liquid distribution of lanthanides at TALSPEAK-related conditions continued in FY11. It has been determined that a classical ion-exchanging phase transfer mechanism, where three HDEHP dimers solvate the metal ion in the organic phase, dominates metal extraction for systems that contain up to 0.1 M free lactate in solution. The correct graphical interpretation of the observed data in those regions relied on incorporating corrections for non-ideal behavior of HDEHP dimer in aliphatic diluents as well as sodium extraction equilibria. When aqueous conditions enter the complex regions of high lactate concentrations, slope analysis is no longer possible. When normalized metal distribution ratios were studied along the increasing concentration of free lactate, a slope of -1 was apparent. Such dependency either indicates aqueous complexing competition from lactate, or, a more likely scenario, a participation of lactate in the extracted metal complex. This finding agrees with our initial assessment of postulated changes in the extraction mechanism as a source of the lactate-mediated loss of extraction efficiency. The observed shape in the lanthanide distribution curve in our studies of TALSPEAK systems was the same for solutions containing no lactate or 2.3 M lactate. As such we may conclude that the mechanism of phase transfer is not altered dramatically and remains similarly sensitive to effective charge density of the metal ion. In addition to these thermodynamics studies, this report also summarizes the first calorimetric determination of heat of extraction of 248Cm in a bi-phasic system. The heat of extraction measured by isothermal titration calorimetry is compared to that determined using van
Fusco, L.; Pigeon, S.; Apollaro, T. J. G.; Xuereb, A.; Mazzola, L.; Campisi, M.; Ferraro, A.; Paternostro, M.; De Chiara, G.
2014-07-01
We analyze the nature of the statistics of the work done on or by a quantum many-body system brought out of equilibrium. We show that, for the sudden quench and for an initial state that commutes with the initial Hamiltonian, it is possible to retrieve the whole nonequilibrium thermodynamics via single projective measurements of observables. We highlight, in a physically clear way, the qualitative implications for the statistics of work coming from considering processes described by operators that either commute or do not commute with the unperturbed Hamiltonian of a given system. We consider a quantum many-body system and derive an expression that allows us to give a physical interpretation, for a thermal initial state, to all of the cumulants of the work in the case of quenched operators commuting with the unperturbed Hamiltonian. In the commuting case, the observables that we need to measure have an intuitive physical meaning. Conversely, in the noncommuting case, we show that, although it is possible to operate fully within the single-measurement framework irrespectively of the size of the quench, some difficulties are faced in providing a clear-cut physical interpretation to the cumulants. This circumstance makes the study of the physics of the system nontrivial and highlights the nonintuitive phenomenology of the emergence of thermodynamics from the fully quantum microscopic description. We illustrate our ideas with the example of the Ising model in a transverse field showing the interesting behavior of the high-order statistical moments of the work distribution for a generic thermal state and linking them to the critical nature of the model itself.
Energy Technology Data Exchange (ETDEWEB)
Cao, Zhaoping [State Key Laboratory of Powder Metallurgy, Central South University, Changsha, Hunan 410083 (China); Liu, Shuhong, E-mail: shhliu@csu.edu.cn [State Key Laboratory of Powder Metallurgy, Central South University, Changsha, Hunan 410083 (China); Sino-German cooperation group “Microstructure in Al alloys”, Central South University, Changsha, Hunan 410083 (China); Fang, Xu; Cheng, Kaiming; Gao, Qiannan [State Key Laboratory of Powder Metallurgy, Central South University, Changsha, Hunan 410083 (China); Du, Yong; Wang, Jiong [State Key Laboratory of Powder Metallurgy, Central South University, Changsha, Hunan 410083 (China); Sino-German cooperation group “Microstructure in Al alloys”, Central South University, Changsha, Hunan 410083 (China); Zhang, Jun; Huang, Weidong [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an 710072 (China); Tang, Chengying [Guangxi Key Laboratory of Informational Materials, Guilin University of Electronic Technology, Guilin, Guangxi 541004 (China)
2014-06-01
Highlights: • The Sc–Ni system is reinvestigated via experiments and thermodynamics. • The homogeneity range and the congruent melting point of Sc{sub 2}Ni are clarified. • First-principles calculations are performed for the enthalpies of formation. • Order-disorder model is used to describe Bcc{sub A}2 and Bcc{sub B}2 (ScNi). • The present thermodynamic parameters can fit the experimental data better. - Abstract: The Sc–Ni binary system was investigated via a hybrid of experiment and thermodynamic calculation. Eleven alloys were prepared by arc melting. The as-cast and annealed samples were analyzed by means of X–ray diffraction, scanning electron microscopy with energy-dispersive X–ray spectrometer, electron probe microanalysis and differential thermal analysis/differential scanning calorimetry. The invariant reactions on Sc-rich side were reinvestigated. Five compounds (ScNi{sub 5}, Sc{sub 2}Ni{sub 7}, ScNi{sub 2}, ScNi and Sc{sub 2}Ni) were observed in the present experiment. Their enthalpies of formation at 0 K were computed via first-principles calculations to supply referable thermodynamic data for the modeling. One single function was used to describe the Gibbs energies of both the ordered Bcc{sub B}2 (ScNi) and disordered Bcc{sub A}2 phases. The presently obtained thermodynamic parameters for the Sc–Ni system can reproduce the experimental data reasonably.
Experimental investigation of passive thermodynamic vent system (TVS) with liquid nitrogen
Bae, Junhyuk; Yoo, Junghyun; Jin, Lingxue; Jeong, Sangkwon
2018-01-01
Thermodynamic vent system (TVS) is an attractive technology to maintain an allowable pressure level of a cryogenic propellant storage in a spacecraft under micro-gravity condition. There are two types of TVS; active or passive. In this paper, the passive TVS which does not utilize a cryogenic liquid circulation pump is experimentally investigated with liquid nitrogen and numerically analyzed by thermodynamic and heat transfer model. A cylindrical copper tank, which is 198 mm in inner diameter and 216 mm in height, is utilized to suppress a thermal-stratification effect of inside cryogenic fluid. A coil heat exchanger, which is 3 m in length and 6.35 mm in outer diameter, and a fixed size orifice of which diameter is 0.4 mm are fabricated to remove heat from the stored fluid to the vented flow. Each vent process is initiated at 140 kPa and ended at 120 kPa with liquid nitrogen fill levels which are 30%, 50% and 70%, respectively. In the numerical model, the fluid in the tank is assumed to be homogeneous saturated liquid-vapor. Mass and energy balance equations with heat transfer conditions suggested in this research are considered to calculate the transient pressure variation in the tank and the amount of heat transfer across the heat exchanger. We achieve the average heat rejection rate of more than 9 W by TVS and conclude that the passive TVS operates satisfactorily. In addition, the prediction model is verified by experimental results. Although the model has limitation in providing accurate results, it can surely predict the tendency of pressure and temperature changes in the tank. Furthermore, the model can suggest how we can improve the heat exchanger design to enhance an overall efficiency of passive TVS. Moreover, the performance of passive TVS is compared with other cryogenic vent systems (direct vent system and active TVS) by suggested performance indicator.
Gladyshev, G P
2002-01-01
The creation of structural hierarchies in open natural biosystems within the framework of quasi-closed systems is investigated by the methods of hierarchic thermodynamics (thermostatics). During the evolution of natural open systems, every higher hierarchic level j appears as a consequence of thermodynamic self-organization (self-assembly) of the structures of the lower (j-1)-th level. Such a self-assembly proceeds as a result of stabilization of the j-th level. This is related to the Gibbs' (Helmholtz') specific function of formation of the structure of the j-th level tending to a minimum. As a result of action of the principle of substance (matter) stability, the structures of the j-th level are enriched with less stable structures of the (j-1)-th level in the course of evolution. This provides a thermodynamic feedback between the structures of the higher j-th level and lower (j-1)-th level, thus preventing full structural stabilization of the j-th level and causing "thermodynamic rejuvenation" of biosystems. The latter enhances "thermodynamic" deceleration of evolution and practically unlimited maintenance of life. Examples of quantitative correlations are provided that call for further application of the substance stability principle to living and nonliving hierarchic structures.
Directory of Open Access Journals (Sweden)
Jeroen Schoenmaker
2014-08-01
Full Text Available We performed an in depth analysis of the subjects of entropy and the second law of thermodynamics and how they are treated in astrophysical systems. These subjects are retraced historically from the early works on thermodynamics to the modern statistical mechanical approach and analyzed in view of specific practices within the field of astrophysics. As often happens in discussions regarding cosmology, the implications of this analysis range from physics to philosophy of science. We argue that the difficult question regarding entropy and the second law in the scope of cosmology is a consequence of the dominating paradigm. We further demonstrate this point by assuming an alternative paradigm, not related to thermodynamics of horizons, and successfully describing entropic behavior of astrophysical systems.
Chen, C C; Zhu, Y; King, J A; Evans, L B
1992-10-01
Under physiological conditions, many polypeptide chains spontaneously fold into discrete and tightly packed three-dimensional structures. The folded polypeptide chain conformation is believed to represent a minimum Gibbs energy of the system, governed by the weak interactions that operate between the amino acid residues and between the residues and the solvent. A semiempirical molecular thermodynamic model is proposed to represent the Gibbs energy of folding of aqueous homopolypeptide systems. The model takes into consideration both the entropy contribution and the enthalpy contribution of folding homopolypeptide chains in aqueous solutions. The entropy contribution is derived from the Flory-Huggins expression for the entropy of mixing. It accounts for the entropy loss in folding a random-coiled polypeptide chain into a specific polypeptide conformation. The enthalpy contribution is derived from a molecular segment-based Non-Random Two Liquid (NRTL) local composition model [H. Renon and J. M. Prausnitz (1968) AIChE J., Vol. 14, pp. 135-142; C.-C. Chen and L. B. Evans (1986) AIChE J., Vol. 32, pp. 444-454], which takes into consideration of the residue-residue, residue-solvent, and solvent-solvent binary physical interactions along with the local compositions of amino acid residues in aqueous homopolypeptides. The UNIFAC group contribution method [A. Fredenslund, R. L. Jones, and J. M. Prausnitz (1975) AIChE J., 21, 1086-1099; A. Fredenslund, J. Gmehling, and P. Rasmussen (1977) Vapor-Liquid Equilibrium Using UNIFAC, Elsevier Scientific Publishing Company, Amsterdam], developed originally to estimate the excess Gibbs energy of solutions of small molecules, was used to estimate the NRTL binary interaction parameters. The model yields a hydrophobicity scale for the 20 amino acid side chains, which compares favorably with established scales [Y. Nozaki and C. Tanford (1971) Journal of Biological Chemistry, Vol. 46, pp. 2211-2217; E. B. Leodidis and T. A. Hatton (1990
Bazant, Martin Z
2017-07-01
Motivated by the possibility of electrochemical control of phase separation, a variational theory of thermodynamic stability is developed for driven reactive mixtures, based on a nonlinear generalization of the Cahn-Hilliard and Allen-Cahn equations. The Glansdorff-Prigogine stability criterion is extended for driving chemical work, based on variations of nonequilibrium Gibbs free energy. Linear stability is generally determined by the competition of chemical diffusion and driven autocatalysis. Novel features arise for electrochemical systems, related to controlled total current (galvanostatic operation), concentration-dependent exchange current (Butler-Volmer kinetics), and negative differential reaction resistance (Marcus kinetics). The theory shows how spinodal decomposition can be controlled by solo-autocatalytic charge transfer, with only a single faradaic reaction. Experimental evidence is presented for intercalation and electrodeposition in rechargeable batteries, and further applications are discussed in solid state ionics, electrovariable optics, electrochemical precipitation, and biological pattern formation.
Methods to Increase the Robustness of Finite-Volume Flow Models in Thermodynamic Systems
Directory of Open Access Journals (Sweden)
Sylvain Quoilin
2014-03-01
Full Text Available This paper addresses the issues linked to simulation failures during integration in finite-volume flow models, especially those involving a two-phase state. This kind of model is particularly useful when modeling 1D heat exchangers or piping, e.g., in thermodynamic cycles involving a phase change. Issues, such as chattering or stiff systems, can lead to low simulation speed, instabilities and simulation failures. In the particular case of two-phase flow models, they are usually linked to a discontinuity in the density derivative between the liquid and two-phase zones. In this work, several methods to tackle numerical problems are developed, described, implemented and compared. In addition, methods available in the literature are also implemented and compared to the proposed approaches. Results suggest that the robustness of the models can be significantly increased with these different methods, at the price of a small increase of the error in the mass and energy balances.
First principles, thermal stability and thermodynamic assessment of the binary Ni-W system
Energy Technology Data Exchange (ETDEWEB)
Isomaeki, Iikka; Haemaelaeinen, Marko; Gasik, Michael [Aalto Univ., Espoo (Finland). School of Chemical Engineering; Braga, Maria H. [Porto Univ. (Portugal). CEMUC, Physics Engineering Dept.
2017-12-15
The Ni-W binary system was assessed using critically evaluated experimental data with assistance from first principles analysis and the CALPHAD method. The solution phases (liquid, fcc-A1 and bcc-A2) were modeled using the substitutional regular solution model. The recently discovered Ni{sub 8}W metastable phase was evaluated as Fe{sub 16}C{sub 2}- like martensite with three sublattices, and shown to be possibly stable according to first principles calculations. Ni{sub 8}W was also modeled as an interstitial compound, but the model is not good because the solubility of tungsten in nickel is very low, especially at low temperatures. There is no experimental evidence for such low solubility. The other binary compounds Ni{sub 4}W and Ni{sub 3}W were assessed as stoichiometric ones. Compared independent experimental and first principles data agree well with the calculated phase diagram using updated thermodynamic parameters.
Thermodynamic analysis in the Li5AlO4-Al system
International Nuclear Information System (INIS)
Tarasov, V.P.; Miklushevskij, V.V.; Vatulin, I.I.; Kulifeev, V.K.
2003-01-01
A rise in the scale of production and application of lithium is accompanied by increasing the volume of lithium-containing waste. Their processing to produce lithium metal is expedient to execute by aluminothermic reduction of lithium aluminates in vacuum where Li 5 AIO 4 five-lithium aluminate, that has the highest lithium content (27.78 %), is used as the starting raw material. Using an integral version of the Knudsen cell in the high-temperature mass-spectrum analyzer, the lithium vapor pressure in the Li 5 AIO 4 -AI system was measured. The standard enthalpy and entropy of five-lithium aluminate were calculated using the results obtained experimentally. According to the thermodynamic calculations, the degree of Li 5 AIO 4 reduction above 90 % under the conditions of process vacuum (∼ Pa) is possible at T> 1100 Deg C [ru
Thermodynamic analysis of solid oxide fuel cell gas turbine systems operating with various biofuels
Energy Technology Data Exchange (ETDEWEB)
Patel, H.C.; Woudstra, T.; Aravind, P.V. [Process and Energy Laboratory, Delft University of Technology, Section Energy Technology, Leeghwaterstraat 44, 2628 CA Delft (Netherlands)
2012-12-15
Solid oxide fuel cell-gas turbine (SOFC-GT) systems provide a thermodynamically high efficiency alternative for power generation from biofuels. In this study biofuels namely methane, ethanol, methanol, hydrogen, and ammonia are evaluated exergetically with respect to their performance at system level and in system components like heat exchangers, fuel cell, gas turbine, combustor, compressor, and the stack. Further, the fuel cell losses are investigated in detail with respect to their dependence on operating parameters such as fuel utilization, Nernst voltage, etc. as well as fuel specific parameters like heat effects. It is found that the heat effects play a major role in setting up the flows in the system and hence, power levels attained in individual components. The per pass fuel utilization dictates the efficiency of the fuel cell itself, but the system efficiency is not entirely dependent on fuel cell efficiency alone, but depends on the split between the fuel cell and gas turbine powers which in turn depends highly on the nature of the fuel and its chemistry. Counter intuitively it is found that with recycle, the fuel cell efficiency of methane is less than that of hydrogen but the system efficiency of methane is higher. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)
Thermodynamics of the formaldehyde-water and formaldehyde-ice systems for atmospheric applications.
Barret, Manuel; Houdier, Stephan; Domine, Florent
2011-01-27
Formaldehyde (HCHO) is a species involved in numerous key atmospheric chemistry processes that can significantly impact the oxidative capacity of the atmosphere. Since gaseous HCHO is soluble in water, the water droplets of clouds and the ice crystals of snow exchange HCHO with the gas phase and the partitioning of HCHO between the air, water, and ice phases must be known to understand its chemistry. This study proposes thermodynamic formulations for the partitioning of HCHO between the gas phase and the ice and liquid water phases. A reanalysis of existing data on the vapor-liquid equilibrium has shown the inadequacy of the Henry's law formulation, and we instead propose the following equation to predict the mole fraction of HCHO in liquid water at equilibrium, X(HCHO,liq), as a function of the partial pressure P(HCHO) (Pa) and temperature T (K): X(HCHO,liq) = 1.700 × 10(-15) e((8014/T))(P(HCHO))(1.105). Given the paucity of data on the gas-ice equilibrium, the solubility of HCHO and the diffusion coefficient (D(HCHO)) in ice were measured by exposing large single ice crystals to low P(HCHO). Our recommended value for D(HCHO) over the temperature range 243-266 K is D(HCHO) = 6 × 10(-12) cm(2) s(-1). The solubility of HCHO in ice follows the relationship X(HCHO,ice) = 9.898 × 10(-13) e((4072/T))(P(HCHO))(0.803). Extrapolation of these data yields the P(HCHO) versus 1/T phase diagram for the H(2)O-HCHO system. The comparison of our results to existing data on the partitioning of HCHO between the snow and the atmosphere in the high arctic highlights the interplay between thermodynamic equilibrium and kinetics processes in natural systems.
Energy Technology Data Exchange (ETDEWEB)
Feidt, M.; Brunin, O.; Lottin, O.; Vidal, J.F. [Universite Henri Poincare Nancy, 54 - Vandoeuvre-les-Nancy (France); Hivet, B. [Electricite de France, 77 - Moret sur Loing (France)
1996-12-31
This paper describes a 5 years joint research work carried out by Electricite de France (EdF) and the ESPE group of the LEMTA on compression-absorption heat pumps. It shows how a thermodynamical model of machinery, completed with precise exchanger-reactor models, allows to simulate and dimension (and eventually optimize) the system. A small power prototype has been tested and the first results are analyzed with the help of the models. A real scale experiment in industrial sites is expected in the future. (J.S.) 20 refs.
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
Thermodynamic analysis of a coal-based polygeneration system with partial gasification
International Nuclear Information System (INIS)
Li, Yuanyuan; Zhang, Guoqiang; Yang, Yongping; Zhai, Dailong; Zhang, Kai; Xu, Gang
2014-01-01
This study proposed a polygeneration system based on coal partial gasification, in which methanol and power were generated. This proposed system, comprising chemical and power islands, was designed and its characteristics are analyzed. The commercial software Aspen Plus was used to perform the system analysis. In the case study, the energy and exergy efficiency values of the proposed polygeneration system were 51.16% and 50.58%, which are 2.34% and 2.10%, respectively, higher than that of the reference system. Energy-Utilization Diagram analysis showed that removing composition adjustment and recycling 72.7% of the unreacted gas could reduce the exergy destruction during methanol synthesis by 46.85% and that the char utilized to preheat the compressed air could reduce the exergy destruction during combustion by 10.28%. Sensitivity analysis was also performed. At the same capacity ratio, the energy and exergy efficiency values of the proposed system were 1.30%–2.48% and 1.21%–2.30% higher than that of the reference system, respectively. The range of chemical-to-power capacity ratio in the proposed system was 0.41–1.40, which was narrower than that in the reference system. But the range of 1.04–1.4 was not recommended for the disappearance of energy saving potential in methanol synthesis. - Highlights: • A novel polygeneration system based on coal partial gasification is proposed. • The efficient conversion method for methanol and power is explored. • The exergy destruction in chemical energy conversion processes is decreased. • Thermodynamic performance and system characteristics are analyzed
Reiss, Howard
1997-01-01
Since there is no shortage of excellent general books on elementary thermodynamics, this book takes a different approach, focusing attention on the problem areas of understanding of concept and especially on the overwhelming but usually hidden role of ""constraints"" in thermodynamics, as well as on the lucid exposition of the significance, construction, and use (in the case of arbitrary systems) of the thermodynamic potential. It will be especially useful as an auxiliary text to be used along with any standard treatment.Unlike some texts, Methods of Thermodynamics does not use statistical m
Thermodynamic assessment of the LiF–ThF4–PuF3–UF4 system
Capelli, E.; Benes, O.; Konings, R.J.M.
2015-01-01
The LiF–ThF4–PuF3–UF4 system is the reference salt mixture considered for the Molten Salt Fast Reactor (MSFR) concept started with PuF3. In order to obtain the complete thermodynamic description of this quaternary system, two binary systems (ThF4–PuF3 and UF4–PuF3) and two ternary systems
Principles of Considering the Effect of the Limited Volume of a System on Its Thermodynamic State
Tovbin, Yu. K.
2018-01-01
The features of a system with a finite volume that affect its thermodynamic state are considered in comparison to describing small bodies in macroscopic phases. Equations for unary and pair distribution functions are obtained using difference derivatives of a discrete statistical sum. The structure of the equation for the free energy of a system consisting of an ensemble of volume-limited regions with different sizes and a full set of equations describing a macroscopic polydisperse system are discussed. It is found that the equations can be applied to molecular adsorption on small faces of microcrystals, to bound and isolated pores of a polydisperse material, and to describe the spinodal decomposition of a fluid in brief periods of time and high supersaturations of the bulk phase when each local region functions the same on average. It is shown that as the size of a system diminishes, corrections must be introduced for the finiteness of the system volume and fluctuations of the unary and pair distribution functions.
Energy Technology Data Exchange (ETDEWEB)
NONE
2000-07-01
This document provides technical guidelines for the realization of various thermodynamical systems for individual air-conditioning. It is presented in two chapters dealing with: 1 - the essential points to be controlled for a conformable installation. This first part lists the different existing thermodynamical systems (air/water, water/water, ground/water, ground/ground, air/air) and recalls for each type of installation the essential points to be controlled (choice and dimensioning of equipment, terminal units, acoustics, hydraulic network, thermal insulation, regulation and operation); 2 - the synthesis of technical rules and practical advices. This chapter is based on the documents jointly established by the scientific and technical committee of air conditioning industries (CoSTIC), Electricite de France (EdF) and the French association of cold engineering (AFF) and presents the realisation rules and advices to be respected in the different parts of an installation (thermal losses, insulation..) and the specific dispositions to take into account according to the system chosen. (J.S.)
International Nuclear Information System (INIS)
Kizilkan, Onder; Dincer, Ibrahim
2015-01-01
Highlights: • Exergy analysis of BTES for heating season is carried out. • Exergy efficiency of BTES is determined to be 41.35% for overall system. • COP HP is determined to be 2.6 for overall system. • Increasing evaporator temperature to 6 °C decreases the exergy destruction rate. • Increasing condenser temperature to 70 °C increases the exergy destruction rate. - Abstract: A comprehensive thermodynamic assessment of a borehole thermal energy storage system (BTES), which helps in meeting the heating and cooling demands of campus buildings of University of Ontario Institute of Technology (UOIT), is presented for the heating case. The BTES located on UOIT campus in Oshawa, Canada is recognized as the world’s second largest BTES system. Energy and exergy analyses of the heating system are performed through the balance equations, and exergy destruction rates are determined for each system component and the overall BTES. In addition, a comparative system performance assessment is carried out. Based on the conducted research for the studied system, COP HP is calculated to be 2.65 for heating applications. Energy and exergy efficiencies of the boilers are determined to be 83.2% and 35.83%, respectively. The results of the exergy analysis show that the boilers are the major contributor to exergy destruction, followed by condenser and evaporator. The effects of condenser and evaporator temperatures of the heat pump systems on energy and exergy efficiencies are also investigated. The overall exergy efficiency of the whole system is calculated to be 41.35%
Yang, Sam
The dissertation presents the mathematical formulation, experimental validation, and application of a volume element model (VEM) devised for modeling, simulation, and optimization of energy systems in their early design stages. The proposed model combines existing modeling techniques and experimental adjustment to formulate a reduced-order model, while retaining sufficient accuracy to serve as a practical system-level design analysis and optimization tool. In the VEM, the physical domain under consideration is discretized in space using lumped hexahedral elements (i.e., volume elements), and the governing equations for the variable of interest are applied to each element to quantify diverse types of flows that cross it. Subsequently, a system of algebraic and ordinary differential equations is solved with respect to time and scalar (e.g., temperature, relative humidity, etc.) fields are obtained in both spatial and temporal domains. The VEM is capable of capturing and predicting dynamic physical behaviors in the entire system domain (i.e., at system level), including mutual interactions among system constituents, as well as with their respective surroundings and cooling systems, if any. The VEM is also generalizable; that is, the model can be easily adapted to simulate and optimize diverse systems of different scales and complexity and attain numerical convergence with sufficient accuracy. Both the capability and generalizability of the VEM are demonstrated in the dissertation via thermal modeling and simulation of an Off-Grid Zero Emissions Building, an all-electric ship, and a vapor compression refrigeration (VCR) system. Furthermore, the potential of the VEM as an optimization tool is presented through the integrative thermodynamic optimization of a VCR system, whose results are used to evaluate the trade-offs between various objective functions, namely, coefficient of performance, second law efficiency, pull-down time, and refrigerated space temperature, in
International Nuclear Information System (INIS)
Wang, Jiangfeng; Yan, Zhequan; Wang, Man; Dai, Yiping
2013-01-01
Due to a good behavior of ammonia-water during the two-phase heat addition process and the liquefied natural gas with great cold energy, an ammonia-water power system with LNG as its heat sink is proposed to utilize the low grade waste heat. Based on the thermodynamic mathematical models, the effects of key thermodynamic design parameters, including turbine inlet pressure, turbine inlet temperature, ammonia mass fraction, pinch temperature difference and approach temperature difference in the heat recovery vapor generator, on the system performance are examined from the view of both thermodynamics and economics. To obtain the optimum performance, multi-objective optimization is conducted to find the best thermodynamic design parameters from both thermodynamic and economic aspects using NSGA-II (Non-dominated sorting genetic algorithm-II). The exergy efficiency, total heat transfer capability and turbine size parameter are selected as three objective functions to maximize the exergy efficiency, and minimize the total heat transfer capability and turbine size parameter under the given waste heat conditions. The results show that turbine inlet pressure, turbine inlet temperature, ammonia mass fraction, pinch temperature difference and approach temperature difference have significant effects on the system performance. By multi-objective optimization, the Pareto frontier solution for the ammonia-water power system is obtained. - Highlights: ► An ammonia-water power system with LNG as its heat sink is proposed. ► The effects of key parameters on the system performance are examined. ► Multi-objective optimization is conducted to obtain optimum system performance
Assessment of the thermodynamic properties and phase diagram of the Bi–Pd system
Czech Academy of Sciences Publication Activity Database
Vřešťál, J.; Pinkas, J.; Watson, A.; Scott, A.; Houserová, Jana; Kroupa, Aleš
2006-01-01
Roč. 30, č. 1 (2006), s. 14-17 ISSN 0364-5916 R&D Projects: GA MŠk(CZ) OC 531.002 Institutional research plan: CEZ:AV0Z2041904 Keywords : phase diagram * thermodynamic modelling Subject RIV: BJ - Thermodynamics Impact factor: 1.432, year: 2006
Experimental study and thermodynamic modelling of the B-Fe-Mn ternary system
Czech Academy of Sciences Publication Activity Database
Repovský, P.; Homolová, V.; Čiripová, L.; Kroupa, Aleš; Zemanová, Adéla
2016-01-01
Roč. 55, DEC (2016), s. 252-259 ISSN 0364-5916 R&D Projects: GA ČR GA14-15576S Institutional support: RVO:68081723 Keywords : thermodynamic modelling * phase diagram * borides Subject RIV: BJ - Thermodynamic s Impact factor: 1.600, year: 2016
The role of Minkowski functionals in the thermodynamics of two-phase systems
Eder, Gerhard
2018-01-01
Within this work quite old concepts from integral geometry are applied to classical equilibrium thermodynamics of two-phase systems. In addition to the area as basic interfacial quantity the full geometric characterization of the interface is used, which includes the two remaining Minkowski functionals, the mean curvature integral and the Euler Poincaré characteristic. The basic energetic characteristic of the interface (i.e. the interfacial tension) is extended by two additional properties: edge force as (up to a factor 4/π) the work necessary to form a right-angled edge of unit length, and item energy as the work to form an additional item in the phase morphology. Both quantities are of increasing importance, when going to micro- and nano-scales. They are subsequently used for interfaces of arbitrary shape to derive a relationship extending the classical Young-Laplace equation. The supplementary contribution is proportional to the Gaussian curvature, with the edge force as proportionality constant. Furthermore, both edge force and item energy are shown to be applicable to the description of crystal nucleation in liquids (extending the classical Becker Döring theory). It turns out, that even above the thermodynamic melting temperature stable nuclei can be present in the liquid phase. They immediately are able to grow when quenched to a temperature below a characteristic temperature. This temperature of spontaneous homogeneous nucleation is simply connected to the edge force, whereas the number of stable clusters per unit volume is dominated by the item energy. Finally, the additional energetic interfacial properties are used in a similar way to characterize the stability of emulsions.
International Nuclear Information System (INIS)
Lunine, J.I.; Stevenson, D.J.
1985-01-01
The thermodynamic stability of clathrate hydrate is calculated under a wide range of temperature and pressure conditions applicable to solar system problems, using a statistical mechanical theory developed by van der Waals an Platteeuw (1959) and existing experimental data on properties of clathrate hydrates and their components. At low pressure, dissociation pressures and partition functions (Langmuir constants) for CO clathrate (hydrate) have been predicted, using the properties of clathrate containing, as guests, molecules similar to CO. The comparable or higher propensity of CO to incorporate in clathrate relative to N 2 is used to argue for high CO-to-N 2 ratios in primordial Titan in N 2 was accreted as clathrate. The relative incorporation of noble gases in clathrate from a solar composition gas at low temperatures is calculated and applied to the case of giant-planet atmospheres and icy satellites. It is argued that nonsolar but well-constrained noble gas abundances will be measured by Galileo in the Jovian atmosphere if the observed carbon enhancement is due to bombardment of the atmosphere by clathrate- bearing planetesimals sometime after planetary formation. The noble gas abundances in Titan's atmosphere are also predicted under the hypothesis that much of the stellite's methane accreted a clathrate. Double occupancy of clathrate cages by H 2 and CH 4 in contact with a solar composition gas is examined, and it is concluded that potentially important amounts of H 2 may have incorporated in satellites as clathrate. The kinetics of clathrate formation is also examined, and it is suggested that, under thermodynamically appropriate conditions, essentially complete clathration of water ice could have occurred in high-pressure nebulae around giant planets but probably not in the outer solar nebula; comets probably did not aggregate as clathrate
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.
Milosevic, M.; Hendriks, I.; Smits, R.E.R.; Schuur, Boelo; de Haan, A.B.
2013-01-01
Liquid–liquid extraction using ethers as solvents is a potentially energy saving alternative for the concentration of aqueous ferric chloride solutions. Adequate thermodynamic models that describe the behavior of the resulting quaternary systems (FeCl3, ether, acid and water) are not available in
Directory of Open Access Journals (Sweden)
Giulio Vialetto
2017-12-01
Full Text Available Transition to alternative energy systems is indicated by EU Commission as a suitable path to energy efficiency and energy saving in the next years. The aims are to decrease greenhouses gases emissions, relevance of fossil fuels in energy production and energy dependence on extra-EU countries. These goals can be achieved increasing renewable energy sources and/or efficiency on energy production processes. In this paper an innovative micro-cogeneration system for household application is presented: it covers heating, domestic hot water and electricity demands for a residential user. Solid oxide fuel cells, heat pump and Stirling engine are utilised as a system to achieve high energy conversion efficiency. A transition from traditional petrol cars to electric mobility is also considered and simulated here. Different types of fuel are considered to demonstrate the high versatility of the simulated cogeneration system by changing the pre-reformer of the fuel cell. Thermodynamic analysis is performed to prove high efficiency with the different fuels.
Thermodynamic analysis of hydrocarbon refrigerants-based ethylene BOG re-liquefaction system
Beladjine, Boumedienne M.; Ouadha, Ahmed; Addad, Yacine
2016-09-01
The present study aims to make a thermodynamic analysis of an ethylene cascade re-liquefaction system that consists of the following two subsystems: a liquefaction cycle using ethylene as the working fluid and a refrigeration cycle operating with a hydrocarbon refrigerant. The hydrocarbon refrigerants considered are propane (R290), butane (R600), isobutane (R600a), and propylene (R1270). A computer program written in FORTRAN is developed to compute parameters for characteristic points of the cycles and the system's performance, which is determined and analyzed using numerical solutions for the refrigerant condensation temperature, temperature in tank, and temperature difference in the cascade condenser. Results show that R600a gives the best performance, followed by (in order) R600, R290, and R1270. Furthermore, it is found that an increase in tank temperature improves system performance but that an increase in refrigerant condensation temperature causes deterioration. In addition, it is found that running the system at a low temperature difference in the cascade condenser is advantageous.
Thermodynamics of solvent extraction on (C8H17)3N-C6H5CH3-UO2Cl2-HCl system
International Nuclear Information System (INIS)
Yigui Li; Jiufang Lu; Xunan Zhou; Teng Teng
1988-01-01
Solvent extraction thermodynamics in the system n-trioctylamine-toluene-UO 2 CL 2 -HCl-water was considered. Pitzer equation and improved Frank-Thompson equation were used to calculate coefficients of electrolyte activity in aqueous phase. Activity coefficients of all components in organic phase were measured or calculated. Thermodynamic equilibrium constants of studied system were obtained
Hovsapian, Zohrob O.
This dissertation presents a contribution to understanding the behavior of solar powered air conditioning and refrigeration systems with a view to determining the manner in which refrigeration rate; mass flows, heat transfer areas, and internal architecture are related. A cogeneration system consisting of a solar concentrator, a cavity-type receiver, a gas burner, and a thermal storage reservoir is devised to simultaneously produce water heating/purification and cooling (absorption refrigerator system). A simplified mathematical model, which combines fundamental and empirical correlations, and principles of classical thermodynamics, mass and heat transfer, is developed. An experimental setup was built to adjust and validate the numerical results obtained with the mathematical model. The proposed model is then utilized to simulate numerically the system transient and steady state response under different operating and design conditions. A system global optimization for maximum performance (or minimum exergy destruction) in the search for minimum pull-down and pull-up times, and maximum system second law efficiency is performed with low computational time. Appropriate dimensionless groups are identified and the results presented in normalized charts for general application. The numerical results show that the three way maximized system second law efficiency, etaII,max,max,max, occurs when three system characteristic mass flow rates are optimally selected in general terms as dimensionless heat capacity rates, i.e., (Psisps , Psiwxwx, PsiHs)opt ≅ (1.43, 0.17, 0.19). The minimum pull-down and pull-up times, and maximum second law efficiencies found with respect to the optimized operating parameters are sharp and, therefore important to be considered in actual design. As a result, the model is expected to be a useful tool for simulation, design, and optimization of solar energy systems in the context of distributed power generation.
Thermodynamic Vent System for an On-Orbit Cryogenic Reaction Control Engine
Hurlbert, Eric A.; Romig, Kris A.; Jimenez, Rafael; Flores, Sam
2012-01-01
A report discusses a cryogenic reaction control system (RCS) that integrates a Joule-Thompson (JT) device (expansion valve) and thermodynamic vent system (TVS) with a cryogenic distribution system to allow fine control of the propellant quality (subcooled liquid) during operation of the device. It enables zero-venting when coupled with an RCS engine. The proper attachment locations and sizing of the orifice are required with the propellant distribution line to facilitate line conditioning. During operations, system instrumentation was strategically installed along the distribution/TVS line assembly, and temperature control bands were identified. A sub-scale run tank, full-scale distribution line, open-loop TVS, and a combination of procured and custom-fabricated cryogenic components were used in the cryogenic RCS build-up. Simulated on-orbit activation and thruster firing profiles were performed to quantify system heat gain and evaluate the TVS s capability to maintain the required propellant conditions at the inlet to the engine valves. Test data determined that a small control valve, such as a piezoelectric, is optimal to provide continuously the required thermal control. The data obtained from testing has also assisted with the development of fluid and thermal models of an RCS to refine integrated cryogenic propulsion system designs. This system allows a liquid oxygenbased main propulsion and reaction control system for a spacecraft, which improves performance, safety, and cost over conventional hypergolic systems due to higher performance, use of nontoxic propellants, potential for integration with life support and power subsystems, and compatibility with in-situ produced propellants.
International Nuclear Information System (INIS)
Liu, Jin-Long; Wang, Jian-Hua
2015-01-01
Based on CAES (compressed air energy storage) and PM (pneumatic motor), a novel tri-generation system (heat energy, mechanical energy and cooling power) is proposed in this paper. Both the cheap electricity generated at night and the excess power from undelivered renewable energy due to instability, can be stored as compressed air and hot water by the proposed system. When energy is in great demand, the compressed air stored in this system is released to drive PM to generate mechanical power. The discharged air from PM can be further utilized as valuable cooling power. Compared to conventional CAES systems, the biggest characteristic of the proposed system is that the discharged air usually abandoned is used as cooling power. In order to study the performances of this system, a thermodynamic analysis and an experimental investigation are carried out. The thermodynamic model is validated by the experimental data. Using the validated thermodynamic model, the mechanical energy output, cooling capacity and temperature of discharged air, as well as the efficiency of the system are analyzed. The theoretical analysis indicates that the additional application of discharged air can improve total energy efficiency by 20–30%. Therefore, this system is very worthy of consideration and being popularized. - Highlights: • The proposed system can provide mechanical energy, heat energy and cooling power. • The exhaust air of pneumatic motor is used as cooling power instead of abandoned. • A thermodynamic model of the proposed system is constructed and validated. • The effects of several parameters on system performance are examined. • The proposed system can improve total energy efficiency of CAES system by 20–30%.
Thermodynamic model of a thermal storage air conditioning system with dynamic behavior
Energy Technology Data Exchange (ETDEWEB)
Fleming, E; Wen, SY; Shi, L; da Silva, AK
2013-12-01
A thermodynamic model was developed to predict transient behavior of a thermal storage system, using phase change materials (PCMs), for a novel electric vehicle climate conditioning application. The main objectives of the paper are to consider the system's dynamic behavior, such as a dynamic air flow rate into the vehicle's cabin, and to characterize the transient heat transfer process between the thermal storage unit and the vehicle's cabin, while still maintaining accurate solution to the complex phase change heat transfer. The system studied consists of a heat transfer fluid circulating between either of the on-board hot and cold thermal storage units, which we refer to as thermal batteries, and a liquid-air heat exchanger that provides heat exchange with the incoming air to the vehicle cabin. Each thermal battery is a shell-and-tube configuration where a heat transfer fluid flows through parallel tubes, which are surrounded by PCM within a larger shell. The system model incorporates computationally inexpensive semianalytic solution to the conjugated laminar forced convection and phase change problem within the battery and accounts for airside heat exchange using the Number of Transfer Units (NTUs) method for the liquid-air heat exchanger. Using this approach, we are able to obtain an accurate solution to the complex heat transfer problem within the battery while also incorporating the impact of the airside heat transfer on the overall system performance. The implemented model was benchmarked against a numerical study for a melting process and against full system experimental data for solidification using paraffin wax as the PCM. Through modeling, we demonstrate the importance of capturing the airside heat exchange impact on system performance, and we investigate system response to dynamic operating conditions, e.g., air recirculation. (C) 2013 Elsevier Ltd. All rights reserved.
International Nuclear Information System (INIS)
Singh, Jayram; Singh, N.B.
2015-01-01
Graphical abstract: The phase diagram of (m-dinitrobenzene + vanillin) system. - Highlights: • (Thaw + melt) method has shown that (m-dinitrobenzene + vanillin) system forms simple eutectic type phase diagram. • Excess thermodynamic functions showed that eutectic mixture is non-ideal. • The flexural strength measurements have shown that in eutectic mixture, crystallization occurs in an ordered way. - Abstract: The phase diagram of (m-dinitrobenzene + vanillin) system has been studied by the thaw melt method and an eutectic type phase diagram was obtained. The linear velocities of crystallization of the parent components and the eutectic mixture were determined. The enthalpy of fusion of the components and the eutectic mixture were determined using the differential scanning calorimetric technique. Excess Gibbs energy, excess entropy, excess enthalpy of mixing, and interfacial energy have been calculated. FTIR spectroscopic studies and flexural strength measurements were also made. The results have shown that the eutectic is a non-ideal mixture of the two components. On the basis of Jackson’s roughness parameter, it is predicted that the eutectic has faceted morphology
Assessment of physical activity of the human body considering the thermodynamic system.
Hochstein, Stefan; Rauschenberger, Philipp; Weigand, Bernhard; Siebert, Tobias; Schmitt, Syn; Schlicht, Wolfgang; Převorovská, Světlana; Maršík, František
2016-01-01
Correctly dosed physical activity is the basis of a vital and healthy life, but the measurement of physical activity is certainly rather empirical resulting in limited individual and custom activity recommendations. Certainly, very accurate three-dimensional models of the cardiovascular system exist, however, requiring the numeric solution of the Navier-Stokes equations of the flow in blood vessels. These models are suitable for the research of cardiac diseases, but computationally very expensive. Direct measurements are expensive and often not applicable outside laboratories. This paper offers a new approach to assess physical activity using thermodynamical systems and its leading quantity of entropy production which is a compromise between computation time and precise prediction of pressure, volume, and flow variables in blood vessels. Based on a simplified (one-dimensional) model of the cardiovascular system of the human body, we develop and evaluate a setup calculating entropy production of the heart to determine the intensity of human physical activity in a more precise way than previous parameters, e.g. frequently used energy considerations. The knowledge resulting from the precise real-time physical activity provides the basis for an intelligent human-technology interaction allowing to steadily adjust the degree of physical activity according to the actual individual performance level and thus to improve training and activity recommendations.
Thermodynamic Modeling of Ag-Ni System Combining Experiments and Molecular Dynamic Simulation
Rajkumar, V. B.; Chen, Sinn-wen
2017-04-01
Ag-Ni is a simple and important system with immiscible liquids and (Ag,Ni) phases. Previously, this system has been thermodynamically modeled utilizing certain thermochemical and phase equilibria information based on conjecture. An attempt is made in this study to determine the missing information which are difficult to measure experimentally. The boundaries of the liquid miscibility gap at high temperatures are determined using a pyrometer. The temperature of the liquid ⇌ (Ag) + (Ni) eutectic reaction is measured using differential thermal analysis. Tie-lines of the Ag-Ni system at 1023 K and 1473 K are measured using a conventional metallurgical method. The enthalpy of mixing of the liquid at 1773 K and the (Ag,Ni) at 973 K is calculated by molecular dynamics simulation using a large-scale atomic/molecular massively parallel simulator. These results along with literature information are used to model the Gibbs energy of the liquid and (Ag,Ni) by a calculation of phase diagrams approach, and the Ag-Ni phase diagram is then calculated.
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...
International Nuclear Information System (INIS)
Yılmaz, İbrahim Halil; Saka, Kenan; Kaynakli, Omer
2016-01-01
One of the parameters affecting the COP of the absorption system can be considered as the thermal balance between the high pressure condenser (HPC) and the low pressure generator (LPG) since heat rejected from the HPC is utilized as an energy source by the LPG. Condensation of the water vapor in the HPC depends on the heat removal via the LPG. This circumstance is significant for making an appropriate design and a controllable system with high performance in practical applications. For this reason, a thermodynamic analysis for the HPC of a double effect series flow water/lithium bromide absorption refrigeration system was emphasized in this study. A simulation was developed to investigate the energy transfer between the HPC and LPG. The results show that the proper designation of the HPC temperature improves the COP and ECOP due its significant impact, and its value necessarily has to be higher than the outlet temperature of the LPG based on the operating scheme. Furthermore, the COP and ECOP of the absorption system can be raised in the range of 9.72–35.09% in case of 2 °C-temperature increment in the HPC under the described conditions to be applied. - Highlights: • Thermal balance in HPC/LPG unit of a double effect absorption system was studied. • A simulation program was developed and its outputs were validated. • A parametric study was conducted for a wide range of component temperatures. • Proper designation of the HPC temperature improves the COP and ECOP. • The system performance raised 9.72–35.09% by controlling the HPC temperature.
International Nuclear Information System (INIS)
Tan, Mehmet; Keçebaş, Ali
2014-01-01
Highlights: • Evaluation of a GDHS using advanced exergy-based methods. • Comparison of the results of the conventional and advanced exergy-based methods. • The modified exergetic efficiency and exergoeconomic factor are found as 45% and 13%. • Improvement and total cost-savings potentials are found to be 3% and 14%. • All the pumps have the highest improvement potential and total cost-savings potential. - Abstract: In this paper, a geothermal district heating system (GDHS) is comparatively evaluated in terms of thermodynamic and economic aspects using advanced exergy-based methods to identify the potential for improvement, the interactions among system components, and the direction and potential for energy savings. The actual operational data are taken from the Sarayköy GDHS, Turkey. In the advanced exergetic and exergoeconomic analyses, the exergy destruction and the total operating cost within each component of the system are split into endogenous/exogenous and unavoidable/avoidable parts. The advantages of these analyses over conventional ones are demonstrated. The results indicate that the advanced exergy-based method is a more meaningful and effective tool than the conventional one for system performance evaluation. The exergetic efficiency and the exergoeconomic factor of the overall system for the Sarayköy GDHS were determined to be 43.72% and 5.25% according to the conventional tools and 45.06% and 12.98% according to the advanced tools. The improvement potential and the total cost-savings potential of the overall system were also determined to be 2.98% and 14.05%, respectively. All of the pumps have the highest improvement potential and total cost-savings potential because the pumps were selected to have high power during installation at the Sarayköy GDHS
Directory of Open Access Journals (Sweden)
Ruberlan Gomes da Silva
2017-01-01
Full Text Available Chemical fertilizers, such as potassium chloride, ammonium nitrate and other chemical products like sodium hydroxide and soda ash are produced from electrolyte solutions or brines with a high content of soluble salts. Some of these products are manufactured by fractional crystallization, when several salts are separated as solid phases with high purity (>90%. Due to the large global demand for potassium fertilizers, a good knowledge about the compositions of salts and brines is helpful to design an effective process. A thermodynamic model based on Pitzer and Harvie's model was used to predict the composition of crystallized salts after water removal by forced evaporation and cooling from multicomponent solutions or brines. Initially, the salts’ solubilities in binary systems (NaCl–H2O, KCl–H2O and MgCl2–H2O and ternary system (KCl–MgCl2–H2O were calculated at 20 °C and compared with literature data. Next, the model was compared to our experimental data on the quinary system NaCl–KCl–MgCl2–CaCl2–H2O system at 20 °C. The Pitzer and Harvie's model represented well both the binary and ternary systems. Besides, for the quinary system the fit was good for brine densities up to 1350 kg/m3. The models were used to estimate the chemical composition of the solutions and salts produced by fractional crystallization and in association with material balance to respond to issues related to the production rates in a solar pond containing several salts dissolved, for instance, NaCl, KCl, MgCl2 and CaCl2.
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
International Nuclear Information System (INIS)
Araoz, Joseph A.; Salomon, Marianne; Alejo, Lucio; Fransson, Torsten H.
2014-01-01
expansion and compression work; the pressure drop and heat flow through the heat exchangers; the conductive, shuttle effect and regenerator thermal losses; the temperature and mass flow distribution along the system; and the power output and efficiency of the engine. These results show that the model allows an extensive study of different parameters of the engine and thus it is suitable for design optimization studies. In addition, it also presents the capability for the integration into overall Stirling engine combined heat and power systems and therefore will allow the performance evaluation of the engine integrated on these systems. - Highlights: • A numerical thermodynamic model for Stirling engine systems was developed. • Thermodynamic equations were coupled with the heat transfer governing equations. • The model was validated with experimental and numerical data. • The brake power and engine efficiency at different conditions were calculated. • Additional model results provide a deeper insight into the engine operation
Thermodynamics Properties of Binary Gas Mixtures for Brayton Space Nuclear Power System
International Nuclear Information System (INIS)
You Ersheng; Shi Lei; Zhang Zuoyi
2014-01-01
Space nuclear power system with closed Brayton cycle has the potential advantages of high cycle efficiency. It can be achieved to limit the specific mass of the system with a competitive design scheme, so as to strengthen the advantage of the nuclear energy applying in space propulsion and electric generating compared to solar or chemical propellant. Whereby, the thermodynamic properties of working fluids have a significant influence on the performance of the plant. Therefore, two binary mixtures helium-nitrogen and helium-carbon dioxide are introduced to analysis the variation in the transport and heat transfer capacity of working fluids. Based on the parameters of pure gases, the heat transfer coefficient, pressure losses and aerodynamic loading are calculated as a function of mole fraction at the temperature of 400 K and 1200 K, as well as the typical operating pressure of 2 MPa. Results indicated that the mixture of helium-carbon dioxide with a mole fraction of 0.4 is a more attractive choice for the high heat transfer coefficient, low aerodynamic loading and acceptable pressure losses in contrast to helium-nitrogen and other mixing ratios of helium-carbon dioxide. Its heat transfer coefficient is almost 20% more than that of pure helium and the normalized aerodynamic loading is less than 34% at 1200 K. However; the pressure losses are a little higher with ~3.5 times those of pure helium. (author)
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 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.
International Nuclear Information System (INIS)
Liu, Qibin; Bai, Zhang; Sun, Jie; Yan, Yuejun; Gao, Zhichao; Jin, Hongguang
2016-01-01
Highlights: • A new concentrating solar power system with a dual-solar field is proposed. • The superheated steam with more than 773 K is produced. • The performances of the proposed system are demonstrated. • The economic feasibility of the proposed system is validated. - Abstract: In this paper, a new parabolic trough solar power system that incorporates a dual-solar field with oil and molten salt as heat transfer fluids (HTFs) is proposed to effectively utilize the solar energy. The oil is chosen as a HTF in the low temperature solar field to heat the feeding water, and the high temperature solar field uses molten salt to superheat the steam that the temperature is higher than 773 K. The produced superheated steam enters a steam turbine to generate power. Energy analysis and exergy analysis of the system are implemented to evaluate the feasibility of the proposed system. Under considerations of variations of solar irradiation, the on-design and off-design thermodynamic performances of the system and the characteristics are investigated. The annual average solar-to-electric efficiency and the nominal efficiency under the given condition for the proposed solar thermal power generation system reach to 15.86% and 22.80%, which are higher than the reference system with a single HTF. The exergy losses within the solar heat transfer process of the proposed system are reduced by 7.8% and 45.23% compared with the solar power thermal systems using oil and molten salt as HTFs, respectively. The integrated approach with oil and molten salt as HTFs can make full use of the different physical properties of the HTFs, and optimize the heat transfer process between the HTFs and the water/steam. The exergy loss in the water evaporation and superheated process are reduced, the system efficiency and the economic performance are improved. The research findings provide a new approach for the improvement of the performances of solar thermal power plants.
Thermodynamic analysis and optimization of a Stirling cycle for lunar surface nuclear power system
International Nuclear Information System (INIS)
Fan, Senqing; Li, Minghai; Li, Sizhong; Zhou, Tong; Hu, Yupeng; Wu, Song
2017-01-01
Highlights: • Lunar surface nuclear power system with Stirling cycle for energy conversion. • A model with finite time thermodynamics to describe the system thermal efficiency. • Higher hot side temperature not exceeds 1050 K increased thermal efficiency. • Higher cold side temperature decreased thermal efficiency but improved heat rejection. • Higher convection heat transfer coefficient improved the thermal efficiency. - Abstract: A model for the description of the thermal efficiency of a lunar surface nuclear reactor power system with eight free piston Stirling engines to generate nominal electrical power of 100 kWe was developed. The heat loss of the hot heat pipes, finite rate heat transfer, regenerative heat loss, finite regeneration process time and conductive thermal bridging losses were considered. The results showed that the thermal efficiency increased and then decreased with the hot side temperature increase. The highest thermal efficiency was about 0.29 under the condition of the effectiveness of the regenerator being 0.9 and compression ratio being 2. Higher cold side temperature had bad effect on the thermal efficiency but could reduce the size of the heat rejection system. When the cold side temperature was designed as 500 K, the lowest power system mass of 6.6 ton could be obtained. Enhanced heat transfer of the heat exchangers would increase the thermal efficiency but higher values of the nominal convection heat transfer coefficient of the heat exchangers would lead to a negligible thermal efficiency increase. The results obtained here may provide a new ideal to design lunar surface nuclear powered Stirling cycle.
Advanced thermodynamics engineering
Annamalai, Kalyan; Jog, Milind A
2011-01-01
Thermolab Excel-Based Software for Thermodynamic Properties and Flame Temperatures of Fuels IntroductionImportance, Significance and LimitationsReview of ThermodynamicsMathematical BackgroundOverview of Microscopic/NanothermodynamicsSummaryAppendix: Stokes and Gauss Theorems First Law of ThermodynamicsZeroth LawFirst Law for a Closed SystemQuasi Equilibrium (QE) and Nonquasi-equilibrium (NQE) ProcessesEnthalpy and First LawAdiabatic Reversible Process for Ideal Gas with Constant Specific HeatsFirst Law for an Open SystemApplications of First Law for an Open SystemIntegral and Differential Form
Abnormal grain growth: a non-equilibrium thermodynamic model for multi-grain binary systems
Czech Academy of Sciences Publication Activity Database
Svoboda, Jiří; Fischer, F. D.
2014-01-01
Roč. 22, č. 1 (2014), Art. No. 015013 ISSN 0965-0393 Institutional support: RVO:68081723 Keywords : grain boundary segregation * abnormal grain growth * theory * modelling * solute drag Subject RIV: BJ - Thermodynamics Impact factor: 2.167, year: 2014
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
Thermodynamics and quantum correlations
Perarnau Llobet, Martí
2016-01-01
Thermodynamics traditionally deals with macroscopic systems at thermal equilibrium. However, since the very beginning of the theory, its range of applicability has only increased, nowadays being applied to virtually every field of science, and to systems of extremely different size. This thesis is devoted to the study of thermodynamics in the quantum regime. It contains original results on topics that include: Work extraction from quantum systems, fluctuations of work, the energetic valu...
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...
Wang, Wei; Yang, Lili; Wang, Nan; Zhang, Haifeng; Jia, Yanping
2018-01-01
The β-Sb3Zn4 intermetallic compound, one of the most promising thermoelectric materials in the mid-1990s, has attracted much interest due to its high thermoelectric performance in the intermediate temperature range. To improve the thermoelectric properties of the compound β-Sb3Zn4, Al doping is an effective method. Therefore, accurate theoretical analysis of the Al-Sb-Zn system is essential for the design of such thermoelectric materials. In this work, the Al-Sb-Zn system was reassessed by means of the calculation of phase diagram (CALPHAD) technique. A set of self-consistent thermodynamic parameters was obtained and can be used to extrapolate to related high-order systems. Some phase equilibria and thermochemical properties can be predicted using the present thermodynamic description.
High-temperature phase relations and thermodynamics in the iron-lead-sulfur system
Eric, R. Hurman; Ozok, Hakan
1994-01-01
The PbS activities in FeS-PbS liquid mattes were obtained at 1100 °C and 1200 °C by the dew-point method. Negative deviations were observed, and the liquid-matte solutions were modeled by the Krupkowski formalism. The liquid boundaries of the FeS-PbS phase diagram were derived from the model equations yielding a eutectic temperature of 842 °C at X Pbs = 0.46. A phase diagram of the pseudobinary FeS-PbS was also verified experimentally by quenching samples equilibrated in evacuated and sealed silica capsules. No terminal solid solution ranges could be found. Within the Fe-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were established at 1200 °C. Activities of Pb were measured by the dew-point technique along the metal-rich boundary of the miscibility gap. Activities of Fe, Pb, and S, along the miscibility gap were also calculated by utilizing the bounding binary thermodynamics, phase equilibria, and tie-lines.
Energy Technology Data Exchange (ETDEWEB)
Venson, Giuliano Gardolinski [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Engenharia Mecanica], e-mail: venson@ufmg.br; Barros, Jose Eduardo Mautone; Pereira, Josemar Figueiredo [Centro Federal de Educacao Tecnologica de Minas Gerais (CEFET-MG), Belo Horizonte, MG (Brazil)], e-mail: mautone@des.cefetmg.br, e-mail: josemar_cefet@yahoo.com.br
2006-07-01
This work presents the modeling of a gas microturbine power generator. The microturbine consists in a small thermo-electrical power unit, design for combined heat and power generation. The unit has an electric generator, coaxially connected with a turbocharger, which one is driven by a fuel burner. The system also incorporates an air regenerator, used for pre-heat the combustion air, and a heat exchanger, used for water heating. The objective of the modeling is the attainment of the electrical performance and the operational limits for the microturbine in function of the subsystems operational conditions. The modeling is based on the first law of the thermodynamic, using specific models for each component. In the combustion chamber is used a model that takes the fuel injection properties, as absolute pressure and temperature. A semi-empirical model, based in the modified Euler equation, is used in the turbocharger. In the air regenerator and heat exchanger, the method of mean logarithmic temperature difference is used. Through the modeling of a commercial microturbine, reference values obtained were used in some subsystems of a new microturbine. The results for this new microturbine in development, based in automotive turbochargers, indicate a nominal electrical power of 38 kW with electrical efficiency of 33% and global efficiency of 73%. (author)
Thermodynamics of Micro- and Nano-Systems Driven by Periodic Temperature Variations
Directory of Open Access Journals (Sweden)
Kay Brandner
2015-08-01
Full Text Available We introduce a general framework for analyzing the thermodynamics of small systems that are driven by both a periodic temperature variation and some external parameter modulating their energy. This setup covers, in particular, periodic micro- and nano-heat engines. In a first step, we show how to express total entropy production by properly identified time-independent affinities and currents without making a linear response assumption. In linear response, kinetic coefficients akin to Onsager coefficients can be identified. Specializing to a Fokker-Planck-type dynamics, we show that these coefficients can be expressed as a sum of an adiabatic contribution and one reminiscent of a Green-Kubo expression that contains deviations from adiabaticity. Furthermore, we show that the generalized kinetic coefficients fulfill an Onsager-Casimir-type symmetry tracing back to microscopic reversibility. This symmetry allows for nonidentical off-diagonal coefficients if the driving protocols are not symmetric under time reversal. We then derive a novel constraint on the kinetic coefficients that is sharper than the second law and provides an efficiency-dependent bound on power. As one consequence, we can prove that the power vanishes at least linearly when approaching Carnot efficiency. We illustrate our general framework by explicitly working out the paradigmatic case of a Brownian heat engine realized by a colloidal particle in a time-dependent harmonic trap subject to a periodic temperature profile. This case study reveals inter alia that our new general bound on power is asymptotically tight.
Thermodynamic model of a thermal storage air conditioning system with dynamic behavior
International Nuclear Information System (INIS)
Fleming, Evan; Wen, Shaoyi; Shi, Li; Silva, Alexandre K. da
2013-01-01
Highlights: • We developed an automotive thermal storage air conditioning system model. • The thermal storage unit utilizes phase change materials. • We use semi-analytic solution to the coupled phase change and forced convection. • We model the airside heat exchange using the NTU method. • The system model can incorporate dynamic inputs, e.g. variable inlet airflow. - Abstract: A thermodynamic model was developed to predict transient behavior of a thermal storage system, using phase change materials (PCMs), for a novel electric vehicle climate conditioning application. The main objectives of the paper are to consider the system’s dynamic behavior, such as a dynamic air flow rate into the vehicle’s cabin, and to characterize the transient heat transfer process between the thermal storage unit and the vehicle’s cabin, while still maintaining accurate solution to the complex phase change heat transfer. The system studied consists of a heat transfer fluid circulating between either of the on-board hot and cold thermal storage units, which we refer to as thermal batteries, and a liquid–air heat exchanger that provides heat exchange with the incoming air to the vehicle cabin. Each thermal battery is a shell-and-tube configuration where a heat transfer fluid flows through parallel tubes, which are surrounded by PCM within a larger shell. The system model incorporates computationally inexpensive semi-analytic solution to the conjugated laminar forced convection and phase change problem within the battery and accounts for airside heat exchange using the Number of Transfer Units (NTUs) method for the liquid–air heat exchanger. Using this approach, we are able to obtain an accurate solution to the complex heat transfer problem within the battery while also incorporating the impact of the airside heat transfer on the overall system performance. The implemented model was benchmarked against a numerical study for a melting process and against full system
Thermodynamics an engineering approach
Cengel, Yunus A
2014-01-01
Thermodynamics, An Engineering Approach, eighth edition, covers the basic principles of thermodynamics while presenting a wealth of real-world engineering examples so students get a feel for how thermodynamics is applied in engineering practice. This text helps students develop an intuitive understanding by emphasizing the physics and physical arguments. Cengel and Boles explore the various facets of thermodynamics through careful explanations of concepts and use of numerous practical examples and figures, having students develop necessary skills to bridge the gap between knowledge and the confidence to properly apply their knowledge. McGraw-Hill is proud to offer Connect with the eighth edition of Cengel/Boles, Thermodynamics, An Engineering Approach. This innovative and powerful new system helps your students learn more efficiently and gives you the ability to assign homework problems simply and easily. Problems are graded automatically, and the results are recorded immediately. Track individual stude...
DEFF Research Database (Denmark)
Westerhoff, Hans V.; Jensen, Peter Ruhdal; Snoep, Jacky L.
1998-01-01
Thermodynamics has always been a remarkable science in that it studies macroscopic properties that are only partially determined by the properties of individual molecules. Entropy and free energy only exist in constellations of more than a single molecule (degree of freedom). They are the so...... 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...... by taking into account both the molecular properties and the emergent properties that are due to (dys)organisation. This redefinition will free nonequilibrium thermodynamics from the limitations imposed by earlier near-equilibrium assumptions, resolve the duality with kinetics, and bridge the apparent gap...
Ozturk, Koray
The thermodynamic database for the Mg-Al-Ca-Sr quaternary system was constructed by combining the thermodynamic descriptions of the constituent binary systems. There are six binaries in the quaternary system: Al-Ca, Al-Mg, Al-Sr, Ca-Sr, Ca-Mg and Mg-Sr. Only two of them had been absent from the databases: Al-Ca and Ca-Sr. Therefore, they were investigated in detail to develop their thermodynamic descriptions. They were evaluated using Thermo-Calc, the software developed at The Royal Institute of Technology, Sweden. It is based on the CALPHAD approach. The modeling in CALPHAD approach relies on the Gibbs energy of individual phases. Therefore, the Gibbs energy functions for each phase in the binaries were defined in the binary databases. The Ca-Sr system was modeled by using random solution model. In modeling of the Al-Ca system, both random solution and associate models were applied to liquid phase. It was also demonstrated for the Al-Ca that the first-principles calculations provide reliable enthalpies of formation for stoichiometric compounds. The constructed quaternary database were used to calculate the liquidus projections of the ternary Mg-Al-Ca, Mg-Al-Sr, Mg-Ca-Sr and Al-Ca-Sr systems. Their primary crystallization fields and invariant reaction points were determined. Two Mg-based Mg-Al-Ca alloys were studied experimentally. The equilibrium phases in the alloys were determined after heat treatment. The present experimental results as well as the literature data were compared with the present thermodynamic calculations. The database was also utilized to understand the microstructures and phase relationships of the two quaternary alloys. Scheil simulations and equilibrium calculations were performed for the solidification process and compared with experimental observations.
Thermodynamic analysis of an in-cylinder waste heat recovery system for internal combustion engines
International Nuclear Information System (INIS)
Zhu, Sipeng; Deng, Kangyao; Qu, Shuan
2014-01-01
In this paper, an in-cylinder waste heat recovery system especially for turbocharged engines is proposed to improve the thermal efficiencies of internal combustion engines. Simplified recovery processes can be described as follows: superheated steam generated by engine waste heat is injected into the pipe before the turbine to increase the boost pressure of the fresh air; intake valve close timing is adjusted to control the amount of fresh air as the original level, and thus the higher pressure charged air expands in the intake stroke and transfers the pressure energy directly to the crankshaft. In this way, the increased turbine output by the pre-turbine steam injection is finally recovered in the cylinder, which is different from the traditional Rankine cycle. The whole energy transfer processes are studied with thermodynamic analyses and numerical simulations. The results show that the mass flow rate of the injected steam has the biggest influence on the energy transfer processes followed by the temperature of the injected steam. With this in-cylinder waste heat recovery system, the fuel economy of a selected turbocharged diesel engine can be improved by 3.2% at the rated operating point when the injected mass flow ratio is set to be 0.1. - Highlights: • An in-cylinder waste heat recovery system is proposed. • Effects of injected parameters are studied with energy and exergy balance theories. • Variations of operating points on the compressor map are studied in detail. • The fuel economy is improved by 3.2% at the rated operating point
Directory of Open Access Journals (Sweden)
Osman Özkaraca
2017-10-01
Full Text Available Geothermal energy is a renewable form of energy, however due to misuse, processing and management issues, it is necessary to use the resource more efficiently. To increase energy efficiency, energy systems engineers carry out careful energy control studies and offer alternative solutions. With this aim, this study was conducted to improve the performance of a real operating air-cooled organic Rankine cycle binary geothermal power plant (GPP and its components in the aspects of thermodynamic modeling, exergy analysis and optimization processes. In-depth information is obtained about the exergy (maximum work a system can make, exergy losses and destruction at the power plant and its components. Thus the performance of the power plant may be predicted with reasonable accuracy and better understanding is gained for the physical process to be used in improving the performance of the power plant. The results of the exergy analysis show that total exergy production rate and exergy efficiency of the GPP are 21 MW and 14.52%, respectively, after removing parasitic loads. The highest amount of exergy destruction occurs, respectively, in condenser 2, vaporizer HH2, condenser 1, pumps 1 and 2 as components requiring priority performance improvement. To maximize the system exergy efficiency, the artificial bee colony (ABC is applied to the model that simulates the actual GPP. Under all the optimization conditions, the maximum exergy efficiency for the GPP and its components is obtained. Two of these conditions such as Case 4 related to the turbine and Case 12 related to the condenser have the best performance. As a result, the ABC optimization method provides better quality information than exergy analysis. Based on the guidance of this study, the performance of power plants based on geothermal energy and other energy resources may be improved.
de Oliveira, Mário J
2017-01-01
This textbook provides an exposition of equilibrium thermodynamics and its applications to several areas of physics with particular attention to phase transitions and critical phenomena. The applications include several areas of condensed matter physics and include also a chapter on thermochemistry. Phase transitions and critical phenomena are treated according to the modern development of the field, based on the ideas of universality and on the Widom scaling theory. For each topic, a mean-field or Landau theory is presented to describe qualitatively the phase transitions. These theories include the van der Waals theory of the liquid-vapor transition, the Hildebrand-Heitler theory of regular mixtures, the Griffiths-Landau theory for multicritical points in multicomponent systems, the Bragg-Williams theory of order-disorder in alloys, the Weiss theory of ferromagnetism, the Néel theory of antiferromagnetism, the Devonshire theory for ferroelectrics and Landau-de Gennes theory of liquid crystals. This new edit...
Daily, Kevin Michael
gases with infinitely large interspecies scattering length, a theoretical framework that describes N-body resonances is developed. The microscopic energy spectra of the trapped two- and three-body systems with unequal masses is used to calculate the second- and third-order virial coefficients. The resulting virial equation of state is used to make the first predictions for the thermodynamic behavior of the normal phase strongly-interacting mass-imbalanced two-component Fermi gases. First predictions for the virial equation of state of bosonic and fermionic dipolar gases with equal masses are presented.
International Nuclear Information System (INIS)
She, Xiaohui; Yin, Yonggao; Zhang, Xiaosong
2014-01-01
Highlights: • An energy-efficient refrigeration system with a novel subcooling method is proposed. • Thermodynamic analysis is conducted to discuss the effects of operation parameters. • Two different utilization ways of condensation heat are compared. • The system achieves much higher COP, even higher than reverse Carnot cycle. • Suggested mass concentration for LiCl–H 2 O is around 32% at a typical case. - Abstract: A new energy-efficient refrigeration system subcooled by liquid desiccant dehumidification and evaporation was proposed in this paper. In the system, liquid desiccant system could produce very dry air for an indirect evaporative cooler, which would subcool the vapor compression refrigeration system to get higher COP than conventional refrigeration system. The desiccant cooling system can use the condensation heat for the desiccant regeneration. Thermodynamic analysis is made to discuss the effects of operation parameters (condensing temperature, liquid desiccant concentration, ambient air temperature and relative humidity) on the system performance. Results show that the proposed hybrid vapor compression refrigeration system achieves significantly higher COP than conventional vapor compression refrigeration system, and even higher than the reverse Carnot cycle at the same operation conditions. The maximum COPs of the hybrid systems using hot air and ambient air are 18.8% and 16.3% higher than that of the conventional vapor compression refrigeration system under varied conditions, respectively
Energy Technology Data Exchange (ETDEWEB)
Fei, Yiyan; Landry, James P.; Zhu, X. D., E-mail: xdzhu@physics.ucdavis.edu [Department of Physics, University of California, One Shields Avenue, Davis, California 95616 (United States); Li, Yanhong; Yu, Hai; Lau, Kam; Huang, Shengshu; Chokhawala, Harshal A.; Chen, Xi [Department of Chemistry, University of California, One Shields Avenue, Davis, California 95616 (United States)
2013-11-15
A biological state is equilibrium of multiple concurrent biomolecular reactions. The relative importance of these reactions depends on physiological temperature typically between 10 °C and 50 °C. Experimentally the temperature dependence of binding reaction constants reveals thermodynamics and thus details of these biomolecular processes. We developed a variable-temperature opto-fluidic system for real-time measurement of multiple (400–10 000) biomolecular binding reactions on solid supports from 10 °C to 60 °C within ±0.1 °C. We illustrate the performance of this system with investigation of binding reactions of plant lectins (carbohydrate-binding proteins) with 24 synthetic glycans (i.e., carbohydrates). We found that the lectin-glycan reactions in general can be enthalpy-driven, entropy-driven, or both, and water molecules play critical roles in the thermodynamics of these reactions.
Thermodynamic study of sodium-iron oxides. Part 2. Ternary phase diagram of the Na-Fe-O system
International Nuclear Information System (INIS)
Huang, Jintao; Furukawa, Tomohiro; Aoto, Kazumi
2003-01-01
Studies on ternary phase diagrams of the Na-Fe-O system have been carried out from the thermodynamic point of view. Thermodynamic data of main ternary Na-Fe oxides Na 4 FeO 3 (s), Na 3 FeO 3 (s), Na 5 FeO 4 (s) and Na 8 Fe 2 O 7 (s) have been assessed. A user database has been created by reviewing literature data together with recent DSC and vapor pressure measurements by the present authors. New ternary phase diagrams of the Na-Fe-O system have been constructed from room temperature to 1000K. Stable conditions of the ternary oxides at 800K were presented in predominance diagram as functions of oxygen pressure and sodium pressure
International Nuclear Information System (INIS)
Hernandez, L.F.
1998-01-01
The technologies developed from 1973 on rational use, conservation and efficiency in the use of energy updated in a framework of sustain ability energetic and environment protection, it has not taken into account the concepts of quality of energy within of any energetic system (Source - Technology - Final Use), neither the favorable economic and technical implications of adopting the concepts of the Exergy and of exegetic efficiency, derivatives from the Second Law of the Thermodynamic, those which should be included as methods in the environmental and economic technical evaluations of an energetic system. This article presents the basic development of the concepts referenced from the Zero Law of the Thermodynamic, illustrating with examples the advantages to incorporate them as valuation and comparison parameters
Directory of Open Access Journals (Sweden)
David Sedmidubsky
2017-07-01
Full Text Available Nonstoichiometric oxides form a new chapter in tailored materials. Founding and construction of thermodynamic functions related to solid (geologic materials is traced showing interactions between Czech Professor F. Wald and Russians R.S. Kurnakov and D.S. Korzhinskiy in the early definition of phases and characterization of partly open systems. Development of thermodynamic concepts regarding solid-state description is reviewed. For the associated definition of a mobile component the hyperfree energy was invented and recently applied on several systems. A novel term plutability is put forward as a measure of material susceptibility towards free component uptake as a result of varying predictors such as temperature, pressure and activity. Ehrenfest-like equations involving the changes of plutabilities were derived.
Thermodynamic analysis and system design of a novel split cycle engine concept
International Nuclear Information System (INIS)
Dong, Guangyu; Morgan, Robert E.; Heikal, Morgan R.
2016-01-01
The split cycle engine is a new reciprocating internal combustion engine with a potential of a radical efficiency improvement. In this engine, the compression and combustion–expansion processes occur in different cylinders. In the compression cylinder, the charge air is compressed through a quasi-isothermal process by direct cooling of the air. The high pressure air is then heated in a recuperator using the waste heat of exhaust gas before induction to the combustion cylinder. The combustion process occurs during the expansion stroke, in a quasi-isobaric process. In this paper, a fundamental theoretical cycle analysis and one-dimensional engine simulation of the split cycle engine was undertaken. The results show that the thermal efficiency (η) is mainly decided by the CR (compression ratio) and ER (expansion ratio), the regeneration effectiveness (σ), and the temperature rising ratio (N). Based on the above analysis, a system optimization of the engine was conducted. The results showed that by increasing CR from 23 to 25, the combustion and recuperation processes could be improved. By increasing the expansion ratio to 26, the heat losses during the gas exchange stroke were further reduced. Furthermore, the coolant temperatures of the compression and expansion chambers can be controlled separately to reduce the wall heat transfer losses. Compared to a conventional engine, a 21% total efficiency improvement was achieved when the split cycle was applied. It was concluded that through the system optimization, a total thermal efficiency of 53% can be achieved on split cycle engine. - Highlights: • Fundamental mechanism of the split cycle engine is investigated. • The key affecting factors of the thermodynamic cycle efficiency are identified. • The practical efficiency of split cycle applying on diesel engine is analysed. • The design optimization on the split cycle engine concept is conducted.
Experimental and thermodynamic study of the Er-H-Zr ternary system
International Nuclear Information System (INIS)
Mascaro, A.
2012-01-01
This work at CEA is being achieved in the framework of the development of an innovating concept including the neutronic solid burnable poison, such as erbium, inside the cladding of pressurized water reactors. These new claddings are constituted by a liner of a zirconium base alloy slightly enriched in erbium between two liners of industrial zirconium alloys. Into the reactor core, the water dissociates at the surface of the cladding. So it is interesting to evaluate the interactions between the hydrogen released and the Zr-Er alloy. To do so, the Er-H-Zr ternary system has to be determined such similarly to its associated binaries. This can be done by experimental determination and by thermodynamic modelling. Both techniques were used in this work. Er-Zr and H-Zr have already been studied experimentally and modelled, but the Er-H binary system is almost unknown. So, we studied it experimentally. Then, it has been modelled using the Calphad method. We obtain a new evaluation of the Er-H binary system with phases limits rather different than what has been proposed in the literature. In order to determine the phase limits and, the potential existence of a ternary compound in the Er-H-Zr ternary system, an experimental study has been carried out. An original technique has been used to obtain the chemical compositions: ERDA combined with RBS. In this study, we propose a new isothermal section at 350 C of the Er-H-Zr ternary system. About the modelling, the compatibility of the three modelled binaries has been checked in order to optimize the ternary system by the projection of the three binaries. The calculation obtained is in good agreement with the experimental isothermal section at 350 C determined in our work. Finally, uniaxial tensile test campaigns have been conducted to evaluate the impact of erbium and/or hydrogen on the mechanical properties of an industrial zirconium pure alloy. We evidenced a hardening effect of erbium and hydrogen but these effects are not
Olander, Donald
2007-01-01
The book’s methodology is unified, concise, and multidisciplinary, allowing students to understand how the principles of thermodynamics apply to all technical fields that touch upon this most fundamental of scientific theories. It also offers a rigorous approach to the quantitative aspects of thermodynamics, accompanied by clear explanations to help students transition smoothly from the physical concepts to their mathematical representations
Thermodynamic estimation: Ionic materials
International Nuclear Information System (INIS)
Glasser, Leslie
2013-01-01
Thermodynamics establishes equilibrium relations among thermodynamic parameters (“properties”) and delineates the effects of variation of the thermodynamic functions (typically temperature and pressure) on those parameters. However, classical thermodynamics does not provide values for the necessary thermodynamic properties, which must be established by extra-thermodynamic means such as experiment, theoretical calculation, or empirical estimation. While many values may be found in the numerous collected tables in the literature, these are necessarily incomplete because either the experimental measurements have not been made or the materials may be hypothetical. The current paper presents a number of simple and relible estimation methods for thermodynamic properties, principally for ionic materials. The results may also be used as a check for obvious errors in published values. The estimation methods described are typically based on addition of properties of individual ions, or sums of properties of neutral ion groups (such as “double” salts, in the Simple Salt Approximation), or based upon correlations such as with formula unit volumes (Volume-Based Thermodynamics). - Graphical abstract: Thermodynamic properties of ionic materials may be readily estimated by summation of the properties of individual ions, by summation of the properties of ‘double salts’, and by correlation with formula volume. Such estimates may fill gaps in the literature, and may also be used as checks of published values. This simplicity arises from exploitation of the fact that repulsive energy terms are of short range and very similar across materials, while coulombic interactions provide a very large component of the attractive energy in ionic systems. Display Omitted - Highlights: • Estimation methods for thermodynamic properties of ionic materials are introduced. • Methods are based on summation of single ions, multiple salts, and correlations. • Heat capacity, entropy
International Nuclear Information System (INIS)
Mashadieva, Leyla F.; Aliev, Ziya S.; Shevelkov, Andrei V.; Babanly, Mahammad B.
2013-01-01
Highlights: ► The self-consistent phase diagram of the Ag–Bi–I system is constructed. ► Ag 2 BiI 5 and AgBi 2 I 7 are the only ternary phases of the system. ► Standard thermodynamic functions of formation and the standard entropies of Ag 2 BiI 5 and AgBi 2 I 7 are calculated. - Abstract: The phase equilibriums in the Ag–Bi–I ternary system and thermodynamic properties of the ternary phases were experimentally determined by using DTA and XRD techniques and EMF measurements with the Ag 4 RbI 5 solid electrolyte. According to the obtained experimental results, the polythermal sections of the ternary phase diagram, its isothermal section at 300 K as well as the projection of the liquids surface have been revised. The fields of the primary crystallization and types and coordinates of nonvariant and monovariant equilibriums were determined. The partial molar functions of silver iodide and silver in the alloys as well as the standard thermodynamic functions of formation and the standard entropies of Ag 2 BiI 5 and AgBi 2 I 7 were calculated based on EMF measurements.
Energy Technology Data Exchange (ETDEWEB)
Hernandez R, Aurelio; Romero S, Antonio; Gomez G, Herminia [Instituto Politecnico Nacional, Mexico, D.F. (Mexico)
1996-02-01
The objective of this paper is to explain the programs that are contained in a Thermodynamic Computer System. Students can use this Computer System to make complicated calculations that are required in Thermodynamic Analysis. One of this programs is used to obtain the expression of heat capacity of pure substances in terms of temperature, at constant pressure. A database of pure substances has been created which retrieves the thermodynamic properties (enthalpy, entropy and Gibbs free energy) in such a format that it is very easy to understand. The changes of state functions for chemical reactions can also be calculated. Another program is used to estimate the equilibrium conditions in multicomponent and multiphase systems. [Spanish] En el presente trabajo se muestran los programas de computo que conforman un Sistema de Analisis Termodinamico desarrollado con el fin de facilitar los calculos y la comprension de algunos principios de la Termodinamica. Este sistema permite obtener la funcionalidad de la capacidad calorifica con la temperatura de sustancias puras, a presion constante; obtener de manera rapida y concisa las propiedades termodinamicas (entalpia, entropia y energia libre de Gibbs) de elementos y compuestos puros almacenados en una base de datos; determinar los cambios en las funciones de estado de reacciones quimicas entre sustancias puras; determinar el equilibrio en sistemas multicomponentes y multifasicos. Se indican los alcances de este grupo de programas de computo asi como su aplicacion a procesos practicos.
International Nuclear Information System (INIS)
Mansson, B.A.
1990-01-01
Economics, as the social science most concerned with the use and distribution of natural resources, must start to make use of the knowledge at hand in the natural sciences about such resources. In this, thermodynamics is an essential part. In a physicists terminology, human economic activity may be described as a dissipative system which flourishes by transforming and exchanging resources, goods and services. All this involves complex networks of flows of energy and materials. This implies that thermodynamics, the physical theory of energy and materials flows, must have implications for economics. On another level, thermodynamics has been recognized as a physical theory of value, with value concepts similar to those of economic theory. This paper discusses some general aspects of the significance of non-equilibrium thermodynamics for economics. The role of exergy, probably the most important of the physical measures of value, is elucidated. Two examples of integration of thermodynamics with economic theory are reviewed. First, a simple model of a steady-state production system is sued to illustrate the effects of thermodynamic process constraints. Second, the framework of a simple macroeconomic growth model is used to illustrate how some thermodynamic limitations may be integrated in macroeconomic theory
Thermodynamic reassessment of the Al–Cr–Si system with the refined description of the Al–Cr system
DEFF Research Database (Denmark)
Hu, Biao; Zhang, Weiwei; Peng, Yingbiao
2013-01-01
Three alloys in the Al–Cr system were investigated by means of X-ray diffraction (XRD) in order to verify the existence of the reported new phase Al11Cr4. The XRD results showed no evidence for the existence of the so-called new phase Al11Cr4. Based on the critically reviewed experimental data av....... The present thermodynamic modeling can satisfactorily account for most of the reliable experimental data in this ternary system. © 2013 Elsevier B.V. All rights reserved.......Three alloys in the Al–Cr system were investigated by means of X-ray diffraction (XRD) in order to verify the existence of the reported new phase Al11Cr4. The XRD results showed no evidence for the existence of the so-called new phase Al11Cr4. Based on the critically reviewed experimental data...... available in the literature and the present experimental results, the Al–Cr system was re-optimized using the CALPHAD approach with sublattice models (Al,Cr)2(Al,Cr)3(Cr)2(Al)6 for γ-H (high temperature phase) and (Al)12(Cr)5(Al,Cr)9 for γ-L (low temperature phase) according to their respective crystal...
International Nuclear Information System (INIS)
Huicochea, Armando; Rivera, Wilfrido; Gutierrez-Urueta, Geydy; Bruno, Joan Carles; Coronas, Alberto
2011-01-01
Combining heating and power systems represent an option to improve the efficiency of energy usage and to reduce thermal pollution toward environment. Microturbines generate electrical power and usable residual heat which can be partially used to activate a thermally driven chiller. The purpose of this paper is to analyze theoretically the thermodynamic performance of a trigeneration system formed by a microturbine and a double-effect water/LiBr absorption chiller. The heat data supplied to the generator of the double effect air conditioning system was acquired from experimental data of a 28 kW E microturbine, obtained at CREVER facilities. A thermodynamic simulator was developed at Centro de Investigacion en Energia in the Universidad Nacional Autonoma de Mexico by using a MATLAB programming language. Mass and energy balances of the main components of the cooling system were obtained with water-lithium bromide solution as working fluid. The trigeneration system was evaluated at different operating conditions: ambient temperatures, generation temperatures and microturbine fuel mass flow rate. The results demonstrated that this system represents an attractive technological alternative to use the energy from the microturbine exhaust gases for electric power generation, cooling and heating produced simultaneously. - Highlights: → The thermodynamic performance of a trigeneration system is analyzed theoretically. → A microturbine and a double-effect H 2 O-LiBr absorption chiller integrate the system. → The heat data supplied to generator was obtained from experimental data. → The trigeneration system was evaluated at different operating conditions. → Results show that this system is an attractive option to use exhaust energy for electricity, cooling and heating generation.
Thermodynamic equilibrium calculations of sulfur poisoning in Ce-O-S and La-O-S systems
Energy Technology Data Exchange (ETDEWEB)
Karjalainen, Heidi; Lassi, Ulla; Rahkamaa-Tolonen, Katariina; Kroeger, Virpi; Keiski, Riitta L. [University of Oulu, Department of Process and Environmental Engineering, P.O. Box 4300, FIN-90014 Oulu (Finland)
2005-02-28
Sulfur poisoning is still a problem in many application areas of exhaust gas catalysts despite the fact that the sulfur levels, e.g. in gasoline are being continuously reduced. The aim of this study was to calculate thermodynamic equilibrium compositions of sulfur in Ce-O-S and La-O-S systems in the presence of precious metals (Pt, Pd, and Rh), which all were considered as bulk materials, in order to understand the experimentally observed sulfur poisoning under the real applications of exhaust gas catalysts. Depending on temperature and oxygen partial pressure, sulfur can be present in the form of sulfates, sulfides and oxysulfides. It is thermodynamically favorable that cerium oxide reacts with SO{sub 2} to form cerium sulfate at low temperatures and cerium oxysulfides at high temperatures. Lanthanum oxide reacts with SO{sub 2} to form sulfate under oxidizing conditions and sulfides under reducing conditions.
Angle, John
2011-01-01
The Inequality Process (IP) and the Saved Wealth Model (SW) are particle system models of income distribution. The IP’s social science meta-theory requires its stationary distribution to fit the distribution of labor income conditioned on education. The Saved Wealth Model (SW) is an ad hoc modification of the particle system model of the Kinetic Theory of Gases (KTG). The KTG implies the laws of gas thermodynamics. The IP is a particle system similar to the SW and KTG, but less closely relate...
Kar, Sujoy Kumar; Dheeradhada, Voramon S.; Lipkin, Don M.
2013-08-01
Alloys in the Mo-rich corner of the Mo-Ti-Zr-C system have found broad applications in non-oxidizing environments requiring structural integrity well beyond 1273 K (1000 °C). Alloys such as TZM (Mo-0.5Ti-0.08Zr-0.03C by weight %) and TZC (Mo-1.2Ti-0.3Zr-0.1C by weight) owe much of their high temperature strength and microstructural stability to MC and M2C carbide phases. In turn, the stability of the respective carbides and the subsequent mechanical behavior of the alloys are strongly dependent on the alloying additions and thermal history. A CALPHAD-based thermodynamic modeling approach is employed to develop a quaternary thermodynamic database for the Mo-Ti-Zr-C system. The thermodynamic database thus developed is validated with diffusion multiple experiments and the validated database is exercised to elucidate the effects of alloying and thermal history on the phase equilibrium in Mo-rich alloys.
International Nuclear Information System (INIS)
Kim, Yoon Jo; Kim, Sarah; Joshi, Yogendra K.; Fedorov, Andrei G.; Kohl, Paul A.
2012-01-01
Thermodynamics of an ionic-liquid (IL) based absorption refrigeration system has been numerically analyzed. It provides an alternative to the normally toxic working fluids, such as the ammonia in conventional absorption systems. The use of ILs also eliminates crystallization and metal-compatibility problems of the water/LiBr system. Mixtures of refrigerants and imidazolium-based ILs are theoretically explored as the working fluid pairs in a miniature absorption refrigeration system, so as to utilize waste-heat to power a refrigeration/heat pump system for electronics cooling. A non-random two-liquid (NRTL) model was built and used to predict the solubility of the mixtures. Saturation temperatures at the evaporator and condenser were set at 25 °C and 50 °C, respectively, with the power dissipation of 100 W. Water in combination with [emim][BF 4 ] (1-ethyl-3-methylimidazolium tetrafluoroborate) gave the highest coefficient of performance (COP) around 0.9. The refrigerant/IL compatibility indicated by the circulation ratio, alkyl chain length of the IL, and thermodynamic properties of the refrigerants, such as latent heat of evaporation were proven to be important factors in determining the performance of the absorption system. The negative effect of high viscosity was mitigated by dilution of the IL with the refrigerant and the use of slightly larger microfluidic channel heat exchangers. -- Highlights: ► Mixtures of refrigerant/ionic-liquid are studied for absorption system. ► We carry out comprehensive theoretical thermodynamic analysis. ► The essential factors of refrigerant/IL affecting the performance are identified. ► Water/[emim][BF 4 ] showed the best performance of COP. ► The effects of high viscosity ILs on the system performance are not significant.
Modelling of physical and thermodynamic properties in systems containing edible oils and biodiesel
DEFF Research Database (Denmark)
Cunico, Larissa; Ceriani, Roberta; Sarup, Bent
The knowledge of physical and thermodynamic properties of pure components and their mixtures is a basic requirement for performing tasks related to process design, simulation, and optimization and also for performing chemical product design using computer aided molecular/mixture design (CAMD) too...
Assessment of the thermodynamic properties and phase diagram of the Bi-Pd system
Czech Academy of Sciences Publication Activity Database
Vřešťál, Jan; Pinkas, J.; Watson, A.; Scott, A.; Houserová, Jana; Kroupa, Aleš
2006-01-01
Roč. 30, č. 1 (2006), s. 14-17 ISSN 0364-5916 R&D Projects: GA MŠk OC 531.001; GA MŠk OC 531.002 Institutional research plan: CEZ:AV0Z20410507 Keywords : phase diagram * ab initio calculations * calorimetry Subject RIV: BJ - Thermodynamics Impact factor: 1.432, year: 2006
Thermodynamic modelling of phase equilibria in Al–Ga–P–As system
Indian Academy of Sciences (India)
A generalized thermodynamic expression of the liquid Al–Ga–P–As alloys is used in conjunction with the solid solution model in determining the solid–liquid equilibria at 1173 K and 1273 K. The liquid solution model contains thirtyseven parameters. Twentyfour of them pertain to those of the six constituent binaries, twelve ...
Arróyave, Raymundo; Liu, Zi-Kui
2006-11-01
A comprehensive analysis of the structural, vibrational, and thermodynamic properties of the intermetallic compounds in the Mg-Ca-Sn system has been performed via first-principles calculations. The enthalpies of formation at 0K for all the known structures in this ternary system are calculated and the results are favorably compared—within ˜5kJ/mol-atom in most cases—to the available experimental data. The vibrational contributions to the thermodynamic properties of fcc Ca, hcp Mg, β-Sn , Mg2Ca , Ca2Sn , CaSn , Ca5Sn3 , CaSn3 , Mg2Sn , and MgCaSn are calculated using the supercell method. In all cases, bond stiffening resulting from compound formation results in upward frequency shifts in the phonon density of states, yielding in turn negative entropies of formation. The effects of volume expansion on the vibrational properties were considered through the quasiharmonic approximation. Thermal electronic contributions were also calculated from the electronic density of states. The electronic degrees of freedom were found to be less important than volume expansion at determining the high temperature thermodynamic properties. The predicted thermodynamic properties of the structures agreed satisfactorily with the experimental data available. The relative importance of these two nonharmonic corrections is reversed when analyzing the formation properties. In all compounds, except for CaSn3 , it was found that the variation of both the formation enthalpies and entropies with temperature is negative. This results in a destabilization of the compounds with respect to their constituent elements as the temperature is increased.
Directory of Open Access Journals (Sweden)
Hisashi Ozawa
2015-01-01
Full Text Available The formation process of circulatory motion of a tropical cyclone is investigated from a thermodynamic viewpoint. The generation rate of mechanical energy by a fluid motion under diabatic heating and cooling, and the dissipation rate of this energy due to irreversible processes are formulated from the first and second laws of thermodynamics. This formulation is applied to a tropical cyclone, and the formation process of the circulatory motion is examined from a balance between the generation and dissipation rates of mechanical energy in the fluid system. We find from this formulation and data analysis that the thermodynamic efficiency of tropical cyclones is about 40% lower than the Carnot maximum efficiency because of the presence of thermal dissipation due to irreversible transport of sensible and latent heat in the atmosphere. We show that a tropical cyclone tends to develop within a few days through a feedback supply of mechanical energy when the sea surface temperature is higher than 300 K, and when the horizontal scale of circulation becomes larger than the vertical height of the troposphere. This result is consistent with the critical radius of 50 km and the corresponding central pressure of about 995 hPa found in statistical properties of typhoons observed in the western North Pacific.
Energy Technology Data Exchange (ETDEWEB)
Cengel, Y.A. [Nevada Univ., Reno, NV (United States). Dept. of Mechanical Engineering
2006-07-01
Green components of thermodynamics were identified and general aspects of green practices associated with thermodynamics were assessed. Energy uses associated with fossil fuels were reviewed. Green energy sources such as solar, wind, geothermal and hydropower were discussed, as well as biomass plantations. Ethanol production practices were reviewed. Conservation practices in the United States were outlined. Energy efficiency and exergy analyses were discussed. Energy intensity measurements and insulation products for houses were also reviewed. Five case studies were presented to illustrate aspects of green thermodynamics: (1) light in a classroom; (2) fuel saved by low-resistance tires; and (3) savings with high-efficiency motors; (4) renewable energy; and (5) replacing a valve with a turbine at a cryogenic manufacturing facility. It was concluded that the main principles of green thermodynamics are to ensure that all material and energy inputs minimize the depletion of energy resources; prevent waste; and improve or innovate technologies that achieve sustainability. 17 refs., 2 tabs., 9 figs.
Comparative thermodynamic analysis of the Pb-Au0.7Sn0.3 section in the Pb-Au-Sn ternary system
International Nuclear Information System (INIS)
Trumic, B.; Zivkovic, D.; Zivkovic, Z.; Manasijevic, D.
2005-01-01
The results of comparative thermodynamic analysis of Pb-Au 0.7 Sn 0.3 section in Pb-Au-Sn system are presented in this paper. Investigation was done comparatively by calorimetric measurements and thermodynamic calculation according to the general solution model. Thermodynamic parameters, such as partial and integral molar quantities, were determined at different temperatures. The comparison between experimental and calculated results showed mutual agreement. Demixing tendency of lead, presented in the positive deviation from ideal behavior, was confirmed through the study of concentration fluctuation in the long-wavelength limit. Also, chosen alloys in the investigated section were characterized using SEM-EDX analysis
Non-Asymptotic Thermodynamic Ensembles
Niven, Robert K.
2008-01-01
Boltzmann's principle is used to select the "most probable" realization (macrostate) of an isolated or closed thermodynamic system, containing a small number of particles ($N \\llsp \\infty$), for both classical and quantum statistics. The inferred probability distributions provide the means to define intensive variables and construct thermodynamic relationships for small microcanonical systems, which do not satisfy the thermodynamic limit. This is of critical importance to nanoscience and quan...
Energy Technology Data Exchange (ETDEWEB)
Yui, Mikazu; Azuma, Jiro; Shibata, Masahiro [Japan Nuclear Cycle Development Inst., Tokai Works, Waste Isolation Research Division, Tokai, Ibaraki (Japan)
1999-11-01
This report is a summary of status, frozen datasets, and future tasks of the JNC (Japan Nuclear Cycle Development Institute) thermodynamic database (JNC-TDB) for assessing performance of high-level radioactive waste in geological environments. The JNC-TDB development was carried out after the first progress report on geological disposal research in Japan (H-3). In the development, thermodynamic data (equilibrium constants at 25degC, I=0) for important radioactive elements were selected/determined based on original experimental data using different models (e.g., SIT, Pitzer). As a result, the reliability and traceability of the data for most of the important elements were improved over those of the PNC-TDB used in H-3 report. For detailed information of data analysis and selections for each element, see the JNC technical reports listed in this document. (author)
Assessment of physical activity of the human body considering the thermodynamic system
Czech Academy of Sciences Publication Activity Database
Hochstein, S.; Rauschenberger, P.; Weigand, B.; Siebert, T.; Schmitt, S.; Schlicht, W.; Převorovská, Světlana; Maršík, F.
2016-01-01
Roč. 19, č. 9 (2016), s. 923-933 ISSN 1025-5842 Institutional support: RVO:61388998 Keywords : physical activity * entropy * activity assessment Subject RIV: BJ - Thermodynamics Impact factor: 1.909, year: 2016 http://www.tandfonline.com/ doi /abs/10.1080/10255842.2015.1076804?journalCode=gcmb20, http://dx. doi . org /10.1080/10255842.2015.1076804, http://www.ncbi.nlm.nih.gov/pubmed/26296149
International Nuclear Information System (INIS)
Gislason, Eric A.; Craig, Norman C.
2005-01-01
The distinction between system-based and surroundings-based definitions of thermodynamic heat (q) and work (w), particularly pressure-volume work, in irreversible processes is introduced and cleanly drawn. A systematic presentation of system-based q and w is given for the first time. This development complements the authors' earlier presentation of surroundings-based work and heat. Either set of definitions can and has been used to develop the laws of thermodynamics. Both sets of definitions are used to analyze examples presented by Kivelson and Oppenheim (KO). It is seen for two KO processes that w(sys-based) and w(surr-based) are not equal. This not uncommon result does not violate the first law because the two q values are also different. One of the KO examples corresponds to a 'quasistatic' process, which is reversible from the point of view of the system but not from the point of view of the system plus surroundings taken together, and, therefore, not reversible overall. A number of reasons are given for preferring surroundings-based definitions of w and q to system-based definitions. Perhaps the most important is the fact that w(sys-based) does not always satisfy the theorem of maximum work in a constant temperature process. Finally, an explanation is presented for why the common use of two different sets of definitions for w and q has not led to greater confusion in the past
Yamada, Akihiro; Shiraishi, Yasuyuki; Miura, Hidekazu; Hashem, Hashem Mohamed Omran; Tsuboko, Yusuke; Yamagishi, Masaaki; Yambe, Tomoyuki
2015-09-01
The Fontan procedure is one of the common surgical treatments for circulatory reconstruction in pediatric patients with congenital heart disease. In Fontan circulation, low pulsatility may induce localized lung ischemia and may impair the development of pulmonary peripheral endothelial cells. To promote pulmonary circulation in Fontan circulation, we have been developing a pediatric pulmonary circulatory pulsation device using shape memory alloy fibers attached from the outside of total cavopulmonary connection. In this study, we developed a new thermal control system for the device and examined its functions. We mounted on the device 16 fibers connected in parallel around an ePTFE graft circumferentially. To provide optimized contraction, we designed the new thermal control system. The system consisted of a thermistor, a pressure sensor, and a regulator that was controlled by the adaptive thermodynamic transfer functions. We monitored the parameters and calculated heat transfer function as well as pressure distribution on the graft surface. Then we examined and compared the dynamic contractile pressure and changes in surface temperature. As a result, by the application of the control based on the new feedback system analysis, the circumferential contractile pressure increased by 35%. The adaptive thermodynamic regulation was useful for the selection of alternative thresholds of the surface temperature of the graft. The system could achieve effective contraction for the pulsatile flow generation by the device.
Assanis, D. N.; Ekchian, J. E.; Frank, R. M.; Heywood, J. B.
1985-01-01
A computer simulation of the turbocharged turbocompounded direct-injection diesel engine system was developed in order to study the performance characteristics of the total system as major design parameters and materials are varied. Quasi-steady flow models of the compressor, turbines, manifolds, intercooler, and ducting are coupled with a multicylinder reciprocator diesel model, where each cylinder undergoes the same thermodynamic cycle. The master cylinder model describes the reciprocator intake, compression, combustion and exhaust processes in sufficient detail to define the mass and energy transfers in each subsystem of the total engine system. Appropriate thermal loading models relate the heat flow through critical system components to material properties and design details. From this information, the simulation predicts the performance gains, and assesses the system design trade-offs which would result from the introduction of selected heat transfer reduction materials in key system components, over a range of operating conditions.
Mitra, Sukanya
2018-01-01
The thermodynamics and covariant kinetic theory are elaborately investigated in a non-extensive environment considering the non-extensive generalization of Bose-Einstein (BE) and Fermi-Dirac (FD) statistics. Starting with Tsallis' entropy formula, the fundamental principles of thermostatistics are established for a grand canonical system having q-generalized BE/FD degrees of freedom. Many particle kinetic theory is set up in terms of the relativistic transport equation with q-generalized Uehling-Uhlenbeck collision term. The conservation laws are realized in terms of appropriate moments of the transport equation. The thermodynamic quantities are obtained in a weak non-extensive environment for a massive pion-nucleon and a massless quark-gluon system with non-zero baryon chemical potential. In order to get an estimate of the impact of non-extensivity on the system dynamics, the q-modified Debye mass and hence the q-modified effective coupling are estimated for a quark-gluon system.
International Nuclear Information System (INIS)
Perez, Brenda; Malpiedi, Luciana Pellegrini; Tubío, Gisela; Nerli, Bibiana; Alcântara Pessôa Filho, Pedro de
2013-01-01
Highlights: ► Binodal data of systems (water + polyethyleneglycol + sodium) succinate are reported. ► Pitzer model describes the phase equilibrium of systems formed by polyethyleneglycol and biodegradable salts satisfactorily. ► This simple thermodynamic framework was able to predict the partitioning behaviour of model proteins acceptably well. - Abstract: Phase diagrams of sustainable aqueous two-phase systems (ATPSs) formed by polyethyleneglycols (PEGs) of different average molar masses (4000, 6000, and 8000) and sodium succinate are reported in this work. Partition coefficients (Kps) of seven model proteins: bovine serum albumin, catalase, beta-lactoglobulin, alpha-amylase, lysozyme, pepsin, urease and trypsin were experimentally determined in these systems and in ATPSs formed by the former PEGs and other biodegradable sodium salts: citrate and tartrate. An extension of Pitzer model comprising long and short-range term contributions to the excess Gibbs free energy was used to describe the (liquid + liquid) equilibrium. Comparison between experimental and calculated tie line data showed mean deviations always lower than 3%, thus indicating a good correlation. The partition coefficients were modeled by using the same thermodynamic approach. Predicted and experimental partition coefficients correlated quite successfully. Mean deviations were found to be lower than the experimental uncertainty for most of the assayed proteins.
Investigation and thermodynamic calculation of phase diagram of CdI2-PbI2-NaI system
International Nuclear Information System (INIS)
Storonkin, A.V.; Vasil'kova, I.V.; Korobkov, S.V.
1976-01-01
Using the thermographic and X-ray phase analyses binary CdI 2 -PbI 2 , PI 2 -NaI, CdI 2 -NaI systems and a triple CdI 2 -PbI 2 -NaI system are investigated and their melting diagrams are plotted. A method of thermodynamic calculation has been proposed and tested of the shape of the eutectic lines for the system CdI 2 -PbI 2 -NaI, taking into account the non-ideality of the liquid phase. The method uses data obtained for the binary systems. The liquidus surface of the triple system has been constructed on the basis of the calculation. The results of the calculation of the triple eutectics are in good agreement with the experimental data
Thermodynamics: The Unique Universal Science
Directory of Open Access Journals (Sweden)
Wassim M. Haddad
2017-11-01
Full Text Available Thermodynamics is a physical branch of science that governs the thermal behavior of dynamical systems from those as simple as refrigerators to those as complex as our expanding universe. The laws of thermodynamics involving conservation of energy and nonconservation of entropy are, without a doubt, two of the most useful and general laws in all sciences. The first law of thermodynamics, according to which energy cannot be created or destroyed, merely transformed from one form to another, and the second law of thermodynamics, according to which the usable energy in an adiabatically isolated dynamical system is always diminishing in spite of the fact that energy is conserved, have had an impact far beyond science and engineering. In this paper, we trace the history of thermodynamics from its classical to its postmodern forms, and present a tutorial and didactic exposition of thermodynamics as it pertains to some of the deepest secrets of the universe.
Energy Technology Data Exchange (ETDEWEB)
Arthur, R.C.; Wei Zhou [Monitor Scientific, LLC, Denver, CO (United States)
2000-12-01
Thermodynamic and kinetic constraints on the chemical buffering properties of natural and engineered-barrier systems are derived in this study from theoretical descriptions, incorporated in the reaction-path model, of reversible and irreversible mass transfer in multicomponent, multiphase systems. The buffering properties of such systems are conditional properties because they refer to a specific aqueous species in a system that is open with respect to a specific reactant. The solution to a mathematical statement of this concept requires evaluation of the dependence of the activity of the buffered species on incremental changes in the overall reaction-progress variable. This dependence can be represented by a truncated Taylor's series expansion, where the values of associated derivatives are calculated using finite-difference techniques and mass-balance, charge-balance and mass-action constraints. Kinetic constraints on buffering behavior can also be described if the relation between reactant flux and reaction rate is well defined. This relation is explicit for the important case of advective groundwater flow and water-rock interaction. We apply the theoretical basis of the chemical buffering concept to processes that could affect the performance of a deep geologic repository for nuclear waste. Specifically, we focus on the likelihood that an inverse relation must exist between the buffer intensity and the migration velocity of reaction fronts in systems involving advective or diffusive mass transport. A quantitative understanding of this relation would provide the basis for evaluating the potential role of chemical buffering in achieving the isolation and retardation functions, of the EBS and geosphere in a KBS-3 repository. Our preliminary evaluation of this role considers the effects of chemical buffering on the propagation velocity of a pH front in both the near- and far field. We use a geochemical modeling technique compatible with the reaction-path model
Directory of Open Access Journals (Sweden)
Arash Nemati
2017-03-01
Full Text Available A thermodynamic modeling and optimization is carried out to compare the advantages and disadvantages of organic Rankine cycle (ORC and Kalina cycle (KC as a bottoming cycle for waste heat recovery from CGAM cogeneration system. Thermodynamic models for combined CGAM/ORC and CGAM/KC systems are performed and the effects of some decision variables on the energy and exergy efficiency and turbine size parameter of the combined systems are investigated. Solving simulation equations and optimization process have been done using direct search method by EES software. It is observed that at the optimum pressure ratio of air compressor, produced power of bottoming cycles has minimum values. Also, evaporator pressure optimizes the performance of cycle, but this optimum pressure level in ORC (11 bar is much lower than that of Kalina (46 bar. In addition, ORC's simpler configuration, higher net produced power and superheated turbine outlet flow, which leads to a reliable performance for turbine, are other advantages of ORC. Kalina turbine size parameter is lower than that of the ORC which is a positive aspect of Kalina cycle. However, by a comprehensive comparison between Kalina and ORC, it is concluded that the ORC has significant privileges for waste heat recovery in this case.
On thermodynamic and microscopic reversibility
International Nuclear Information System (INIS)
Crooks, Gavin E
2011-01-01
The word 'reversible' has two (apparently) distinct applications in statistical thermodynamics. A thermodynamically reversible process indicates an experimental protocol for which the entropy change is zero, whereas the principle of microscopic reversibility asserts that the probability of any trajectory of a system through phase space equals that of the time reversed trajectory. However, these two terms are actually synonymous: a thermodynamically reversible process is microscopically reversible, and vice versa
Computational applications of the thermodynamic local potential: The case of pattern forming systems
International Nuclear Information System (INIS)
Hubert, J.Z.
1986-09-01
Using the thermodynamic local potential Φ a single variational principle may be formulated for a broad class of pattern formation phenomena (this class contains patterns which are: macroscopic, possess steady states, are degenerate at least with respect to one parameter, approach the steady state via fluctuations in the coarsely grained (macroscopic) phase space and so have no memory of the initial conditions). When a steady state is reached Φ assumes its minimum value with respect to distribution function and a maximum with respect to the actually assumed values of free parameters. (author)
Ge, Hao; Qian, Hong
2009-10-02
We show that the thermodynamic limit of a bistable phosphorylation-dephosphorylation cycle has a selection rule for the "more stable" macroscopic steady state. The analysis is akin to the Maxwell construction. Based on the chemical master equation approach, it is shown that, except at a critical point, bistability disappears in the stochastic model when fluctuation is sufficiently low but unneglectable. Onsager's Gaussian fluctuation theory applies to the unique macroscopic steady state. With an initial state in the basin of attraction of the "less stable" steady state, the deterministic dynamics obtained by the law of mass action is a metastable phenomenon. Stability and robustness in cell biology are emergent stochastic concepts.
Mass spectrometric study of thermodynamic properties in the Gd2O3-Y2O3system at high temperatures.
Kablov, Eugene N; Stolyarova, Valentina L; Lopatin, Sergey I; Vorozhtcov, Viktor A; Karachevtsev, Fedor N; Folomeikin, Yuriy I
2017-03-30
The Gd 2 O 3 -Y 2 O 3 system possesses a number of practical applications, one of the most important of them being production of casting molds for gas turbine engine blades. The components of this system are often added to zirconia or hafnia to obtain high-temperature ceramics which are used for the development of thermal barrier coatings. However, Gd 2 O 3 and Y 2 O 3 are more volatile than zirconia or hafnia and may vaporize selectively during synthesis or usage of high-temperature materials which may lead to changes in their physicochemical properties. Therefore, information on the vaporization processes and thermodynamic properties of the Gd 2 O 3 -Y 2 O 3 system is of great importance. High-temperature Knudsen effusion mass spectrometry was used to study the vaporization processes and to determine the thermodynamic properties of the Gd 2 O 3 -Y 2 O 3 system. Measurements were performed with a MS-1301 mass spectrometer. Vaporization was carried out using a tungsten twin effusion cell containing the sample under study and pure Gd 2 O 3 as a reference substance. Electron ionization at an energy of 25 eV was employed. At the temperature of 2630 K, GdO, YO and O vapor species were identified over the samples in the Gd 2 O 3 -Y 2 O 3 system. The Gd 2 O 3 and Y 2 O 3 activities and the vaporization rates of samples as functions of composition in the Gd 2 O 3 -Y 2 O 3 system were derived from the partial pressures of the vapor species mentioned. Using these data the Gibbs energy of mixing and excess Gibbs energy of the hexagonal solid solution in this system were calculated at 2630 K. The thermodynamic properties of the Gd 2 O 3 -Y 2 O 3 system, such as the activities of components and the excess Gibbs energy, obtained in the present study using Knudsen mass spectrometry at 2630 K, demonstrated significant negative deviations from ideal behavior. The vaporization rates of the samples were found to decrease as the Y 2 O 3 content increased. Copyright © 2016 John
KINETIC AND THERMODYNAMIC STUDY ON ADSORPTION BY STARCHY MATERIALS IN THE ETHANOL-WATER SYSTEM
Directory of Open Access Journals (Sweden)
M.J. Carmo
1997-09-01
Full Text Available Improving adsorptive processes demands a constant search for new adsorbents. In the specific case of ethanol-water separation, A zeolites are successfully being used. The use of nonconventional adsorbents to substitute zeolites, mainly starchy adsorbents in virtue of their known chemical affinity water, has recently been proposed. In this work a thermodynamic and kinetic study has been undertaken on the liquid phase adsorption of water from an ethanol-water mixture using manioc starch pellets as the adsorbent. The fundamental thermodynamic data were obtained by means of the static method, using a thermostated bath at four different temperatures (25, 40, 50 and 60° C, and could be correlated by means of a semi-empirical isotherm. The kinetic data, in turn, were obtained in a finite circulating liquid bath cell, enabling the construction of uptake rate curves, whereby the influence of temperature, interstitial velocity and adsorbent mean particle size on the adsorption rate was analyzed. The effective internal diffusivities at the experimental temperatures were estimated by a pore diffusion model and the results obtained were compared with those for commercial 3A zeolite
Dotov, D G; Kim, S; Frank, T D
2015-02-01
We derive explicit expressions for the non-equilibrium thermodynamical variables of a canonical-dissipative limit cycle oscillator describing rhythmic motion patterns of active systems. These variables are statistical entropy, non-equilibrium internal energy, and non-equilibrium free energy. In particular, the expression for the non-equilibrium free energy is derived as a function of a suitable control parameter. The control parameter determines the Hopf bifurcation point of the deterministic active system and describes the effective pumping of the oscillator. In analogy to the equilibrium free energy of the Landau theory, it is shown that the non-equilibrium free energy decays as a function of the control parameter. In doing so, a similarity between certain equilibrium and non-equilibrium phase transitions is pointed out. Data from an experiment on human rhythmic movements is presented. Estimates for pumping intensity as well as the thermodynamical variables are reported. It is shown that in the experiment the non-equilibrium free energy decayed when pumping intensity was increased, which is consistent with the theory. Moreover, pumping intensities close to zero could be observed at relatively slow intended rhythmic movements. In view of the Hopf bifurcation underlying the limit cycle oscillator model, this observation suggests that the intended limit cycle movements were actually more similar to trajectories of a randomly perturbed stable focus. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.
Thermodynamic analysis of Mo(VI)-Fe(III)-S(VI)-H2O system for separation of molybdenum and iron
Xiao, Chao; Zeng, Li; Xiao, Liansheng; Zhang, Guiqing
2017-11-01
The separation of molybdenum and iron is one of key issues of the hydrometallurgical preparation of pure molybdenum chemical products. The thermodynamic equilibrium diagrams for distribution of species at different pH values and different concentrations of molybdenum, iron and sulfur with the systems of Mo(VI)-H2O, Fe(III)-S(VI)-H2O and Mo(VI)-Fe(III)-S(VI)-H2O at 298 K were established, separately. Thermodynamic analysis results revealed that both molybdenum and iron were transformed from their anions to cations with the decrease in pH values. The pHMf0.5 for the conversion of molybdenum anions to cations decreased from 0.92 to 0.20 with the increase in the molybdenum concentration from 0.05 mol/L to 1 mol/L (pHMf50 is defined as the pH value when target metal anions occupy 50% mole fraction of total). The total sulfur concentration has significant effect on the conversion of iron (III) species with the pH change. The separation of molybdenum (VI) and iron (III) from acidic solutions using a tertiary amine extractant N235 could be achieved by decreasing the total sulfur concentration and controlling the equilibrium pH in an optimum range. The verification test results showed that the operating window for the separation of Mo(VI) and Fe(III) from a solution containing 0.01 mol/L [Mo]T, 0.05 mol/L [Fe]T and 1.15 mol/L [S]T was in the pH range of 0.5-1.0, which was consistent with the thermodynamic analysis.
Energy Technology Data Exchange (ETDEWEB)
Gong, Xi Wu [Zhejiang Ocean University, Zhejian (China); Wang, Xiao Qiong; Li, You Rong; Wu, Chun Mei [Chongqing University, Chongqing (China)
2015-07-15
We present a novel coupled organic Rankine cycle (CORC) system driven by the low-grade waste heat, which couples a transcritical organic Rankine cycle with a subcritical organic Rankine cycle. Based on classical thermodynamic theory, a detailed performance analysis on the novel CORC system was performed. The results show that the pressure ratio of the expander is decreased in the CORC and the selection of the working fluids becomes more flexible and abundant. With the increase of the pinch point temperature difference of the internal heat exchanger, the net power output and thermal efficiency of the CORC all decrease. With the increase of the critical temperature of the working fluid, the system performance of the CORC is improved. The net power output and thermal efficiency of the CORC with isentropic working fluids are higher than those with dry working fluids.
Schrödinger, Erwin
1952-01-01
Nobel Laureate's brilliant attempt to develop a simple, unified standard method of dealing with all cases of statistical thermodynamics - classical, quantum, Bose-Einstein, Fermi-Dirac, and more.The work also includes discussions of Nernst theorem, Planck's oscillator, fluctuations, the n-particle problem, problem of radiation, much more.
Quantum and thermodynamic aspects of Black Holes
International Nuclear Information System (INIS)
Sande e Lemos, J.P. de; Videira, A.L.L.
1983-01-01
The main results originating from the attempts of trying to incorporate quantum and thermodynamic properties and concepts to the gravitational system black hole, essentially the Hawking effect and the four laws of thermodynamics are reviewed. (Author) [pt
Cano-Andrade, Sergio
In this dissertation, applications of thermodynamics at the macroscopic and quantum levels of description are developed. Within the macroscopic level, an upper-level Sustainability Assessment Framework (SAF) is proposed for evaluating the sustainable and resilient synthesis/design and operation of sets of small renewable and non-renewable energy production technologies coupled to power production transmission and distribution networks via microgrids. The upper-level SAF is developed in accord with the four pillars of sustainability, i.e., economic, environmental, technical and social. A superstructure of energy producers with a fixed transmission network initially available is synthesized based on the day with the highest energy demand of the year, resulting in an optimum synthesis, design, and off-design network configuration. The optimization is developed in a quasi-stationary manner with an hourly basis, including partial-load behavior for the producers. Since sustainability indices are typically not expressed in the same units, multicriteria decision making methods are employed to obtain a composite sustainability index. Within the quantum level of description, steepest-entropy-ascent quantum thermodynamics (SEA-QT) is used to model the phenomenon of decoherence. The two smallest microscopic composite systems encountered in Nature are studied. The first of these is composed of two two-level-type particles, while the second one is composed of a two-level-type particle and an electromagnetic field. Starting from a non-equilibrium state of the composite and for each of the two different composite systems, the time evolution of the state of the composite as well as that of the reduced and locally-perceived states of the constituents are traced along their relaxation towards stable equilibrium at constant system energy. The modeling shows how the initial entanglement and coherence between constituents are reduced during the relaxation towards a state of stable
Acoustic and thermodynamic properties of the binary liquid system n-dodecane+ n-hexadecane
Khasanshin, T. S.; Samuilov, V. S.; Shchemelev, A. P.; Mosbach, F. M.
2010-11-01
By the method of direct measurement of the pulse-passage time, the velocity of sound in a binary liquid mixture n-dodecane+ n-hexadecane has been investigated in the temperature range 298-433 K and in the pressure range 0.1-100.1 MPa. The maximum measurement error is 0.1%. Experimental data on the velocity of sound for the investigated mixture have been obtained for the first time. On the basis of the data on the velocity of sound, we have determined the density, the isobaric expansion coefficient, the isobaric and isochoric heat capacities, and the isothermal compressibility coefficient of a mixture of three compositions in the 298-433 K temperature range and in the 0.1-100.1 MPa range of pressures. The coefficients of the Tate equations in the above range of parameters have been calculated. A table of thermodynamic properties of the mixture is presented.
International Nuclear Information System (INIS)
Lecompte, J.-C.; Buisson, Jacques.
1981-01-01
Neutronics and thermodynamics measuring devices realize the control and nuclear safety of the reactor and the core. They cause the emergency stop of the reactor if the informations given by the sensors are out of the normal operation tolerances. Defining and assuring a protection level sufficiently high against electromagnetic disturbances is essential for avoiding those measuring devices of giving erroneous indications in the environment where they are located. To obtain this result, one procceds according to the following three steps: a) In situ measurements of the ambient level of disturbances (oscilloscope analysis, statistical measurements). b) Measurement in laboratory of the immunity against the disturbances caused by every constituent of the device (electronic cables, connectors) and then the complete device. c) In situ simulation on the devices of the perturbations caused by the measured ambient level [fr
Impact of Aerosols and Atmospheric Thermodynamics on Cloud Properties within the Climate System
Matsui, Toshihisa; Masunaga, Hirohiko; Pielke, Roger, Sr.; Tao, Wei-Kuo
2003-01-01
A combination of cloud-top and columnar droplet sizes derived from the multi Tropical Rainfall Measurement Mission (TRMM) sensors reveals the sensitivity of the aerosols effect on cloud-precipitation process due to environmental vertical thermodynamic structure. First, the magnitude of aerosol indirect effect could be larger with the analysis of columnar droplet sizes than that derived from the cloud-top droplet sizes, since column-droplet size can account for the broader droplet spectra in the cloud layers. Second, a combination of cloud- top and columnar droplet sizes reveals that the warm rain process is prevented regardless of the aerosols concentration under a high static stability such as when a strong temperature inversion exists, while a high aerosol concentration suppresses the warm rain formulation under a low static stability.
Energy Technology Data Exchange (ETDEWEB)
Kabadi, V.N.
1995-06-30
The work on this project was initiated on September 1, 1991. The project consisted of two different tasks: (1) Development of a model to compute viscosities of coal derived liquids, and (2) Investigate new models for estimation of thermodynamic properties of solid and liquid compounds of the type that exist in coal, or are encountered during coal processing. As for task 1, a model for viscosity computation of coal model compound liquids and coal derived liquids has been developed. The detailed model is presented in this report. Two papers, the first describing the pure liquid model and the second one discussing the application to coal derived liquids, are expected to be published in Energy & Fuels shortly. Marginal progress is reported on task 2. Literature review for this work included compilation of a number of data sets, critical investigation of data measurement techniques available in the literature, investigation of models for liquid and solid phase thermodynamic computations. During the preliminary stages it was discovered that for development of a liquid or solid state equation of state, accurate predictive models for a number of saturation properties, such as, liquid and solid vapor pressures, saturated liquid and solid volumes, heat capacities of liquids and solids at saturation, etc. Most the remaining time on this task was spent in developing predictive correlations for vapor pressures and saturated liquid volumes of organic liquids in general and coal model liquids in particular. All these developments are discussed in this report. Some recommendations for future direction of research in this area are also listed.
Internally consistent thermodynamic data for aqueous species in the system Na-K-Al-Si-O-H-Cl
Miron, George D.; Wagner, Thomas; Kulik, Dmitrii A.; Heinrich, Christoph A.
2016-08-01
A large amount of critically evaluated experimental data on mineral solubility, covering the entire Na-K-Al-Si-O-H-Cl system over wide ranges in temperature and pressure, was used to simultaneously refine the standard state Gibbs energies of aqueous ions and complexes in the framework of the revised Helgeson-Kirkham-Flowers equation of state. The thermodynamic properties of the solubility-controlling minerals were adopted from the internally consistent dataset of Holland and Powell (2002; Thermocalc dataset ds55). The global optimization of Gibbs energies of aqueous species, performed with the GEMSFITS code (Miron et al., 2015), was set up in such a way that the association equilibria for ion pairs and complexes, independently derived from conductance and potentiometric data, are always maintained. This was achieved by introducing reaction constraints into the parameter optimization that adjust Gibbs energies of complexes by their respective Gibbs energy effects of reaction, whenever the Gibbs energies of reactant species (ions) are changed. The optimized thermodynamic dataset is reported with confidence intervals for all parameters evaluated by Monte Carlo trial calculations. The new thermodynamic dataset is shown to reproduce all available fluid-mineral phase equilibria and mineral solubility data with good accuracy and precision over wide ranges in temperature (25-800 °C), pressure (1 bar to 5 kbar) and composition (salt concentrations up to 5 molal). The global data optimization process adopted in this study can be readily repeated any time when extensions to new chemical elements and species are needed, when new experimental data become available, or when a different aqueous activity model or equation of state should be used. This work serves as a proof of concept that our optimization strategy is feasible and successful in generating a thermodynamic dataset reproducing all fluid-mineral and aqueous speciation equilibria in the Na-K-Al-Si-O-H-Cl system within
Thermodynamics of negative absolute pressures
International Nuclear Information System (INIS)
Lukacs, B.; Martinas, K.
1984-03-01
The authors show that the possibility of negative absolute pressure can be incorporated into the axiomatic thermodynamics, analogously to the negative absolute temperature. There are examples for such systems (GUT, QCD) processing negative absolute pressure in such domains where it can be expected from thermodynamical considerations. (author)
Energy Technology Data Exchange (ETDEWEB)
Steele, W.V.; Chirico, R.D.; Klots, T.D.
1993-03-01
A detailed vibrational spectroscopic study of furan, pyrrole, and thiophene has been completed. These compounds form part of the base of five-membered ring systems on which the rest of the research program will be built Several methyl-substituted derivatives were also studied. The results will be used to confirm the model for alkyl- substitution in the ring systems. Gas-phase spectra and fundamental- frequency assignments were completed for 2,3- and 2,5-dihydrofuran. Those compounds initiate work on ring-puckering within the research program. A paper describing the need for third virial estimation, when using the virial equation of state to derive thermodynamic properties at pressures greater than 1 bar was completed.
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.
Hou, Minqiang; Zhang, Jianling; Han, Buxing; Mei, Qingqing; Ning, Hui; Yang, Dezhong
2013-07-14
In this work we propose a new thermodynamic principle in which a supercritical fluid (SCF)-solid system is divided into a solid phase, a cluster phase, and a bulk fluid phase, i.e., the molecular clusters in the system are considered as an individual phase. The phase equilibria of various SCF-solid systems are calculated using this principle in combination with Monte Carlo simulation and the Peng-Robinson equation of state (PR-EOS). It is shown that in the critical region of the supercritical (SC) solvents where the clustering is significant, the results calculated using this thermodynamic principle are much more consistent with the experimental data than those calculated using the conventional thermodynamic principle, confirming the validity of the principle proposed in this work.
Critical Evaluation and Thermodynamic Optimization of the Na2O-FeO-Fe2O3-SiO2 System
Moosavi-Khoonsari, Elmira; Jung, In-Ho
2016-02-01
A complete literature review, critical evaluation, and thermodynamic optimization of phase diagrams and thermodynamic properties of the Na2O-FeO-Fe2O3-SiO2 system were performed at 1 atm total pressure. A set of optimized model parameters obtained for all phases present in this system reproduces available and reliable thermodynamic properties and phase equilibria within experimental error limits from 298 K (25 °C) to above liquidus temperatures for all compositions and oxygen partial pressures from metallic Fe saturation to 1 atm. The liquid phase was modeled based on the Modified Quasichemical Model considering the possible formation of NaFeO2 associate in the liquid state. The NaFeO2 metaoxide solid solutions containing the excess SiO2 were described within the framework of Compound Energy Formalism. Based on the thermodynamic models and model parameters, unexplored thermodynamic properties and phase diagrams of the Na2O-FeO-Fe2O3-SiO2 system were predicted.
Mechanics, Waves and Thermodynamics
Ranjan Jain, Sudhir
2016-05-01
Figures; Preface; Acknowledgement; 1. Energy, mass, momentum; 2. Kinematics, Newton's laws of motion; 3. Circular motion; 4. The principle of least action; 5. Work and energy; 6. Mechanics of a system of particles; 7. Friction; 8. Impulse and collisions; 9. Central forces; 10. Dimensional analysis; 11. Oscillations; 12. Waves; 13. Sound of music; 14. Fluid mechanics; 15. Water waves; 16. The kinetic theory of gases; 17. Concepts and laws of thermodynamics; 18. Some applications of thermodynamics; 19. Basic ideas of statistical mechanics; Bibliography; Index.
Concise chemical thermodynamics
Peters, APH
2010-01-01
EnergyThe Realm of ThermodynamicsEnergy BookkeepingNature's Driving ForcesSetting the Scene: Basic IdeasSystem and SurroundingsFunctions of StateMechanical Work and Expanding GasesThe Absolute Temperature Scale Forms of Energy and Their Interconversion Forms of Renewable Energy Solar Energy Wind Energy Hydroelectric Power Geothermal Energy Biomass Energy References ProblemsThe First Law of Thermodynamics Statement of the First Law Reversible Expansion of an Ideal GasConstant-Volume ProcessesConstant-Pressure ProcessesA New Function: EnthalpyRelationship between ?H and ?UUses and Conventions of
Thermodynamics of Crystalline States
Fujimoto, Minoru
2010-01-01
Thermodynamics is a well-established discipline of physics for properties of matter in thermal equilibrium surroundings. Applying to crystals, however, the laws encounter undefined properties of crystal lattices, which therefore need to be determined for a clear and well-defined description of crystalline states. Thermodynamics of Crystalline States explores the roles played by order variables and dynamic lattices in crystals in a wholly new way. This book is divided into three parts. The book begins by clarifying basic concepts for stable crystals. Next, binary phase transitions are discussed to study collective motion of order variables, as described mostly as classical phenomena. In the third part, the multi-electron system is discussed theoretically, as a quantum-mechanical example, for the superconducting state in metallic crystals. Throughout the book, the role played by the lattice is emphasized and examined in-depth. Thermodynamics of Crystalline States is an introductory treatise and textbook on meso...
Extended Irreversible Thermodynamics
Jou, David
2010-01-01
This is the 4th edition of the highly acclaimed monograph on Extended Irreversible Thermodynamics, a theory that goes beyond the classical theory of irreversible processes. In contrast to the classical approach, the basic variables describing the system are complemented by non-equilibrium quantities. The claims made for extended thermodynamics are confirmed by the kinetic theory of gases and statistical mechanics. The book covers a wide spectrum of applications, and also contains a thorough discussion of the foundations and the scope of the current theories on non-equilibrium thermodynamics. For this new edition, the authors critically revised existing material while taking into account the most recent developments in fast moving fields such as heat transport in micro- and nanosystems or fast solidification fronts in materials sciences. Several fundamental chapters have been revisited emphasizing physics and applications over mathematical derivations. Also, fundamental questions on the definition of non-equil...
DEFF Research Database (Denmark)
Westerhoff, Hans V.; Jensen, Peter Ruhdal; Snoep, Jacky L.
1998-01-01
the thesis that the aforesaid holds a fortiori for the living cell: Much of the essence of the live state depends more on the manner in which the molecules are organised than on the properties of single molecules. This is due to the phenomenon of 'Complexity'. BioComplexity is defined here as the phenomenon...... 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...... with metabolic control analysis. Subsequently, the complexity of the control of the energy metabolism of E. coli will be analysed in detail. New control theorems will be derived for newly defined control coefficients. It will become transparent that molecular genetic experimentation will allow one to penetrate...
Thermodynamic study of the rich-Bi2O3 region of the Bi2O3-ZnO system
Serena Palomares, Sara; Rubia, Miguel Ángel de la; Caballero Cuesta, Amador; Caballero Cuesta, Ángel
2006-01-01
[EN] Precise knowledge of the Bi2O3-ZnO system is fundamental to control the functional microstructure of ZnO-based varistors. Also the potential applications of materials based on ZnO and Bi2O3 as dielectric materials in the high frequency range have renewed the interest in this binary system. The aim of the present work is to carry out a thermodynamic analysis of the Bi2O3-ZnO phase diagram, taking into account the existing experimental information. Thermodynamic calculation has...
Gering, Kevin Leslie
A molecular formulation based on modern liquid state theory is applied to the properties and phase behavior of electrolyte systems containing volatile species. An electrolyte model based on the exponential modification of the Mean Spherical Approximation (EXP-MSA) is used to describe the cation-cation, cation-anion, and anion-anion distributions of the ionic species. This theory represents an improvement over the nonmodified MSA approach, and goes beyond the usual Debye-Huckel theory and Pitzer correlation for treating concentrated solutions. Electrolyte solutions such as water-salt, ammonia-salt, mixed salts, and mixed -solvent systems are investigated over a wide range of temperatures, pressures, and compositions. The usual salt properties, such as osmotic and mean activity coefficients and other thermodynamic properties (enthalpies), are calculated. The predictions are accurate to saturation limits. In addition, an iterative method is presented that is used to predict vapor-liquid equilibria (VLE) and thermodynamic properties of single-salt multisolvent electrolytes of the form solvent-cosolvent-salt. In this method, a local composition model (LCM) and EXP-MSA theory are combined with traditional phase equilibria relations to estimate the pressures and compositions of a vapor phase in equilibrium with a binary-solvent electrolyte. Also, a pseudo-solvent model is proposed as a means of obtaining a variety of averaged liquid phase electrolyte properties. To predict preferential solvation in mixed solvents, a general framework is developed that is based on predicted solvation numbers of each solvent. Preferential solvation will be shown to influence VLE. Results show that phase equilibria is accurately predicted by the above iterative method. Three mixed-solvent electrolyte systems are investigated: water -ethylene glycol-LiBr, ammonia-water-LiBr, and methanol -water-LiCl. Finally, the above electrolyte model is utilized in predicting design criteria for a single
Energy Technology Data Exchange (ETDEWEB)
Lu, Xingxu [School of Materials Science and Engineering, Central South University, Changsha, Hunan 410083 (China); State Key Laboratory of Powder Metallurgy, Central South University, Changsha, Hunan 410083 (China); Liu, Shuhong, E-mail: shhliu@csu.edu.cn [State Key Laboratory of Powder Metallurgy, Central South University, Changsha, Hunan 410083 (China); Sino-German Cooperation Group “Microstructure in Al alloys”, Central South University, Changsha, Hunan 410083 (China); Cheng, Kaiming; Tang, Ying [State Key Laboratory of Powder Metallurgy, Central South University, Changsha, Hunan 410083 (China); Ou, Pengfei [School of Materials Science and Engineering, Central South University, Changsha, Hunan 410083 (China); State Key Laboratory of Powder Metallurgy, Central South University, Changsha, Hunan 410083 (China); Nash, Philip [Thermal Processing Technology Center, Illinois Institute of Technology (IIT), 10 West 32nd Street, Chicago, IL 60616 (United States); Sundman, Bo [INSTN, CEA Saclay, 91191 Gif-Sur-Yvette Cedex (France); Du, Yong [State Key Laboratory of Powder Metallurgy, Central South University, Changsha, Hunan 410083 (China); Sino-German Cooperation Group “Microstructure in Al alloys”, Central South University, Changsha, Hunan 410083 (China); Zheng, Feng [School of Materials Science and Engineering, Central South University, Changsha, Hunan 410083 (China)
2015-05-20
Highlights: • Heat contents of Co{sub 2}Hf and CoHf{sub 2} were measured by drop calorimetry. • Enthalpy of formation for Co{sub 23}Hf{sub 6} was computed via first-principles calculations. • Co–Hf system was assessed by means of CALPHAD approach. • Order–disorder model is used to describe B2 (CoHf) and A2 (βHf). • Glass forming range of the Co–Hf amorphous alloys was predicted. - Abstract: Phase equilibria and thermodynamic properties of the Co–Hf system were investigated via calorimetric measurements, first-principles calculations and thermodynamic modeling. Heat contents of Co{sub 2}Hf and CoHf{sub 2} were measured by drop calorimetry from 300 to 1200 °C. The enthalpy of formation for Co{sub 23}Hf{sub 6} at 0 K was computed via first-principles calculations. Based on the experimental measurements and first-principles calculations from the present work and the literature, the Co–Hf system was assessed by means of CALPHAD (CALculation of PHAse Diagram) approach. The excess Gibbs energy of solution phases was modeled with Redlich–Kister polynomial. Sublattice models were employed to describe the homogeneity ranges of Co{sub 2}Hf, CoHf and CoHf{sub 2}. The order–disorder transition between B2 (CoHf) and A2 (βHf) phases was taken into account in the current optimization. Using the optimized parameters, glass forming range (GFR) of the Co–Hf amorphous alloys was predicted to be 15–75 at.% Hf, which is in satisfactory agreement with the experimental observation.
Wellen Rudd, Bethany A; Vidalis, Andrew S; Allen, Heather C
2018-04-16
Of the major cations in seawater (Na+, Mg2+, Ca2+, K+), Ca2+ is found to be the most enriched in fine sea spray aerosols (SSA). In this work, we investigate the binding of Ca2+ to the carboxylic acid headgroup of palmitic acid (PA), a marine-abundant fatty acid, and the impact such binding has on the stability of PA monolayers in both equilibrium and non-equilibrium systems. A range of Ca2+ conditions from 10 μM to 300 mM was utilized to represent the relative concentration of Ca2+ in high and low relative humidity aerosol environments. The CO2- stretching modes of PA detected by surface-sensitive infrared reflection-absorption spectroscopy (IRRAS) reveal ionic binding motifs of the Ca2+ ion to the carboxylate group with varying degrees of hydration. Surface tensiometry was used to determine the thermodynamic equilibrium spreading pressure (ESP) of PA on the various aqueous CaCl2 subphases. Up to concentrations of 1 mM Ca2+, each system reached equilibrium, and Ca2+:PA surface complexation gave rise to a lower energy state revealed by elevated surface pressures relative to water. We show that PA films are not thermodynamically stable at marine aerosol-relevant Ca2+ concentrations ([Ca2+] ≥ 10 mM). IRRAS and vibrational sum frequency generation (VSFG) spectroscopy were used to investigate the surface presence of PA on high concentration Ca2+ aqueous subphases. Non-equilibrium relaxation (NER) experiments were also conducted and monitored by Brewster angle microscopy (BAM) to determine the effect of the Ca2+ ions on PA stability. At high surface pressures, the relaxation mechanisms of PA varied among the systems and were dependent on Ca2+ concentration.
Some thermodynamic and photovoltaic studies of the uranyl-uranium(IV) system
International Nuclear Information System (INIS)
Gayer, K.H.; Kothari, P.
1977-01-01
Thermochemical measurements have been made in perchloric acid medium and the following thermodynamic constants have been determined for the reaction: Usub(aq)sup(4+) + 2H 2 O → UOsub(2aq)sup(2+) + 4Hsub(aq)sup(+) + 2e - (ΔH 0 =126.23 kJ; ΔG 0 =63.18 kJ; ΔS 0 =211.53 J). Photovoltaic studies were made in acetic acid medium utilizing the following cell: Pt/UO 2 2+ , CH 3 COOH, C 2 H 5 OH//C 2 H 5 OH, CH 3 COOH/H 2 (Pt). The effect of varying uranyl ion concentration, pH and ethyl alcohol concentration on E.M.F. of this cell in the presence and absence of light has been studied. The nature of the reaction occurring in the above cell and its reversibility in the presence and absence of light has been established. A mechanism for reduction of uranyl ions in organic media in presence of light has been proposed. (author)
Energy Technology Data Exchange (ETDEWEB)
Allenson, Stephen; Johnston, Angela [Nalco Energy Services, Sugar Land, TX (United States)
2008-07-01
This paper presents the development of a new additive that was developed to improve the effectiveness of the treatment two to four fold when added to the thermodynamic hydrate inhibitor (THI). Consequently, the THI/additive treatment can now enable the system to handle two to four times the amount of water production or can allow treatment of the same amount of water at half to quarter the dosage of THI. This new additive extends the performance of the THI and allows for a significant increase in production or a significant drop in the amount of THI usage with a corresponding drop in cost. This paper will further discuss the overall process of THI enhancement and will present several case studies where the enhanced THI has been successfully applied. (author)
Eiperimental and thermodynamic study od curve of retrograde solidus in InP-Ge quasi-binary system
International Nuclear Information System (INIS)
Glazov, V.M.; Pavlova, L.M.; Perederij, L.I.
1983-01-01
Germanium solubility in indium phosphide at different temperatures is experimentally investigated, and it is shown that the solidus curve in the portion adjoining InP is of a retrograde character. The method of radioactive tracers has been used to determine the coefficient of germanium distribution between the liquid and solid phases at a melting point of indium phosphide. Concentration dependence of the number of electrons at indium phosphide doping with germanium is investigated, and violation of the ionization equality is shown that is explained by an amphoteric character of o.ermanium behaviour in the InP base solid solution resulting in a self-compensation effect. The retrograde solidus curve in the InP-Ge system is calculated thermodynamically with the use of model representations on the composition of solid and liquid solutions. The ionization degree of doping impurity and self-compensation effect are taken account in calculation. Good agreement of the calculated and experimental data is observed
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.
Kleidon, Axel
2012-01-01
The Earth's chemical composition far from chemical equilibrium is unique in our Solar System, and this uniqueness has been attributed to the presence of widespread life on the planet. Here, I show how this notion can be quantified using non-equilibrium thermodynamics. Generating and maintaining disequilibrium in a thermodynamic variable requires the extraction of power from another thermodynamic gradient, and the second law of thermodynamics imposes fundamental limits on how much power can be extracted. With this approach and associated limits, I show that the ability of abiotic processes to generate geochemical free energy that can be used to transform the surface–atmosphere environment is strongly limited to less than 1 TW. Photosynthetic life generates more than 200 TW by performing photochemistry, thereby substantiating the notion that a geochemical composition far from equilibrium can be a sign for strong biotic activity. Present-day free energy consumption by human activity in the form of industrial activity and human appropriated net primary productivity is of the order of 50 TW and therefore constitutes a considerable term in the free energy budget of the planet. When aiming to predict the future of the planet, we first note that since global changes are closely related to this consumption of free energy, and the demands for free energy by human activity are anticipated to increase substantially in the future, the central question in the context of predicting future global change is then how human free energy demands can increase sustainably without negatively impacting the ability of the Earth system to generate free energy. This question could be evaluated with climate models, and the potential deficiencies in these models to adequately represent the thermodynamics of the Earth system are discussed. Then, I illustrate the implications of this thermodynamic perspective by discussing the forms of renewable energy and planetary engineering that would
Kleidon, Axel
2012-03-13
The Earth's chemical composition far from chemical equilibrium is unique in our Solar System, and this uniqueness has been attributed to the presence of widespread life on the planet. Here, I show how this notion can be quantified using non-equilibrium thermodynamics. Generating and maintaining disequilibrium in a thermodynamic variable requires the extraction of power from another thermodynamic gradient, and the second law of thermodynamics imposes fundamental limits on how much power can be extracted. With this approach and associated limits, I show that the ability of abiotic processes to generate geochemical free energy that can be used to transform the surface-atmosphere environment is strongly limited to less than 1 TW. Photosynthetic life generates more than 200 TW by performing photochemistry, thereby substantiating the notion that a geochemical composition far from equilibrium can be a sign for strong biotic activity. Present-day free energy consumption by human activity in the form of industrial activity and human appropriated net primary productivity is of the order of 50 TW and therefore constitutes a considerable term in the free energy budget of the planet. When aiming to predict the future of the planet, we first note that since global changes are closely related to this consumption of free energy, and the demands for free energy by human activity are anticipated to increase substantially in the future, the central question in the context of predicting future global change is then how human free energy demands can increase sustainably without negatively impacting the ability of the Earth system to generate free energy. This question could be evaluated with climate models, and the potential deficiencies in these models to adequately represent the thermodynamics of the Earth system are discussed. Then, I illustrate the implications of this thermodynamic perspective by discussing the forms of renewable energy and planetary engineering that would
Oktavian, Rama; Darmawan, Rhezaldian Eka; Diarahmawati, Ayu; Kartiko, Intan Dyah; Rachmawati, Rizqi Tri
2017-03-01
The increasing consumption of fossil fuel in Indonesia is not followed by the rising on domestic oil production. This will lead to the depletion of fossil fuel reserves that will affect the availability of energy resources. Biofuel is considered as the critical solution to solve this problem in Indonesia. In recent years, alcohol produced from biomass has been used as an oxygenated compound in gasoline to increase the octane number and reduce pollutants resulting from motor vehicle exhaust emissions. However, the use of alcohol as an additive compounds is still limited to ethanol. In fact, the use of higher-chain alcohol such as 1-butanol offers more benefits over ethanol due to its higher calorific value. 1-butanol also has good characteristics for gasoline mixture such as less corrosive than ethanol, more resistant to water contamination, its low vapor pressure which leads to more safety application. This work investigated the effect of 1-butanol addition on the thermodynamic properties of gasoline-ethanol blend, in the form of density values, isobaric expansion coefficient, and the calorific value. The addition of 1-butanol up to 15% weight (80% RON 92-5% ethanol-15% 1-butanol) gives higher density to alcohol-gasoline blend up to 2% compared with pure RON 92 gasoline. Moreover, this addition produces the calorific value of gasoline blend of 11,313 cal/gr compared to pure RON 92 gasoline with the calorific value of 12,117 cal/gram. This blend can reduce the RON 92 gasoline consumption up to 15% from calorific value perspective.
International Nuclear Information System (INIS)
Witkowski, Andrzej; Rusin, Andrzej; Majkut, Mirosław; Rulik, Sebastian; Stolecka, Katarzyna
2013-01-01
Highlights: • Comprehensive analysis of the efficiency and safety strategies of transport CO 2 . • Selection of safety zones around pipelines transporting CO 2 . • Optimization of CO 2 pipeline transportation conditions. - Abstract: The aim of this paper is to analyze CO 2 compression and transportation processes with safety issues for post-combustion CO 2 capture applications for basic technological concepts of a 900 MW pulverized coal-fired power plant. Four various types of compressors including a conventional multistage centrifugal compressor, an integrally geared centrifugal compressor, a supersonic shock wave compressor, and pump machines were used. This study emphasizes that total compression power is a strong function of the thermodynamic process and is not only determined by the compressor efficiency. The compressor increases the CO 2 pressure from normal pressure to critical pressure and the boosting pump continues to increase the pressure to the required pressure for the pipeline inlet. Another problem analyzed in this study is the transport of CO 2 by pipeline from the compressor outlet site to the disposal site under heat transfer conditions. Simulations were made to determine maximum safe pipeline distance to subsequent booster stations depending on inlet pressure, environmental temperature, the thermal insulation thickness and the ground level heat transfer conditions. From the point of view of environmental protection, the most important problem is to identify the hazards which indirectly affect CO 2 transportation in a strict and reliable manner. This identification is essential for effective hazard management. A failure of pipelines is usually caused by corrosion, material defects, ground movement or third party interference. After the rupture of the pipeline transporting liquid CO 2 , a large pressure drop will occur. The pressure will continue to fall until the liquid becomes a mixture of saturated vapour/liquid. In the vicinity of the
Effect of phosphines on the thermodynamics of the cobalt catalyzed hydroformylation system.
Energy Technology Data Exchange (ETDEWEB)
Klingler, R. J.; Chen, M. J.; Rathke, J. W.; Kramarz, K. W.; Chemical Engineering; BASF Corp.
2007-01-01
Thermodynamic parameters relevant to the phosphine-modified cobalt hydroformylation reaction are reported. Equilibrium constants for the hydrogenation of Co{sub 2}(CO){sub 6}L{sub 2} to yield HCo(CO){sub 3}L were determined using in situ {sup 1}H and {sup 31}P NMR spectroscopy between 75 and 175 C for various solvents and phosphine ligands. Special emphasis was placed on n-Bu{sub 3}P, as this ligand is prototypical of the Shell hydroformylation process. The resultant van't Hoff plots yield the enthalpy and entropy change (H = 7.0 {+-} 0.4 kcal/mol and {Delta}S = 2 {+-} 1 cal/mol {center_dot} K) for the case of L = n-Bu{sub 3}P in benzene solvent. These parameters were found to be relatively insensitive to changes in the solvent, suggesting that the hydride product is not very polar. Even for isobutyl alcohol solvent, the resultant enthalpy and entropy changes (H = 5.8 {+-} 0.4 kcal/mol and S = -2 {+-} 1 cal/mol {center_dot} K) were found to be similar to those obtained in benzene and dioxane. Analysis of the {sup 31}P NMR line widths allows rigorous lower limits to be established for the catalytically relevant Co-Co and Co-H bond energies in the case of L = n-Bu{sub 3}P (Co-Co 23 kcal/mol and Co-H 60 kcal/mol) relative to the previously reported values for the case of L = CO (Co-Co = 19 {+-} 2 kcal/mol and Co-H = 59 {+-} 1 kcal/mol).
Thermodynamic cost of acquiring information.
Micadei, Kaonan; Serra, Roberto M; Céleri, Lucas C
2013-12-01
Connections between information theory and thermodynamics have proven to be very useful to establish bounding limits for physical processes. Ideas such as Landauer's erasure principle and information-assisted work extraction have greatly contributed not only to broadening our understanding about the fundamental limits imposed by nature, but also paving the way for practical implementations of information-processing devices. The intricate information-thermodynamics relation also entails a fundamental limit on parameter estimation, establishing a thermodynamic cost for information acquisition. We show that the amount of information that can be encoded in a physical system by means of a unitary process is limited by the dissipated work during the implementation of the process. This includes a thermodynamic tradeoff for information acquisition. Likewise, the information acquisition process is ultimately limited by the second law of thermodynamics. This tradeoff for information acquisition may find applications in several areas of knowledge.
Thermodynamics in Loop Quantum Cosmology
International Nuclear Information System (INIS)
Li, L.F.; Zhu, J.Y.
2009-01-01
Loop quantum cosmology (LQC) is very powerful to deal with the behavior of early universe. Moreover, the effective loop quantum cosmology gives a successful description of the universe in the semiclassical region. We consider the apparent horizon of the Friedmann-Robertson-Walker universe as a thermodynamical system and investigate the thermodynamics of LQC in the semiclassical region. The effective density and effective pressure in the modified Friedmann equation from LQC not only determine the evolution of the universe in LQC scenario but also are actually found to be the thermodynamic quantities. This result comes from the energy definition in cosmology (the Misner-Sharp gravitational energy) and is consistent with thermodynamic laws. We prove that within the framework of loop quantum cosmology, the elementary equation of equilibrium thermodynamics is still valid.
Paduszyński, Kamil; Domańska, Urszula
2012-04-26
We present the results of an extensive study on a novel approach of modeling ionic liquids (ILs) and their mixtures with molecular compounds, incorporating perturbed-chain statistical associating fluid theory (PC-SAFT). PC-SAFT was used to calculate the thermodynamic properties of different homologous series of ILs based on the bis(trifluormethylsulfonyl)imide anion ([NTf2]). First, pure fluid parameters were obtained for each IL by means of fitting the model predictions to experimental liquid densities over a broad range of temperature and pressure. The reliability and physical significance of the parameters as well as the employed molecular scheme were tested by calculation of density, vapor pressure, and other properties of pure ILs (e.g., critical properties, normal boiling point). Additionally, the surface tension of pure ILs was calculated by coupling the PC-SAFT equation of state with density gradient theory (DGT). All correlated/predicted results were compared with literature experimental or simulation data. Afterward, we attempted to model various thermodynamic properties of some binary systems composed of IL and organic solvent or water. The properties under study were the binary vapor-liquid, liquid-liquid, and solid-liquid equilibria and the excess enthalpies of mixing. To calculate cross-interaction energies we used the standard combining rules of Lorentz-Berthelot, Kleiner-Sadowski, and Wolbach-Sandler. It was shown that incorporation of temperature-dependent binary corrections was required to obtain much more accurate results than in the case of conventional predictions. Binary corrections were adjusted to infinite dilution activity coefficients of a particular solute in a given IL determined experimentally or predicted by means of the modified UNIFAC (Dortmund) group contribution method. We concluded that the latter method allows accurate and reliable calculations of bulk-phase properties in a totally predictive manner.
DEFF Research Database (Denmark)
Kontogeorgis, Georgios
2017-01-01
The book Classical Thermodynamics of Fluid Systems: Principles and Applications written by professor Juan H. Vera and Dr. Grazyna Wilczek-Vera is undoubtably a book written in a most personal style by the two distinguished authors.The book contains four sections and a fifth one with appendices (m...
Thermodynamics and performance of the Mg-H-F system for thermochemical energy storage applications.
Tortoza, Mariana S; Humphries, Terry D; Sheppard, Drew A; Paskevicius, Mark; Rowles, Matthew R; Sofianos, M Veronica; Aguey-Zinsou, Kondo-Francois; Buckley, Craig E
2018-01-24
Magnesium hydride (MgH 2 ) is a hydrogen storage material that operates at temperatures above 300 °C. Unfortunately, magnesium sintering occurs above 420 °C, inhibiting its application as a thermal energy storage material. In this study, the substitution of fluorine for hydrogen in MgH 2 to form a range of Mg(H x F 1-x ) 2 (x = 1, 0.95, 0.85, 0.70, 0.50, 0) composites has been utilised to thermodynamically stabilise the material, so it can be used as a thermochemical energy storage material that can replace molten salts in concentrating solar thermal plants. These materials have been studied by in situ synchrotron X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, temperature-programmed-desorption mass spectrometry and Pressure-Composition-Isothermal (PCI) analysis. Thermal analysis has determined that the thermal stability of Mg-H-F solid solutions increases proportionally with fluorine content, with Mg(H 0.85 F 0.15 ) 2 having a maximum rate of H 2 desorption at 434 °C, with a practical hydrogen capacity of 4.6 ± 0.2 wt% H 2 (theoretical 5.4 wt% H 2 ). An extremely stable Mg(H 0.43 F 0.57 ) 2 phase is formed upon the decomposition of each Mg-H-F composition of which the remaining H 2 is not released until above 505 °C. PCI measurements of Mg(H 0.85 F 0.15 ) 2 have determined the enthalpy (ΔH des ) to be 73.6 ± 0.2 kJ mol -1 H 2 and entropy (ΔS des ) to be 131.2 ± 0.2 J K -1 mol -1 H 2 , which is slightly lower than MgH 2 with ΔH des of 74.06 kJ mol -1 H 2 and ΔS des = 133.4 J K -1 mol -1 H 2 . Cycling studies of Mg(H 0.85 F 0.15 ) 2 over six absorption/desorption cycles between 425 and 480 °C show an increased usable cycling temperature of ∼80 °C compared to bulk MgH 2 , increasing the thermal operating temperatures for technological applications.
Thermodynamics Far from the Thermodynamic Limit.
de Miguel, Rodrigo; Rubí, J Miguel
2017-11-16
Understanding how small systems exchange energy with a heat bath is important to describe how their unique properties can be affected by the environment. In this contribution, we apply Landsberg's theory of temperature-dependent energy levels to describe the progressive thermalization of small systems as their spectrum is perturbed by a heat bath. We propose a mechanism whereby the small system undergoes a discrete series of excitations and isentropic spectrum adjustments leading to a final state of thermal equilibrium. This produces standard thermodynamic results without invoking system size. The thermal relaxation of a single harmonic oscillator is analyzed as a model example of a system with a quantized spectrum than can be embedded in a thermal environment. A description of how the thermal environment affects the spectrum of a small system can be the first step in using environmental factors, such as temperature, as parameters in the design and operation of nanosystem properties.
Energy Technology Data Exchange (ETDEWEB)
Wang, Han, E-mail: wang-han@iapcm.ac.cn [CAEP Software Center for High Performance Numerical Simulation, Huayuan Road 6, 100088 Beijing, China and Zuse Institute Berlin (ZIB), Berlin (Germany); Nakamura, Haruki [Institute for Protein Research, Osaka University, 3-2 Yamadaoka, Suita, Osaka 565-0871 (Japan); Fukuda, Ikuo, E-mail: ifukuda@protein.osaka-u.ac.jp [Institute for Protein Research, Osaka University, 3-2 Yamadaoka, Suita, Osaka 565-0871 (Japan); RIKEN (The Institute of Physical and Chemical Research), 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan)
2016-03-21
We performed extensive and strict tests for the reliability of the zero-multipole (summation) method (ZMM), which is a method for estimating the electrostatic interactions among charged particles in a classical physical system, by investigating a set of various physical quantities. This set covers a broad range of water properties, including the thermodynamic properties (pressure, excess chemical potential, constant volume/pressure heat capacity, isothermal compressibility, and thermal expansion coefficient), dielectric properties (dielectric constant and Kirkwood-G factor), dynamical properties (diffusion constant and viscosity), and the structural property (radial distribution function). We selected a bulk water system, the most important solvent, and applied the widely used TIP3P model to this test. In result, the ZMM works well for almost all cases, compared with the smooth particle mesh Ewald (SPME) method that was carefully optimized. In particular, at cut-off radius of 1.2 nm, the recommended choices of ZMM parameters for the TIP3P system are α ≤ 1 nm{sup −1} for the splitting parameter and l = 2 or l = 3 for the order of the multipole moment. We discussed the origin of the deviations of the ZMM and found that they are intimately related to the deviations of the equilibrated densities between the ZMM and SPME, while the magnitude of the density deviations is very small.
Gray, William G; Miller, Cass T
2009-08-01
This work is the seventh in a series that introduces and employs the thermodynamically constrained averaging theory (TCAT) for modeling flow and transport in multiscale porous medium systems. This paper expands the previous analyses in the series by developing models at a scale where spatial variations within the system are not considered. Thus the time variation of variables averaged over the entire system is modeled in relation to fluxes at the boundary of the system. This implementation of TCAT makes use of conservation equations for mass, momentum, and energy as well as an entropy balance. Additionally, classical irreversible thermodynamics is assumed to hold at the microscale and is averaged to the megascale, or system scale. The fact that the local equilibrium assumption does not apply at the megascale points to the importance of obtaining closure relations that account for the large-scale manifestation of small-scale variations. Example applications built on this foundation are suggested to stimulate future work.
Thermodynamic analyses and assessments of various thermal energy storage systems for buildings
International Nuclear Information System (INIS)
Caliskan, Hakan; Dincer, Ibrahim; Hepbasli, Arif
2012-01-01
Highlights: ► Proposing a novel latent (PCM), thermochemical and sensible (aquifer) TES combination for building heating. ► Performing comprehensive environmental, energy, exergy and sustainability analyses. ► Investigating the effect of varying dead state temperatures on the TESs. - Abstract: In this study, energetic, exergetic, environmental and sustainability analyses and their assessments are carried out for latent, thermochemical and sensible thermal energy storage (TES) systems for phase change material (PCM) supported building applications under varying environment (surrounding) temperatures. The present system consists of a floor heating system, System-I, System-II and System-III. The floor heating system stays at the building floor supported with a floor heating unit and pump. The System-I includes a latent TES system and a fan. The latent TES system is comprised of a PCM supported building envelope, in which from outside to inside; glass, transparent insulation material, PCM, air channel and insulation material are placed, respectively. Furthermore, System-II mainly has a solar-thermochemical TES while there are an aquifer TES and a heat pump in System-III. Among the TESs, the hot and cold wells of the aquifer TES have maximum exergetic efficiency values of 88.782% and 69.607% at 8 °C dead state temperature, respectively. According to the energy efficiency aspects of TESs, the discharging processes of the latent TES and the hot well of the aquifer TES possess the minimum and maximum values of 5.782% and 94.118% at 8 °C dead state temperature, respectively. Also, the fan used with the latent TES is the most environmentally-benign system component among the devices. Furthermore, the most sustainable TES is found for the aquifer TES while the worst sustainable system is the latent TES.
Auger, P
2013-01-01
One of the most fundamental and efficient ways of conceptualizing complex systems is to organize them hierarchically. A hierarchically organized system is represented by a network of interconnected subsystems, each of which has its own network of subsystems, and so on, until some elementary subsystems are reached that are not further decomposed. This original and important book proposes a general mathematical theory of a hierarchical system and shows how it can be applied to very different topics such as physics (Hamiltonian systems), biology (coupling the molecular and the cellular levels), e
Thermo-dynamic analysis and simulation of a combined air and hydro energy storage (CAHES) system
International Nuclear Information System (INIS)
Bi, Xianyun; Liu, Pei; Li, Zheng
2016-01-01
Large-scale energy storage is essential for the stability of a grid, especially for those with large proportion of intermittent renewable energy sources. The efficiency of a conventional compressed air energy storage (CAES) technology is limited by compression heat loss and changing working conditions. In this manuscript, a combined air and hydro energy storage (CAHES) system is proposed, which realizes a higher exergy efficiency compared with conventional CAES systems by reducing compression heat losses and addressing issues of changing working conditions through thermal compensation from solar radiation. The configuration and two operating modes of the proposed CAHES system are firstly introduced, followed by theoretical analysis and numerical simulation under different operating modes to analyze system performances. Impacts of external and internal factors on the system performances are analyzed. The practical feasibility of the system is also investigated. Results show that the exergy efficiency of the system reaches approximately 50%, whilst the charging electricity ratio reaches over 80%. - Highlights: • A combined air and hydro energy storage system is proposed. • High exergy efficiency is achieved and consumption of fossil fuel is eliminated. • The system performance is affected by compression ratio and solar radiation.
Energy Technology Data Exchange (ETDEWEB)
Strečka, Jozef, E-mail: jozef.strecka@upjs.sk [Department of Theoretical Physics and Astrophysics, Faculty of Science, P.J. Šafárik University, Park Angelinum 9, 040 01 Košice (Slovakia); Čenčariková, Hana [Institute of Experimental Physics, Slovak Academy of Sciences, Watsonova 47, 040 01 Košice (Slovakia); Lyra, Marcelo L. [Instituto de Fisica, Universidade Federal de Alagoas, 57072-970 Maceió, AL (Brazil)
2015-12-04
Phase diagrams and thermodynamic properties of a correlated spin–electron system considering localized Ising spins on nodal sites and mobile electrons on decorating sites of doubly decorated planar lattices are rigorously examined with the help of generalized decoration–iteration transformation. The investigated model defined on loose-packed (honeycomb and square) lattices exhibits the phase diagram including a spontaneous ferromagnetic and antiferromagnetic order in a vicinity of quarter and half-filling, respectively, while the same model on close-packed (triangular and kagome) lattices only shows a spontaneous ferromagnetic order due to a kinetically-driven spin frustration at high electron concentrations. The lower critical concentration, at which the ferromagnetic order appears, is remarkably close to a bond percolation threshold in spite of the annealed character of the developed procedure. The specific heat exhibits at the critical temperature either a logarithmic divergence for integer-valued electron concentrations or it shows a finite-cusp for any non-integer electron concentration due to the annealed bond disorder. - Highlights: • Correlated spin–electron system on decorated 2D lattices is exactly solved. • Phase diagrams involve ferro- and antiferromagnetic order near 1/4 and 1/2 filling. • Magnetization is not saturated at zero temperature due to the annealed disorder. • Specific heat displays a finite cusp at the critical temperature.
International Nuclear Information System (INIS)
Rokni, Masoud
2014-01-01
Thermodynamic and thermoeconomic investigations of a small-scale integrated gasification solid oxide fuel cell (SOFC) and Stirling engine for combined heat and power (CHP) with a net electric capacity of 120 kW e have been performed. Woodchips are used as gasification feedstock to produce syngas, which is then utilized to feed the anode side of the SOFC stacks. A thermal efficiency of 0.424 LHV (lower heating value) for the plant is found to use 89.4 kg/h of feedstock to produce the above mentioned electricity. Thermoeconomic analysis shows that the production price of electricity is 0.1204 $/kWh. Furthermore, hot water is considered as a by-product, and the cost of hot water is found to be 0.0214 $/kWh. When compared to other renewable systems of similar scales, this result shows that if both SOFC and Stirling engine technology enter the commercialization phase, then they can deliver electricity at a cost that is competitive with the corresponding renewable systems of the same size. - Highlights: • A 120 kW e integrated gasification SOFC–Stirling CHP is presented. • Effect of important parameters on plant characteristic and economy are studied. • A modest thermal efficiency of 0.41 is found after thermoeconomic optimization. • Reducing stack numbers cuts cost of electricity at expense of thermal efficiency. • The plant cost is estimated to be about 3433 $/kW when disposal costs are neglected
Computing Thermodynamic And Transport Properties
Mcbride, B.; Gordon, Sanford
1993-01-01
CET89 calculates compositions in chemical equilibrium and properties of mixtures of any chemical system for which thermodynamic data available. Provides following options: obtains chemical-equilibrium compositions and corresponding thermodynamic mixture properties for assigned thermodynamic states; calculates dilute-gas transport properties of complex chemical mixtures; obtains Chapman-Jouguet detonation properties for gaseous mixtures; calculates properties of incident and reflected shocks in terms of assigned velocities; and calculates theoretical performance of rocket for both equilibrium and frozen compositions during expansion. Rocket performance based on optional models of finite or infinite area combustor.
Thermodynamic analysis of siphon flash evaporation desalination system using ocean thermal energy
International Nuclear Information System (INIS)
Jin, Zhi-jiang; Ye, Hao; Wang, Hao; Li, Hao; Qian, Jin-yuan
2017-01-01
Highlights: • Siphon flash evaporation desalination system using ocean thermal energy. • Exergy efficiency under design conditions. • Parametric studies using ASPEN Plus. • Experimental studies on the performance of the system. - Abstract: Ocean thermal energy refers to the thermal potential energy produced by the temperature difference between the warm surface seawater and the cold deep seawater. In this paper, a siphon flash evaporation desalination system using ocean thermal energy is proposed. Because it can utilize the ocean thermal energy directly for desalination, siphon flash evaporation desalination system has relatively higher energy efficiency compared with converting ocean thermal energy into electric energy and then using electric energy for desalination. The working principle of this system is introduced firstly. Then, the exergy, exergy loss and exergy efficiency in the flash evaporation, condensation and the whole system are carried out quantitatively. The results show that the exergy efficiency of the system which directly utilizing ocean thermal energy for desalination reaches to 7.81% under design conditions; lower surface seawater temperature, higher deep seawater temperature and higher flash temperature can result in an increasing of system efficiency, while the whole energy consumption shall also be taken into consideration. Then the simulation model of the whole system is created in ASPEN PLUS in order to investigate the influence of some most important parameters, such as surface seawater temperatures, deep seawater temperatures and difference of inlet temperature between surface and deep seawater. Finally, an experimental platform is established based on the working principle and process to verify the validity of the working principle and the simulation model. The siphon flash evaporation desalination system provides a novel method of direct high efficient conversion and utilization of ocean thermal energy and this work can provide
Thermodynamic analysis of a novel hybrid wind-solar-compressed air energy storage system
International Nuclear Information System (INIS)
Ji, Wei; Zhou, Yuan; Sun, Yu; Zhang, Wu; An, Baolin; Wang, Junjie
2017-01-01
Highlights: • We present a novel hybrid wind-solar-compressed air energy storage system. • Wind and solar power are transformed into stable electric energy and hot water. • The system output electric power is 8053 kWh with an exergy efficiency of 65.4%. • Parametric sensitivity analysis is presented to optimize system performance. - Abstract: Wind and solar power have embraced a strong development in recent years due to the energy crisis in China. However, owing to their nature of fluctuation and intermittency, some power grid management problems can be caused. Therefore a novel hybrid wind-solar-compressed air energy storage (WS-CAES) system was proposed to solve the problems. The WS-CAES system can store unstable wind and solar power for a stable output of electric energy and hot water. Also, combined with organic Rankin cycle (ORC), the cascade utilization of energy with different qualities was achieved in the WS-CAES system. Aiming to obtain the optimum performance, the analysis of energy, exergy and parametric sensitivity were all conducted for this system. Furthermore, exergy destruction ratio of each component in the WS-CAES system was presented. The results show that the electric energy storage efficiency, round trip efficiency and exergy efficiency can reach 87.7%, 61.2% and 65.4%, respectively. Meanwhile, the parameters analysis demonstrates that the increase of ambient temperature has a negative effect on the system performance, while the increase of turbine inlet temperature has a positive effect. However, when the air turbine inlet pressure varies, there is a tradeoff between the system performance and the energy storage density.
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)
Thermodynamic analyses of a biomass-coal co-gasification power generation system.
Yan, Linbo; Yue, Guangxi; He, Boshu
2016-04-01
A novel chemical looping power generation system is presented based on the biomass-coal co-gasification with steam. The effects of different key operation parameters including biomass mass fraction (Rb), steam to carbon mole ratio (Rsc), gasification temperature (Tg) and iron to fuel mole ratio (Rif) on the system performances like energy efficiency (ηe), total energy efficiency (ηte), exergy efficiency (ηex), total exergy efficiency (ηtex) and carbon capture rate (ηcc) are analyzed. A benchmark condition is set, under which ηte, ηtex and ηcc are found to be 39.9%, 37.6% and 96.0%, respectively. Furthermore, detailed energy Sankey diagram and exergy Grassmann diagram are drawn for the entire system operating under the benchmark condition. The energy and exergy efficiencies of the units composing the system are also predicted. Copyright © 2016 Elsevier Ltd. All rights reserved.
Thermo-dynamical measurements for ATLAS Inner Detector (evaporative cooling system)
Bitadze, Alexander; Buttar, Craig
During the construction, installation and initial operation of the Evaporative Cooling System for the ATLAS Inner Detector SCT Barrel Sub-detector, some performance characteristics were observed to be inconsistent with the original design specifications, therefore the assumptions made in the ATLAS Inner Detector TDR were revisited. The main concern arose because of unexpected pressure drops in the piping system from the end of the detector structure to the distribution racks. The author of this theses made a series of measurements of these pressure drops and the thermal behavior of SCT-Barrel cooling Stave. Tests were performed on the installed detector in the pit, and using a specially assembled full scale replica in the SR1 laboratory at CERN. This test setup has been used to perform extensive tests of the cooling performance of the system including measurements of pressure drops in different parts of system, studies of the thermal profile along the stave pipe for different running conditions / parameters a...
Smolenski, Valeri; Novoselova, Alena; Volkovich, Vladimir A.
2017-11-01
Separation of lanthanides and actinides can be achieved in a unique "molten chloride - liquid metal" system. Electrode potentials were recorded vs. Cl-/Cl2 reference electrode and the temperature dependencies of the apparent standard potentials of La-(Ga-In) and U-(Ga-In) alloys were determined. Thermodynamic properties and separation factor of lanthanum and uranium were calculated. The obtained data show the perspective for using this system in future innovation method for recovery of nuclear waste.
Vialetto, Giulio; Noro, Marco; Rokni, Masoud
2017-01-01
Transition to alternative energy systems is indicated by EU Commission as a suitable path to energy efficiency and energy saving in the next years. The aims are to decrease greenhouses gases emissions, relevance of fossil fuels in energy production and energy dependence on extra-EU countries. These goals can be achieved increasing renewable energy sources and/or efficiency on energy production processes. In this paper an innovative micro-cogeneration system for household application is presen...
Mrzljak, Vedran; Poljak, Igor; Medica-Viola, Vedran
2017-01-01
Nowadays diesel engines prevail as ship propulsion. However, steam propulsion is still primary drive for LNG carriers. In the presented paper high-pressure feed water heater was analyzed, as one of the essential components in LNG carrier steam propulsion system. Measurements of all operating parameters (fluid streams) at the analyzed heat exchanger inlets and outlets were performed. Change of the operating parameters was measured at different steam system loads, not at full load as usual. Thr...
Thermodynamic modelling of phase equilibria in Al–Ga–P–As system
Indian Academy of Sciences (India)
Unknown
The integral excess free energy for a binary system may ... 1–2–3, 1–2–4, 1–3–4 and 2–3–4. The components of the quaternary system, Al–Ga–P–As have been desig- nated as 1, 2, 3 and 4, respectively. The integral excess ...... Comparison of the solidus compositional data with the calculated values at 1173 K and 1273 K.
Energy Technology Data Exchange (ETDEWEB)
Pinto, Leandro F.; Segalen da Silva, Diogo Italo [Department of Chemical Engineering, Federal University of Parana, CEP 81531-990, Curitiba, PR (Brazil); Rosa da Silva, Fabiano; Ramos, Luiz P. [Department of Chemistry, Federal University of Parana, CEP 81531-990, Curitiba, PR (Brazil); Ndiaye, Papa M. [Department of Chemical Engineering, Federal University of Parana, CEP 81531-990, Curitiba, PR (Brazil); Corazza, Marcos L., E-mail: corazza@ufpr.br [Department of Chemical Engineering, Federal University of Parana, CEP 81531-990, Curitiba, PR (Brazil)
2012-01-15
Highlights: > We measured phase behavior for the system involving {l_brace}CO{sub 2} + biodiesel + methanol{r_brace}. > The saturation pressures were obtained using a variable-volume view cell. > The experimental data were modeled using PR-vdW2 and PR-WS equations of state. - Abstract: The main objective of this work was to investigate the high pressure phase behavior of the binary systems {l_brace}CO{sub 2}(1) + methanol(2){r_brace} and {l_brace}CO{sub 2}(1) + soybean methyl esters (biodiesel)(2){r_brace} and the ternary system {l_brace}CO{sub 2}(1) + biodiesel(2) + methanol(3){r_brace} were determined. Biodiesel was produced from soybean oil, purified, characterized and used in this work. The static synthetic method, using a variable-volume view cell, was employed to obtain the experimental data in the temperature range of (303.15 to 343.15) K and pressures up to 21 MPa. The mole fractions of carbon dioxide were varied according to the systems as follows: (0.2383 to 0.8666) for the binary system {l_brace}CO{sub 2}(1) + methanol(2){r_brace}; (0.4201 to 0.9931) for the binary system {l_brace}CO{sub 2}(1) + biodiesel(2){r_brace}; (0.4864 to 0.9767) for the ternary system {l_brace}CO{sub 2}(1) + biodiesel(2) + methanol(3){r_brace} with a biodiesel to methanol molar ratio of (1:3); and (0.3732 to 0.9630) for the system {l_brace}CO{sub 2} + biodiesel + methanol{r_brace} with a biodiesel to methanol molar ratio of (8:1). For these systems, (vapor + liquid), (liquid + liquid), (vapor + liquid + liquid) transitions were observed. The phase equilibrium data obtained for the systems were modeled using the Peng-Robinson equation of state with the classical van der Waals (PR-vdW2) and Wong-Sandler (PR-WS) mixing rules. Both thermodynamic models were able to satisfactorily correlate the phase behavior of the systems investigated and the PR-WS presented the best performance.
Riggins, David
2003-01-01
The performance continuum for air-breathing engines is formally developed and illustrated in terms of fundamental thermodynamic quantities including heat and work interactions and the irreversibility occurring in the flow-path of the engine. The thermodynamically consistent base-line from which performance losses due to irreversibility must be measured is clearly defined based on this analysis. Issues and problems with conventional flow availability (flow exergy) in terms of the assessment (d...
A thermodynamic study of the BeO-BeSO4 system using solid electrolytes (Paper No. 34)
International Nuclear Information System (INIS)
Kelly, R.G.; Biswas, A.K.
1979-01-01
The thermodynamics of BeO-BeSO 4 has been studied in the temperature range 950-1130 K using solid electrolyte oxygen sensing cell as well as total pressure measurements. This enabled calculation of true thermodynamic data regardless of whether significant thermal segregation occurred or not. The temperature dependence of the free energy of decomposition of BeSO 4 has been suggested. (auth.)
Hisashi Ozawa; Shinya Shimokawa
2015-01-01
The formation process of circulatory motion of a tropical cyclone is investigated from a thermodynamic viewpoint. The generation rate of mechanical energy by a fluid motion under diabatic heating and cooling, and the dissipation rate of this energy due to irreversible processes are formulated from the first and second laws of thermodynamics. This formulation is applied to a tropical cyclone, and the formation process of the circulatory motion is examined from a balance between the generation ...
Kartsev, V. N.; Polikhronidi, N. G.; Batov, D. V.; Shtykov, S. N.; Stepanov, G. V.
2010-02-01
An approach to the thermodynamics of microemulsions based on the use of the two-phase model was suggested. In this model, one phase is the dispersion medium, and the other, the sum of disperse phase nanodrops. Experimental estimation of the adequacy of this approach showed that the model can be used to quantitatively satisfactorily solve microemulsion thermodynamics problems. The degree of two-phase model inadequacy did not exceed 10%.
DEFF Research Database (Denmark)
Bang-Møller, Christian; Rokni, Masoud
2010-01-01
University of Denmark. The SOFC converts the syngas more efficiently than the MGT, which is reflected by the energetic electrical efficiency of the gasifier and MGT system in opposition to the gasifier and SOFC configuration – η_el = 28.1% versus η_el = 36.4%. By combining the SOFC and MGT, the unconverted......A system level modelling study of three combined heat and power systems based on biomass gasification is presented. Product gas is converted in a micro gas turbine (MGT) in the first system, in a solid oxide fuel cell (SOFC) in the second system and in a combined SOFC–MGT arrangement in the third...... system. An electrochemical model of the SOFC has been developed and calibrated against published data from Topsoe Fuel Cells A/S and the Risø National Laboratory. The modelled gasifier is based on an up scaled version (~500 kW_th) of the demonstrated low tar gasifier, Viking, situated at the Technical...
International Nuclear Information System (INIS)
Ribeiro, Guilherme B.; Braz Filho, Francisco A.; Guimarães, Lamartine N.F.
2015-01-01
Nuclear power systems turned to space electric propulsion differ strongly from usual ground-based power systems regarding the importance of overall size and mass. For propulsion power systems, size and mass are essential drivers that should be minimized during conception processes. Considering this aspect, this paper aims the development of a design-based model of a Closed Regenerative Brayton Cycle that applies the thermal conductance of the main components in order to predict the energy conversion performance, allowing its use as a preliminary tool for heat exchanger and radiator panel sizing. The centrifugal-flow turbine and compressor characterizations were achieved using algebraic equations from literature data. A binary mixture of Helium–Xenon with molecular weight of 40 g/mole is applied and the impact of the components sizing in the energy efficiency is evaluated in this paper, including the radiator panel area. Moreover, an optimization analysis based on the final mass of heat the exchangers is performed. - Highlights: • A design-based model of a Closed Brayton Cycle is proposed for nuclear space needs. • Turbomachinery efficiency presented a strong influence on the system efficiency. • Radiator area presented the highest potential to increase the system efficiency. • There is maximum system efficiency for each total mass of heat exchangers. • Size or efficiency optimization was performed by changing heat exchanger proportion.
International Nuclear Information System (INIS)
Soltani, Reza; Dincer, Ibrahim; Rosen, Marc A.
2015-01-01
A Rankine cycle-driven heat pump system is modeled for district heating applications with superheated steam and hot water as products. Energy and exergy analyses are performed, followed by parametric studies to determine the effects of varying operating conditions and environmental parameters on the system performance. The district heating section is observed to be the most inefficient part of system, exhibiting a relative irreversibility of almost 65%, followed by the steam evaporator and the condenser, with relative irreversibilities of about 18% and 9%, respectively. The ambient temperature is observed to have a significant influence on the overall system exergy destruction. As the ambient temperature decreases, the system exergy efficiency increases. The electricity generated can increase the system exergy efficiency at the expense of a high refrigerant mass flow rate, mainly due to the fact that the available heat source is low quality waste heat. For instance, by adding 2 MW of excess electricity on top of the targeted 6 MW of product heat, the refrigerant mass flow rate increases from 12 kg/s (only heat) to 78 kg/s (heat and electricity), while the production of 8 MW of product heat (same total output, but in form of heat) requires a refrigerant mass flow rate of only 16 kg/s. - Highlights: • A new integrated heat pump system is developed for district heating applications. • An analysis and assessment study is undertaken through exergy analysis methodology. • A comparative efficiency evaluation is performed for practical applications. • A parametric study is conducted to investigate how varying operating conditions and state properties affect energy and exergy efficiencies.
DEFF Research Database (Denmark)
Vialetto, Giulio; Noro, Marco; Rokni, Masoud
2017-01-01
Transition to alternative energy systems is indicated by EU Commission as a suitable path to energy efficiency and energy saving in the next years. The aims are to decrease greenhouses gases emissions, relevance of fossil fuels in energy production and energy dependence on extra-EU countries....... These goals can be achieved increasing renewable energy sources and/or efficiency on energy production processes. In this paper an innovative micro-cogeneration system for household application is presented: it covers heating, domestic hot water and electricity demands for a residential user. Solid oxide fuel...... cells, heat pump and Stirling engine are utilised as a system to achieve high energy conversion efficiency. A transition from traditional petrol cars to electric mobility is also considered and simulated here. Different types of fuel are considered to demonstrate the high versatility of the simulated...
International Nuclear Information System (INIS)
Salgado, R.; Belmonte, J.F.; Almendros-Ibáñez, J.A.; Molina, A.E.
2017-01-01
A high percentage of the heat that is supplied to thermoelectric power plants is discarded to ambient and must be handled by an external cooling system. This cooling system typically consists of wet cooling towers because of the excellent thermo-physical properties of water. However, the amount of water consumed for power production has reached alarming levels in developed countries. Air-cooled heat exchangers (ACHXs) appear to be the most adequate technology to substitute for wet cooling towers, but the use of this technology has some limitations. The most important limitation is the higher condenser pressures in the cycle, which produce backpressures at the condensing turbine's exit, increases in heat rejection and losses in the net plant efficiency. This paper presents a concept for the use of ACHXs in the cooling systems of power plants using an absorption refrigeration system (ARS) as an intermediary. Heat from the steam condenser is handled by the evaporator of the ARS and “lifted” to a higher temperature level, where the ACHXs are fitted to work. The generator of the ARS is fed by the power plant itself, extracting (bleeding off) some of the steam that flows through the steam turbine at the correct pressure and temperature. - Highlights: • Integration of absorption refrigeration system into the Rankine cycle of power plant. • The absorption refrigeration system will be driven by bleeding off steam turbine. • Lift rejection temperatures to a higher level to operate with air cooled condensers. • The water savings are estimated to be in the range of 1.12–5.58 m 3 /MWh. • Studying the integration with single- and double-effect absorption machines.
International Nuclear Information System (INIS)
Jourdan, J.
2009-11-01
This work is a contribution to the development of innovative concepts for fuel cladding in pressurized water nuclear reactors. This concept implies the insertion of rare earth (erbium and gadolinium) in the zirconium fuel cladding. The determination of phase equilibria in the systems is essential prior to the implementation of such a promising solution. This study consisted in an experimental determination of the erbium-zirconium phase diagram. For this, we used many different techniques in order to obtain diagram data such as solubility limits, solidus, liquidus or invariant temperatures. These data allowed us to present a new diagram, very different from the previous one available in the literature. We also assessed the diagram using the CALPHAD approach. In the gadolinium-zirconium system, we determined experimentally the solubility limits. Those limits had never been determined before, and the values we obtained showed a very good agreement with the experimental and assessed versions of the diagram. Because these alloys are subjected to oxygen diffusion throughout their life, we focused our attention on the erbium-oxygen-zirconium and gadolinium-oxygen-zirconium systems. The first system has been investigated experimentally. The alloys fabrication has been performed using powder metallurgy. In order to obtain pure raw materials, we fabricated powder from erbium and zirconium bulk metals using hydrogen absorption/desorption. The characterisation of the ternary pellets allowed the determination of two ternary isothermal sections at 800 and 1100 C. For the gadolinium-oxygen-zirconium system, we calculated the phase equilibria at temperatures ranging from 800 to 1100 C, using a homemade database compiled from literature assessments of the oxygen-zirconium, gadolinium-zirconium and gadolinia-zirconia systems. Finally, we determined the mechanical properties, in connexion with the microstructure, of industrial quality alloys in order to identify the influence of
An analytical approach of thermodynamic behavior in a gas target system on a medical cyclotron.
Jahangiri, Pouyan; Zacchia, Nicholas A; Buckley, Ken; Bénard, François; Schaffer, Paul; Martinez, D Mark; Hoehr, Cornelia
2016-01-01
An analytical model has been developed to study the thermo-mechanical behavior of gas targets used to produce medical isotopes, assuming that the system reaches steady-state. It is based on an integral analysis of the mass and energy balance of the gas-target system, the ideal gas law, and the deformation of the foil. The heat transfer coefficients for different target bodies and gases have been calculated. Excellent agreement is observed between experiments performed at TRIUMF's 13 MeV cyclotron and the model. Copyright © 2015 Elsevier Ltd. All rights reserved.
Physical and Thermodynamical Properties of Water Phases in Hardening Portland Cement Systems
DEFF Research Database (Denmark)
Hansen, T. Bæk
The present study is devoted to the description of water phases in hardening portland cement paste systems containing a significant amount of micro-filler and having a low to moderate water/powder ratio. Emphasis has been placed on the early stages of the hardening process.......The present study is devoted to the description of water phases in hardening portland cement paste systems containing a significant amount of micro-filler and having a low to moderate water/powder ratio. Emphasis has been placed on the early stages of the hardening process....
Todoshchenko, I.
2018-04-01
We have measured the equilibrium melting pressure of helium-4 as a function of the crystal size. Negative compressibility of a liquid with an inclusion of solid seed is predicted theoretically and verified experimentally with helium-4 crystal-superfluid system at 0.15 K. This two-phase system is shown to be stable if the crystal size is large enough, which is proven by the experiment. Crystal seeds that are too small spontaneously either melt completely or grow to a large enough size.
DEFF Research Database (Denmark)
Cherny, Izhack; Overgaard, Martin; Borch, Jonas
2007-01-01
The RelE and RelB proteins constitute the RNA interferase (toxin) and its cognate inhibitor (antitoxin) components of the Escherichia coli relBE toxin-antitoxin system. Despite the well-described functionality and physiological activity of this system in E. coli, no structural study was performed...... on the folding and stability of the protein pair in solution. Here we structurally and thermodynamically characterize the RelBE system components from E. coli in solution, both separately and in their complexed state. The RelB antitoxin, an alpha-helical protein according to circular dichroism and infrared......, our results support that RelB protein from E. coli is similar to ParD and CcdA antitoxins in both fold and thermodynamic properties. The differential folding state of the proteins is discussed in the context of their physiological activities....
International Nuclear Information System (INIS)
Bermudez Martinez, A.; Damiani, D.; Guzman Martinez, F.; Rodriguez Hoyos, O.; Rodriguez Manso, A.
2015-01-01
Cluster emission at pre-equilibrium stage, in heavy ion fusion reactions of 12 C and 16 O nuclei with 116 Sn, 208 Pb, 238 U are studied. the energy of the projectile nuclei was chosen at 0.25GeV, 0.5GeV and 1GeV. A cluster formation model is developed in order to calculate the cluster size. Thermodynamics of small systems was used in order to examine the cluster behavior inside the nuclear media. This model is based on considering two phases inside the compound nucleus, on one hand the nuclear media phase, and on the other hand the cluster itself. The cluster acts like an instability inside the compound nucleus, provoking an exchange of nucleons with the nuclear media through its surface. The processes were simulated using Monte Carlo methods. We obtained that the cluster emission probability shows great dependence on the cluster size. This project is aimed to implement cluster emission processes, during the pre-equilibrium stage, in the frame of CRISP code (Collaboration Rio-Sao Paulo). (Author)
Experimental and Thermodynamic Study of Selected in-Situ Composites from the Fe-Cr-Ni-Mo-C System
Directory of Open Access Journals (Sweden)
Wieczerzak K.
2016-06-01
Full Text Available The aim of the study was to synthesize and characterize the selected in-situ composites from the Fe-Cr-Ni-Mo-C system, additionally strengthened by intermetallic compounds. The project of the alloys was supported by thermodynamic simulations using Calculation of Phase Diagram approach via Thermo-Calc. Selected alloys were synthesized in an arc furnace in a high purity argon atmosphere using a suction casting unit. The studies involved a range of experimental techniques to characterize the alloys in the as-cast state, including optical emission spectrometry, light microscopy, scanning electron microscopy, electron microprobe analysis, X-ray diffraction and microhardness tests. These experimental studies were compared with the Thermo-Calc data and high resolution dilatometry. The results of investigations presented in this paper showed that there is a possibility to introduce intermetallic compounds, such as χ and σ, through modification of the chemical composition of the alloy with respect to Nieq and Creq. It was found that the place of intermetallic compounds precipitation strongly depends on matrix nature. Results presented in this paper may be successfully used to build a systematic knowledge about the group of alloys with a high volume fraction of complex carbides, and high physicochemical properties, additionally strengthened by intermetallic compounds.
Chemical thermodynamics of the system Cs--U--Zr--H--I--O in the LWR fuel-clad gap
International Nuclear Information System (INIS)
Besmann, T.M.; Lindemer, T.B.
1978-01-01
Equilibrium thermodynamic calculations were performed on the are Cs-U-Zr-H-I-O system that is assumed to exist in the fuel-clad gap of light water reactor fuel under in-reactor, steam, and 50% steam--50% air conditions. The in-reactor oxygen potential is assumed to be controlled by UO/sub 2+x/ rather than Zr + ZrO 2 . Thus, the important condensed phases present are UO/sub 2+x/, Cs 2 UO 4 , and CsI, and the major gaseous species are Cs, CsI, and Cs 2 I 2 . The presence of steam does not alter the species present, although CsOH also becomes a major gaseous species. In a 50% steam--50% air mixture, the condensed phases U 3 O 8 or UO 3 , Cs 2 U 15 O 46 , and ZrI 3 or liquid ZrI 2 are present at equilibrium, and the gaseous species ZrI 2 , ZrI 3 , and ZrI 4 have large partial pressures
International Nuclear Information System (INIS)
Hoehn, R.; Herzig, C.
1986-01-01
The thermodynamic activity of the gold component was directly measured in Au-Pd alloys in the concentration range between X Au =0.048 and 0.850 and in the temperature range 1070 and 1300 K. The ratio of the vapour pressures of pure gold and of the gold component of the alloys was determined - after effusion from a Knudsen twin cell and condensation on a collecting plate - by analysing the decay rate of the radioisotopes 195 Au and 198 Au in an intrinsic germanium well-type detector. The partial mixing enthalpy and the partial mixing entropy of Au were directly obtained from these results. By Gibbs-Duhem integration the integral mixing functions were deduced. Similar measurements were performed in several ternary Au-Ag-Pd alloys of fixed mole fraction X Ag /X Pd =1/9. A comparison of the directly measured partial free excess enthalpy of Au in these ternary alloys with data obtained by the approximate models of Kohler, Toop and Bonnier using data of the corresponding three binary systems yields satisfactory agreement. (orig.) [de
International Nuclear Information System (INIS)
Alonso, Regina P.
1997-01-01
Two regions in the zirconium-platinum system (Zr-Pt) were investigated, namely, the zirconium rich and the platinum rich regions. With this purpose, five alloys were obtained. The performed experiences consisted on heat treatments and electrical resistivity variations with temperature measurements. The appearing phases were analyzed by optical and scanning electron microscopy (SEM), quantitative microanalysis and X-ray diffraction techniques. Besides that, the existing phases in the rich zirconium region between 0 and 50 % at. Pt were thermodynamically modelled and the resulting diagram was calculated by means of the Thermocalc computational program. Several proposals were formulated: a) A change in the eutectoid transformation temperature βZr ↔ αZr + pp (800 C degrees according to this work); b) The existence of the phase Zr 3 Pt in the equilibrium diagram; c) The existence of the peritectic transformation Liquid + Zr 5 Pt 3 ↔ Zr 3 Pt; d) The occurrence of the two - phases region ZrPt 3 + ZrPt 8 between 1050 and 1320 C degrees, and finally; e) The occurrence of the peritectic transformation ZrPt 3 + Liquid ↔ γPt was verified. (author)
Vlad, Marcel O; Popa, Vlad T; Ross, John
2011-02-03
We examine the problem of consistency between the kinetic and thermodynamic descriptions of reaction networks. We focus on reaction networks with linearly dependent (but generally kinetically independent) reactions for which only some of the stoichiometric vectors attached to the different reactions are linearly independent. We show that for elementary reactions without constraints preventing the system from approaching equilibrium there are general scaling relations for nonequilibrium rates, one for each linearly dependent reaction. These scaling relations express the ratios of the forward and backward rates of the linearly dependent reactions in terms of products of the ratios of the forward and backward rates of the linearly independent reactions raised to different scaling powers; the scaling powers are elements of the transformation matrix, which relates the linearly dependent stoichiometric vectors to the linearly independent stoichiometric vectors. These relations are valid for any network of elementary reactions without constraints, linear or nonlinear kinetics, far from equilibrium or close to equilibrium. We show that similar scaling relations for the reaction routes exist for networks of nonelementary reactions described by the Horiuti-Temkin theory of reaction routes where the linear dependence of the mechanistic (elementary) reactions is transferred to the overall (route) reactions. However, in this case, the scaling conditions are valid only at the steady state. General relationships between reaction rates of the two levels of description are presented. These relationships are illustrated for a specific complex reaction: radical chlorination of ethylene.
International Nuclear Information System (INIS)
Zamora-López, Héctor S.; Galicia-Luna, Luis A.; Elizalde-Solis, Octavio; Hernández-Rosales, Irma P.; Méndez-Lango, Edgar
2012-01-01
Highlights: ► Experimental density data are reported for (ethanol + decane) and (ethanol + decane + CO 2 ) mixtures. ► Compressed liquid densities were measured in a vibrating tube densimeter from (313 to 363) K. ► Excess molar volumes for (ethanol + decane) mixtures are positive. ► The presence of carbon dioxide in the (ethanol + decane) mixture causes negative excess molar volumes. - Abstract: Volumetric properties for the binary (ethanol + decane) and ternary (ethanol + decane + carbon dioxide) systems are reported from (313 to 363) K and pressures up to 20 MPa. Compressed liquid densities of both systems were measured in a vibrating tube densimeter at different compositions. Binary mixtures {x 1 ethanol + (1-x 1 ) decane} were prepared at x 1 = 0.0937, 0.1011, 0.2507, 0.4963, 0.7526, 0.9014. Compositions for the ternary system were prepared by varying the ethanol/decane relation and trying to keep constant the presence of carbon dioxide at about 0.2 mole fraction. These were {x 1 ethanol + x 2 decane + (1-x 1 -x 2 ) carbon dioxide} x 1 = 0.0657, 0.1986, 0.4087, 0.6042, 0.7109. Density results were correlated using an empirical model with five parameters. Deviations between experimental and calculated values agree and are within the experimental uncertainty. Isobaric expansivity, isothermal compressibility, thermal pressure coefficient, and internal pressure have been calculated for both binary and ternary systems using the empirical model.
Besseling, N.A.M.
1993-01-01
The aim of the present study was to develop a lattice theory for systems, homogeneous as well as heterogeneous, containing molecules with orientation- dependent interactions such as water. It was soon recognised that the so-called Bragg-Williams mean-field approximation is not capable of
Energy Technology Data Exchange (ETDEWEB)
Foerstendorf, Harald; Stockmann, Madlen; Heim, Karsten; Mueller, Katharina; Brendler, Vinzenz [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes; Comarmond, M.J.; Payne, T.E. [Australian Nuclear Science and Technology Organisation, Lucas Heights (Australia); Steudtner, Robin [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Inst. of Resource Ecology
2017-06-01
Spectroscopic data of sorption processes potentially provide direct impact on Surface Complexation Modelling (SCM) approaches. Based on spectroscopic data of the ternary sorption system U(VI)/phosphate/silica strongly suggesting the formation of a precipitate as the predominant surface process, SCM calculations accurately reproduced results from classical batch experiments.
Sagis, L.M.C.; Öttinger, H.C.
2013-01-01
In this paper we present a general model for the dynamic behavior of multiphase systems in which the bulk phases and interfaces have a complex microstructure (for example, immiscible polymer blends with added compatibilizers, or polymer stabilized emulsions with thickening agents dispersed in the
Equilibrium thermodynamics of the ternary membrane-forming system nylon, formic acid and water
Bulte, A.M.W.; Bulte, A.M.W.; Naafs, E.M.; van Eeten, F.; Mulder, M.H.V.; Smolders, C.A.; Smolders, C.A.; Strathmann, H.
1996-01-01
The binary Flory-Huggins interaction parameters for the ternary membrane-forming system nylon, formic acid and water have been obtained from literature data, swelling values and melting point depression. Nylon 4,6 nylon 6 and a copolymer of nylon 4,6 and 6 were examined. The isothermal
Metal-hydrogen systems with an exceptionally large and tunable thermodynamic destabilization
Ngene, Peter; Longo, Alessandro; Mooij, L.P.A.; Bras, Wim; Dam, B.
2017-01-01
Hydrogen is a key element in the energy transition. Hydrogen-metal systems have been studied for various energy-related applications, e.g., for their use in reversible hydrogen storage, catalysis, hydrogen sensing, and rechargeable batteries. These applications depend strongly on the
Withag, Jan A.M.; Smeets, Jules R.; Bramer, Eduard A.; Brem, Gerrit
2012-01-01
This article presents a system model for the process of gasification of biomass model compounds in supercritical water. Supercritical water gasification of wet biomass (water content of 70 wt% or more) has as the main advantage that conversion may take place without the costly drying step. The
Directory of Open Access Journals (Sweden)
Igor Poljak
2017-01-01
Full Text Available Nowadays diesel engines prevail as ship propulsion. However, steam propulsion is still primary drive for LNG carriers. In the presented paper high-pressure feed water heater was analyzed, as one of the essential components in LNG carrier steam propulsion system. Measurements of all operating parameters (fluid streams at the analyzed heat exchanger inlets and outlets were performed. Change of the operating parameters was measured at different steam system loads, not at full load as usual. Through these measurements was enabled the insight into the behaviour of the heat exchanger operating parameters during the whole exploitation. The numerical analysis was performed, based on the measured data. The changes in energy and exergy efficiency of the heat exchanger were analyzed. Energetic and exergetic power inputs and outputs were also calculated, which enabled an insight into the change of energetic and exergetic power losses of the heat exchanger at different steam system loads. Change in energetic and exergetic power losses and operating parameters, which have the strongest influence on the high-pressure feed water heater losses, were described. Analyzed heat exchanger was compared with similar heat exchangers in the base loaded conventional steam power plants. From the conducted analysis, it is concluded that the adjustment and control modes of these high-pressure heat exchangers are equal, regardless of whether they were mounted in the base loaded conventional steam power plants or marine steam systems, while their operating parameters and behaviour patterns differ greatly.
Molecular Thermodynamic Modeling and Design of Microencapsulation Systems for Drug Delivery
DEFF Research Database (Denmark)
Abildskov, Jens; O’Connell, John P.
2011-01-01
A systematic design strategy is given for computer-aided design of microparticle drug-delivery systems produced by solvent evaporation. In particular, design of solvents, polymer material, and external phase composition are considered for the case when the active ingredient is known. The procedur...
International Nuclear Information System (INIS)
Foerstendorf, Harald; Stockmann, Madlen; Heim, Karsten; Mueller, Katharina; Brendler, Vinzenz; Steudtner, Robin
2017-01-01
Spectroscopic data of sorption processes potentially provide direct impact on Surface Complexation Modelling (SCM) approaches. Based on spectroscopic data of the ternary sorption system U(VI)/phosphate/silica strongly suggesting the formation of a precipitate as the predominant surface process, SCM calculations accurately reproduced results from classical batch experiments.
International Nuclear Information System (INIS)
Utlu, Zafer; Aydın, Devrim; Kıncay, Olcay
2014-01-01
Highlights: • An experimental thermal investigation of hybrid renewable heating system is presented. • Analyses were done by using real data obtained from a prototype structure. • Exergy efficiency of system components investigated during discharging period are close to each other as 32%. • The average input energy and exergy rates to the LHS were 0.770 and 0.027 kW. • Overall total energy and exergy efficiencies of LHS calculated as 72% and 28.4%. - Abstract: In this study an experimental thermal investigation of hybrid renewable heating system is presented. Latent heat storage stores energy, gained by solar collectors and supplies medium temperature heat to heat pump both day time also night time while solar energy is unavailable. In addition to this an accumulation tank exists in the system as sensible heat storage. It provides supply–demand balance with storing excess high temperature heat. Analyses were done according to thermodynamic’s first and second laws by using real data obtained from a prototype structure, built as part of a project. Results show that high percent of heat loses took place in heat pump with 1.83 kW where accumulator-wall heating cycle followed it with 0.42 kW. Contrarily highest break-down of exergy loses occur accumulator-wall heating cycle with 0.28 kW. Averagely 2.42 kW exergy destruction took place in whole system during the experiment. Solar collectors and heat pump are the promising components in terms of exergy destruction with 1.15 kW and 1.09 kW respectively. Exergy efficiency of system components, investigated during discharging period are in a close approximately of 32%. However, efficiency of solar collectors and charging of latent heat storage are 2.3% and 7% which are relatively low. Average overall total energy and exergy efficiencies of latent heat storage calculated as 72% and 28.4% respectively. Discharging energy efficiency of latent heat storage is the highest through all system components. Also heat
International Nuclear Information System (INIS)
Tang, Ying; Du, Yong; Zhang, Lijun; Yuan, Xiaoming; Kaptay, George
2012-01-01
Highlights: ► An exponential formulation to describe ternary excess Gibbs energy is proposed. ► Theoretical analysis is performed to verify stability of phase using new formulation. ► Al–Mg–Si system and its boundary binaries have been assessed by the new formulation. ► Present calculations for Al–Mg–Si system are more reasonable than previous ones. - Abstract: An exponential formulation was proposed to replace the linear interaction parameter in the Redlich–Kister (R–K) polynomial for the excess Gibbs energy of ternary solution phase. The theoretical analysis indicates that the proposed new exponential formulation can not only avoid the artificial miscibility gap at high temperatures but also describe the ternary system well. A thermodynamic description for the Al–Mg–Si system and its boundary binaries was then performed by using both R–K linear and exponential formulations. The inverted miscibility gaps occurring in the Mg–Si and the Al–Mg–Si systems at high temperatures due to the use of R–K linear polynomials are avoided by using the new formulation. Besides, the thermodynamic properties predicted with the new formulation confirm the general thermodynamic belief that the solution phase approaches to the ideal solution at infinite temperatures, which cannot be described with the traditional R–K linear polynomials.
Thermodynamic system analyse and evaluate for steam turbine of unclear power plant
International Nuclear Information System (INIS)
Wang Shiyong; Hu Youqing; Xu Qiao; Xu Damao
2014-01-01
In the process of turbine bid assessment for steam turbine of nuclear projects, there were problems with the scheme of thermal system provided by suppliers due to mistakes or commercial interests, such as unreasonable preferences and incorrect calculation methods, etc. A kind of calculation method for steam enthalpy values of stages with partly drains and completely drains was presented in this paper, and power was chosed to evaluate efficiencies which was more precise and closer to the truth compared with enthalpy drop, also performance indicators such as ideal power, equivalent flow and ideal enthalpy drop were gived and applied for analysis and evaluation of the scheme, which made the errors revealed promptly and looked after owner's interests. The method was also applied for calculating and analysis of thermal system of steam turbine for in-service nuclear power station, and revealed some problems and gived the solutions. (authors)
Kleidon, Axel
2016-04-01
The Earth is, undoubtedly, a vastly complex system that is shaped by a range of processes, from solar radiation to planetary motion, geochemical cycling, biotic and human activity, all interacting across a range of time scales to shape the emergent state of the system. The common approach to deal with modelling parts of or the whole Earth system is to build increasingly more comprehensive models, with higher resolutions, a greater range of processes, and a greater number of interactions being represented. Yet, this also yields increasingly incomprehensible models in which the underlying assumptions in the model parameterizations are obscured. I present an alternative approach to model the complex Earth system that focuses on fundamental physical constraints and that allows for insights from simple, back-of-the-envelope calculations. This approach is based on describing the Earth as a thermodynamic system with dynamics that are driven by energy conversions, and in which its complexity is dealt with by the assumption that the dynamics operate at their thermodynamic limit. It requires us to think of Earth system processes in terms of the energy that they convert, the origin of this energy, the interactions that result from the energy conversion, and how these factors shape the resulting thermodynamic limit. The behavior of the complex Earth system then becomes predictable by relatively simple means, not because we deal with a simple system, but because it is so complex that it is ultimately constrained by fundamental thermodynamic limits that can be derived by comparably simple means. I illustrate this approach with three examples, dealing with the hydrologic sensitivity to global warming, the surface energy balance partitioning on land at the diurnal scale, and the limits to wind power as renewable energy. Each example shows that the approach matches observations or complex climate models very well, highlighting that this approach provides a simple alternative to
Stolyarova, V L; Shilov, A L; Lopatin, S I; Shugurov, S M
2014-04-15
Binary glass-forming systems containing bismuth(III) oxide, especially the Bi2O3-SiO2 system, are of great importance in modern materials science: preparation of thin films, fiber optics, potential solar converters, and radiation shields in nuclear physics. Information on vaporization processes and thermodynamic properties obtained in the present study and the results of modeling of this system will be useful for optimization of the synthesis and applications of Bi2O3-containing materials at high temperatures. High-temperature Knudsen effusion mass spectrometry was used to study the vaporization processes and to determine the partial pressures of components of the Bi2O3-SiO2 system. Measurements were performed with a MS-1301 mass spectrometer. Vaporization was carried out using two iridium-plated molybdenum effusion cells containing the sample under study and pure bismuth(III) oxide (reference substance). Modeling of the thermodynamic properties and structure of glasses and melts in the Bi2O3-SiO2 and Bi2O3-B2O3 systems was performed using a modified approach based on the generalized lattice theory of associated solutions (GLTAS). At a temperature of 1000 K, Bi and O2 were found to be the main vapor species over the samples studied. The Bi2O3 activity as a function of composition of the Bi2O3-SiO2 system was obtained from the measured partial pressures of the vapor species. The thermodynamic properties of mixing from oxides in this system were calculated. The advantages of GLTAS for modeling of glasses and melts in the binary systems containing Bi2O3 were demonstrated. The thermodynamic functions of mixing in glasses and melts of the Bi2O3-SiO2 system determined at 1000 K in the present study, as well as in the Bi2O3-B2O3 system, demonstrated negative deviations from ideality. Modeling of the obtained experimental data using GLTAS allowed a correlation to be found between the thermodynamic properties and the relative number of bonds of various types formed in
High temperature thermodynamics and vaporization of the zirconium--niobium--oxygen system
International Nuclear Information System (INIS)
Rinehart, G.H.
1978-01-01
The vaporization behavior of the Zr--Nb--O system was studied by means of successive vaporization, Knudsen effusion-target collection experiments, and mass spectrometric analysis of the vapors effusing from a Knudsen crucible. The successive vaporization experiments were performed on two ternary samples in open crucibles. X-ray powder diffraction patterns of the residues and x-ray fluorescence analysis of the condensates and residues indicated the preferential vaporization of niobium-containing species with the composition of the residue subsequently becoming closer to that of congruently vaporizing ZrO/sub 2-x/. The Knudsen effusion-target collection experiments were employed on two samples, pure NbO 2 (s) and a two-phase ZrO 2 --NbO 2 mixture, in order to obtain information on the activity of NbO 2 in the two-phase mixture. Second law enthalpies and entropies of sublimation as well as third law enthalpies were obtained for both systems. The vaporization behaviors of five compositions in the Zr--Nb--O system, NbO 2 , NbO, a ZrO 2 --NbO 2 two-phase mixture, Nb 2 O 5 , and Zr 6 Nb 2 O 17 , were investigated. Above Nb 2 O 5 and the fully oxidized Zr 6 Nb 2 O 17 oxygen is preferentially lost; over NbO 2 , the two-phase ZrO 2 --NbO 2 system, and NbO the principal gaseous species is NbO 2
Hossein Safaei; Michael J. Aziz
2017-01-01
We present analyses of three families of compressed air energy storage (CAES) systems: conventional CAES, in which the heat released during air compression is not stored and natural gas is combusted to provide heat during discharge; adiabatic CAES, in which the compression heat is stored; and CAES in which the compression heat is used to assist water electrolysis for hydrogen storage. The latter two methods involve no fossil fuel combustion. We modeled both a low-temperature and a high-temper...
Energy Technology Data Exchange (ETDEWEB)
Charin, Rafael M. [Department of Chemical Engineering, Federal University of Parana (UFPR), Polytechnic Center (DTQ/ST/UFPR), Jardim das Americas, Curitiba 82530-990, PR (Brazil); Department of Food Engineering, URI - Campus de Erechim, Av. Sete de Setembro, 1621, Erechim 99700-000, RS (Brazil); Corazza, Marcos L.; Ndiaye, Papa M. [Department of Chemical Engineering, Federal University of Parana (UFPR), Polytechnic Center (DTQ/ST/UFPR), Jardim das Americas, Curitiba 82530-990, PR (Brazil); Rigo, Aline A.; Mazutti, Marcio A. [Department of Food Engineering, URI - Campus de Erechim, Av. Sete de Setembro, 1621, Erechim 99700-000, RS (Brazil); Vladimir Oliveira, J., E-mail: vladimir@uricer.edu.b [Department of Food Engineering, URI - Campus de Erechim, Av. Sete de Setembro, 1621, Erechim 99700-000, RS (Brazil)
2011-03-15
Reported in this work are phase equilibrium data at high pressures for the binary and ternary systems formed by {l_brace}propane + N,N-dimethylformamide (DMF) + methanol{r_brace}. Phase equilibrium measurements were performed in a high-pressure, variable-volume view cell, following the static synthetic method for obtaining the experimental bubble and dew points transition data over the temperature range of (363 to 393) K, pressures up to 11.5 MPa and overall mole fraction of the lighter component varying from 0.1 to 0.995. For the systems investigated, vapour-liquid (VLE), liquid-liquid (LLE) and vapour-liquid-liquid (VLLE) phase transitions were visually recorded. Results show that the systems investigated present UCST (upper critical solution temperature) phase transition curves with an UCEP (upper critical end point) at a temperature higher than the propane critical temperature. The experimental data were modelled using the Peng-Robinson equation of state with the Wong-Sandler and the classical quadratic mixing rules, affording a satisfactory representation of the experimental data.
Rosinberg, M. L.; Munakata, T.; Tarjus, G.
2015-04-01
Response lags are generic to almost any physical system and often play a crucial role in the feedback loops present in artificial nanodevices and biological molecular machines. In this paper, we perform a comprehensive study of small stochastic systems governed by an underdamped Langevin equation and driven out of equilibrium by a time-delayed continuous feedback control. In their normal operating regime, these systems settle in a nonequilibrium steady state in which work is permanently extracted from the surrounding heat bath. By using the Fokker-Planck representation of the dynamics, we derive a set of second-law-like inequalities that provide bounds to the rate of extracted work. These inequalities involve additional contributions characterizing the reduction of entropy production due to the continuous measurement process. We also show that the non-Markovian nature of the dynamics requires a modification of the basic relation linking dissipation to the breaking of time-reversal symmetry at the level of trajectories. The modified relation includes a contribution arising from the acausal character of the reverse process. This, in turn, leads to another second-law-like inequality. We illustrate the general formalism with a detailed analytical and numerical study of a harmonic oscillator driven by a linear feedback, which describes actual experimental setups.
Directory of Open Access Journals (Sweden)
Hossein Safaei
2017-07-01
Full Text Available We present analyses of three families of compressed air energy storage (CAES systems: conventional CAES, in which the heat released during air compression is not stored and natural gas is combusted to provide heat during discharge; adiabatic CAES, in which the compression heat is stored; and CAES in which the compression heat is used to assist water electrolysis for hydrogen storage. The latter two methods involve no fossil fuel combustion. We modeled both a low-temperature and a high-temperature electrolysis process for hydrogen production. Adiabatic CAES (A-CAES with physical storage of heat is the most efficient option with an exergy efficiency of 69.5% for energy storage. The exergy efficiency of the conventional CAES system is estimated to be 54.3%. Both high-temperature and low-temperature electrolysis CAES systems result in similar exergy efficiencies (35.6% and 34.2%, partly due to low efficiency of the electrolyzer cell. CAES with high-temperature electrolysis has the highest energy storage density (7.9 kWh per m3 of air storage volume, followed by A-CAES (5.2 kWh/m3. Conventional CAES and CAES with low-temperature electrolysis have similar energy densities of 3.1 kWh/m3.
Thermodynamics of Crystalline States
Fujimoto, Minoru
2013-01-01
Thermodynamics is a well-established discipline of physics for properties of matter in thermal equilibrium with the surroundings. Applying to crystals, however, the laws encounter undefined properties of crystal lattice, which therefore need to be determined for a clear and well-defined description of crystalline states. Thermodynamics of Crystalline States explores the roles played by order variables and dynamic lattices in crystals in a wholly new way. The book begins by clarifying basic concepts for stable crystals. Next, binary phase transitions are discussed to study collective motion of order variables, as described mostly as classical phenomena. New to this edition is the examination of magnetic crystals, where magnetic symmetry is essential for magnetic phase transitions. The multi-electron system is also discussed theoretically, as a quantum-mechanical example, for superconductivity in metallic crystals. Throughout the book, the role played by the lattice is emphasized and studied in-depth. Thermod...
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)
Thermodynamic study of preventing the corrosion of plutonium surface with CO and H2 system
International Nuclear Information System (INIS)
Li Quan; Gao Tao; Wang Hongyan; Jiang Gang; Zhu Zhenghe
1999-08-01
The calculated results of the temperature dependence of standard Gibbs free energy change ΔG 0 of the reactions of CO and H 2 with Pu, PuO, Pu 2 O 3 , PuO 2 , respectively, show that the CO-H 2 system enables a passive surface film to be formed on the compact and stable crystal surface of Pu 2 O 3 to prevent the metallic plutonium from further corrosion by the inward diffusive CO and H 2 gas. It is presumably like the protecting aluminum surface with its oxidized layer
Thermodynamic fingerprints of non-Markovianity in a system of coupled superconducting qubits
Hamedani Raja, Sina; Borrelli, Massimo; Schmidt, Rebecca; Pekola, Jukka P.; Maniscalco, Sabrina
2018-03-01
The exploitation and characterization of memory effects arising from the interaction between system and environment is a key prerequisite for quantum reservoir engineering beyond the standard Markovian limit. In this paper we investigate a prototype of non-Markovian dynamics experimentally implementable with superconducting qubits. We rigorously quantify non-Markovianity, highlighting the effects of the environmental temperature on the Markovian to non-Markovian crossover. We investigate how memory effects influence, and specifically suppress, the ability to perform work on the driven qubit. We show that the average work performed on the qubit can be used as a diagnostic tool to detect the presence or absence of memory effects.
Phase equilibria and thermodynamic studies in the titanium-nickel and titanium-nickel-oxygen systems
International Nuclear Information System (INIS)
Chattopadhyay, G.; Kleykamp, H.; Laumer, W.
1983-01-01
The isothermal section of the Ti-Ni-O system was examined at 1200 K in the regions between the Ni(Ti) solid solution and the binary oxides of titanium. The relative partial Gibbs energies of oxygen over the Ti 2 O 3 -Ti 3 O 5 region and of titanium in the Ni(Ti) solid solution as well as the Gibbs energies of formation of NiTiO 3 , Ti 3 O 5 and TiNi 3 were determined between 1100 and 1300 K by use of solid electrolyte galvanic cells. (orig.) [de
2012-01-11
integrate-and-fire model of Lapicque and proceeding through the modeling of the 21 action potential by Hodgkin and Huxley to the current era of mathematical...Analysis: Hybrid Systems, vol. 4, pp. 557-573, 2010. [13] K. Y . Volyanskyy and W. M. Haddad, “A Q-Modification Neuroadaptive Control Ar- chitecture for...Conf. Contr. Autom., pp. 1361-1366, Thessaloniki, Greece, June 2009. [30] T. Yucelen, A. J. Calise, W. H. Haddad, and K. Y . Volyanskyy, A Comparison of a
Thermodynamics of ordered and disordered phases in the binary Mo-Ru system
DEFF Research Database (Denmark)
Kissavos, A.E.; Shallcross, Sam; Kaufman, L.
2007-01-01
We have performed ab initio calculations of the mixing enthalpy for the Mo-Ru alloy system. Both completely random alloys on the fcc, bcc, and hcp lattices as well as ordered and partially ordered structures based on the hcp lattice and a sigma phase have been examined. Further, we have performed...... a ground-state search for the Ru-rich region using ab initio derived effective interactions, and find a series of structures below the tie line of the simple compounds. Using the structures from this ground-state search, we are able to make an estimation of the contribution to the total energy due...
International Nuclear Information System (INIS)
Fu Lian; Fang Shengqiang; Yao Zhongqi; Gao Zhichang; Tan Ganzhu
1989-01-01
The published data up to now concerning polyether-lithium liquid-liquid extraction systems, can be summarized by the equation, ε p = (α-1)/[1 + 0.46(1-P)], where α denotes the isotope separation factor; P - the ratio of the lithium concentration in the organic phase to the initial concentration of crown ethers; ε p -the enrichment coefficient as P = 100%. Based on the changes in ε p , P, α and D(distribution ratio), the functions of factors such as polyether's structure, polyether's side group, polyether's concentration, organic solvent, negative ion of lithium salt and lithium salt's concentration, are discussed and reported
Thermodynamics of Radiation Modes
Pina, Eduardo; de la Selva, Sara Maria Teresa
2010-01-01
We study the equilibrium thermodynamics of the electromagnetic radiation in a cavity of a given volume and temperature. We found three levels of description, the thermodynamics of one mode, the thermodynamics of the distribution of frequencies in a band by summing over the frequencies in it and the global thermodynamics by summing over all the…
Thermodynamic analysis of feed water pre-heaters in multiple effect distillation systems
International Nuclear Information System (INIS)
Kouhikamali, R.
2013-01-01
The purpose of this article is to investigate the influence of using feed water pre-heaters in multiple effect distillation systems with thermal vapor compression (MED-TVC). By using these heat exchangers, temperature difference between feed water and steam in each effect would be constant. In this way, the required energy for preheating the feed water will decrease and the feed water evaporates as soon as it enters the effect. In this article, it is shown preheating the feed water has a great influence on decreasing the energy consumption of MED-TVC distillation systems. The influence of different configurations of feed water preheating on energy consumption of MED-TVC process is investigated as well. Results show that the energy consumption will be minimum if the pre-heaters increase the feed water temperature in such a way that their temperature difference is equal to that of effects. - Highlights: ► A modified process design of MED-TVC packages has been presented in this article. ► Preheating the feed water results in a remarkable decrease in energy consumption. ► Using feed pre-heaters for warmer effects have more effect on increasing in GOR.
Phase rule calculations and the thermodynamics of reactive systems under chemical equilibrium
Directory of Open Access Journals (Sweden)
PLATT G. M.
1999-01-01
Full Text Available In this paper, we examine the resolution of some phase rule problems within the context of multiple chemical equilibrium reactions, using cubic equations of state and an activity coefficient model. Bubble and dew reactive surfaces, reactive azeotropic loci and reactive critical loci are generated and presented in graphical form. Also isobaric bubble and dew reactive enthalpy loci, which may be useful in the modeling of reactive distillation operations, are depicted. All the formalism here employed is developed within the coordinate transformation of Ung and Doherty, which is appropriate for equilibrium reactive or multireactive systems. The major contribution of this work is the determination of critical loci for reactive or multireactive equilibrium systems. Since it is known that for some class of chemical reactions the kinetics and product distribution exhibit high sensitivity to pressure near criticality, the present study may be useful as a predicting tool in these cases if the chemical equilibrium condition is not too far from the real phenomenon.
Experimental approaches to membrane thermodynamics
DEFF Research Database (Denmark)
Westh, Peter
2009-01-01
Thermodynamics describes a system on the macroscopic scale, yet it is becoming an important tool for the elucidation of many specific molecular aspects of membrane properties. In this note we discuss this application of thermodynamics, and give a number of examples on how thermodynamic measuremen...... have contributed to the understanding of specific membrane phenomena. We mainly focus on non-specific interactions of bilayers and small molecules (water and solutes) in the surrounding solvent, and the changes in membrane properties they bring about. Differences between thermodynamic...... and stoichiometric (structural) definitions of non-specific binding or partitioning are emphasized, and it is concluded that this distinction is important for weak, but not for strong, interactions....
Thermodynamic analysis of load-leveling hyper energy converting and utilization system
International Nuclear Information System (INIS)
Kiani, Behdad; Akisawa, Atsushi; Kashiwagi, Takao
2008-01-01
Load-leveling hyper energy converting and utilization system (LHECUS) is a hybrid cycle which utilizes ammonia-water mixture as the working fluid in a combined power generation and refrigeration cycle. The power generation cycle functions as a Kalina cycle and an absorption refrigeration cycle is combined with it as a bottoming cycle. LHECUS is designed to utilize the waste heat from industry to produce cooling and power simultaneously. The refrigeration effect can be either transported to end-use sectors by means of a solution transportation absorption chiller (STA) as solution concentration difference or stored for demand load leveling. This paper shows a simulation of the LHECUS cycle. A computer model was written to balance the cycle and key parameters for optimizing the cycle were identified
Analyses and predictions of the thermodynamic properties and phase diagrams of silicate systems
Energy Technology Data Exchange (ETDEWEB)
Blander, M. [Argonne National Lab., IL (United States); Pelton, A.; Eriksson, G. [Ecole Polytechnique, Montreal, PQ (Canada). Dept. of Metallurgy and Materials Engineering
1992-07-01
Molten silicates are ordered solutions which can not be well represented by the usual polynomial representation of deviations from ideal solution behavior (i.e. excess free energies of mixing). An adaptation of quasichemical theory which is capable of describing the properties of ordered solutions represents the measured properties of binary silicates over broad ranges of composition and temperature. For simple silicates such as the MgO-FeO-SiO{sub 2} ternary system, in which silica is the only acid component, a combining rule generally leads to good predictions of ternary solutions from those of the binaries. In basic solutions, these predictions are consistent with those of the conformal ionic solution theory. Our results indicate that our approach could provide a potentially powerful tool for representing and predicting the properties of multicomponent molten silicates.
Analyses and predictions of the thermodynamic properties and phase diagrams of silicate systems
Energy Technology Data Exchange (ETDEWEB)
Blander, M. (Argonne National Lab., IL (United States)); Pelton, A.; Eriksson, G. (Ecole Polytechnique, Montreal, PQ (Canada). Dept. of Metallurgy and Materials Engineering)
1992-01-01
Molten silicates are ordered solutions which can not be well represented by the usual polynomial representation of deviations from ideal solution behavior (i.e. excess free energies of mixing). An adaptation of quasichemical theory which is capable of describing the properties of ordered solutions represents the measured properties of binary silicates over broad ranges of composition and temperature. For simple silicates such as the MgO-FeO-SiO{sub 2} ternary system, in which silica is the only acid component, a combining rule generally leads to good predictions of ternary solutions from those of the binaries. In basic solutions, these predictions are consistent with those of the conformal ionic solution theory. Our results indicate that our approach could provide a potentially powerful tool for representing and predicting the properties of multicomponent molten silicates.
Chemical Equilibrium as Balance of the Thermodynamic Forces
Zilbergleyt, B.
2004-01-01
The article sets forth comprehensive basics of thermodynamics of chemical equilibrium as balance of the thermodynamic forces. Based on the linear equations of irreversible thermodynamics, De Donder definition of the thermodynamic force, and Le Chatelier's principle, new thermodynamics of chemical equilibrium offers an explicit account for multiple chemical interactions within the system. Basic relations between energetic characteristics of chemical transformations and reaction extents are bas...
Thermodynamic properties of organic compounds estimation methods, principles and practice
Janz, George J
1967-01-01
Thermodynamic Properties of Organic Compounds: Estimation Methods, Principles and Practice, Revised Edition focuses on the progression of practical methods in computing the thermodynamic characteristics of organic compounds. Divided into two parts with eight chapters, the book concentrates first on the methods of estimation. Topics presented are statistical and combined thermodynamic functions; free energy change and equilibrium conversions; and estimation of thermodynamic properties. The next discussions focus on the thermodynamic properties of simple polyatomic systems by statistical the
Domańska, Urszula; Kozłowska, Marta Karolina
2005-01-07
Isotactic crystalline low-molecular-weight poly(1-butene), iPBu-1, was synthesised by using a metallocene catalyst. The molecular weight was determined by GPC. The chemical structure of iPBu-1 was verified by using high-temperature (13)C NMR spectroscopy and the thermal properties by differential scanning calorimetry (DSC). The (solid+liquid) equilibria, SLE, of iPBu-1 with different hydrocarbons (n-hexadecane, 1-heptene, 1-heptyne, cyclopentane, cyclohexane, cycloheptane, cyclooctane, benzene and propylbenzene) were studied by a dynamic method. By performing these experiments over a large concentration range, the temperature-mole fraction phase diagrams of the polymer-solvent systems could be constructed. From these diagrams it was found that iPBu-1 had the highest solubility in small-ring cycloalkanes and the lowest in n-hexadecane, 1-heptyne and benzene in the mole fraction range measured. The excess Gibbs energy models were used to describe the nonideal behaviour of the liquid phase and to estimate the solubility of iPBu-1 in the whole mole fraction range. Activity coefficients at infinite dilution of polymer and solvent were determined from the solubility measurements and were predicted by using the UNIFAC FV model and molecular Monte Carlo simulations.
The thermodynamic characteristics of vaporization in the NaI-PrI3 system
Motalov, V. B.; Kudin, L. S.; Markus, T.
2009-05-01
The vaporization of the NaI-PrI3 quasi-binary system was studied by high-temperature mass spectrometry over the whole concentration range. At 623-994 K, saturated vapor contained not only (NaI) n and (PrI3) n molecules ( n = 1, 2) and Na+(NaI) n ( n = 0-4) and I-(PrI3) n ( n = 1-2) ions but also mixed molecular and ionic associates recorded for the first time (NaPrI4, Na2PrI5, NaPrI{3/+}, Na2PrI{4/+}, Na3PrI{5/+}, Na4PrI{6/+}, NaPrI{5/-}, and NaPr2I{8/-}). The partial vapor pressures of molecules were calculated, and the equilibrium constants of the dissociation of neutral and charged associates were measured. The enthalpies of molecular and ion-molecular reactions were determined, and the enthalpies of formation of gaseous molecules and ions were obtained.
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
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)
International Nuclear Information System (INIS)
Chandran, K.; Brahmananda, C.V.S.; Anthonysamy, S.; Srinivasan, T.G.; Ganesan, V.
2013-01-01
as exhibited by TBP-HNO 3 systems. (author)
The thermodynamic properties of a new type catcher bearing used in active magnetic bearings system
International Nuclear Information System (INIS)
Jin, Chaowu; Zhu, Yili; Xu, Longxiang; Xu, Yuanping; Zheng, Yantong
2015-01-01
Normally a rotor levitated by active magnetic bearings (AMBs) system would rotate without contacting with any stator component, but the possibility still remains that the supporting force might lose temporarily or permanently, thus requiring the Catcher bearings (CBs) to provide backup protection in case of the failure of AMBs. A new type CB with two separate rolling element bearing series could have the speed distribution between the inner race and intermediate race according to certain ratio, in which the speed of each roller element bearing decreases with the limit speed of the whole CB increasing, offering high capability to sustain its initial rotation speed. Based on the theory of heat transfer, tribology, and rotor dynamics, this paper analyzes the thermal structure of double-decker catcher bearing (DDCB) and single-decker catcher bearing (SDCB), respectively. Through this structure, the thermal resistances and equations of heat transfer can be obtained. Then we calculate the friction heat and temperature distribution in the various CBs upon rotor's dropping on SDCB or DDCB, followed by the discussion on the CBs temperature rise's effects on lubrication conditions and rotor dynamics parameters. Finally various experiments are carried out to measure the temperature rise of different CBs. The results obtained validate the theoretical analysis and also provide main methods to reduce heat generation. Using DDCB is proved to be effective to reduce the temperature rise. - Highlights: • The DDCB is a more suitable catcher bearing for AMBs. • Compared to SDCB, using DDCB, the temperature rise can decrease in the same states. • A lower viscosity of lubricant may induce a lower temperature rise. • The inner raceway temperature of the first layer bearing is the highest. • Reducing the unbalance mass of the rotor is a method to decrease the temperature rise
Thermal fluids for CSP systems: Alkaline nitrates/nitrites thermodynamics modelling method
Tizzoni, A. C.; Sau, S.; Corsaro, N.; Giaconia, A.; D'Ottavi, C.; Licoccia, S.
2016-05-01
Molten salt (MS) mixtures are used for the transport (HTF-heat transfer fluid) and storage of heat (HSM-heat storage material) in Concentration Solar Plants (CSP). In general, alkaline and earth-alkaline nitrate/nitrite mixtures are employed. Along with its upper stability temperature, the melting point (liquidus point) of a MS mixture is one of the main parameters which defines its usefulness as a HTF and HSM medium. As a result, we would like to develop a predictive model which will allow us to forecast freezing points for different MS mixture compositions; thus circumventing the need to determine experimentally the phase diagram for each MS mixture. To model ternary/quaternary phase diagram, parameters for the binary subsystems are to be determined, which is the purpose of the concerned work. In a binary system with components A and B, in phase equilibrium conditions (e.g. liquid and solid) the chemical potentials (partial molar Gibbs energy) for each component in each phase are equal. For an ideal solution it is possible to calculate the mixing (A+B) Gibbs energy:ΔG = ΔH - TΔS = RT(xAlnxA + xBlnxB) In case of non-ideal solid/liquid mixtures, such as the nitrates/nitrites compositions investigated in this work, the actual value will differ from the ideal one by an amount defined as the "mixing" (mix) Gibbs free energy. If the resulting mixtures is assumed, as indicated in the previous literature, to follow a "regular solution" model, where all the non-ideality is considered included in the enthalpy of mixing value and considering, for instance, the A component:Δ G ≡0 =(Δ HA-T Δ SA)+(ΔH¯ m i x AL-T ΔS¯ m i x AL)-(ΔH¯ m i x AS-T ΔS¯ m i x AS)where the molar partial amounts can be calculated from the total value by the Gibbs Duhem equation: (ΔH¯m i x AL=ΔHm i x-XB Ld/Δ Hm i x d XB L ) L;(ΔH¯m i x AS=ΔHm i x-XB Sd/Δ Hm i x d XB S ) S and, in general, it is possible to express the mixing enthalpy for solids and liquids as a function of the mol
International Nuclear Information System (INIS)
Zhang, Z. D.; Wang, J.
2014-01-01
We established a theoretical framework in terms of the curl flux, population landscape, and coherence for non-equilibrium quantum systems at steady state, through exploring the energy and charge transport in molecular processes. The curl quantum flux plays the key role in determining transport properties and the system reaches equilibrium when flux vanishes. The novel curl quantum flux reflects the degree of non-equilibriumness and the time-irreversibility. We found an analytical expression for the quantum flux and its relationship to the environmental pumping (non-equilibriumness quantified by the voltage away from the equilibrium) and the quantum tunneling. Furthermore, we investigated another quantum signature, the coherence, quantitatively measured by the non-zero off diagonal element of the density matrix. Populations of states give the probabilities of individual states and therefore quantify the population landscape. Both curl flux and coherence depend on steady state population landscape. Besides the environment-assistance which can give dramatic enhancement of coherence and quantum flux with high voltage at a fixed tunneling strength, the quantum flux is promoted by the coherence in the regime of small tunneling while reduced by the coherence in the regime of large tunneling, due to the non-monotonic relationship between the coherence and tunneling. This is in contrast to the previously found linear relationship. For the systems coupled to bosonic (photonic and phononic) reservoirs the flux is significantly promoted at large voltage while for fermionic (electronic) reservoirs the flux reaches a saturation after a significant enhancement at large voltage due to the Pauli exclusion principle. In view of the system as a quantum heat engine, we studied the non-equilibrium thermodynamics and established the analytical connections of curl quantum flux to the transport quantities such as energy (charge) transfer efficiency, chemical reaction efficiency, energy
Thermodynamic tables to accompany Modern engineering thermodynamics
Balmer, Robert T
2011-01-01
This booklet is provided at no extra charge with new copies of Balmer's Modern Engineering Thermodynamics. It contains two appendices. Appendix C contains 40 thermodynamic tables, and Appendix D consists of 6 thermodynamic charts. These charts and tables are provided in a separate booklet to give instructors the flexibility of allowing students to bring the tables into exams. The booklet may be purchased separately if needed.
Thermodynamic Analysis of Biodegradation Pathways
Finley, Stacey D.; Broadbelt, Linda J.
2014-01-01
Microorganisms provide a wealth of biodegradative potential in the reduction and elimination of xenobiotic compounds in the environment. One useful metric to evaluate potential biodegradation pathways is thermodynamic feasibility. However, experimental data for the thermodynamic properties of xenobiotics is scarce. The present work uses a group contribution method to study the thermodynamic properties of the University of Minnesota Biocatalysis/Biodegradation Database. The Gibbs free energies of formation and reaction are estimated for 914 compounds (81%) and 902 reactions (75%), respectively, in the database. The reactions are classified based on the minimum and maximum Gibbs free energy values, which accounts for uncertainty in the free energy estimates and a feasible concentration range relevant to biodegradation. Using the free energy estimates, the cumulative free energy change of 89 biodegradation pathways (51%) in the database could be estimated. A comparison of the likelihood of the biotransformation rules in the Pathway Prediction System and their thermodynamic feasibility was then carried out. This analysis revealed that when evaluating the feasibility of biodegradation pathways, it is important to consider the thermodynamic topology of the reactions in the context of the complete pathway. Group contribution is shown to be a viable tool for estimating, a priori, the thermodynamic feasibility and the relative likelihood of alternative biodegradation reactions. This work offers a useful tool to a broad range of researchers interested in estimating the feasibility of the reactions in existing or novel biodegradation pathways. PMID:19288443
Classical and statistical thermodynamics
Rizk, Hanna A
2016-01-01
This is a text book of thermodynamics for the student who seeks thorough training in science or engineering. Systematic and thorough treatment of the fundamental principles rather than presenting the large mass of facts has been stressed. The book includes some of the historical and humanistic background of thermodynamics, but without affecting the continuity of the analytical treatment. For a clearer and more profound understanding of thermodynamics this book is highly recommended. In this respect, the author believes that a sound grounding in classical thermodynamics is an essential prerequisite for the understanding of statistical thermodynamics. Such a book comprising the two wide branches of thermodynamics is in fact unprecedented. Being a written work dealing systematically with the two main branches of thermodynamics, namely classical thermodynamics and statistical thermodynamics, together with some important indexes under only one cover, this treatise is so eminently useful.
International Nuclear Information System (INIS)
Boer, R. de; Haije, W.G.; Veldhuis, J.B.J.
2002-01-01
Structural, thermodynamic and phase properties in the Na 2 S-H 2 O system for application in a chemical heat pump have been investigated using XRD, TG/DTA and melting point and vapour pressure determinations. Apart from the known crystalline phases Na 2 S·9H 2 O, Na 2 S·5H 2 O and Na 2 S a new phase Na 2 S·2H 2 O has been proven to exist. Na 2 S·((1)/(2))H 2 O is not a phase but a 3:1 mixture of Na 2 S and Na 2 S·2H 2 O, presumably stabilised by very slow dehydration kinetics. The vapour pressure-temperature equilibria of the sodium sulphide hydrates have been determined and a consistent set of thermodynamic functions for these compounds has been derived. XRD measurements indicate the topotactic character of the transitions between the hydration states
Feng, Dawei
2014-01-01
Gold and silver chalcogenides are significant minerals and major carriers of precious metals, and silver palladium alloy is one of the most important silver alloys with various industrial applications. The Ag-Au-Se ternary system and the Ag-Pd binary system have been investigated by the electromotive force (EMF) method in this study. For the Ag-Au-Se ternary system, the numerical values of the standard thermodynamic functions of the compounds Ag2Se (naumannite), AuSe, and Ag3AuSe2 (fisches...
International Nuclear Information System (INIS)
Kwon, Choah; Kang, Joonhee; Kang, Woojong; Kwak, Dohyun; Han, Byungchan
2016-01-01
Using first principles density functional theory (DFT) calculations we obtain thermodynamic and kinetic properties of U in an electrorefining process for spent nuclear fuels using a LiCl-KCl eutectic molten salt and Mo as a cathode. The thermodynamic stability of electrodeposited U from the molten salt onto the Mo(110) surface electrode is evaluated by activity coefficients as function of surface coverages of U and Cl. Additionally, ab-initio molecular dynamic simulations combined with the Stokes-Einstein-Sutherland relation enables us to calculate the viscosity of the LiCl-KCl eutectic molten salt. Our results well agree with previously reported experimental data endorsing the credibility. Based on our atomic-level mechanical understanding we propose that an accurate computational model system incorporating the electrochemical conditions of the electrorefining process essential for the purpose of establishing thermodynamic and kinetic database of U, otherwise critical deviations are inevitable. More interestingly, the effect of coadsorption of Cl with U on the Mo(110) surface plays a key role in stabilizing electrodeposited U on the cathode. Our approach can be useful for validating published experimental database and for identifying key factors guiding a rational design of highly efficient electrorefining system for spent nuclear fuels, and thus reducing high-level radioactive nuclear wastes.
DEFF Research Database (Denmark)
Rokni, Masoud
2014-01-01
Thermodynamic and thermoeconomic investigations of a small-scale integrated gasification solid oxide fuel cell (SOFC) and Stirling engine for combined heat and power (CHP) with a net electric capacity of 120kWe have been performed. Woodchips are used as gasification feedstock to produce syngas...
Thermodynamic evaluation of Cu-H-O-S-P system - Phase stabilities and solubilities for OFP-copper
Energy Technology Data Exchange (ETDEWEB)
Magnusson, Hans; Frisk, Karin [Swerea KIMAB, Kista (Sweden)
2013-04-15
A thermodynamic evaluation for Cu-H-O-S-P has been made, with special focus on the phase stabilities and solubilities for OFP-copper. All binary systems including copper have been reviewed. Gaseous species and stoichiometric crystalline phases have been included for higher systems. Sulphur in OFP-copper will be found in sulphides. The sulphide can take different morphologies but constant stoichiometry Cu{sub 2}S. The solubility of sulphur in FCC-copper reaches ppm levels already at 550 deg C and decreases with lower temperature. No phosphorus-sulphide will be stable, although the copper sulphide can be replaced by copper sulphates at high partial pressure oxygen like in the oxide scale. Phosphorus has a high affinity to oxygen, and phosphorus oxide P{sub 4}O{sub 10} and copper phosphates (Cu{sub 2}P{sub 2}O{sub 7} and Cu{sub 3}(PO{sub 4}){sub 2}) are all more stable than copper oxide Cu{sub 2}O. With hydrogen present at atmospheric pressure, copper phosphates Cu{sub 2}P{sub 2}O{sub 7} and Cu{sub 3}(P{sub 2}O{sub 6}OH){sub 2} are both more stable than water vapour or aqueous water at temperatures below 400 deg C. At high pressure conditions, the copper phosphates can be reduced giving water. However, the phosphates are still more stable than water vapour. The solubility limit of phosphorus in FCC-copper at 25 deg C is 510 ppm, in equilibrium with copper phosphide Cu{sub 3}P. The major part of phosphorus in OFP-copper will be in solid solution. Oxygen in FCC-copper has a very low solubility. In the presence of a strong oxide forming element such as phosphorus in OFP-copper, the solubility decreases even more. Copper oxides will become stable first when all phosphorus has been consumed, which takes place at twice the phosphorus content, calculated in weight. Hydrogen has a low solubility in copper, calculated as 0.1 ppm at 675 deg C. No crystalline hydrogen phase has been found stable at atmospheric pressures and above 400 deg C. At lower temperatures the hydrogen
Structural Properties and Thermodynamic Stability of Metastable Phases in the Zr-Nb and Ti-V Systems
International Nuclear Information System (INIS)
Aurelio, Gabriela
2003-01-01
The structural properties and relative stability of metastable phases have been studied in the Zr-Nb and Ti-V systems.The first part of this Thesis is connected to a previous work performed in our Group (G. Grad, PhD Thesis, Instituto Balseiro, Argentina, 1999).It presents a phenomenological analysis of the systematics of interatomic distances in the omega (Ω ) and bcc (β) phases of the transition metals, which concerns a parameter entering into Pauling's resonating-valence- bond-theory and the structural and bonding properties of the Ω and β phases.Neutron diffraction experiments in Zr-Nb and Ti-V alloys are reported, aimed at studying possible atomic ordering in the Ω phase and the composition dependence of its interatomic distances.An extensive neutron diffraction study was performed on a series of Zr-Nb and Ti-V alloys quenched from high temperatures, where β is the stable phase.Upon quenching, three metastable structures are formed, viz., the hcp (∝ q ) phase, the Ω q phase, and the untransformed β q phase.The structural properties of these metastable phases were determined as a function of the Nb and V contents to generate a reliable experimental database.With such data, a series of issues are discussed related to the structure, relative stability, and phase relations in the alloys and its constitutive elements.The effect of composition upon the lattice parameters of the metastable β q and Ω q phases was combined in a consistent way with a critical analysis of structural and thermophysical data on the metastable phases of Ti and Zr.The relative stability of the metastable ∝ q , Ω q and β q phases in Zr-Nb alloys, and its evolution towards thermodynamic equilibrium, were studied combining neutron thermodiffraction and analytical electron microscopy techniques.During isothermal heat treatments performed at high temperature, the structural properties of the alloys were determined as a function of temperature, time and composition.A method of
Thermodynamic Database for Zirconium Alloys
International Nuclear Information System (INIS)
Jerlerud Perez, Rosa
2003-05-01
For many decades zirconium alloys have been commonly used in the nuclear power industry as fuel cladding material. Besides their good corrosion resistance and acceptable mechanical properties the main reason of using these alloys is the low neutron absorption. Zirconium alloys are exposed to a very severe environment during the nuclear fission process and there is a demand for better design of this material. To meet this requirement a thermodynamic database is developed to support material designers. In this thesis some aspects about the development of a thermodynamic database for zirconium alloys are presented. A thermodynamic database represents an important facility in applying thermodynamic equilibrium calculations for a given material providing: 1) relevant information about the thermodynamic properties of the alloys e.g. enthalpies, activities, heat capacity, and 2) significant information for the manufacturing process e.g. heat treatment temperature. The basic information in the database is first the unary data, i.e. pure elements; those are taken from the compilation of the Scientific Group Thermodata Europe (SGTE) and then the binary and ternary systems. All phases present in those binary and ternary systems are described by means of the Gibbs energy dependence on composition and temperature. Many of those binary systems have been taken from published or unpublished works and others have been assessed in the present work. All the calculations have been made using Thermo C alc software and the representation of the Gibbs energy obtained by applying Calphad technique
Tanasescu, Speranta; Yáng, Zhèn; Martynczuk, Julia; Varazashvili, Vera; Maxim, Florentina; Teodorescu, Florina; Botea, Alina; Totir, Nicolae; Gauckler, Ludwig J.
2013-04-01
The thermodynamic stability of the perovskite-type oxides in the BaxSr1-xCo0.8Fe0.2O3-δ (BSCF) system was investigated with varying Ba:Sr ratios (x=0.2, 0.4, 0.5, 0.6, 0.8) and correlated with the charge compensation mechanism and the change in the oxygen stoichiometry of the materials. Thermodynamic properties represented by the relative partial molar free energies, enthalpies and entropies of oxygen dissolution in the perovskite phase, as well as the equilibrium partial pressures of oxygen have been obtained in the temperature range of 823-1273 K using solid electrolyte electrochemical cells (EMF) method. The influence of the oxygen stoichiometry change on the thermodynamic properties was examined using a coulometric titration technique coupled with EMF measurements. The temperature dependence of enthalpy increment (HT-H298) in the temperature range of 700-900 K was measured by drop calorimetry. The energetic parameters allow for the correlation of the structural and electrical stability with the defect structures.
Thermodynamics for Chemists, Physicists and Engineers
Hołyst, Robert
2012-01-01
Thermodynamics is an essential part of chemical physics and is of fundamental importance in physics, chemistry and engineering courses. This textbook takes an interdisciplinary approach to the subject and is therefore suitable for undergraduates in all those courses. The book is an introduction to phenomenological thermodynamics and its applications to phase transitions and chemical reactions, with some references to statistical mechanics. It strikes the balance between the rigorousness of the Callen text and phenomenological approach of the Atkins text. The book is divided in three parts. The first introduces the postulates and laws of thermodynamics and complements these initial explanations with practical examples. The second part is devoted to applications of thermodynamics to phase transitions in pure substances and mixtures. The third part covers thermodynamic systems in which chemical reactions take place. There are some sections on more advanced topics such as thermodynamic potentials, natural variabl...
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Belgacem-Bouzida, A. [Laboratoire d' etude Physico-Chimique des Materiaux, Departement de Physique, Faculte des Sciences, Universite de Batna, Rue Chahid Boukhlouf, 05000 Batna (Algeria)]. E-mail: bouzida.aissa@caramail.com; Djaballah, Y. [Laboratoire d' etude Physico-Chimique des Materiaux, Departement de Physique, Faculte des Sciences, Universite de Batna, Rue Chahid Boukhlouf, 05000 Batna (Algeria)]. E-mail: djaballah.y@caramail.com; Notin, M. [Laboratoire de Chimie du Solide Mineral, Faculte des Sciences, Universite Henri Poincare Nancy I, B.P. 239, F-54506 Vandoeuvre-les-Nancy Cedex (France)
2005-07-19
The enthalpies of formation have been measured for the two binary compounds Cr{sub 3}Ga and CrGa{sub 4} richest and least rich in chromium of the (Cr-Ga) system. We have used two types of calorimetric method: direct reaction and progressive precipitation calorimetry. Thermodynamic optimizations for the binary (Cr-Ga) system using Calphad method are investigated and a set of parameters describing the Gibbs energy of the different phases is given, the phase diagram has been also calculated and presented.
Thermodynamic Phase Relations in the MgO-FeO-SiO2 System in the Lower Mantle
Wolf, A. S.; Caracas, R.; Asimow, P. D.
2008-12-01
The perovskite (Pv) to post-perovskite (PPv) phase transition at pressures near the Earth's core-mantle boundary (CMB) is currently the favored candidate for explaining most, if not all, of the peculiarities of the D" layer (~200 km region above core) [1, 2]. Additionally, the pressure- and temperature-dependence of this phase boundary in the Earth provides the possibility of an important new thermo-barometer at the bottom of the convecting mantle. The post-perovskite phase boundary in pure MgSiO3 is fairly well known, but the experimental and calculated results on the partitioning of Fe among the stable coexisting phases and its influence on the transition pressure are currently contradictory [3, 4, 5, 6]. Using density functional theory (DFT), we investigate the MgO-FeO-SiO2 ternary system over the temperatures and pressures relevant to the core-mantle boundary. We use DFT to calculate the energies of the relevant stable phases (Pv, PPv, (Mg,Fe)O magnesio-wustite, and SiO2 stishovite) for a range of Fe compositions along the Mg-Fe binary. These results are fit with a Vinet equation of state, allowing us to parameterize the effect of both pressure and Fe composition. The effect of temperature is modeled using a Grüneisen thermal correction, where the vibrational heat capacities are determined using DFT perturbation calculations and the quasi-harmonic approximation. These pressure-, temperature-, and composition-dependent equations of state are then used to explore the predicted phase relations. The results of this investigation are a complete thermodynamic description of the stable phases for this simplified chemistry and a theoretical prediction for iron partioning in the lower mantle. In particular, we find that there may be a coincidence point (azeotrope) on the Pv-PPv phase loop, across which the sense of Fe-partitioning changes sign, as well as significant immiscibility between Mg-rich and Fe-rich post-perovskite. These findings help explain many of the
Coherence and measurement in quantum thermodynamics.
Kammerlander, P; Anders, J
2016-02-26
Thermodynamics is a highly successful macroscopic theory widely used across the natural sciences and for the construction of everyday devices, from car engines to solar cells. With thermodynamics predating quantum theory, research now aims to uncover the thermodynamic laws that govern finite size systems which may in addition host quantum effects. Recent theoretical breakthroughs include the characterisation of the efficiency of quantum thermal engines, the extension of classical non-equilibrium fluctuation theorems to the quantum regime and a new thermodynamic resource theory has led to the discovery of a set of second laws for finite size systems. These results have substantially advanced our understanding of nanoscale thermodynamics, however putting a finger on what is genuinely quantum in quantum thermodynamics has remained a challenge. Here we identify information processing tasks, the so-called projections, that can only be formulated within the framework of quantum mechanics. We show that the physical realisation of such projections can come with a non-trivial thermodynamic work only for quantum states with coherences. This contrasts with information erasure, first investigated by Landauer, for which a thermodynamic work cost applies for classical and quantum erasure alike. Repercussions on quantum work fluctuation relations and thermodynamic single-shot approaches are also discussed.
The Thermodynamic Machinery of Life
Kurzynski, Michal
2006-01-01
Living organisms are open thermodynamic systems whose functional structure has developed and been kinetically frozen during the historical process of biological evolution. A thermodynamics of both nonequilibrium and complex systems is needed for their description. In this book, the foundations of such a thermodynamics are presented. Biological processes at the cellular level are considered as coupled chemical reactions and transport processes across internal and the cytoplasmic membrane. All these processes are catalyzed by specific enzymes hence the kinetics of enzymatic catalysis and its control are described here in detail. The coupling of several processes through a common enzyme is considered in the context of free energy or signal transduction. Special attention is paid to evidence for a rich stochastic internal dynamics of native proteins and its possible role in the control of enzyme activity and in the action of biological molecular machines.
Sheehan, D. P.; Garamella, J. T.; Mallin, D. J.; Sheehan, W. F.
2012-11-01
Differences in gas reaction rates between disparate surfaces have been proposed as a means to achieve steady-state pressure and temperature gradients within a single blackbody cavity, thereby challenging the second law of thermodynamics (Sheehan 1998 Phys. Rev. E 57 6660; Sheehan 2001 Phys. Lett. A 280 185; Capek and Sheehan 2005 Challenges to the Second Law of Thermodynamics (Theory and Experiment) (Fundamental Theories of Physics Series vol 146) (Dordrecht: Springer)). This paper reports on laboratory tests of this hypothesis; specifically, molecular hydrogen is found to dissociate preferentially on rhenium surfaces versus tungsten at identical elevated temperatures and reduced pressures (T ⩽ 2100 K {\\cal P} \\leqslant 30\\,{ {Torr}} ). Steady-state nonequilibrium H/H2 ratios over the surfaces suggest that temperature gradients could be maintained under blackbody cavity conditions. Preliminary results from bimetallic blackbody cavity experiments are discussed.
Cano-Andrade, Sergio
2014-01-01
In this dissertation, applications of thermodynamics at the macroscopic and quantum levels of description are developed. Within the macroscopic level, an upper-level Sustainability Assessment Framework (SAF) is proposed for evaluating the sustainable and resilient synthesis/design and operation of sets of small renewable and non-renewable energy production technologies coupled to power production transmission and distribution networks via microgrids. The upper-level SAF is developed in accord...
Ruggiero, Flavia; Netti, Paolo Antonio; Torino, Enza
2015-12-01
Fundamental understanding of thermodynamic of phase separation plays a key role in tuning the desired features of biomedical devices. In particular, phase separation of ternary solution is of remarkable interest in processes to obtain biodegradable and biocompatible architectures applied as artificial devices to repair, replace, or support damaged tissues or organs. In these perspectives, thermally induced phase separation (TIPS) is the most widely used technique to obtained porous morphologies and, in addition, among different ternary systems, polylactic acid (PLLA)/dioxane/water has given promising results and has been largely studied. However, to increase the control of TIPS-based processes and architectures, an investigation of the basic energetic phenomena occurring during phase separation is still required. Here we propose an experimental investigation of the selected ternary system by using isothermal titration calorimetric approach at different solvent/antisolvent ratio and a thermodynamic explanation related to the polymer-solvents interactions in terms of energetic contribution to the phase separation process. Furthermore, relevant information about the phase diagrams and interaction parameters of the studied systems are furnished in terms of liquid-liquid miscibility gap. Indeed, polymer-solvents interactions are responsible for the mechanism of the phase separation process and, therefore, of the final features of the morphologies; the knowledge of such data is fundamental to control processes for the production of membranes, scaffolds and several nanostructures. The behavior of the polymer at different solvent/nonsolvent ratios is discussed in terms of solvation mechanism and a preliminary contribution to the understanding of the role of the hydrogen bonding in the interface phenomena is also reported. It is the first time that thermodynamic data of a ternary system are collected by mean of nano-isothermal titration calorimetry (nano-ITC). Supporting