WorldWideScience

Sample records for thermodynamical equilibrium applications

  1. Equilibrium thermodynamics

    CERN Document Server

    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...

  2. Thermodynamic equilibrium-air correlations for flowfield applications

    Science.gov (United States)

    Zoby, E. V.; Moss, J. N.

    1981-01-01

    Equilibrium-air thermodynamic correlations have been developed for flowfield calculation procedures. A comparison between the postshock results computed by the correlation equations and detailed chemistry calculations is very good. The thermodynamic correlations are incorporated in an approximate inviscid flowfield code with a convective heating capability for the purpose of defining the thermodynamic environment through the shock layer. Comparisons of heating rates computed by the approximate code and a viscous-shock-layer method are good. In addition to presenting the thermodynamic correlations, the impact of several viscosity models on the convective heat transfer is demonstrated.

  3. Non-equilibrium thermodynamics

    CERN Document Server

    De Groot, Sybren Ruurds

    1984-01-01

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

  4. Understanding Non-equilibrium Thermodynamics Foundations, Applications, Frontiers

    CERN Document Server

    Jou, David; Lebon, Georgy

    2007-01-01

    This book offers a homogeneous presentation of the many faces of non-equilibrium thermodynamics. The first part is devoted to a description of the nowadays thermodynamic formalism recognized as the classical theory of non-equilibrium processes. This part of the book may serve as a basis to an introductory course dedicated to first-year graduate students in sciences and engineering. The classical description can however not be complete, as it rests on the hypothesis of local equilibrium. This has fostered the development of many theories going beyond local equilibrium and which cannot be put aside. The second part of the book is concerned with these different approaches, and will be of special interest for PhD students and researchers. For the sake of homogeneity, the authors have used the general structure and methods presented in the first part. Indeed, besides their differences, all these formalisms are not closed boxes but present some overlappings and parallelisms which are emphasized in this book. For pe...

  5. Application of constrained equilibrium thermodynamics to irradiated alloy systems

    Science.gov (United States)

    Holloway, James Paul; Stubbins, James F.

    1984-05-01

    Equilibrium thermodynamics are applied to systems with an excess of point defects to calculate the relative stability of phases. It is possible to model systems with supersaturation levels of vacancies and interstitials, such as those found under irradiation. The calculations reveal the extent to which phase compositional boundaries could shift when one phase or both in a two phase system contain an excess of point defects. Phase boundary shifts in the Ni-Si, Fe-Ni, Ni-Cr, and Fe-Cr systems are examined as a function of the number of excess defects in each phase. It is also found that the critical temperature of the sigma phase in the Fe-Cr system and the fcc-bcc transition in the Fe-Ni are sensitive to excess defect concentrations. These results may apply to local irradiation-induced phase transformations in the presence of solute segregation.

  6. Equilibrium thermodynamics - Callen's postulational approach

    NARCIS (Netherlands)

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

    2001-01-01

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

  7. Thermodynamic theory of equilibrium fluctuations

    International Nuclear Information System (INIS)

    Mishin, Y.

    2015-01-01

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

  8. An introduction to equilibrium thermodynamics

    CERN Document Server

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

    1973-01-01

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

  9. Monte Carlo simulations for thermodynamical properties calculations of plasmas at thermodynamical equilibrium. Applications to opacity and equation of state calculations

    International Nuclear Information System (INIS)

    Gilles, D.

    2005-01-01

    This report is devoted to illustrate the power of a Monte Carlo (MC) simulation code to study the thermodynamical properties of a plasma, composed of classical point particles at thermodynamical equilibrium. Such simulations can help us to manage successfully the challenge of taking into account 'exactly' all classical correlations between particles due to density effects, unlike analytical or semi-analytical approaches, often restricted to low dense plasmas. MC simulations results allow to cover, for laser or astrophysical applications, a wide range of thermodynamical conditions from more dense (and correlated) to less dense ones (where potentials are long ranged type). Therefore Yukawa potentials, with a Thomas-Fermi temperature- and density-dependent screening length, are used to describe the effective ion-ion potentials. In this report we present two MC codes ('PDE' and 'PUCE') and applications performed with these codes in different fields (spectroscopy, opacity, equation of state). Some examples of them are discussed and illustrated at the end of the report. (author)

  10. Fundamental functions in equilibrium thermodynamics

    NARCIS (Netherlands)

    Horst, H.J. ter

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

  11. Coherent application of a contact structure to formulate Classical Non-Equilibrium Thermodynamics

    NARCIS (Netherlands)

    Knobbe, E; Roekaerts, D.J.E.M.

    2017-01-01

    This contribution presents an outline of a new mathematical formulation for
    Classical Non-Equilibrium Thermodynamics (CNET) based on a contact
    structure in differential geometry. First a non-equilibrium state space is introduced as the third key element besides the first and second law of

  12. Vapor-liquid equilibrium thermodynamics of N2 + CH4 - Model and Titan applications

    Science.gov (United States)

    Thompson, W. R.; Zollweg, John A.; Gabis, David H.

    1992-01-01

    A thermodynamic model is presented for vapor-liquid equilibrium in the N2 + CH4 system, which is implicated in calculations of the Titan tropospheric clouds' vapor-liquid equilibrium thermodynamics. This model imposes constraints on the consistency of experimental equilibrium data, and embodies temperature effects by encompassing enthalpy data; it readily calculates the saturation criteria, condensate composition, and latent heat for a given pressure-temperature profile of the Titan atmosphere. The N2 content of condensate is about half of that computed from Raoult's law, and about 30 percent greater than that computed from Henry's law.

  13. Non-Equilibrium Thermodynamics in Multiphase Flows

    CERN Document Server

    Mauri, Roberto

    2013-01-01

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

  14. Thermodynamic evolution far from equilibrium

    Science.gov (United States)

    Khantuleva, Tatiana A.

    2018-05-01

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

  15. Application of non-equilibrium thermodynamics to two-phase flows with a change of phase

    International Nuclear Information System (INIS)

    Delhaye, J.M.

    1969-01-01

    In this report we use the methods of non-equilibrium thermodynamics in two-phase flows. This paper follows a prior one in which we have studied the conservation laws and derived the general equations of two-phase flow. In the first part the basic ideas of thermodynamics of irreversible systems are given. We follow the classical point of view. The second part is concerned with the derivation of a closed set of equations for the two phase elementary volume model. In this model we assume that the elementary volume contains two phases and that it is possible to define a volumetric local concentration. To obtain the entropy balance we can choose either the reversibility of the barycentric motion or the reversibility of each phase. We adopt the last assumption and our derivation is the same as this of I.Prigogine and P. Mazur about the hydrodynamics of liquid helium. The scope of this work is not to find a general solution to the problems of two phase flows but to obtain a new set of equations which may be used to explain some characteristic phenomena of two-phase flow such as wave propagation or critical states. (author) [fr

  16. Electrolytes: transport properties and non-equilibrium thermodynamics

    International Nuclear Information System (INIS)

    Miller, D.G.

    1980-12-01

    This paper presents a review on the application of non-equilibrium thermodynamics to transport in electrolyte solutions, and some recent experimental work and results for mutual diffusion in electrolyte solutions

  17. Stochastic approach to equilibrium and nonequilibrium thermodynamics.

    Science.gov (United States)

    Tomé, Tânia; de Oliveira, Mário J

    2015-04-01

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

  18. Combined steam and carbon dioxide reforming of methane and side reactions: Thermodynamic equilibrium analysis and experimental application

    International Nuclear Information System (INIS)

    Jang, Won-Jun; Jeong, Dae-Woon; Shim, Jae-Oh; Kim, Hak-Min; Roh, Hyun-Seog; Son, In Hyuk; Lee, Seung Jae

    2016-01-01

    Highlights: • Selected variables have a significant influence on yields of synthesis gas. • (CO_2 + H_2O)/CH_4 affects the temperature which can achieve the maximum conversion. • Coke is formed at low temperatures even with excess oxidizing agent. • The occurrence of RWGS becomes critical in real chemical reactions. • Equilibrium conversions are maintained for 500 h without detectable deactivation. - Abstract: Thermodynamic equilibrium analysis of the combined steam and carbon dioxide reforming of methane (CSCRM) and side reactions was performed using total Gibbs free energy minimization. The effects of (CO_2 + H_2O)/CH_4 ratio (0.9–2.9), CO_2:H_2O ratio (3:1–1:3), and temperature (500–1000 °C) on the equilibrium conversions, yields, coke yield, and H_2/CO ratio were investigated. A (CO_2 + H_2O)/CH_4 ratio greater than 1.2, a CO_2:H_2O ratio of 1:2.1, and a temperature of at least 850 °C are preferable reaction conditions for the synthesis gas preparation in the gas to liquid process. Simulated conditions were applied to the CSCRM reaction and the experimental data were compared with the thermodynamic equilibrium results. The thermodynamic equilibrium results were mostly consistent with the experimental data, but the reverse water gas shift reaction rapidly occurred in the real chemical reaction and under excess oxidizing agent conditions. In addition, a long-term stability test (under simulated conditions) showed that the equilibrium conversion was maintained for 500 h and that the coke formation on the used catalyst was not observed.

  19. An Investigation of Applications for Thermodynamic Work Potential Methods: Working Tables and Charts for Estimation of Thermodynamic Work Potential in Equilibrium Mixtures of Jet-A and Air

    Science.gov (United States)

    Mavris, Dimitri; Roth, Bryce; McDonald, Rob

    2002-01-01

    The objective of this report is to provide a tool to facilitate the application of thermodynamic work potential methods to aircraft and engine analysis. This starts with a discussion of the theoretical background underlying these methods, which is then used to derive various equations useful for thermodynamic analysis of aircraft engines. The work potential analysis method is implemented in the form of a set of working charts and tables that can be used to graphically evaluate work potential stored in high-enthalpy gas. The range of validity for these tables is 300 to 36,000 R, pressures between between 0.01 atm and 100 atm, and fuel-air ratios from zero to stoichiometric. The derivations and charts assume mixtures of Jet-A and air as the working fluid. The thermodynamic properties presented in these charts were calculated based upon standard thermodynamic curve fits.

  20. A Laser Induced Breakdown Spectroscopy application based on Local Thermodynamic Equilibrium assumption for the elemental analysis of alexandrite gemstone and copper-based alloys

    Energy Technology Data Exchange (ETDEWEB)

    De Giacomo, A. [Department of Chemistry, University of Bari, Via Orabona 4, 70126 Bari (Italy); Institute of Inorganic Methodologies and Plasmas - CNR, U.O.S. Bari, Via Amendola 122/D, 70126 Bari (Italy); Dell' Aglio, M. [Institute of Inorganic Methodologies and Plasmas - CNR, U.O.S. Bari, Via Amendola 122/D, 70126 Bari (Italy); Gaudiuso, R., E-mail: rosalba.gaudiuso@ba.imip.cnr.it [Institute of Inorganic Methodologies and Plasmas - CNR, U.O.S. Bari, Via Amendola 122/D, 70126 Bari (Italy); Santagata, A. [Institute of Inorganic Methodologies and Plasmas - CNR, U.O.S. Potenza, Via S. Loja, Zona Ind., 85050 Tito Scalo (PZ) (Italy); Senesi, G.S. [Institute of Inorganic Methodologies and Plasmas - CNR, U.O.S. Bari, Via Amendola 122/D, 70126 Bari (Italy); Rossi, M.; Ghiara, M.R. [Department of Earth Sciences, University of Naples ' Federico II' , Via Mezzocannone 8, 80134 Naples (Italy); Capitelli, F. [Institute of Crystallography - CNR, Via Salaria Km 29.300, 00015 Monterotondo (Roma) (Italy); De Pascale, O. [Institute of Inorganic Methodologies and Plasmas - CNR, U.O.S. Bari, Via Amendola 122/D, 70126 Bari (Italy)

    2012-04-04

    Graphical abstract: Self-calibrated analytical techniques based on the approximation of Local Thermodynamic Equilibrium (LTE) have been employed for the analysis of gemstones and copper-based alloys by LIBS (Laser Induced Breakdown Spectroscopy), with a special focus on LTE conditions in laser induced plasmas. Highlights: Black-Right-Pointing-Pointer Discussion of Local Thermodynamic Equilibrium (LTE) condition in laser-induced plasmas. Black-Right-Pointing-Pointer LIBS enables elemental analysis with self-calibrated LTE-based methods. Black-Right-Pointing-Pointer Be detection in alexandrite gemstone is made possible by LIBS. - Abstract: Laser Induced Breakdown Spectroscopy (LIBS) is an appealing technique to study laser-induced plasmas (LIPs), both from the basic diagnostics point of view and for analytical applications. LIPs are complex dynamic systems, expanding at supersonic velocities and undergoing a transition between different plasma regimes. If the Local Thermodynamic Equilibrium (LTE) condition is valid for such plasmas, several analytical methods can be employed and fast quantitative analyses can be performed on a variety of samples. In the present paper, a discussion about LTE is carried out and an innovative application to the analysis of the alexandrite gemstone is presented. In addition, a study about the influence of plasma parameters on the performance of LTE-based methods is reported for bronze and brass targets.

  1. Equilibrium thermodynamics in modified gravitational theories

    International Nuclear Information System (INIS)

    Bamba, Kazuharu; Geng, C.-Q.; Tsujikawa, Shinji

    2010-01-01

    We show that it is possible to obtain a picture of equilibrium thermodynamics on the apparent horizon in the expanding cosmological background for a wide class of modified gravity theories with the Lagrangian density f(R,φ,X), where R is the Ricci scalar and X is the kinetic energy of a scalar field φ. This comes from a suitable definition of an energy-momentum tensor of the 'dark' component that respects to a local energy conservation in the Jordan frame. In this framework the horizon entropy S corresponding to equilibrium thermodynamics is equal to a quarter of the horizon area A in units of gravitational constant G, as in Einstein gravity. For a flat cosmological background with a decreasing Hubble parameter, S globally increases with time, as it happens for viable f(R) inflation and dark energy models. We also show that the equilibrium description in terms of the horizon entropy S is convenient because it takes into account the contribution of both the horizon entropy S in non-equilibrium thermodynamics and an entropy production term.

  2. 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)

  3. Thermodynamic and transport properties of gaseous tetrafluoromethane in chemical equilibrium

    Science.gov (United States)

    Hunt, J. L.; Boney, L. R.

    1973-01-01

    Equations and in computer code are presented for the thermodynamic and transport properties of gaseous, undissociated tetrafluoromethane (CF4) in chemical equilibrium. The computer code calculates the thermodynamic and transport properties of CF4 when given any two of five thermodynamic variables (entropy, temperature, volume, pressure, and enthalpy). Equilibrium thermodynamic and transport property data are tabulated and pressure-enthalpy diagrams are presented.

  4. Chemical Equilibrium as Balance of the Thermodynamic Forces

    OpenAIRE

    Zilbergleyt, B.

    2004-01-01

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

  5. Hot nuclear matter and thermodynamical equilibrium

    International Nuclear Information System (INIS)

    Borderie, B.; Bacri, C.O.; Dore, D.; Frankland, J.D.; Plagnol, E.; Rivet, M.F.; Tassan-Got, L.

    1999-01-01

    Quasi-complete events from collisions between 36 Ar and 58 Ni corresponding to vaporized sources have been detected with the multidetector INDRA over the excitation energy range 10 - 28 AMeV. For the first time complete information concerning kinematical properties of emitted particles and chemical composition (mean values but also variances) are derived. Despite the very extreme conditions in which such sources are produced (binary collisions with short reaction times and source life-times), their properties are in agreement with the results of a statistical model including a final state excluded volume interaction and describing a gas of fermions and bosons in thermodynamical equilibrium. (authors)

  6. Thermodynamics Far from Equilibrium: from Glasses to Black Holes

    OpenAIRE

    Nieuwenhuizen, Th. M.

    2001-01-01

    A framework for the non-equilibrium thermodynamics of glasses is discussed. It also explains the non-equilibrium thermodynamics of a black hole isolated from matter. The first and second laws of black dynamics and black hole thermodynamics are shown to coincide, while the third laws deal with different issues.

  7. Stochastic thermodynamics of quantum maps with and without equilibrium.

    Science.gov (United States)

    Barra, Felipe; Lledó, Cristóbal

    2017-11-01

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

  8. Classical or equilibrium thermodynamics: basic conceptual aspects

    Directory of Open Access Journals (Sweden)

    Luiz Augusto Calvo Tiritan

    2008-08-01

    Full Text Available The Classical or Equilibrium Thermodynamics is one of the most consolidated fields of Physics. It is synthesized by a well-known and self coherent knowledge structure. The essence of the Classical Thermodynamics theoretical structure consists of a set of natural laws that rule the macroscopic physical systems behavior. These laws were formulated based on observations generalizations and are mostly independent of any hypotheses concerning the microscopic nature of the matter. In general, the approaches established for the Classical Thermodynamics follow one of the following alternatives: the historical approach that describes chronologically the evolution of ideas, concepts and facts, and the postulational approach in which postulates are formulated but are not demonstrated a priori but can be confirmed a posteriori. In this work, a brief review of the pre-classical historical approach conceptual evolution is elaborated, from the beginning of the seventeenth century to the middle of the nineteenth century. As for this, the following themes are dealt with in an evolutionary and phenomenological way: heat nature, thermometry, calorimetry, Carnot’s heat engine, heat mechanical equivalent and the first and second laws. The Zeroth law that was formulated afterwards is included in the discussion.

  9. Teaching Chemical Equilibrium and Thermodynamics in Undergraduate General Chemistry Classes.

    Science.gov (United States)

    Banerjee, Anil C.

    1995-01-01

    Discusses some of the conceptual difficulties encountered by undergraduate students in learning certain aspects of chemical equilibrium and thermodynamics. Discusses teaching strategies for dealing with these difficulties. (JRH)

  10. Application of the thermodynamic extremal principle to phase-field modeling of non-equilibrium solidification in multi-component alloys

    International Nuclear Information System (INIS)

    Zhang, Xiao; Wang, Haifeng; Kuang, Wangwang; Zhang, Jianbao

    2017-01-01

    Modeling of non-equilibrium solidification in multi-component alloys is of singular importance in microstructure control, which however owing to the complex systems with complex additional constraints is still an open problem. In this work, the thermodynamic extremal principle was applied to solve the complex additional constraints self-consistently in thermodynamics. Consequently, short-range solute redistribution and long-range solute diffusion that share the same mobility are integrated naturally into the solute diffusion equations, thus avoiding the introduction of additional kinetic coefficients (e.g. interface permeability) to describe solute redistribution. Application to the non-equilibrium solidification of Al-Si-Cu alloys shows that anomalous solute trapping and anomalous solute profiles within the diffuse interface could occur, thus highlighting the important effect of the interaction among the component elements on the interface kinetics. The current phase-field model might be preferred for simulations not only because of its simplest form of evolution equations but also its feasibility to increase the simulation efficiency by the “thin interface limit” analysis.

  11. Thermodynamic chemical energy transfer mechanisms of non-equilibrium, quasi-equilibrium, and equilibrium chemical reactions

    International Nuclear Information System (INIS)

    Roh, Heui-Seol

    2015-01-01

    Chemical energy transfer mechanisms at finite temperature are explored by a chemical energy transfer theory which is capable of investigating various chemical mechanisms of non-equilibrium, quasi-equilibrium, and equilibrium. Gibbs energy fluxes are obtained as a function of chemical potential, time, and displacement. Diffusion, convection, internal convection, and internal equilibrium chemical energy fluxes are demonstrated. The theory reveals that there are chemical energy flux gaps and broken discrete symmetries at the activation chemical potential, time, and displacement. The statistical, thermodynamic theory is the unification of diffusion and internal convection chemical reactions which reduces to the non-equilibrium generalization beyond the quasi-equilibrium theories of migration and diffusion processes. The relationship between kinetic theories of chemical and electrochemical reactions is also explored. The theory is applied to explore non-equilibrium chemical reactions as an illustration. Three variable separation constants indicate particle number constants and play key roles in describing the distinct chemical reaction mechanisms. The kinetics of chemical energy transfer accounts for the four control mechanisms of chemical reactions such as activation, concentration, transition, and film chemical reactions. - Highlights: • Chemical energy transfer theory is proposed for non-, quasi-, and equilibrium. • Gibbs energy fluxes are expressed by chemical potential, time, and displacement. • Relationship between chemical and electrochemical reactions is discussed. • Theory is applied to explore nonequilibrium energy transfer in chemical reactions. • Kinetics of non-equilibrium chemical reactions shows the four control mechanisms

  12. On the forces and fluxes in non-equilibrium thermodynamics

    International Nuclear Information System (INIS)

    Kitahara, Kazuo

    1986-01-01

    A formulation of non-equilibrium thermodynamics of continuum systems based on local equilibrium assumption is reported. Thermodynamic forces are defined from a generalized local entropy and irreversible fluxes are defined as non-advective parts of fluxes of conservative quantities. The validity of the general evolution criterion and its generalization is discussed. (author)

  13. Are the Concepts of Dynamic Equilibrium and the Thermodynamic Criteria for Spontaneity, Nonspontaneity, and Equilibrium Compatible?

    Science.gov (United States)

    Silverberg, Lee J.; Raff, Lionel M.

    2015-01-01

    Thermodynamic spontaneity-equilibrium criteria require that in a single-reaction system, reactions in either the forward or reverse direction at equilibrium be nonspontaneous. Conversely, the concept of dynamic equilibrium holds that forward and reverse reactions both occur at equal rates at equilibrium to the extent allowed by kinetic…

  14. Non-Equilibrium Thermodynamics of Self-Replicating Protocells

    DEFF Research Database (Denmark)

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

    2018-01-01

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

  15. EquilTheTA: Thermodynamic and transport properties of complex equilibrium plasmas

    International Nuclear Information System (INIS)

    Colonna, G.; D'Angola, A.

    2012-01-01

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

  16. College Physical Chemistry Students' Conceptions of Equilibrium and Fundamental Thermodynamics.

    Science.gov (United States)

    Thomas, Peter L.; Schwenz, Richard W.

    1998-01-01

    Focuses on many alternative conceptions and nonconceptions about material related to equilibrium and thermodynamics. Uses interviews and compares the concepts from these with those expressed by experts in textbooks. (DDR)

  17. Application of Glycyrrhiza glabra Root as a Novel Adsorbent in the Removal of Toluene Vapors: Equilibrium, Kinetic, and Thermodynamic Study

    Directory of Open Access Journals (Sweden)

    Fazel Mohammadi-Moghadam

    2013-01-01

    Full Text Available The aim of this paper is to investigate the removal of toluene from gaseous solution through Glycyrrhiza glabra root (GGR as a waste material. The batch adsorption experiments were conducted at various conditions including contact time, adsorbate concentration, humidity, and temperature. The adsorption capacity was increased by raising the sorbent humidity up to 50 percent. The adsorption of toluene was also increased over contact time by 12 h when the sorbent was saturated. The pseudo-second-order kinetic model and Freundlich model fitted the adsorption data better than other kinetic and isotherm models, respectively. The Dubinin-Radushkevich (D-R isotherm also showed that the sorption by GGR was physical in nature. The results of the thermodynamic analysis illustrated that the adsorption process is exothermic. GGR as a novel adsorbent has not previously been used for the adsorption of pollutants.

  18. Methane on Mars: Thermodynamic Equilibrium and Photochemical Calculations

    Science.gov (United States)

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

    2010-01-01

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

  19. Supersymmetric Field Theory of Non-Equilibrium Thermodynamic System

    OpenAIRE

    Olemskoi, Alexander I.; Brazhnyi, Valerii A.

    1998-01-01

    On the basis of Langevin equation the optimal SUSY field scheme is formulated to discribe a non-equilibrium thermodynamic system with quenched disorder and non-ergodicity effects. Thermodynamic and isothermal susceptibilities, memory parameter and irreversible response are determined at different temperatures and quenched disorder intensities.

  20. Considerations on non equilibrium thermodynamics of interactions

    Science.gov (United States)

    Lucia, Umberto

    2016-04-01

    Nature can be considered the ;first; engineer! For scientists and engineers, dynamics and evolution of complex systems are not easy to predict. A fundamental approach to study complex system is thermodynamics. But, the result is the origin of too many schools of thermodynamics with a consequent difficulty in communication between thermodynamicists and other scientists and, also, among themselves. The solution is to obtain a unified approach based on the fundamentals of physics. Here we suggest a possible unification of the schools of thermodynamics starting from two fundamental concepts of physics, interaction and flows.

  1. Non-equilibrium thermodynamics in cells.

    Science.gov (United States)

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

    2018-03-15

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

  2. Statistical thermodynamics of equilibrium polymers at interfaces

    NARCIS (Netherlands)

    Gucht, van der J.; Besseling, N.A.M.

    2002-01-01

    The behavior of a solution of equilibrium polymers (or living polymers) at an interface is studied, using a Bethe-Guggenheim lattice model for molecules with orientation dependent interactions. The density profile of polymers and the chain length distribution are calculated. For equilibrium polymers

  3. A survey of upwind methods for flows with equilibrium and non-equilibrium chemistry and thermodynamics

    Science.gov (United States)

    Grossman, B.; Garrett, J.; Cinnella, P.

    1989-01-01

    Several versions of flux-vector split and flux-difference split algorithms were compared with regard to general applicability and complexity. Test computations were performed using curve-fit equilibrium air chemistry for an M = 5 high-temperature inviscid flow over a wedge, and an M = 24.5 inviscid flow over a blunt cylinder for test computations; for these cases, little difference in accuracy was found among the versions of the same flux-split algorithm. For flows with nonequilibrium chemistry, the effects of the thermodynamic model on the development of flux-vector split and flux-difference split algorithms were investigated using an equilibrium model, a general nonequilibrium model, and a simplified model based on vibrational relaxation. Several numerical examples are presented, including nonequilibrium air chemistry in a high-temperature shock tube and nonequilibrium hydrogen-air chemistry in a supersonic diffuser.

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

    Science.gov (United States)

    Kleidon, Axel

    2010-01-13

    The present-day atmosphere is in a unique state far from thermodynamic equilibrium. This uniqueness is for instance reflected in the high concentration of molecular oxygen and the low relative humidity in the atmosphere. Given that the concentration of atmospheric oxygen has likely increased throughout Earth-system history, we can ask whether this trend can be generalized to a trend of Earth-system evolution that is directed away from thermodynamic equilibrium, why we would expect such a trend to take place and what it would imply for Earth-system evolution as a whole. The justification for such a trend could be found in the proposed general principle of maximum entropy production (MEP), which states that non-equilibrium thermodynamic systems maintain steady states at which entropy production is maximized. Here, I justify and demonstrate this application of MEP to the Earth at the planetary scale. I first describe the non-equilibrium thermodynamic nature of Earth-system processes and distinguish processes that drive the system's state away from equilibrium from those that are directed towards equilibrium. I formulate the interactions among these processes from a thermodynamic perspective and then connect them to a holistic view of the planetary thermodynamic state of the Earth system. In conclusion, non-equilibrium thermodynamics and MEP have the potential to provide a simple and holistic theory of Earth-system functioning. This theory can be used to derive overall evolutionary trends of the Earth's past, identify the role that life plays in driving thermodynamic states far from equilibrium, identify habitability in other planetary environments and evaluate human impacts on Earth-system functioning. This journal is © 2010 The Royal Society

  5. Non-equilibrium thermodynamics and physical kinetics

    CERN Document Server

    Bikkin, Halid

    2014-01-01

    This graduate textbook covers contemporary directions of non-equilibrium statistical mechanics as well as classical methods of kinetics. With one of the main propositions being to avoid terms such as "obviously" and "it is easy to show", this treatise is an easy-to-read introduction into this traditional, yet vibrant field.

  6. Non-equilibrium Thermodynamics and the Production of Entropy Life, Earth, and Beyond

    CERN Document Server

    Kleidon, Axel

    2005-01-01

    The present volume studies the application of concepts from non-equilibrium thermodynamics to a variety of research topics. Emphasis is on the Maximum Entropy Production (MEP) principle and applications to Geosphere-Biosphere couplings. Written by leading researchers form a wide range of background, the book proposed to give a first coherent account of an emerging field at the interface of thermodynamics, geophysics and life sciences.

  7. Equilibrium and out-of-equilibrium thermodynamics in supercooled liquids and glasses

    International Nuclear Information System (INIS)

    Mossa, S; Nave, E La; Tartaglia, P; Sciortino, F

    2003-01-01

    We review the inherent structure thermodynamical formalism and the formulation of an equation of state (EOS) for liquids in equilibrium based on the (volume) derivatives of the statistical properties of the potential energy surface. We also show that, under the hypothesis that during ageing the system explores states associated with equilibrium configurations, it is possible to generalize the proposed EOS to out-of-equilibrium (OOE) conditions. The proposed formulation is based on the introduction of one additional parameter which, in the chosen thermodynamic formalism, can be chosen as the local minimum where the slowly relaxing OOE liquid is trapped

  8. Experimental determination of thermodynamic equilibrium in biocatalytic transamination.

    Science.gov (United States)

    Tufvesson, Pär; Jensen, Jacob S; Kroutil, Wolfgang; Woodley, John M

    2012-08-01

    The equilibrium constant is a critical parameter for making rational design choices in biocatalytic transamination for the synthesis of chiral amines. However, very few reports are available in the scientific literature determining the equilibrium constant (K) for the transamination of ketones. Various methods for determining (or estimating) equilibrium have previously been suggested, both experimental as well as computational (based on group contribution methods). However, none of these were found suitable for determining the equilibrium constant for the transamination of ketones. Therefore, in this communication we suggest a simple experimental methodology which we hope will stimulate more accurate determination of thermodynamic equilibria when reporting the results of transaminase-catalyzed reactions in order to increase understanding of the relationship between substrate and product molecular structure on reaction thermodynamics. Copyright © 2012 Wiley Periodicals, Inc.

  9. Equilibrium Molecular Thermodynamics from Kirkwood Sampling

    OpenAIRE

    Somani, Sandeep; Okamoto, Yuko; Ballard, Andrew J.; Wales, David J.

    2015-01-01

    We present two methods for barrierless equilibrium sampling of molecular systems based on the recently proposed Kirkwood method (J. Chem. Phys. 2009, 130, 134102). Kirkwood sampling employs low-order correlations among internal coordinates of a molecule for random (or non-Markovian) sampling of the high dimensional conformational space. This is a geometrical sampling method independent of the potential energy surface. The first method is a variant of biased Monte Carlo, wher...

  10. Thermodynamics of ion exchange equilibrium for some uni ...

    African Journals Online (AJOL)

    The study on thermodynamics of ion exchange equilibrium for uni-univalent Cl-/I-, Cl-/Br-, and uni-divalent Cl-/SO42-, Cl-/C2O42- reaction systems was carried out using ion exchange resin Indion FF-IP. The equilibrium constant K was calculated by taking into account the activity coefficient of ions both in solution as well as ...

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

    NARCIS (Netherlands)

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

    1982-01-01

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

  12. Noncompact Equilibrium Points and Applications

    Directory of Open Access Journals (Sweden)

    Zahra Al-Rumaih

    2012-01-01

    Full Text Available We prove an equilibrium existence result for vector functions defined on noncompact domain and we give some applications in optimization and Nash equilibrium in noncooperative game.

  13. Thermodynamics of the Rhodamine B Lactone--Zwitterion Equilibrium.

    Science.gov (United States)

    Hinckley, Daniel A.; Seybold, Paul G.

    1987-01-01

    Discusses the benefits of thermochromic transformations for studying thermodynamic properties. Describes an experiment that uses a commercially available dye, attains equilibrium rapidly, employs a simple, single-beam spectrophotometer, and is suitable for both physical chemistry and introductory chemistry laboratories. (TW)

  14. Kinetic, Equilibrium and thermodynamic studies on the biosorption ...

    African Journals Online (AJOL)

    The kinetics, equilibrium and thermodynamics of the biosorption of Cd (II) from aqueous solution by the leaf biomass of Calotropis procera popularly known in western Nigeria as 'bom bom'and genrally known as Sodom apple were investigated at different experimental conditions. Optimum conditions of pH, contact time, ...

  15. Thermodynamic equilibrium and heavy particles near a black hole

    Energy Technology Data Exchange (ETDEWEB)

    Zeldovich, Ya B [AN SSSR, Moscow

    1976-02-23

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

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

    Science.gov (United States)

    Glavatskiy, K S

    2015-10-28

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

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

    International Nuclear Information System (INIS)

    Glavatskiy, K. S.

    2015-01-01

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

  18. Equilibrium and thermodynamics of azo dyes biosorption onto Spirulina platensis

    Directory of Open Access Journals (Sweden)

    G. L. Dotto

    2013-03-01

    Full Text Available The equilibrium and thermodynamics of azo dye (tartrazine and allura red biosorption onto Spirulina platensis biomass were investigated. The equilibrium curves were obtained at 298, 308, 318 and 328 K, and four isotherm models were fitted the experimental data. Biosorption thermodynamic parameters (ΔG, ΔH and ΔS were estimated. The results showed that the biosorption was favored by a temperature decrease. For both dyes, the Sips model was the best to represent the equilibrium experimental data (R²>0.99 and ARE<5.0% and the maximum biosorption capacities were 363.2 and 468.7 mg g-1 for tartrazine and allura red, respectively, obtained at 298 K. The negative values of ΔG and ΔH showed that the biosorption of both dyes was spontaneous, favorable and exothermic. The positive values of ΔS suggested that the system disorder increases during the biosorption process.

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

    International Nuclear Information System (INIS)

    Wu, Wei; Wang, Jin

    2014-01-01

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

  20. Influence of the choice of internal temperatures on the composition of CxHyOzNt plasmas out of thermodynamic equilibrium: Application to CH2 plasma

    International Nuclear Information System (INIS)

    Koalaga, Zacharie

    2002-01-01

    The purpose of this paper is to study the influence of the choice of internal temperatures on the composition of C x H y O z N t plasmas out of thermodynamic equilibrium. The numerical calculation is specially performed for CH 2 plasma in the pressure range 0.1-1 MPa and for the electron temperature range 5000-30 000 K. Precisely, the investigation of this plasma allows one to show that the choice of internal temperatures can have more influence on plasma composition than the choice of the form of the two-temperature Saha and Guldberg-Waage laws. Indeed, for one of the supposed hypotheses, it is observed that the two forms of the two-temperature system used here can give the same equilibrium composition by uncoupling the excitation temperature of the diatomic and the monatomic species. Great attention must then be given to the adopted hypothesis for internal temperature and not only to the form of the two temperature system used. An accurate comparison between the two models requires the measurement of plasma parameters such as the various internal temperatures and the species concentration. Therefore, we have also carried out an analysis of the potential experimental diagnostics of these plasma parameters. Such diagnostics can help to test and validate theoretical models

  1. Equilibrium sampling for a thermodynamic assessment of contaminated sediments

    DEFF Research Database (Denmark)

    ) govern diffusive uptake and partitioning. Equilibrium sampling of sediment was introduced 15 years ago to measure Cfree, and it has since developed into a straightforward, precise and sensitive approach for determining Cfree and other exposure parameters that allow for thermodynamic assessment...... of polluted sediments. Glass jars with µm-thin silicone coatings on the inner walls can be used for ex situ equilibration while a device housing several silicone-coated fibers can be used for in situ equilibration. In both cases, parallel sampling with varying silicone thicknesses can be applied to confirm...... will focus at the latest developments in equilibrium sampling concepts and methods. Further, we will explain how these approaches can provide a new basis for a thermodynamic assessment of polluted sediments....

  2. Modelling non-equilibrium thermodynamic systems from the speed-gradient principle.

    Science.gov (United States)

    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).

  3. The Rate-Controlled Constrained-Equilibrium Approach to Far-From-Local-Equilibrium Thermodynamics

    Directory of Open Access Journals (Sweden)

    Hameed Metghalchi

    2012-01-01

    Full Text Available The Rate-Controlled Constrained-Equilibrium (RCCE method for the description of the time-dependent behavior of dynamical systems in non-equilibrium states is a general, effective, physically based method for model order reduction that was originally developed in the framework of thermodynamics and chemical kinetics. A generalized mathematical formulation is presented here that allows including nonlinear constraints in non-local equilibrium systems characterized by the existence of a non-increasing Lyapunov functional under the system’s internal dynamics. The generalized formulation of RCCE enables to clarify the essentials of the method and the built-in general feature of thermodynamic consistency in the chemical kinetics context. In this paper, we work out the details of the method in a generalized mathematical-physics framework, but for definiteness we detail its well-known implementation in the traditional chemical kinetics framework. We detail proofs and spell out explicit functional dependences so as to bring out and clarify each underlying assumption of the method. In the standard context of chemical kinetics of ideal gas mixtures, we discuss the relations between the validity of the detailed balance condition off-equilibrium and the thermodynamic consistency of the method. We also discuss two examples of RCCE gas-phase combustion calculations to emphasize the constraint-dependent performance of the RCCE method.

  4. Application of novel nanobiocomposites for removal of nickel(II) from aqueous environments: Equilibrium, kinetics, thermodynamics and ex-situ studies

    Energy Technology Data Exchange (ETDEWEB)

    Varghese, Lina Rose; Das, Devlina; Das, Nilanjana [VIT University, Tamil Nadu (India)

    2016-01-15

    The current study presents a novel approach for the removal of Ni(II) from aqueous environments using plant gum-based (PG) and clay-based (CL) nanobiocomposite (NBC) composed of ZnO nanoparticles and chitosan. Parameters like pH, contact time, temperature, initial metal concentration and adsorbent dosage were optimized. Under optimized conditions, maximum removal of Ni(II) was noted as 90.1% and 95.5% in the case of PG-NBC and CLNBC, respectively. Equilibrium studies suggested a homogeneous mode of adsorption. Good linearity was observed for the pseudo-first order kinetic model, suggesting a physical mode of adsorption. Thermodynamic studies showed an endothermic and spontaneous nature of adsorption. The mechanism was further elucidated using SEM, EDX, AFM and FT-IR analysis. Ex-situ studies showed a maximum Ni(II) removal of 87.34% from electroplating wastewater using CL-NBC in column mode. Regeneration studies suggested that CL-NBC could be consistently reused up to 4 cycles.

  5. Thermodynamics of open, nonisothermal chemical systems far from equilibrium

    International Nuclear Information System (INIS)

    Yoshida, Nobuo

    1992-01-01

    The thermodynamic behavior of kinetic models based on a continuously stirred tank reactor (CSTR) is studied in an attempt to seek general trends in the thermodynamic properties of open nonlinear systems. The models consist of two reversible reactions, A + nB rightleftharpoons (n + 1) B (n = 0,1,or 2) and B rightleftharpoons C, taking place in an adiabatic CSTR. The heat of reaction is incorporated, and the rate constants are assumed to follow an Arrhenius temperature dependence. The models give rise to multiple stationary states and sustained oscillations (limit cycles). The entropy difference between stationary or oscillatory states and equilibrium and the rate of entropy production in the these states are calculated as a function of the residence time in the reactor. The entropy difference and entropy production may be taken, to some extent, as indicative of the influence of irreversible processes, which disappears at equilibrium. The results of the calculations reveal the following systematic trends: (I) The entropy difference or entropy production for stable states or both always increase as the residence time is shortened, namely, as the system is displaced further from equilibrium. (II) If stable and unstable states (stationary or oscillatory) coexist under identical conditions, then the stable state invariably has a smaller value of the entropy difference or entropy production or both than the corresponding unstable state. 26 refs., 3 figs

  6. Finite-size polyelectrolyte bundles at thermodynamic equilibrium

    Science.gov (United States)

    Sayar, M.; Holm, C.

    2007-01-01

    We present the results of extensive computer simulations performed on solutions of monodisperse charged rod-like polyelectrolytes in the presence of trivalent counterions. To overcome energy barriers we used a combination of parallel tempering and hybrid Monte Carlo techniques. Our results show that for small values of the electrostatic interaction the solution mostly consists of dispersed single rods. The potential of mean force between the polyelectrolyte monomers yields an attractive interaction at short distances. For a range of larger values of the Bjerrum length, we find finite-size polyelectrolyte bundles at thermodynamic equilibrium. Further increase of the Bjerrum length eventually leads to phase separation and precipitation. We discuss the origin of the observed thermodynamic stability of the finite-size aggregates.

  7. Extended irreversible thermodynamics and non-equilibrium temperature

    Directory of Open Access Journals (Sweden)

    Casas-Vazquez, Jose'

    2008-02-01

    Full Text Available We briefly review the concept of non-equilibrium temperature from the perspectives of extended irreversible thermodynamics, fluctuation theory, and statistical mechanics. The relations between different proposals are explicitly examined in two especially simple systems: an ideal gas in steady shear flow and a forced harmonic oscillator in a thermal bath. We examine with special detail temperatures related to the average molecular kinetic energy along different spatial directions, to the average configurational energy, to the derivative of the entropy with respect to internal energy, to fluctuation-dissipation relation and discuss their measurement.

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

    Science.gov (United States)

    Sousa, Tânia; Domingos, Tiago

    2006-11-01

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

  9. Non-local Thermodynamic Equilibrium Stellar Spectroscopy with 1D and Models. I. Methods and Application to Magnesium Abundances in Standard Stars

    Science.gov (United States)

    Bergemann, Maria; Collet, Remo; Amarsi, Anish M.; Kovalev, Mikhail; Ruchti, Greg; Magic, Zazralt

    2017-09-01

    We determine Mg abundances in six Gaia benchmark stars using theoretical one-dimensional (1D) hydrostatic model atmospheres, as well as temporally and spatially averaged three-dimensional () model atmospheres. The stars cover a range of Teff from 4700 to 6500 K, log g from 1.6 to 4.4 dex, and [Fe/H] from -3.0 dex to solar. Spectrum synthesis calculations are performed in local thermodynamic equilibrium (LTE) and in non-LTE (NLTE) using the oscillator strengths recently published by Pehlivan Rhodin et al. We find that: (a) Mg abundances determined from the infrared spectra are as accurate as the optical diagnostics, (b) the NLTE effects on Mg I line strengths and abundances in this sample of stars are minor (although for a few Mg I lines the NLTE effects on abundance exceed 0.6 dex in and 0.1 dex in 1D, (c) the solar Mg abundance is 7.56+/- 0.05 dex (total error), in excellent agreement with the Mg abundance measured in CI chondritic meteorites, (d) the 1D NLTE and NLTE approaches can be used with confidence to analyze optical Mg I lines in spectra of dwarfs and sub-giants, but for red giants the Mg I 5711 Å line should be preferred, (e) low-excitation Mg I lines are sensitive to the atmospheric structure; for these lines, LTE calculations with models lead to significant systematic abundance errors. The methods developed in this work will be used to study Mg abundances of a large sample of stars in the next paper in the series.

  10. Equilibrium sampling to determine the thermodynamic potential for bioaccumulation of persistent organic pollutants from sediment.

    Science.gov (United States)

    Jahnke, Annika; MacLeod, Matthew; Wickström, Håkan; Mayer, Philipp

    2014-10-07

    Equilibrium partitioning (EqP) theory is currently the most widely used approach for linking sediment pollution by persistent hydrophobic organic chemicals to bioaccumulation. Most applications of the EqP approach assume (I) a generic relationship between organic carbon-normalized chemical concentrations in sediments and lipid-normalized concentrations in biota and (II) that bioaccumulation does not induce levels exceeding those expected from equilibrium partitioning. Here, we demonstrate that assumption I can be obviated by equilibrating a silicone sampler with chemicals in sediment, measuring chemical concentrations in the silicone, and applying lipid/silicone partition ratios to yield concentrations in lipid at thermodynamic equilibrium with the sediment (CLip⇌Sed). Furthermore, we evaluated the validity of assumption II by comparing CLip⇌Sed of selected persistent, bioaccumulative and toxic pollutants (polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB)) to lipid-normalized concentrations for a range of biota from a Swedish background lake. PCBs in duck mussels, roach, eel, pikeperch, perch and pike were mostly below the equilibrium partitioning level relative to the sediment, i.e., lipid-normalized concentrations were ≤CLip⇌Sed, whereas HCB was near equilibrium between biota and sediment. Equilibrium sampling allows straightforward, sensitive and precise measurement of CLip⇌Sed. We propose CLip⇌Sed as a metric of the thermodynamic potential for bioaccumulation of persistent organic chemicals from sediment useful to prioritize management actions to remediate contaminated sites.

  11. Equilibrium Sampling to Determine the Thermodynamic Potential for Bioaccumulation of Persistent Organic Pollutants from Sediment

    DEFF Research Database (Denmark)

    Jahnke, Annika; MacLeod, Matthew; Wickström, Håkan

    2014-01-01

    Equilibrium partitioning (EqP) theory is currently the most widely used approach for linking sediment pollution by persistent hydrophobic organic chemicals to bioaccumulation. Most applications of the EqP approach assume (I) a generic relationship between organic carbon-normalized chemical...... chemical concentrations in the silicone, and applying lipid/silicone partition ratios to yield concentrations in lipid at thermodynamic equilibrium with the sediment (CLip⇌Sed). Furthermore, we evaluated the validity of assumption II by comparing CLip⇌Sed of selected persistent, bioaccumulative and toxic...... organic chemicals from sediment useful to prioritize management actions to remediate contaminated sites....

  12. Computation of thermodynamic equilibrium in systems under stress

    Science.gov (United States)

    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

  13. Local thermodynamic equilibrium in rapidly heated high energy density plasmas

    International Nuclear Information System (INIS)

    Aslanyan, V.; Tallents, G. J.

    2014-01-01

    Emission spectra and the dynamics of high energy density plasmas created by optical and Free Electron Lasers (FELs) depend on the populations of atomic levels. Calculations of plasma emission and ionization may be simplified by assuming Local Thermodynamic Equilibrium (LTE), where populations are given by the Saha-Boltzmann equation. LTE can be achieved at high densities when collisional processes are much more significant than radiative processes, but may not be valid if plasma conditions change rapidly. A collisional-radiative model has been used to calculate the times taken by carbon and iron plasmas to reach LTE at varying densities and heating rates. The effect of different energy deposition methods, as well as Ionization Potential Depression are explored. This work shows regimes in rapidly changing plasmas, such as those created by optical lasers and FELs, where the use of LTE is justified, because timescales for plasma changes are significantly longer than the times needed to achieve an LTE ionization balance

  14. SOLGAS refined: A computerized thermodynamic equilibrium calculation tool

    Energy Technology Data Exchange (ETDEWEB)

    Trowbridge, L.D.; Leitnaker, J.M.

    1993-11-01

    SOLGAS, an early computer program for calculating equilibrium in a chemical system, has been made more user-friendly, and several{open_quote} bells and whistles{close_quotes} have been added. The necessity to include elemental species has been eliminated. The input of large numbers of starting conditions has been automated. A revised format for entering data simplifies and reduces chances for error. Calculated errors by SOLGAS are flagged, and several programming errors are corrected. Auxiliary programs are available to assemble and partially automate plotting of large amounts of data. Thermodynamic input data can be changed {open_quotes}on line.{close_quote} The program can be operated with or without a co-processor. Copies of the program, suitable for the IBM-PC or compatible with at least 384 bytes of low RAM, are available from the authors.

  15. Thermodynamic Equilibrium Calculations on Cd Transformation during Sewage Sludge Incineration.

    Science.gov (United States)

    Liu, Jing-yong; Huang, Limao; Sun, Shuiyu; Ning, Xun'an; Kuo, Jiahong; Sun, Jian; Wang, Yujie; Xie, Wuming

    2016-06-01

    Thermodynamic equilibrium calculations were performed to reveal the distribution of cadmium during the sewage sludge incineration process. During sludge incineration in the presence of major minerals, such as SiO2, Al2O3 and CaO, the strongest effect was exerted by SiO2 on the Cd transformation compared with the effect of others. The stable solid product of CdSiO3 was formed easily with the reaction between Cd and SiO2, which can restrain the emissions of gaseous Cd pollutants. CdCl2 was formed more easily in the presence of chloride during incineration, thus, the volatilization of Cd was advanced by increasing chlorine content. At low temperatures, the volatilization of Cd was restrained due to the formation of the refractory solid metal sulfate. At high temperatures, the speciation of Cd was not affected by the presence of sulfur, but sulfur could affect the formation temperature of gaseous metals.

  16. SOLGAS refined: A computerized thermodynamic equilibrium calculation tool

    International Nuclear Information System (INIS)

    Trowbridge, L.D.; Leitnaker, J.M.

    1993-11-01

    SOLGAS, an early computer program for calculating equilibrium in a chemical system, has been made more user-friendly, and several open-quote bells and whistlesclose quotes have been added. The necessity to include elemental species has been eliminated. The input of large numbers of starting conditions has been automated. A revised format for entering data simplifies and reduces chances for error. Calculated errors by SOLGAS are flagged, and several programming errors are corrected. Auxiliary programs are available to assemble and partially automate plotting of large amounts of data. Thermodynamic input data can be changed open-quotes on line.close-quote The program can be operated with or without a co-processor. Copies of the program, suitable for the IBM-PC or compatible with at least 384 bytes of low RAM, are available from the authors

  17. Equilibrium sampling for a thermodynamic assessment of contaminated sediments

    DEFF Research Database (Denmark)

    Mayer, Philipp; Nørgaard Schmidt, Stine; Mäenpää, Kimmo

    Hydrophobic organic contaminants (HOCs) reaching the aquatic environment are largely stored in sediments. The risk of contaminated sediments is challenging to assess since traditional exhaustive extraction methods yield total HOC concentrations, whereas freely dissolved concentrations (Cfree......) govern diffusive uptake and partitioning. Equilibrium sampling of sediment was introduced 15 years ago to measure Cfree, and it has since developed into a straightforward, precise and sensitive approach for determining Cfree and other exposure parameters that allow for thermodynamic assessment...... of polluted sediments. Glass jars with µm-thin silicone coatings on the inner walls can be used for ex situ equilibration while a device housing several silicone-coated fibers can be used for in situ equilibration. In both cases, parallel sampling with varying silicone thicknesses can be applied to confirm...

  18. Coronal and local thermodynamic equilibriums in a hollow cathode discharge

    International Nuclear Information System (INIS)

    Zheng Xutao

    2005-01-01

    A characteristic two-section profile of excited-state populations is observed in a hollow cathode discharge and is explained by coexistence of the coronal equilibrium (CE) and the local thermodynamic equilibrium (LTE). At helium pressure 0.1 Torr and cathode current 200-300 mA, vacuum ultraviolet radiations from He I 1snp 1 P (n=2-16) and He II np 2 P (n=2-14) are resolved with a 2.2-M McPherson spectrometer. Relative populations of these states are deduced from the discrete line intensities and are plotted against energy levels. For both the He I and He II series, as energy level increases, populations of high-n (n>10) states are found to decrease much more quickly than low-n (n<7) populations. While low-n populations are described with the CE dominated by direct electron-impact excitations, high-n populations are fitted with the LTE to calculate the population temperatures of gas atoms and ions. Validities of the CE and LTE in different n-ranges are considered on the competition between radiative decays of the excited states and their collisions with gas atoms. (author)

  19. GEODAT. Development of thermodynamic data for the thermodynamic equilibrium modeling of processes in deep geothermal formations. Combined report

    International Nuclear Information System (INIS)

    Moog, Helge C.; Regenspurg, Simona; Voigt, Wolfgang

    2015-02-01

    The concept for geothermal energy application for electricity generation can be differentiated into three compartments: In the geologic compartment cooled fluid is pressed into a porous or fractured rock formation, in the borehole compartment a hot fluid is pumped to the surface and back into the geothermal reservoir, in the aboveground facility the energy is extracted from the geothermal fluid by heat exchangers. Pressure and temperature changes influence the thermodynamic equilibrium of a system. The modeling of a geothermal system has therefore to consider besides the mass transport the heat transport and consequently changing solution compositions and the pressure/temperature effected chemical equilibrium. The GEODAT project is aimed to simulate the reactive mass transport in a geothermal reservoir in the North German basin (Gross Schoenebeck). The project was performed by the cooperation of three partners: Geoforschungsinstitut Potsdam, Bergakademie Freiberg and GRS.

  20. A basic introduction to the thermodynamics of the Earth system far from equilibrium and maximum entropy production

    Science.gov (United States)

    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

  1. A basic introduction to the thermodynamics of the Earth system far from equilibrium and maximum entropy production.

    Science.gov (United States)

    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.

  2. Local thermodynamic equilibrium considerations in powerchip laser-induced plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Merten, Jonathan A., E-mail: jmerten@astate.edu; Smith, Benjamin W., E-mail: bwsmith@chem.ufl.edu; Omenetto, Nicoló, E-mail: omenetto@chem.ufl.edu

    2013-05-01

    Time-resolved emission experiments are reported in the fast-decaying transient plasma induced by a microchip laser on an aluminum target in three different cover gases, i.e., air, argon and helium. The laser operates at 532 nm, with a repetition frequency of 1 kHz and a pulse width of less than 0.5 ns. The overall persistence of plasma emission is of the order of 100 ns. We examine the existence of local thermodynamic equilibrium (LTE) by evaluating the temporal criteria required (in addition to the McWhirter criterion), as recommended by Cristoforetti et al. (Spectrochim. Acta Part B 65, 2010, 86–95). The temporal criteria examine the evolution of temperature and electron number density and compare their rate of change to the rate at which electron collisions can thermalize the change. These considerations are used to determine time windows in which LTE may be present. Our results suggest that calibration-free LIBS measurements with these lasers may be possible for some elements at early times, especially under argon. - Highlights: ► Powerchip laser-induced plasma evolution is affected by cover gas. ► Plasma often out of LTE, despite fulfilling the McWhirter criterion ► Calibration-free LIBS may be possible with powerchip laser plasmas.

  3. Local thermodynamic equilibrium considerations in powerchip laser-induced plasmas

    International Nuclear Information System (INIS)

    Merten, Jonathan A.; Smith, Benjamin W.; Omenetto, Nicoló

    2013-01-01

    Time-resolved emission experiments are reported in the fast-decaying transient plasma induced by a microchip laser on an aluminum target in three different cover gases, i.e., air, argon and helium. The laser operates at 532 nm, with a repetition frequency of 1 kHz and a pulse width of less than 0.5 ns. The overall persistence of plasma emission is of the order of 100 ns. We examine the existence of local thermodynamic equilibrium (LTE) by evaluating the temporal criteria required (in addition to the McWhirter criterion), as recommended by Cristoforetti et al. (Spectrochim. Acta Part B 65, 2010, 86–95). The temporal criteria examine the evolution of temperature and electron number density and compare their rate of change to the rate at which electron collisions can thermalize the change. These considerations are used to determine time windows in which LTE may be present. Our results suggest that calibration-free LIBS measurements with these lasers may be possible for some elements at early times, especially under argon. - Highlights: ► Powerchip laser-induced plasma evolution is affected by cover gas. ► Plasma often out of LTE, despite fulfilling the McWhirter criterion ► Calibration-free LIBS may be possible with powerchip laser plasmas

  4. Analysis of radioactive-matter interaction near thermodynamical equilibrium states

    International Nuclear Information System (INIS)

    Damamme, G.

    1993-01-01

    We study the absorption/emission process of photon by matter in the framework of a radiativo-collisionnal model of atom, a thermodynamical approach being used. The considered matter description is the atomic sphere one. First we give the expression of the balance equation around an equilibrium state. Then we express the atomic populations in function of the characteristics of the radiation and of the free electrons and of their time history. This permit us to interpret the photon balance as being due to true emission/absorption process of photons as well as fluorescence terms, all these processes being affected by relaxation effects. The total energy balance between matter and radiation can also be analyzed in the same way and conduct to introduce one photon effective interactions terms for each radiative proper mode, terms also affected by retardation effects. Such a taking into account of atom populations has no consequence on the radiative flux equation (i.e. the transfer opacity) but can considerably modify the energy balance between matter and radiation. (author). 11 refs., 3 figs

  5. Non-equilibrium statistical thermodynamics of neutron gas in reactor

    International Nuclear Information System (INIS)

    Hayasaka, Hideo

    1977-01-01

    The thermodynamic structures of non-equilibrium steady states of highly rarefied neutron gas in various media are considered for the irreversible processes owing to creative and destructive reactions of neutrons with nuclei of these media and supply from the external sources. Under the so-called clean and cold condition in reactor, the medium is regarded virtually as offering the different chemical potential fields for each subsystem of a steady neutron gas system. The fluctuations around a steady state are considered in a Markovian-Gaussian process. The generalized Einstein relations are derived for stationary neutron gas systems. The forces and flows of neutron gases in a medium are defined upon the general stationary solution of the Fokker-Planck equation. There exist the symmetry of the kinetic coefficients, and the minimum entropy production upon neutron-nuclear reactions. The distribution functions in various media are determined by each corresponding extremum condition under the vanishing of changes of the respective total entropies in the Gibbs equation. (auth.)

  6. Biochemical thermodynamics: applications of Mathematica.

    Science.gov (United States)

    Alberty, Robert A

    2006-01-01

    The most efficient way to store thermodynamic data on enzyme-catalyzed reactions is to use matrices of species properties. Since equilibrium in enzyme-catalyzed reactions is reached at specified pH values, the thermodynamics of the reactions is discussed in terms of transformed thermodynamic properties. These transformed thermodynamic properties are complicated functions of temperature, pH, and ionic strength that can be calculated from the matrices of species values. The most important of these transformed thermodynamic properties is the standard transformed Gibbs energy of formation of a reactant (sum of species). It is the most important because when this function of temperature, pH, and ionic strength is known, all the other standard transformed properties can be calculated by taking partial derivatives. The species database in this package contains data matrices for 199 reactants. For 94 of these reactants, standard enthalpies of formation of species are known, and so standard transformed Gibbs energies, standard transformed enthalpies, standard transformed entropies, and average numbers of hydrogen atoms can be calculated as functions of temperature, pH, and ionic strength. For reactions between these 94 reactants, the changes in these properties can be calculated over a range of temperatures, pHs, and ionic strengths, and so can apparent equilibrium constants. For the other 105 reactants, only standard transformed Gibbs energies of formation and average numbers of hydrogen atoms at 298.15 K can be calculated. The loading of this package provides functions of pH and ionic strength at 298.15 K for standard transformed Gibbs energies of formation and average numbers of hydrogen atoms for 199 reactants. It also provides functions of temperature, pH, and ionic strength for the standard transformed Gibbs energies of formation, standard transformed enthalpies of formation, standard transformed entropies of formation, and average numbers of hydrogen atoms for 94

  7. A redefinition of Hawking temperature on the event horizon: Thermodynamical equilibrium

    International Nuclear Information System (INIS)

    Saha, Subhajit; Chakraborty, Subenoy

    2012-01-01

    In this Letter we have used the recently introduced redefined Hawking temperature on the event horizon and investigated whether the generalized second law of thermodynamics (GSLT) and thermodynamic equilibrium holds for both the event and the apparent horizons. Here we have considered FRW universe and examined the GSLT and thermodynamic equilibrium with three examples. Finally, we have concluded that from the thermodynamic viewpoint, the universe bounded by the event horizon is more realistic than that by the apparent horizon at least for some examples.

  8. Applicability of Donnan equilibrium theory at nanochannel-reservoir interfaces.

    Science.gov (United States)

    Tian, Huanhuan; Zhang, Li; Wang, Moran

    2015-08-15

    Understanding ionic transport in nanochannels has attracted broad attention from various areas in energy and environmental fields. In most pervious research, Donnan equilibrium has been applied widely to nanofluidic systems to obtain ionic concentration and electrical potential at channel-reservoir interfaces; however, as well known that Donnan equilibrium is derived from classical thermodynamic theories with equilibrium assumptions. Therefore the applicability of the Donnan equilibrium may be questionable when the transport at nanochannel-reservoir interface is strongly non-equilibrium. In this work, the Poisson-Nernst-Planck model for ion transport is numerically solved to obtain the exact distributions of ionic concentration and electrical potential. The numerical results are quantitatively compared with the Donnan equilibrium predictions. The applicability of Donnan equilibrium is therefore justified by changing channel length, reservoir ionic concentration, surface charge density and channel height. The results indicate that the Donnan equilibrium is not applicable for short nanochannels, large concentration difference and wide openings. A non-dimensional parameter, Q factor, is proposed to measure the non-equilibrium extent and the relation between Q and the working conditions is studied in detail. Copyright © 2015 Elsevier Inc. All rights reserved.

  9. A conservative multicomponent diffusion algorithm for ambipolar plasma flows in local thermodynamic equilibrium

    International Nuclear Information System (INIS)

    Peerenboom, Kim; Van Boxtel, Jochem; Janssen, Jesper; Van Dijk, Jan

    2014-01-01

    The usage of the local thermodynamic equilibrium (LTE) approximation can be a very powerful assumption for simulations of plasmas in or close to equilibrium. In general, the elemental composition in LTE is not constant in space and effects of mixing and demixing have to be taken into account using the Stefan–Maxwell diffusion description. In this paper, we will introduce a method to discretize the resulting coupled set of elemental continuity equations. The coupling between the equations is taken into account by the introduction of the concept of a Péclet matrix. It will be shown analytically and numerically that the mass and charge conservation constraints can be fulfilled exactly. Furthermore, a case study is presented to demonstrate the applicability of the method to a simulation of a mercury-free metal-halide lamp. The source code for the simulations presented in this paper is provided as supplementary material (stacks.iop.org/JPhysD/47/425202/mmedia). (paper)

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

    International Nuclear Information System (INIS)

    Zaghloul, Mofreh R.

    2003-01-01

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

  11. Application of acidic treated pumice as an adsorbent for the removal of azo dye from aqueous solutions: kinetic, equilibrium and thermodynamic studies

    Directory of Open Access Journals (Sweden)

    Samarghandi Mohammad

    2012-11-01

    Full Text Available Abstract Colored effluents are one of the important environment pollution sources since they contain unused dye compounds which are toxic and less-biodegradable. In this work removal of Acid Red 14 and Acid Red 18 azo dyes was investigated by acidic treated pumice stone as an efficient adsorbent at various experimental conditions. Removal of dye increased with increase in contact time and initial dye concentration, while decreased for increment in solution temperature and pH. Results of the equilibrium study showed that the removal of AR14 and AR18 followed Freundlich (r2>0.99 and Langmuir (r2>0.99 isotherm models. Maximum sorption capacities were 3.1 and 29.7 mg/g for AR 14 and AR18, namely significantly higher than those reported in the literature, even for activated carbon. Fitting of experimental data onto kinetic models showed the relevance of the pseudo-second order (r2>0.99 and intra-particle diffusion (r2>0.98 models for AR14 and AR18, respectively. For both dyes, the values of external mass transfer coefficient decreased for increasing initial dye concentrations, showing increasing external mass transfer resistance at solid/liquid layer. Desorption experiments confirmed the relevance of pumice stone for dye removal, since the pH regeneration method showed 86% and 89% regeneration for AR14 and AR18, respectively.

  12. Application of Acidic Treated Pumice as an Adsorbent for the Removal of Azo Dye from Aqueous Solutions:kinetic, Equilibrium and Thermodynamic Studies

    Directory of Open Access Journals (Sweden)

    Saied Bashiri

    2012-11-01

    Full Text Available Colored effluents are one of the important environment pollution sources since they contain unused dye compounds which are toxic and less-biodegradable. In this work removal of Acid Red 14 and Acid Red 18 azo dyes was investigated by acidic treated pumice stone as anefficient adsorbent at various experimental conditions. Removal of dye increased with increase in contact time and initial dye concentration, while decreased for increment in solution temperature and pH. Results of the equilibrium study showed that the removal ofAR14 and AR18 followed Freundlich (r2>0.99 and Langmuir (r2>0.99 isotherm models.Maximum sorption capacities were 3.1 and 29.7 mg/g for AR 14 and AR18, namely significantly higher than those reported in the literature, even for activated carbon. Fitting of experimental data onto kinetic models showed the relevance of the pseudo-second order (r2>0.99 and intra-particle diffusion (r2>0.98 models for AR14 and AR18, respectively. For both dyes, the values of external mass transfer coefficient decreased for increasing initial dye concentrations, showing increasing external mass transfer resistance at solid/liquid layer.Desorption experiments confirmed the relevance of pumice stone for dye removal, since the pH regeneration method showed 86% and 89 % regeneration for AR14 and AR18,respectively.

  13. Experimental determination of thermodynamic equilibrium in biocatalytic transamination

    DEFF Research Database (Denmark)

    Tufvesson, Pär; Jensen, Jacob Skibsted; Kroutil, Wolfgang

    2012-01-01

    The equilibrium constant is a critical parameter for making rational design choices in biocatalytic transamination for the synthesis of chiral amines. However, very few reports are available in the scientific literature determining the equilibrium constant (K) for the transamination of ketones....... Various methods for determining (or estimating) equilibrium have previously been suggested, both experimental as well as computational (based on group contribution methods). However, none of these were found suitable for determining the equilibrium constant for the transamination of ketones. Therefore...

  14. Thermodynamics foundations and applications

    CERN Document Server

    Gyftopoulos, Elias P

    2005-01-01

    Designed by two MIT professors, this authoritative text discusses basic concepts and applications in detail, emphasizing generality, definitions, and logical consistency. More than 300 solved problems cover realistic energy systems and processes.

  15. Quantum thermodynamics of nanoscale steady states far from equilibrium

    Science.gov (United States)

    Taniguchi, Nobuhiko

    2018-04-01

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

  16. Thermodynamic properties and equilibrium constant of chemical reaction in nanosystem: An theoretical and experimental study

    International Nuclear Information System (INIS)

    Du, Jianping; Zhao, Ruihua; Xue, Yongqiang

    2012-01-01

    Highlights: ► There is an obvious influence of the size on thermodynamic properties for the reaction referring nano-reactants. ► Gibbs function, enthalpy, entropy and equilibrium constant are dependent on the reactant size. ► There is an approximate linear relation between them. - Abstract: The theoretical relations of thermodynamic properties, the equilibrium constant and reactant size in nanosystem are described. The effects of size on thermodynamic properties and the equilibrium constant were studied using nanosize zinc oxide and sodium bisulfate solution as a reaction system. The experimental results indicated that the molar Gibbs free energy, the molar enthalpy and the molar entropy of the reaction decrease, but the equilibrium constant increases with decreasing reactant size. Linear trends were observed between the reciprocal of size for nano-reactant and thermodynamic variable, which are consistent with the theoretical relations.

  17. Non-equilibrium thermodynamics of radiation-induced processes in solids

    International Nuclear Information System (INIS)

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

    2005-01-01

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

  18. Studies on the formulation of thermodynamics and stochastic theory for systems far from equilibrium

    Energy Technology Data Exchange (ETDEWEB)

    Ross, J. [Stanford Univ., CA (United States)

    1995-12-31

    We have been working for some time on the formulation of thermodynamics and the theory of fluctuations in systems far from equilibrium and progress in several aspects of that development are reported here.

  19. Deviation from local thermodynamical equilibrium in the solar atmosphere. Metodology. The line source function

    International Nuclear Information System (INIS)

    Shchukina, N.G.

    1980-01-01

    The methodology of the problem of deviation from local thermodynamical equilibrium in the solar atmosphere is presented. The difficulties of solution and methods of realization are systematized. The processes of line formation are considered which take into account velocity fields, structural inhomogeneity, radiation non-coherence etc. as applied to a quiet solar atmosphere. The conclusion is made on the regularity of deviation of the local thermodynamic equilibrium in upper layers of the solar atmosphere

  20. A Unified Graphical Representation of Chemical Thermodynamics and Equilibrium

    Science.gov (United States)

    Hanson, Robert M.

    2012-01-01

    During the years 1873-1879, J. Willard Gibbs published his now-famous set of articles that form the basis of the current perspective on chemical thermodynamics. The second article of this series, "A Method of Geometrical Representation of the Thermodynamic Properties of Substances by Means of Surfaces," published in 1873, is particularly notable…

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-06-10

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

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  3. The Donnan equilibrium: I. On the thermodynamic foundation of the Donnan equation of state

    NARCIS (Netherlands)

    Philipse, A.P.; Vrij, A.

    2011-01-01

    The thermodynamic equilibrium between charged colloids and an electrolyte reservoir is named after Frederic Donnan who first published on it one century ago (Donnan 1911 Z. Electrochem. 17 572). One of the intriguing features of the Donnan equilibrium is the ensuing osmotic equation of state which

  4. Chemical equilibrium. [maximizing entropy of gas system to derive relations between thermodynamic variables

    Science.gov (United States)

    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.

  5. Basic Thermodynamics

    International Nuclear Information System (INIS)

    Duthil, P

    2014-01-01

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

  6. Basic Thermodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Duthil, P [Orsay, IPN (France)

    2014-07-01

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

  7. Thermodynamic quantities and defect equilibrium in La2-xSrxNiO4+δ

    International Nuclear Information System (INIS)

    Nakamura, Takashi; Yashiro, Keiji; Sato, Kazuhisa; Mizusaki, Junichiro

    2009-01-01

    In order to elucidate the relation between thermodynamic quantities, the defect structure, and the defect equilibrium in La 2-x Sr x NiO 4+δ , statistical thermodynamic calculation is carried out and calculated results are compared to those obtained from experimental data. Partial molar enthalpy of oxygen and partial molar entropy of oxygen are obtained from δ-P(O 2 )-T relation by using Gibbs-Helmholtz equation. Statistical thermodynamic model is derived from defect equilibrium models proposed before by authors, localized electron model and delocalized electron model which could well explain the variation of oxygen content of La 2-x Sr x NiO 4+δ . Although assumed defect species and their equilibrium are different, the results of thermodynamic calculation by localized electron model and delocalized electron model show minor difference. Calculated results by the both models agree with the thermodynamic quantities obtained from oxygen nonstoichiometry of La 2-x Sr x NiO 4+δ . - Graphical abstract: In order to elucidate the relation between thermodynamic quantities, the defect structure, and the defect equilibrium in La 2-x Sr x NiO 4+δ , statistics thermodynamic calculation is carried out and calculated results are compared to those obtained from experimental data.

  8. Diffusion approximations to the chemical master equation only have a consistent stochastic thermodynamics at chemical equilibrium.

    Science.gov (United States)

    Horowitz, Jordan M

    2015-07-28

    The stochastic thermodynamics of a dilute, well-stirred mixture of chemically reacting species is built on the stochastic trajectories of reaction events obtained from the chemical master equation. However, when the molecular populations are large, the discrete chemical master equation can be approximated with a continuous diffusion process, like the chemical Langevin equation or low noise approximation. In this paper, we investigate to what extent these diffusion approximations inherit the stochastic thermodynamics of the chemical master equation. We find that a stochastic-thermodynamic description is only valid at a detailed-balanced, equilibrium steady state. Away from equilibrium, where there is no consistent stochastic thermodynamics, we show that one can still use the diffusive solutions to approximate the underlying thermodynamics of the chemical master equation.

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

    Science.gov (United States)

    Lebon, G.; Jou, D.

    2015-06-01

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

  10. Chemical Thermodynamics and Information Theory with Applications

    CERN Document Server

    Graham, Daniel J

    2011-01-01

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

  11. Departure from Local Thermodynamic Equilibrium in argon plasmas sustained in a Torche à Injection Axiale sur Guide d'Ondes

    International Nuclear Information System (INIS)

    Rincón, R.; Muñoz, J.; Calzada, M.D.

    2015-01-01

    Plasma torches are suitable plasma sources for a wide range of applications. The capability of these discharges to produce processes like sample excitation or decomposition of molecules inside them depends on the density of the plasma species and their energies (temperatures). The relation between these parameters determines the specific state of thermodynamic equilibrium in the discharge. Thus, the understanding of plasma possibilities for application purposes is related to the knowledge of the plasma thermodynamic equilibrium degree. In this paper a discussion about the equilibrium state for Ar plasmas generated by using a Torche à Injection Axiale sur Guide d'Ondes, TIAGO device, is presented. Emission spectroscopy techniques were used to measure gas temperature and electron density at the exit of the nozzle torch and along the dart. Boltzmann-plots as well as b p parameters were calculated to characterize the type and degree of departure from partial Local Saha Equilibrium (pLSE). This study indicates that the closer situation to Local Thermodynamic Equilibrium (LTE) of the plasma corresponds to larger Ar flows which highlights the importance of the nitrogen (atmosphere surrounding the plasma) in the kinetics of Ar-TIAGO discharges. - Highlights: • Discharges sustained in Ar using a TIAGO Torch show a significant departure from Local Thermodynamic Equilibrium. • Nitrogen entrance from surrounding air highly influences Thermodynamic Equilibrium. • Departure from LTE has been studied by means of Boltzmann plots and b p parameters. • The discharge is ionizing at the nozzle exit plasma, while along the dart it becomes recombining

  12. thermodynamics of ion exchange equilibrium for some uni

    African Journals Online (AJOL)

    a

    equilibrium studies [9-30], extending over a wide range of composition of solution and ... by dissolving their corresponding potassium salts (Analytical grade) in distilled ... calculated from which average value of K for that set of experiment was ...

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

    Energy Technology Data Exchange (ETDEWEB)

    Gilles, D

    2005-07-01

    This report is devoted to illustrate the power of a Monte Carlo (MC) simulation code to study the thermodynamical properties of a plasma, composed of classical point particles at thermodynamical equilibrium. Such simulations can help us to manage successfully the challenge of taking into account 'exactly' all classical correlations between particles due to density effects, unlike analytical or semi-analytical approaches, often restricted to low dense plasmas. MC simulations results allow to cover, for laser or astrophysical applications, a wide range of thermodynamical conditions from more dense (and correlated) to less dense ones (where potentials are long ranged type). Therefore Yukawa potentials, with a Thomas-Fermi temperature- and density-dependent screening length, are used to describe the effective ion-ion potentials. In this report we present two MC codes ('PDE' and 'PUCE') and applications performed with these codes in different fields (spectroscopy, opacity, equation of state). Some examples of them are discussed and illustrated at the end of the report. (author)

  14. Local Thermodynamic Equilibrium in Laser-Induced Breakdown Spectroscopy: Beyond the McWhirter criterion

    International Nuclear Information System (INIS)

    Cristoforetti, G.; De Giacomo, A.; Dell'Aglio, M.; Legnaioli, S.; Tognoni, E.; Palleschi, V.; Omenetto, N.

    2010-01-01

    In the Laser-Induced Breakdown Spectroscopy (LIBS) technique, the existence of Local Thermodynamic Equilibrium (LTE) is the essential requisite for meaningful application of theoretical Boltzmann-Maxwell and Saha-Eggert expressions that relate fundamental plasma parameters and concentration of analyte species. The most popular criterion reported in the literature dealing with plasma diagnostics, and usually invoked as a proof of the existence of LTE in the plasma, is the McWhirter criterion [R.W.P. McWhirter, in: Eds. R.H. Huddlestone, S.L. Leonard, Plasma Diagnostic Techniques, Academic Press, New York, 1965, pp. 201-264]. However, as pointed out in several papers, this criterion is known to be a necessary but not a sufficient condition to insure LTE. The considerations reported here are meant to briefly review the theoretical analysis underlying the concept of thermodynamic equilibrium and the derivation of the McWhirter criterion, and to critically discuss its application to a transient and non-homogeneous plasma, like that created by a laser pulse on solid targets. Specific examples are given of theoretical expressions involving relaxation times and diffusion coefficients, as well as a discussion of different experimental approaches involving space and time-resolved measurements that could be used to complement a positive result of the calculation of the minimum electron number density required for LTE using the McWhirter formula. It is argued that these approaches will allow a more complete assessment of the existence of LTE and therefore permit a better quantitative result. It is suggested that the mere use of the McWhirter criterion to assess the existence of LTE in laser-induced plasmas should be discontinued.

  15. Thermodynamic formalism the mathematical structures of equilibrium statistical mechanics

    CERN Document Server

    Ruelle, David

    2004-01-01

    Reissued in the Cambridge Mathematical Library, this classic book outlines the theory of thermodynamic formalism which was developed to describe the properties of certain physical systems consisting of a large number of subunits. Background material on physics has been collected in appendices to help the reader. Supplementary work is provided in the form of exercises and problems that were "open" at the original time of writing.

  16. Application of thermodynamics to silicate crystalline solutions

    Science.gov (United States)

    Saxena, S. K.

    1972-01-01

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

  17. A spreadsheet-coupled SOLGAS: A computerized thermodynamic equilibrium calculation tool. Revision 1

    Energy Technology Data Exchange (ETDEWEB)

    Trowbridge, L.D.; Leitnaker, J.M. [Oak Ridge K-25 Site, TN (United States). Technical Analysis and Operations Div.

    1995-07-01

    SOLGAS, an early computer program for calculating equilibrium in a chemical system, has been made more user-friendly, and several ``bells and whistles`` have been added. The necessity to include elemental species has been eliminated. The input of large numbers of starting conditions has been automated. A revised spreadsheet-based format for entering data, including non-ideal binary and ternary mixtures, simplifies and reduces chances for error. Calculational errors by SOLGAS are flagged, and several programming errors are corrected. Auxiliary programs are available to assemble and partially automate plotting of large amounts of data. Thermodynamic input data can be changed on line. The program can be operated with or without a co-processor. Copies of the program, suitable for the IBM-PC or compatibles with at least 384 bytes of low RAM, are available from the authors. This user manual contains appendices with examples of the use of SOLGAS. These range from elementary examples, such as, the relationships among water, ice, and water vapor, to more complex systems: phase diagram calculation of UF{sub 4} and UF{sub 6} system; burning UF{sub 4} in fluorine; thermodynamic calculation of the Cl-F-O-H system; equilibria calculations in the CCl{sub 4}--CH{sub 3}OH system; and limitations applicable to aqueous solutions. An appendix also contains the source code.

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

    International Nuclear Information System (INIS)

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

    2013-01-01

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

  19. Calculation of thermodynamic equilibrium for reactions of plutonium with air

    International Nuclear Information System (INIS)

    Zou Lexi; Sun Ying; Luo Deli; Xue Weidong; Zhu Zhenghe; Wang Rong

    2000-01-01

    There are six independent component with 4 chemical elements, i.e. PuH 2.7 (s), PuN(s), Pu 2 O 3 (s), N 2 (g) and H 2 (g), therefore, the system described involves of 2 independent reactions, both ΔG degree << O. The mass balances calculated for gas and solid phases are in good agreement with those of experimental, indicating the chemical equilibrium is nearly approached. So, it is believed that the reaction ratio of plutonium hydride with air is extremely rapid. The results are meaningful to the storage of plutonium

  20. Study of the influence of gravity on the thermodynamic equilibrium of a liquid alloy, and on its solidification: application to eutectic Al-Ge and monotectic Al-In alloys

    International Nuclear Information System (INIS)

    Vinet, Bernard

    1981-01-01

    After having recalled the meaning of gravity, this research thesis addresses the study of movements within the Earth gravity field to assess accelerations for a centrifuged system, and to describe conditions which create weightlessness. The various actions of gravity on fluid phases are analysed by highlighting phenomena of convection and segregation. In a second part, the author addresses the issue of local order. The third part addresses the influence of gravity conditions on the distribution of components of a binary liquid alloy in thermodynamic equilibrium. The fourth part addresses experimental means. The next parts address the eutectic Al-Ge alloy and the monotectic Al-In alloy. Results obtained for liquid alloy are presented, and the author analyse segregations which appeared during solidification in gravity conditions between 40 and 100 g. The influence of these conditions of the structure of both alloys is then studied

  1. Relation between absorbed dose, charged particle equilibrium and nuclear transformations: A non-equilibrium thermodynamics point of view

    International Nuclear Information System (INIS)

    Alvarez-Romero, J. T.

    2006-01-01

    We present a discussion to show that the absorbed dose D is a time-dependent function. This time dependence is demonstrated based on the concepts of charged particle equilibrium and on radiation equilibrium within the context of thermodynamic non-equilibrium. In the latter, the time dependence is due to changes of the rest mass energy of the nuclei and elementary particles involved in the terms ΣQ and Q that appear in the definitions of energy imparted ε and energy deposit ε i , respectively. In fact, nothing is said about the averaging operation of the non-stochastic quantity mean energy imparted ε-bar, which is used in the definition of D according to ICRU 60. It is shown in this research that the averaging operation necessary to define the ε-bar employed to get D cannot be performed with an equilibrium statistical operator ρ(r) as could be expected. Rather, the operation has to be defined with a time-dependent non-equilibrium statistical operator (r, t) therefore, D is a time-dependent function D(r, t). (authors)

  2. The energy balance of a plasma in partial local thermodynamic equilibrium

    NARCIS (Netherlands)

    Kroesen, G.M.W.; Schram, D.C.; Timmermans, C.J.; de Haas, J.C.M.

    1990-01-01

    The energy balance for electrons and heavy particles constituting a plasma in partial local thermodynamic equilibrium is derived. The formulation of the energy balance used allows for evaluation of the source terms without knowledge of the particle and radiation transport situation, since most of

  3. The Matrix model, a driven state variables approach to non-equilibrium thermodynamics

    NARCIS (Netherlands)

    Jongschaap, R.J.J.

    2001-01-01

    One of the new approaches in non-equilibrium thermodynamics is the so-called matrix model of Jongschaap. In this paper some features of this model are discussed. We indicate the differences with the more common approach based upon internal variables and the more sophisticated Hamiltonian and GENERIC

  4. An Easy and Effective Demonstration of Enzyme Stereospecificity and Equilibrium Thermodynamics

    Science.gov (United States)

    Herdman, Chelsea; Dickman, Michael

    2011-01-01

    Enzyme stereospecificity and equilibrium thermodynamics can be demonstrated using the coupling of two amino acid derivatives by Thermoase C160. This protease will catalyze peptide bond formation between Z-L-AspOH and L-PheOMe to form the Aspartame precursor Z-L-Asp-L-PheOMe. Reaction completion manifests itself by precipitation of the product. As…

  5. Dilepton production from quark gluon plasma using non-equilibrium thermodynamics

    International Nuclear Information System (INIS)

    Sinha, B.

    1984-01-01

    The importance of the approach phase to the thermodynamic equilibrium has been investigated for dilepton production from quark-gluon plasma - an effective temperature for the quarks as Brounian particle in a heat bath of gluons has been suggested. The spectrum for low invariant mass is, as a consequence, sharper

  6. Thermodynamics of the multicomponent vapor-liquid equilibrium under capillary pressure difference

    DEFF Research Database (Denmark)

    Shapiro, Alexander; Stenby, Erling Halfdan

    2001-01-01

    We discuss the two-phase multicomponent equilibrium, provided that the phase pressures are different due to the action of capillary forces. We prove the two general properties of such an equilibrium, which have previously been known for a single-component case, however, to the best of our knowledge......, not for the multicomponent mixtures. The importance is emphasized on the space of the intensive variables P, T and mu (i), where the laws of capillary equilibrium have a simple geometrical interpretation. We formulate thermodynamic problems specific to such an equilibrium, and outline changes to be introduced to common...... algorithms of flash calculations in order to solve these problems. Sample calculations show large variation of the capillary properties of the mixture in the very neighborhood of the phase envelope and the restrictive role of the spinodal surface as a boundary for possible equilibrium states with different...

  7. Equilibrium thermodynamics and neutrino decoupling in quasi-metric cosmology

    Science.gov (United States)

    Østvang, Dag

    2018-05-01

    The laws of thermodynamics in the expanding universe are formulated within the quasi-metric framework. The quasi-metric cosmic expansion does not directly influence momenta of material particles, so the expansion directly cools null particles only (e.g., photons). Therefore, said laws differ substantially from their counterparts in standard cosmology. Consequently, all non-null neutrino mass eigenstates are predicted to have the same energy today as they had just after neutrino decoupling in the early universe. This indicates that the predicted relic neutrino background is strongly inconsistent with detection rates measured in solar neutrino detectors (Borexino in particular). Thus quasi-metric cosmology is in violent conflict with experiment unless some exotic property of neutrinos makes the relic neutrino background essentially undetectable (e.g., if all massive mass eigenstates decay into "invisible" particles over cosmic time scales). But in absence of hard evidence in favour of the necessary exotic neutrino physics needed to resolve said conflict, the current status of quasi-metric relativity has been changed to non-viable.

  8. Phase equilibrium engineering

    CERN Document Server

    Brignole, Esteban Alberto

    2013-01-01

    Traditionally, the teaching of phase equilibria emphasizes the relationships between the thermodynamic variables of each phase in equilibrium rather than its engineering applications. This book changes the focus from the use of thermodynamics relationships to compute phase equilibria to the design and control of the phase conditions that a process needs. Phase Equilibrium Engineering presents a systematic study and application of phase equilibrium tools to the development of chemical processes. The thermodynamic modeling of mixtures for process development, synthesis, simulation, design and

  9. Entropy production in a fluid-solid system far from thermodynamic equilibrium.

    Science.gov (United States)

    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.

  10. The Donnan equilibrium: I. On the thermodynamic foundation of the Donnan equation of state

    International Nuclear Information System (INIS)

    Philipse, A; Vrij, A

    2011-01-01

    The thermodynamic equilibrium between charged colloids and an electrolyte reservoir is named after Frederic Donnan who first published on it one century ago (Donnan 1911 Z. Electrochem. 17 572). One of the intriguing features of the Donnan equilibrium is the ensuing osmotic equation of state which is a nonlinear one, even when both colloids and ions obey Van 't Hoff's ideal osmotic pressure law. The Donnan equation of state, nevertheless, is internally consistent; we demonstrate it to be a rigorous consequence of the phenomenological thermodynamics of a neutral bulk suspension equilibrating with an infinite salt reservoir. Our proof is based on an exact thermodynamic relation between osmotic pressure and salt adsorption which, when applied to ideal ions, does indeed entail the Donnan equation of state. Our derivation also shows that, contrary to what is often assumed, the Donnan equilibrium does not require ideality of the colloids: the Donnan model merely evaluates the osmotic pressure of homogeneously distributed ions, in excess of the pressure exerted by an arbitrary reference fluid of uncharged colloids. We also conclude that results from the phenomenological Donnan model coincide with predictions from statistical thermodynamics in the limit of weakly charged, point-like colloids.

  11. Non-equilibrium Thermodynamic Dissolution Theory for Multi-Component Solid/Liquid Surfaces Involving Surface Adsorption and Radiolysis Kinetics

    International Nuclear Information System (INIS)

    Stout, R B

    2001-01-01

    A theoretical expression is developed for the dissolution rate response for multi-component radioactive materials that have surface adsorption kinetics and radiolysis kinetics when wetted by a multi-component aqueous solution. An application for this type of dissolution response is the performance evaluation of multi-component spent nuclear fuels (SNFs) for long term interim storage and for geological disposition. Typically, SNF compositions depend on initial composition, uranium oxide and metal alloys being most common, and on reactor burnup which results in a wide range of fission product and actinide concentrations that decay by alpha, beta, and gamma radiation. These compositional/burnup ranges of SNFs, whether placed in interim storage or emplaced in a geologic repository, will potentially be wetted by multi-component aqueous solutions, and these solutions may be further altered by radiolytic aqueous species due to three radiation fields. The solid states of the SNFs are not thermodynamically stable when wetted and will dissolve, with or without radiolysis. The following development of a dissolution theory is based on a non-equilibrium thermodynamic analysis of energy reactions and energy transport across a solid-liquid phase change discontinuity that propagates at a quasi-steady, dissolution velocity. The integral form of the energy balance equation is used for this spatial surface discontinuity analysis. The integral formulation contains internal energy functional of classical thermodynamics for both the SNFs' solid state and surface adsorption species, and the adjacent liquid state, which includes radiolytic chemical species. The steady-state concentrations of radiolytic chemical species are expressed by an approximate analysis of the decay radiation transport equation. For purposes of illustration a modified Temkin adsorption isotherm was assumed for the surface adsorption kinetics on an arbitrary, finite area of the solid-liquid dissolution interface. For

  12. Aerospace Applications of Non-Equilibrium Plasma

    Science.gov (United States)

    Blankson, Isaiah M.

    2016-01-01

    Nonequilibrium plasma/non-thermal plasma/cold plasmas are being used in a wide range of new applications in aeronautics, active flow control, heat transfer reduction, plasma-assisted ignition and combustion, noise suppression, and power generation. Industrial applications may be found in pollution control, materials surface treatment, and water purification. In order for these plasma processes to become practical, efficient means of ionization are necessary. A primary challenge for these applications is to create a desired non-equilibrium plasma in air by preventing the discharge from transitioning into an arc. Of particular interest is the impact on simulations and experimental data with and without detailed consideration of non-equilibrium effects, and the consequences of neglecting non-equilibrium. This presentation will provide an assessment of the presence and influence of non-equilibrium phenomena for various aerospace needs and applications. Specific examples to be considered will include the forward energy deposition of laser-induced non-equilibrium plasmoids for sonic boom mitigation, weakly ionized flows obtained from pulsed nanosecond discharges for an annular Hall type MHD generator duct for turbojet energy bypass, and fundamental mechanisms affecting the design and operation of novel plasma-assisted reactive systems in dielectric liquids (water purification, in-pipe modification of fuels, etc.).

  13. Thermodynamic parameters for adsorption equilibrium of heavy metals and dyes from wastewaters.

    Science.gov (United States)

    Liu, Xiang; Lee, Duu-Jong

    2014-05-01

    This meta-analysis evaluates adsorption studies that report thermodynamic parameters for heavy metals and dyes from wastewaters. The adsorbents were derived from agricultural waste, industrial wastes, inorganic particulates, or some natural products. The adsorption mechanisms, derivation of thermodynamic relationships, and possible flaws made in such evaluation are discussed. This analysis shows that conclusions from the examined standard enthalpy and entropy changes are highly contestable. The reason for this flaw may be the poor physical structure of adsorbents tested, such that pore transport controlled the solute flux, leaving a surface reaction process near equilibrium. Copyright © 2013 Elsevier Ltd. All rights reserved.

  14. Thermodynamics from concepts to applications

    CERN Document Server

    Shavit, Arthur

    2008-01-01

    The book presents a logical methodology for solving problems in the context of conservation laws and property tables or equations. The authors elucidate the terms around which thermodynamics has historically developed, such as work, heat, temperature, energy, and entropy. Using a pedagogical approach that builds from basic principles to laws and eventually corollaries of the laws, the text enables students to think in clear and correct thermodynamic terms as well as solve real engineering problems.

  15. Modeling the nonequilibrium effects in a nonquasi-equilibrium thermodynamic cycle based on steepest entropy ascent and an isothermal-isobaric ensemble

    International Nuclear Information System (INIS)

    Li, Guanchen; Spakovsky, Michael R. von

    2016-01-01

    Conventional first principle approaches for studying nonequilibrium or far-from-equilibrium processes depend on the mechanics of individual particles or quantum states. They also require many details of the mechanical features of a system to arrive at a macroscopic property. In contrast, thermodynamics provides an approach for determining macroscopic property values without going into these details, because the overall effect of particle dynamics results, for example, at stable equilibrium in an invariant pattern of the “Maxwellian distribution”, which in turn leads to macroscopic properties. However, such an approach is not generally applicable to a nonequilibrium process except in the near-equilibrium realm. To adequately address these drawbacks, steepest-entropy-ascent quantum thermodynamics (SEAQT) provides a first principle, thermodynamic-ensemble approach applicable to the entire nonequilibrium realm. Based on prior developments by the authors, this paper applies the SEAQT framework to modeling the nonquasi-equilibrium cycle, which a system with variable volume undergoes. Using the concept of hypoequilibrium state and nonequilibrium intensive properties, this framework provides a complete description of the nonequilibrium evolution in state of the system. Results presented here reveal how nonequilibrium effects influence the performance of the cycle. - Highlights: • First-principles nonequilibrium model of thermodynamic cycles. • Study of thermal efficiency losses due to nonequilibrium effects. • Study of systems undergoing nonquasi-equilibrium processes. • Study of the coupling of system relaxation and interaction with a reservoir.

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

    Science.gov (United States)

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

    2003-01-01

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

  17. A development of multi-Species mass transport model considering thermodynamic phase equilibrium

    DEFF Research Database (Denmark)

    Hosokawa, Yoshifumi; Yamada, Kazuo; Johannesson, Björn

    2008-01-01

    ) variation in solid-phase composition when using different types of cement, (ii) physicochemical evaluation of steel corrosion initiation behaviour by calculating the molar ratio of chloride ion to hydroxide ion [Cl]/[OH] in pore solution, (iii) complicated changes of solid-phase composition caused......In this paper, a multi-species mass transport model, which can predict time dependent variation of pore solution and solid-phase composition due to the mass transport into the hardened cement paste, has been developed. Since most of the multi-species models established previously, based...... on the Poisson-Nernst-Planck theory, did not involve the modeling of chemical process, it has been coupled to thermodynamic equilibrium model in this study. By the coupling of thermodynamic equilibrium model, the multi-species model could simulate many different behaviours in hardened cement paste such as: (i...

  18. Disposal of high level nuclear wastes: Thermodynamic equilibrium and environment ethics

    Institute of Scientific and Technical Information of China (English)

    RANA Mukhtar Ahmed

    2009-01-01

    Contamination of soil, water or air, due to a failure of containment or disposal of high level nuclear wastes, can potentially cause serious hazards to the environment or human health. Essential elements of the environment and radioactivity dangers to it are illustrated. Issues of high level nuclear waste disposal are discussed with a focus on thermodynamic equilibrium and environment ethics. Major aspects of the issues are analyzed and described briefly to build a perception of risks involved and ethical implications. Nuclear waste containment repository should be as close as possible to thermodynamic equilibrium. A clear demonstration about safety aspects of nuclear waste management is required in gaining public and political confidence in any possible scheme of permanent disposal. Disposal of high level nuclear waste offers a spectrum of environment connected challenges and a long term future of nuclear power depends on the environment friendly solution of the problem of nuclear wastes.

  19. Disposal of high level nuclear wastes: thermodynamic equilibrium and environment ethics

    International Nuclear Information System (INIS)

    Rana, M.A.

    2009-01-01

    Contamination of soil, water or air, due to a failure of containment or disposal of high level nuclear wastes, can potentially cause serious hazards to the environment or human health. Essential elements of the environment and radioactivity dangers to it are illustrated. Issues of high level nuclear waste disposal are discussed with a focus on thermodynamic equilibrium and environment ethics. Major aspects of the issues are analyzed and described briefly to build a perception of risks involved and ethical implications. Nuclear waste containment repository should be as close as possible to thermodynamic equilibrium. A clear demonstration about safety aspects of nuclear waste management is required in gaining public and political confidence in any possible scheme of permanent disposal. Disposal of high level nuclear waste offers a spectrum of environment connected challenges and a long term future of nuclear power depends on the environment friendly solution of the problem of nuclear wastes. (authors)

  20. Thermodynamic parameters for mixtures of quartz under shock wave loading in views of the equilibrium model

    International Nuclear Information System (INIS)

    Maevskii, K. K.; Kinelovskii, S. A.

    2015-01-01

    The numerical results of modeling of shock wave loading of mixtures with the SiO 2 component are presented. The TEC (thermodynamic equilibrium component) model is employed to describe the behavior of solid and porous multicomponent mixtures and alloys under shock wave loading. State equations of a Mie–Grüneisen type are used to describe the behavior of condensed phases, taking into account the temperature dependence of the Grüneisen coefficient, gas in pores is one of the components of the environment. The model is based on the assumption that all components of the mixture under shock-wave loading are in thermodynamic equilibrium. The calculation results are compared with the experimental data derived by various authors. The behavior of the mixture containing components with a phase transition under high dynamic loads is described

  1. Effect of configuration widths on the spectra of local thermodynamic equilibrium plasmas

    International Nuclear Information System (INIS)

    Bar-Shalom, A.; Oreg, J.; Goldstein, W.H.

    1995-01-01

    We present the extension of the supertransition-array (STA) theory to include configuration widths in the spectra of local thermodynamic equilibrium (LTE) plasmas. Exact analytic expressions for the moments of a STA are given, accounting for the detailed contributions of individual levels within the configurations that belong to a STA. The STA average energy is shifted and an additional term appears in its variance. Various cases are presented, demonstrating the effect of these corrections on the LTE spectrum

  2. Allowance for effects of thermodynamic nonideality in sedimentation equilibrium distributions reflecting protein dimerization.

    Science.gov (United States)

    Wills, Peter R; Scott, David J; Winzor, Donald J

    2012-03-01

    This reexamination of a high-speed sedimentation equilibrium distribution for α-chymotrypsin under slightly acidic conditions (pH 4.1, I(M) 0.05) has provided experimental support for the adequacy of nearest-neighbor considerations in the allowance for effects of thermodynamic nonideality in the characterization of protein self-association over a moderate concentration range (up to 8 mg/mL). A widely held but previously untested notion about allowance for thermodynamic nonideality effects is thereby verified experimentally. However, it has also been shown that a greater obstacle to better characterization of protein self-association is likely to be the lack of a reliable estimate of monomer net charge, a parameter that has a far more profound effect on the magnitude of the measured equilibrium constant than any deficiency in current procedures for incorporating the effects of thermodynamic nonideality into the analysis of sedimentation equilibrium distributions reflecting reversible protein self-association. Copyright © 2011 Elsevier Inc. All rights reserved.

  3. Non-equilibrium thermodynamics theory of econometric source discovery for large data analysis

    Science.gov (United States)

    van Bergem, Rutger; Jenkins, Jeffrey; Benachenhou, Dalila; Szu, Harold

    2014-05-01

    Almost all consumer and firm transactions are achieved using computers and as a result gives rise to increasingly large amounts of data available for analysts. The gold standard in Economic data manipulation techniques matured during a period of limited data access, and the new Large Data Analysis (LDA) paradigm we all face may quickly obfuscate most tools used by Economists. When coupled with an increased availability of numerous unstructured, multi-modal data sets, the impending 'data tsunami' could have serious detrimental effects for Economic forecasting, analysis, and research in general. Given this reality we propose a decision-aid framework for Augmented-LDA (A-LDA) - a synergistic approach to LDA which combines traditional supervised, rule-based Machine Learning (ML) strategies to iteratively uncover hidden sources in large data, the artificial neural network (ANN) Unsupervised Learning (USL) at the minimum Helmholtz free energy for isothermal dynamic equilibrium strategies, and the Economic intuitions required to handle problems encountered when interpreting large amounts of Financial or Economic data. To make the ANN USL framework applicable to economics we define the temperature, entropy, and energy concepts in Economics from non-equilibrium molecular thermodynamics of Boltzmann viewpoint, as well as defining an information geometry, on which the ANN can operate using USL to reduce information saturation. An exemplar of such a system representation is given for firm industry equilibrium. We demonstrate the traditional ML methodology in the economics context and leverage firm financial data to explore a frontier concept known as behavioral heterogeneity. Behavioral heterogeneity on the firm level can be imagined as a firm's interactions with different types of Economic entities over time. These interactions could impose varying degrees of institutional constraints on a firm's business behavior. We specifically look at behavioral heterogeneity for firms

  4. Equilibrium and Thermodynamic Studies of Anionic Dyes Removal by an Anionic Clay-Layered Double Hydroxide

    International Nuclear Information System (INIS)

    Kantasamy, N.; Siti Mariam Sumari

    2016-01-01

    Adsorption isotherm describes the interaction of adsorbates with adsorbent in equilibrium. Equilibrium data was examined using Langmuir and Freundlich isotherm models. Thermodynamic studies were used to evaluate the thermodynamic parameters; heat of enthalpy change (ΔH degree), Gibbs free energy change (ΔG degree) and heat of entropy change (ΔSdegree) in order to gain information regarding the nature of adsorption (exothermic or endothermic). Four reactive dyes of anionic type, Acid Blue 29 (AB29), Reactive Black 5 (RB5), Reactive Orange 16 (RO16) and Reactive Red 120 (RR120) were used to obtain equilibrium isotherms at 25, 35, 45 and 55 degree Celsius. Based on Giles' classification, the isotherm produced were of L2-type, indicating strong dye affinity towards the adsorbent, and with weak competition with the solvent molecules for active adsorption sites. Equilibrium data fitted both Langmuir and Freundlich isotherm models with high correlation coefficient (R"2 > 0.91) indicating the possibility of both homogeneity and heterogeneous nature of adsorption. The negative values of ΔGdegree indicate the adsorption processes were spontaneous and feasible. The negative values of ΔHdegree lie between -20 to -75 kJ/ mol, suggesting these processes were exothermic and physical in nature. The negative values of ΔSdegree are indication of decreased disorder and randomness of spontaneous adsorption of reactive dyes on layered double hydroxide as adsorbent. (author)

  5. Nonequilibrium thermodynamic models and applications to hydrogen plasma

    International Nuclear Information System (INIS)

    Cho, K.Y.

    1988-01-01

    A generalized multithermal equilibrium (GMTE) thermodynamic model is developed and presented with applications to hydrogen. A new chemical equilibrium equation for GMTE is obtained without the ensemble temperature concept, used by a previous MTE model. The effects of the GMTE model on the derivation and calculation of the thermodynamic, transport, and radiative properties are presented and significant differences from local thermal equilibrium (LTE) and two temperature model are discussed. When the electron translational temperature (T e ) is higher than the translational temperature of the heavy particles, the effects of hydrogen molecular species to the properties are significant at high T e compared with LTE results. The density variations of minor species are orders of magnitude with kinetic nonequilibrium at a constant electron temperature. A collisional-radiative model is also developed with the GMTE chemical equilibrium equation to study the effects of radiative transfer and the ambipolar diffusion on the population distribution of the excited atoms. The nonlocal radiative transfer effect is parameterized by an absorption factor, which is defined as a ratio of the absorbed intensity to the spontaneous emission coefficient

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

    International Nuclear Information System (INIS)

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

    1984-01-01

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

  7. The zeroth law of thermodynamics and volume-preserving conservative system in equilibrium with stochastic damping

    International Nuclear Information System (INIS)

    Qian, Hong

    2014-01-01

    We propose a mathematical formulation of the zeroth law of thermodynamics and develop a stochastic dynamical theory, with a consistent irreversible thermodynamics, for systems possessing sustained conservative stationary current in phase space while in equilibrium with a heat bath. The theory generalizes underdamped mechanical equilibrium: dx=gdt+{−D∇ϕdt+√(2D)dB(t)}, with ∇⋅g=0 and {⋯} respectively representing phase-volume preserving dynamics and stochastic damping. The zeroth law implies stationary distribution u ss (x)=e −ϕ(x) . We find an orthogonality ∇ϕ⋅g=0 as a hallmark of the system. Stochastic thermodynamics based on time reversal (t,ϕ,g)→(−t,ϕ,−g) is formulated: entropy production e p # (t)=−dF(t)/dt; generalized “heat” h d # (t)=−dU(t)/dt, U(t)=∫ R n ϕ(x)u(x,t)dx being “internal energy”, and “free energy” F(t)=U(t)+∫ R n u(x,t)lnu(x,t)dx never increases. Entropy follows (dS)/(dt) =e p # −h d # . Our formulation is shown to be consistent with an earlier theory of P. Ao. Its contradistinctions to other theories, potential-flux decomposition, stochastic Hamiltonian system with even and odd variables, Klein–Kramers equation, Freidlin–Wentzell's theory, and GENERIC, are discussed.

  8. Thermodynamics

    CERN Document Server

    Fermi, Enrico

    1956-01-01

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

  9. Stability of the thermodynamic equilibrium - A test of the validity of dynamic models as applied to gyroviscous perpendicular magnetohydrodynamics

    Science.gov (United States)

    Faghihi, Mustafa; Scheffel, Jan; Spies, Guenther O.

    1988-05-01

    Stability of the thermodynamic equilibrium is put forward as a simple test of the validity of dynamic equations, and is applied to perpendicular gyroviscous magnetohydrodynamics (i.e., perpendicular magnetohydrodynamics with gyroviscosity added). This model turns out to be invalid because it predicts exponentially growing Alfven waves in a spatially homogeneous static equilibrium with scalar pressure.

  10. Stability of the thermodynamic equilibrium: A test of the validity of dynamic models as applied to gyroviscous perpendicular magnetohydrodynamics

    International Nuclear Information System (INIS)

    Faghihi, M.; Scheffel, J.; Spies, G.O.

    1988-01-01

    Stability of the thermodynamic equilibrium is put forward as a simple test of the validity of dynamic equations, and is applied to perpendicular gyroviscous magnetohydrodynamics (i.e., perpendicular magnetohydrodynamics with gyroviscosity added). This model turns out to be invalid because it predicts exponentially growing Alfven waves in a spatially homogeneous static equilibrium with scalar pressure

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

    International Nuclear Information System (INIS)

    Salvestrini, Stefano; Leone, Vincenzo; Iovino, Pasquale; Canzano, Silvana; Capasso, Sante

    2014-01-01

    Highlights: • Different methods to derive sorption thermodynamic parameters have been discussed. • ΔG° and, ΔS° values depend on the selected standard states. • Isosteric heat values help in evaluating the applicability of the sorption models. -- Abstract: This is a comparative analysis of popular methods currently in use to derive sorption thermodynamic parameters from temperature dependence of sorption isotherms. It is emphasized that the standard and isosteric thermodynamic parameters have sharply different meanings. Moreover, it is shown with examples how the sorption model adopted conditions the standard state and consequently the value of ΔG° and ΔS°. These trivial but often neglected aspects should carefully be considered when comparing thermodynamic parameters from different literature sources. An effort by the scientific community is needed to define criteria for the choice of the standard state in sorption processes

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

    Science.gov (United States)

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

    2018-05-01

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

  13. Quantum corrections to the stress-energy tensor in thermodynamic equilibrium with acceleration

    Science.gov (United States)

    Becattini, F.; Grossi, E.

    2015-08-01

    We show that the stress-energy tensor has additional terms with respect to the ideal form in states of global thermodynamic equilibrium in flat spacetime with nonvanishing acceleration and vorticity. These corrections are of quantum origin and their leading terms are second order in the gradients of the thermodynamic fields. Their relevant coefficients can be expressed in terms of correlators of the stress-energy tensor operator and the generators of the Lorentz group. With respect to previous assessments, we find that there are more second-order coefficients and that all thermodynamic functions including energy density receive acceleration and vorticity dependent corrections. Notably, also the relation between ρ and p , that is, the equation of state, is affected by acceleration and vorticity. We have calculated the corrections for a free real scalar field—both massive and massless—and we have found that they increase, particularly for a massive field, at very high acceleration and vorticity and very low temperature. Finally, these nonideal terms depend on the explicit form of the stress-energy operator, implying that different stress-energy tensors of the scalar field—canonical or improved—are thermodynamically inequivalent.

  14. Equilibrium, thermodynamic and kinetic investigations for biosorption of uranium with green algae (Cladophora hutchinsiae).

    Science.gov (United States)

    Bağda, Esra; Tuzen, Mustafa; Sarı, Ahmet

    2017-09-01

    Removal of toxic chemicals from environmental samples with low-cost methods and materials are very useful approach for especially large-scale applications. Green algae are highly abundant biomaterials which are employed as useful biosorbents in many studies. In the present study, an interesting type of green algae, Cladophora hutchinsiae (C. hutchinsiae) was used for removal of highly toxic chemical such as uranium. The pH, biosorbent concentration, contact time and temperature were optimized as 5.0, 12 g/L, 60 min and 20 °C, respectively. For the equilibrium calculations, three well known isotherm models (Langmuir, Freundlich and Dubinin-Radushkevich) were employed. The maximum biosorption capacity of the biosorbent was calculated as about 152 mg/g under the optimum batch conditions. The mean energy of biosorption was calculated as 8.39 kJ/mol from the D-R biosorption isotherm. The thermodynamic and kinetic characteristics of biosorption were also investigated to explain the nature of the process. The kinetic data best fits the pseudo-second-order kinetic model with a regression coefficient of >0.99 for all studied temperatures. The calculated ΔH° and ΔG° values showed that the biosorption process is exothermic and spontaneous for temperatures between 293 and 333 K. Furthermore, after seven cycling process, the sorption and desorption efficiencies of the biosorbent were found to be 70, and 58%, respectively meaning that the biosorbent had sufficiently high reusability performance as a clean-up tool. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Deviation from local thermodynamic equilibrium in a cesium-seeded argon plasma

    International Nuclear Information System (INIS)

    Stefanov, B.; Zarkova, L.

    1985-11-01

    The possibility of deviations from local thermodynamic equilibrium of a cesium seeded argon plasma has been analyzed. A four level model of cesium has been employed. Overpopulations of the ground state and the first excited state as well as the corresponding reduction of the electron density are calculated for cylindrical discharge structures by solving stationary rate equations. Numerical results are presented. These results indicate that in a large regime of plasma conditions the LTE assumption is valid for electron temperatures larger than 3000 K. (orig.)

  16. Equilibrium, kinetics and thermodynamics studies of textile dyes adsorption on modified Tunisian clay

    Directory of Open Access Journals (Sweden)

    naghmouchi nahed

    2016-04-01

    Full Text Available The adsorption capacity of two anionic textile dyes (RR120 and BB150 on DMSO intercalated Tunisian raw clay was investigated with respect to contact time, initial dye concentration, pH and Temperature. The equilibrium data were fitted into Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherms. The kinetic parameters were calculated using pseudo-first order, pseudo second-order, intra-particle diffusion and Elovich kinetic models. The thermodynamic parameters (DH°, DS° and DG° of the adsorption process were also evaluated.

  17. Non-equilibrium thermodynamics of highly rarefied neutron gas under creative and destructive reactions

    International Nuclear Information System (INIS)

    Hayasaka, Hideo

    1978-01-01

    The thermodynamic structures of non-equilibrium steady states of a highly rarefied neutron gas in various media are considered in terms of the irreversible processes due to creative and destructive reactions of neutrons with nuclei of these media and to neutrons supplied from external sources. The respective subsystems of the stationary neutron gas are regarded as imperfect equilibrium systems in the presence of the medium and the external neutron sources, and are treated like different species in a mixture. The entropy production due to neutron-nuclear reactions has a minimum value at the steady state. The distribution function of such a neutron gas is determined from the extremum condition in which entropy does not change, and is expressed as a shifted Boltzmann distribution specified by the respective values of the generalized chemical potential for each energy level. (author)

  18. Formation of super disperse phase and its influence on equilibrium and thermodynamics of thermal dehydration

    Energy Technology Data Exchange (ETDEWEB)

    Polyachenok, O.G. [Department of Chemistry, Mogilev State University of Foodstuffs, 212027 (Belarus)], E-mail: polyachenok@mogilev.by; Dudkina, E.N.; Branovitskaya, N.V. [Department of Chemistry, Mogilev State University of Foodstuffs, 212027 (Belarus); Polyachenok, L.D. [Department of Chemistry, Mogilev State University of A.A. Kuleshov, 212022 (Belarus)

    2008-01-30

    New data on the dehydration and rehydration processes of calcium, manganese and copper dichlorides are presented that reveal surprising, in a certain sense, behaviour difficult to be explained for the last two chlorides in terms of the usual conception of thermodynamic equilibrium. A substantial role of a super disperse phase at studying the equilibrium of the thermal decomposition of a hydrate is postulated to explain the experimental results for manganese and copper dichlorides. It is shown that the formation of such a phase of the hydrate is able to change appreciably the experimental results, causing the increase of water vapour pressure and the decrease of the derived enthalpy of a reaction. The results obtained allow to understand the reasons for considerable differences of some literature data. They enable to receive more precise and reliable data for thermal dehydration and probably for some other decomposition processes.

  19. Classical relativistic ideal gas in thermodynamic equilibrium in a uniformly accelerated reference frame

    International Nuclear Information System (INIS)

    Louis-Martinez, Domingo J

    2011-01-01

    A classical (non-quantum-mechanical) relativistic ideal gas in thermodynamic equilibrium in a uniformly accelerated frame of reference is studied using Gibbs's microcanonical and grand canonical formulations of statistical mechanics. Using these methods explicit expressions for the particle, energy and entropy density distributions are obtained, which are found to be in agreement with the well-known results of the relativistic formulation of Boltzmann's kinetic theory. Explicit expressions for the total entropy, total energy and rest mass of the gas are obtained. The position of the center of mass of the gas in equilibrium is found. The non-relativistic and ultrarelativistic approximations are also considered. The phase space volume of the system is calculated explicitly in the ultrarelativistic approximation.

  20. Thermodynamic parameters for adsorption equilibrium of heavy metals and dyes from wastewaters: Research updated.

    Science.gov (United States)

    Chang, Yingju; Lai, Juin-Yih; Lee, Duu-Jong

    2016-12-01

    The standard Gibbs free energy, enthalpy and entropy change data for adsorption equilibrium reported in biosorption literature during January 2013-May2016 were listed. Since the studied biosorption systems are all near-equilibrium processes, the enthalpy and entropy change data evaluated by fitting temperature-dependent free energy data using van Hoff's equation reveal a compensation artifact. Additional confusion is introduced with arbitrarily chosen adsorbate concentration unit in bulk solution that added free energy change of mixing into the reported free energy and enthalpy change data. Different standard states may be chosen for properly describing biosorption processes; however, this makes the general comparison between data from different systems inappropriate. No conclusion should be drawn based on unjustified thermodynamic parameters reported in biosorption studies. Copyright © 2016 Elsevier Ltd. All rights reserved.

  1. Elemental transport coefficients in viscous plasma flows near local thermodynamic equilibrium

    International Nuclear Information System (INIS)

    Orsini, Alessio; Kustova, Elena V.

    2009-01-01

    We propose a convenient formulation of elemental transport coefficients in chemically reacting and plasma flows locally approaching thermodynamic equilibrium. A set of transport coefficients for elemental diffusion velocities, heat flux, and electric current is introduced. These coefficients relate the transport fluxes with the electric field and with the spatial gradients of elemental fractions, pressure, and temperature. The proposed formalism based on chemical elements and fully symmetric with the classical transport theory based on chemical species, is particularly suitable to model mixing and demixing phenomena due to diffusion of chemical elements. The aim of this work is threefold: to define a simple and rigorous framework suitable for numerical implementation, to allow order of magnitude estimations and qualitative predictions of elemental transport phenomena, and to gain a deeper insight into the physics of chemically reacting flows near local equilibrium.

  2. Local thermodynamic equilibrium in a laser-induced plasma evidenced by blackbody radiation

    Science.gov (United States)

    Hermann, Jörg; Grojo, David; Axente, Emanuel; Craciun, Valentin

    2018-06-01

    We show that the plasma produced by laser ablation of solid materials in specific conditions has an emission spectrum that is characterized by the saturation of the most intense spectral lines at the blackbody radiance. The blackbody temperature equals the excitation temperature of atoms and ions, proving directly and unambiguously a plasma in local thermodynamic equilibrium. The present investigations take benefit from the very rich and intense emission spectrum generated by ablation of a nickel-chromium-molybdenum alloy. This alternative and direct proof of the plasma equilibrium state re-opens the perspectives of quantitative material analyses via calibration-free laser-induced breakdown spectroscopy. Moreover, the unique properties of this laser-produced plasma promote its use as radiation standard for intensity calibration of spectroscopic instruments.

  3. Is applicable thermodynamics of negative temperature for living organisms?

    Science.gov (United States)

    Atanasov, Atanas Todorov

    2017-11-01

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

  4. Thermodynamic equilibrium solubility measurements in simulated fluids by 96-well plate method in early drug discovery.

    Science.gov (United States)

    Bharate, Sonali S; Vishwakarma, Ram A

    2015-04-01

    An early prediction of solubility in physiological media (PBS, SGF and SIF) is useful to predict qualitatively bioavailability and absorption of lead candidates. Despite of the availability of multiple solubility estimation methods, none of the reported method involves simplified fixed protocol for diverse set of compounds. Therefore, a simple and medium-throughput solubility estimation protocol is highly desirable during lead optimization stage. The present work introduces a rapid method for assessment of thermodynamic equilibrium solubility of compounds in aqueous media using 96-well microplate. The developed protocol is straightforward to set up and takes advantage of the sensitivity of UV spectroscopy. The compound, in stock solution in methanol, is introduced in microgram quantities into microplate wells followed by drying at an ambient temperature. Microplates were shaken upon addition of test media and the supernatant was analyzed by UV method. A plot of absorbance versus concentration of a sample provides saturation point, which is thermodynamic equilibrium solubility of a sample. The established protocol was validated using a large panel of commercially available drugs and with conventional miniaturized shake flask method (r(2)>0.84). Additionally, the statistically significant QSPR models were established using experimental solubility values of 52 compounds. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. Closed power cycles thermodynamic fundamentals and applications

    CERN Document Server

    Invernizzi, Costante Mario

    2013-01-01

    With the growing attention to the exploitation of renewable energies and heat recovery from industrial processes, the traditional steam and gas cycles are showing themselves often inadequate. The inadequacy is due to the great assortment of the required sizes power and of the large kind of heat sources. Closed Power Cycles: Thermodynamic Fundamentals and Applications offers an organized discussion about the strong interaction between working fluids, the thermodynamic behavior of the cycle using them and the technological design aspects of the machines. A precise treatment of thermal engines op

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

    Science.gov (United States)

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

    2015-05-01

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

  7. Equilibrium, kinetic and thermodynamic studies of adsorption of Th(IV) from aqueous solution onto kaolin

    International Nuclear Information System (INIS)

    Hongxia Zhang; Zhiwei Niu; Zhi Liu; Zhaodong Wen; Weiping Li; Xiaoyun Wang; Wangsuo Wu

    2015-01-01

    The kinetics and thermodynamics of the adsorption of Th(IV) on the kaolin were studied by using batch method. In addition, the experimental data were studied by dynamic and thermodynamic models. The results showed that the adsorption capacity of the adsorbent increased with increasing temperature and solid liquid ratio, but decreased with increasing initial Th(IV) ion concentration, and the best fit was obtained for the pseudo-second-order kinetics model. The calculated activation energy for adsorption was about 45 kJ/mol, which indicated the adsorption process to be chemisorption. The adsorption isotherm data could be well described by the Langmuir as well as Dubinin-Radushkevich model. The mean free energy (E) of adsorption was calculated to be about 15 kJ/mol. The thermodynamic data calculated showed that the adsorption was spontaneous and enhanced at higher temperature. Considering kinetics and equilibrium studies, the adsorption on the sites was the rate-limiting step and that adsorption was mainly a chemisorption process through cation exchange. (author)

  8. Adsorption of cadmium from aqueous solution onto untreated coffee grounds: Equilibrium, kinetics and thermodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Azouaou, N., E-mail: azouaou20@yahoo.fr [Laboratory of Reaction Genius, Faculty of Mechanical and Processes Genius, University of Sciences and Technology Houari - Boumediene, USTHB, BP no 32 El Alia bab ezzouar, 16111 Algiers (Algeria); Sadaoui, Z. [Laboratory of Reaction Genius, Faculty of Mechanical and Processes Genius, University of Sciences and Technology Houari - Boumediene, USTHB, BP no 32 El Alia bab ezzouar, 16111 Algiers (Algeria); Djaafri, A. [Central laboratory, SEAAL, 97 Parc ben omar, Kouba, Algiers (Algeria); Mokaddem, H. [Laboratory of Reaction Genius, Faculty of Mechanical and Processes Genius, University of Sciences and Technology Houari - Boumediene, USTHB, BP no 32 El Alia bab ezzouar, 16111 Algiers (Algeria)

    2010-12-15

    Adsorption can be used as a cost effective and efficient technique for the removal of toxic heavy metals from wastewater. Waste materials with no further treatment such as coffee grounds from cafeterias may act as adsorbents for the removal of cadmium. Batch kinetic and equilibrium experiments were conducted to study the effects of contact time, adsorbent dose, initial pH, particle size, initial concentration of cadmium and temperature. Three adsorption isotherm models namely, Langmuir, Freundlich and Dubinin-Radushkevich were used to analyse the equilibrium data. The Langmuir isotherm which provided the best correlation for Cd{sup 2+} adsorption onto coffee grounds, shows that the adsorption was favourable and the adsorption capacity found was equal to 15.65 mg g{sup -1}. Thermodynamic parameters were evaluated and the adsorption was exothermic. The equilibrium was achieved less than 120 min. The adsorption kinetic data was fitted with first and second order kinetic models. Finally it was concluded that the cadmium adsorption kinetic onto coffee grounds was well fitted by second order kinetic model rather than first order model. The results suggest that coffee grounds have high possibility to be used as effective and economical adsorbent for Cd{sup 2+} removal.

  9. Adsorption of cadmium from aqueous solution onto untreated coffee grounds: Equilibrium, kinetics and thermodynamics

    International Nuclear Information System (INIS)

    Azouaou, N.; Sadaoui, Z.; Djaafri, A.; Mokaddem, H.

    2010-01-01

    Adsorption can be used as a cost effective and efficient technique for the removal of toxic heavy metals from wastewater. Waste materials with no further treatment such as coffee grounds from cafeterias may act as adsorbents for the removal of cadmium. Batch kinetic and equilibrium experiments were conducted to study the effects of contact time, adsorbent dose, initial pH, particle size, initial concentration of cadmium and temperature. Three adsorption isotherm models namely, Langmuir, Freundlich and Dubinin-Radushkevich were used to analyse the equilibrium data. The Langmuir isotherm which provided the best correlation for Cd 2+ adsorption onto coffee grounds, shows that the adsorption was favourable and the adsorption capacity found was equal to 15.65 mg g -1 . Thermodynamic parameters were evaluated and the adsorption was exothermic. The equilibrium was achieved less than 120 min. The adsorption kinetic data was fitted with first and second order kinetic models. Finally it was concluded that the cadmium adsorption kinetic onto coffee grounds was well fitted by second order kinetic model rather than first order model. The results suggest that coffee grounds have high possibility to be used as effective and economical adsorbent for Cd 2+ removal.

  10. A new perspective on the electron transfer: recovering the Butler-Volmer equation in non-equilibrium thermodynamics.

    Science.gov (United States)

    Dreyer, Wolfgang; Guhlke, Clemens; Müller, Rüdiger

    2016-09-28

    Electron transfer reactions are commonly described by the phenomenological Butler-Volmer equation which has its origin in kinetic theories. The Butler-Volmer equation relates interfacial reaction rates to bulk quantities like the electrostatic potential and electrolyte concentrations. Although the general structure of the equation is well accepted, for modern electrochemical systems like batteries and fuel cells there is still intensive discussion about the specific dependencies of the coefficients. A general guideline for the derivation of Butler-Volmer type equations is missing in the literature. We derive very general relations of Butler-Volmer structure which are based on a rigorous non-equilibrium thermodynamic model and allow for adaption to a wide variety of electrochemical systems. We discuss the application of the new thermodynamic approach to different scenarios like the classical electron transfer reactions at metal electrodes and the intercalation process in lithium-iron-phosphate electrodes. Furthermore we show that under appropriate conditions also adsorption processes can lead to Butler-Volmer equations. We illustrate the application of our theory by a strongly simplified example of electroplating.

  11. Non-equilibrium thermodynamical description of rhythmic motion patterns of active systems: a canonical-dissipative approach.

    Science.gov (United States)

    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.

  12. Non-equilibrium thermodynamics, heat transport and thermal waves in laminar and turbulent superfluid helium

    Science.gov (United States)

    Mongiovì, Maria Stella; Jou, David; Sciacca, Michele

    2018-01-01

    This review paper puts together some results concerning non equilibrium thermodynamics and heat transport properties of superfluid He II. A one-fluid extended model of superfluid helium, which considers heat flux as an additional independent variable, is presented, its microscopic bases are analyzed, and compared with the well known two-fluid model. In laminar situations, the fundamental fields are density, velocity, absolute temperature, and heat flux. Such a theory is able to describe the thermomechanical phenomena, the propagation of two sounds in liquid helium, and of fourth sound in superleak. It also leads in a natural way to a two-fluid model on purely macroscopical grounds and allows a small amount of entropy associated with the superfluid component. Other important features of liquid He II arise in rotating situations and in superfluid turbulence, both characterized by the presence of quantized vortices (thin vortex lines whose circulation is restricted by a quantum condition). Such vortices have a deep influence on the transport properties of superfluid helium, as they increase very much its thermal resistance. Thus, heat flux influences the vortices which, in turn, modify the heat flux. The dynamics of vortex lines is the central topic in turbulent superfluid helium. The model is generalized to take into account the vortices in different cases of physical interest: rotating superfluids, counterflow superfluid turbulence, combined counterflow and rotation, and mass flow in addition to heat flow. To do this, the averaged vortex line density per unit volume L, is introduced and its dynamical equations are considered. Linear and non-linear evolution equations for L are written for homogeneous and inhomogeneous, isotropic and anisotropic situations. Several physical experiments are analyzed and the influence of vortices on the effective thermal conductivity of turbulent superfluid helium is found. Transitions from laminar to turbulent flows, from diffusive to

  13. A New Application for Radioimmunoassay: Measurement of Thermodynamic Constants.

    Science.gov (United States)

    Angstadt, Carol N.; And Others

    1983-01-01

    Describes a laboratory experiment in which an equilibrium radioimmunoassay (RIA) is used to estimate thermodynamic parameters such as equilibrium constants. The experiment is simple and inexpensive, and it introduces a technique that is important in the clinical chemistry and research laboratory. Background information, procedures, and results are…

  14. Heat pipe thermodynamic cycle and its applications

    International Nuclear Information System (INIS)

    Kobayashi, Y.

    1985-01-01

    A new type of thermodynamic cycle originating from extended application of the heat pipe principle is proposed and its thermal cycle is discussed from the viewpoint of theoretical thermal efficiency and Coefficient of Performance. An idealized structure that will meet the basic function for thermal systems is also suggested. A significant advantage of these systems is their use with lowtemperature energy sources found in nature or heat rejected from industrial sites

  15. Correlations in plasma in thermodynamic equilibrium; Les correlations dans un plasma en equilibre

    Energy Technology Data Exchange (ETDEWEB)

    Yvon, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1958-07-01

    This paper treats of a fully, ionized plasma in thermodynamic equilibrium. An attempt is made at reviewing the calculation of spatial correlations in such a plasma. The equation of recurrence and the principle of superposition are used. The linear approximation is first treated. The next higher approximation is studied in the case of a neutral homogeneous and isotropic plasma. (author) [French] Un plasma completement ionise est en equilibre thermodynamique. On tente une mise au point du calcul des correlations de position dans ce plasma. On utilise les equations de recurrence et le principe de superposition. On expose d'abord l'approximation lineaire. Dans le cas d'un plasma neutre homogene et isotrope l'etude est poursuivie a l'approximation suivante. (auteur)

  16. Non local-thermodynamical-equilibrium effects in the simulation of laser-produced plasmas

    Science.gov (United States)

    Klapisch, M.; Bar-Shalom, A.; Oreg, J.; Colombant, D.

    1998-05-01

    Local thermodynamic equilibrium (LTE) breaks down in directly or indirectly driven laser plasmas because of sharp gradients, energy deposition, etc. For modeling non-LTE effects in hydrodynamical simulations, Busquet's model [Phys. Fluids B 5, 4191 (1993)] is very convenient and efficient. It uses off-line generated LTE opacities and equation of states via an effective, radiation-dependent ionization temperature Tz. An overview of the model is given. The results are compared with an elaborate collisional radiative model based on superconfigurations. The agreements for average charge Z* and opacities are surprisingly good, even more so when the plasma is immersed in a radiation field. Some remaining discrepancy at low density is attributed to dielectronic recombination. Improvement appears possible, especially for emissivities, because the concept of ionization temperature seems to be validated.

  17. Non local-thermodynamical-equilibrium effects in the simulation of laser-produced plasmas

    International Nuclear Information System (INIS)

    Klapisch, M.; Bar-Shalom, A.; Oreg, J.; Colombant, D.

    1998-01-01

    Local thermodynamic equilibrium (LTE) breaks down in directly or indirectly driven laser plasmas because of sharp gradients, energy deposition, etc. For modeling non-LTE effects in hydrodynamical simulations, Busquet close-quote s model [Phys. Fluids B 5, 4191 (1993)] is very convenient and efficient. It uses off-line generated LTE opacities and equation of states via an effective, radiation-dependent ionization temperature T z . An overview of the model is given. The results are compared with an elaborate collisional radiative model based on superconfigurations. The agreements for average charge Z * and opacities are surprisingly good, even more so when the plasma is immersed in a radiation field. Some remaining discrepancy at low density is attributed to dielectronic recombination. Improvement appears possible, especially for emissivities, because the concept of ionization temperature seems to be validated. copyright 1998 American Institute of Physics

  18. Telon Blue AGLF Adsorption by NiO Based Nanomaterials:Equilibrium, Kinetic And Thermodynamic Approach

    Directory of Open Access Journals (Sweden)

    Gizem Biçer

    2017-06-01

    Full Text Available In this study, the effects of adsorption parameters such as initial pH, initial dye concentration, temperature and adsorbent dosage on the colour removal from aqueous solution containing Telon Blue AGLF(TB AGLF textile dye were investigated by NiO based nanomaterials and then the compliance of the equilibrium data with the different isotherm models in the literature was evaluated. In the next step, the adsorption sytem was analyzed in terms of kinetics and thermodynamics. At the end of the study, XRD, SEM and FTIR analysis methods were used for the particle characterization. As a result of the experimental studies, it was detected the successful use of NiO based nanomaterials synthesized by aqueous solution method rarely seen in literature for colour removal. Through this study, it is believed that the additional contributions are provided to the scientific investigations about the recovery of the water resources.

  19. A non-equilibrium thermodynamic model for tumor extracellular matrix with enzymatic degradation

    Science.gov (United States)

    Xue, Shi-Lei; Li, Bo; Feng, Xi-Qiao; Gao, Huajian

    2017-07-01

    The extracellular matrix (ECM) of a solid tumor not only affords scaffolding to support tumor architecture and integrity but also plays an essential role in tumor growth, invasion, metastasis, and therapeutics. In this paper, a non-equilibrium thermodynamic theory is established to study the chemo-mechanical behaviors of tumor ECM, which is modeled as a poroelastic polyelectrolyte consisting of a collagen network and proteoglycans. By using the principle of maximum energy dissipation rate, we deduce a set of governing equations for drug transport and mechanosensitive enzymatic degradation in ECM. The results reveal that osmosis is primarily responsible for the compression resistance of ECM. It is suggested that a well-designed ECM degradation can effectively modify the tumor microenvironment for improved efficiency of cancer therapy. The theoretical predictions show a good agreement with relevant experimental observations. This study aimed to deepen our understanding of tumor ECM may be conducive to novel anticancer strategies.

  20. Computer codes for the evaluation of thermodynamic and transport properties for equilibrium air to 30000 K

    Science.gov (United States)

    Thompson, Richard A.; Lee, Kam-Pui; Gupta, Roop N.

    1991-01-01

    The computer codes developed here provide self-consistent thermodynamic and transport properties for equilibrium air for temperatures from 500 to 30000 K over a temperature range of 10 (exp -4) to 10 (exp -2) atm. These properties are computed through the use of temperature dependent curve fits for discrete values of pressure. Interpolation is employed for intermediate values of pressure. The curve fits are based on mixture values calculated from an 11-species air model. Individual species properties used in the mixture relations are obtained from a recent study by the present authors. A review and discussion of the sources and accuracy of the curve fitted data used herein are given in NASA RP 1260.

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

    Science.gov (United States)

    Barsuk, Alexandr A.; Paladi, Florentin

    2018-04-01

    The dynamic behavior of thermodynamic system, described by one order parameter and one control parameter, in a small neighborhood of ordinary and bifurcation equilibrium values of the system parameters is studied. Using the general methods of investigating the branching (bifurcations) of solutions for nonlinear equations, we performed an exhaustive analysis of the order parameter dependences on the control parameter in a small vicinity of the equilibrium values of parameters, including the stability analysis of the equilibrium states, and the asymptotic behavior of the order parameter dependences on the control parameter (bifurcation diagrams). The peculiarities of the transition to an unstable state of the system are discussed, and the estimates of the transition time to the unstable state in the neighborhood of ordinary and bifurcation equilibrium values of parameters are given. The influence of an external field on the dynamic behavior of thermodynamic system is analyzed, and the peculiarities of the system dynamic behavior are discussed near the ordinary and bifurcation equilibrium values of parameters in the presence of external field. The dynamic process of magnetization of a ferromagnet is discussed by using the general methods of bifurcation and stability analysis presented in the paper.

  2. Effect of heavy ion irradiation on thermodynamically equilibrium Zr-Excel alloy

    Science.gov (United States)

    Yu, Hongbing; Liang, Jianlie; Yao, Zhongwen; Kirk, Mark A.; Daymond, Mark R.

    2017-05-01

    The thermodynamically equilibrium state was achieved in a Zr-Sn-Nb-Mo alloy by long-term annealing at an intermediate temperature. The fcc intermetallic Zr(Mo, Nb)2 enriched with Fe was observed at the equilibrium state. In-situ 1 MeV Kr2+ heavy ion irradiation was performed in a TEM to study the stability of the intermetallic particles under irradiation and the effects of the intermetallic particle on the evolution of type dislocation loops at different temperatures from 80 to 550 °C. Chemi-STEM elemental maps were made at the same particles before and after irradiation up to 10 dpa. It was found that no elemental redistribution occurs at 200 °C and below. Selective depletion of Fe was observed from some precipitates under irradiation at higher temperatures. No change in the morphology of particles and no evidence showing a crystalline to amorphous transformation were observed at all irradiation temperatures. The formation of type dislocation loops was observed under irradiation at 80 and 200 °C, but not at 450 and 550 °C. The loops were non-uniformly distributed; a localized high density of type dislocation loops were observed near the second phase particles; we suggest that loop nucleation is favored as a result of the stress induced by the particles, rather than by elemental redistribution. The stability of the second phase particles and the formation of the type loops under heavy ion irradiation are discussed.

  3. Thermodynamic and structure-property study of liquid-vapor equilibrium for aroma compounds.

    Science.gov (United States)

    Tromelin, Anne; Andriot, Isabelle; Kopjar, Mirela; Guichard, Elisabeth

    2010-04-14

    Thermodynamic parameters (T, DeltaH degrees , DeltaS degrees , K) were collected from the literature and/or calculated for five esters, four ketones, two aldehydes, and three alcohols, pure compounds and compounds in aqueous solution. Examination of correlations between these parameters and the range values of DeltaH degrees and DeltaS degrees puts forward the key roles of enthalpy for vaporization of pure compounds and of entropy in liquid-vapor equilibrium of compounds in aqueous solution. A structure-property relationship (SPR) study was performed using molecular descriptors on aroma compounds to better understand their vaporization behavior. In addition to the role of polarity for vapor-liquid equilibrium of compounds in aqueous solution, the structure-property study points out the role of chain length and branching, illustrated by the correlation between the connectivity index CHI-V-1 and the difference between T and log K for vaporization of pure compounds and compounds in aqueous solution. Moreover, examination of the esters' enthalpy values allowed a probable conformation adopted by ethyl octanoate in aqueous solution to be proposed.

  4. Determination and correlation thermodynamic models for solid–liquid equilibrium of the Nifedipine in pure and mixture organic solvents

    International Nuclear Information System (INIS)

    Wu, Gang; Hu, Yonghong; Gu, Pengfei; Yang, Wenge; Wang, Chunxiao; Ding, Zhiwen; Deng, Renlun; Li, Tao; Hong, Housheng

    2016-01-01

    Highlights: • The solubility increased with increasing temperature. • The data were fitted using the modified Apelblat equation in pure solvents. • The data were fitted using the CNIBS/R-K model in binary solvent mixture. - Abstract: Knowledge of thermodynamic parameters on corresponding solid-liquid equilibrium of nifedipine in different solvents is essential for a preliminary study of pharmaceutical engineering and industrial applications. In this paper, a gravimetric method was used to correct the solid-liquid equilibrium of nifedipine in methanol, ethanol, 1-butanol, acetone, acetonitrile, ethyl acetate and tetrahydrofuran pure solvents as well as in the (tetrahydrofuran + acetonitrile) mixture solvents at temperatures from 278.15 K to 328.15 K under 0.1 MPa. For the temperature range investigation, the solubility of nifedipine in the solvents increased with increasing temperature. The solubility of nifedipine in tetrahydrofuran is superior to other selected pure solvents. The modified Apelblat model, the Buchowski-Ksiazaczak λh model, and the ideal model were adopted to describe and predict the change tendency of solubility. Computational results showed that the modified Apelblat model stood out to be more suitable with the higher accuracy. The solubility values were fitted using a modified Apelblat model, a variant of the combined nearly ideal binary solvent/Redich-Kister (CNIBS/R-K) model and Jouyban-Acree model in (tetrahydrofuran + acetonitrile) binary solvent mixture. Computational results showed that the CNIBS/R-K model had more advantages than other models.

  5. Halogen bonding in solution: thermodynamics and applications.

    Science.gov (United States)

    Beale, Thomas M; Chudzinski, Michael G; Sarwar, Mohammed G; Taylor, Mark S

    2013-02-21

    Halogen bonds are noncovalent interactions in which covalently bound halogens act as electrophilic species. The utility of halogen bonding for controlling self-assembly in the solid state is evident from a broad spectrum of applications in crystal engineering and materials science. Until recently, it has been less clear whether, and to what extent, halogen bonding could be employed to influence conformation, binding or reactivity in the solution phase. This tutorial review summarizes and interprets solution-phase thermodynamic data for halogen bonding interactions obtained over the past six decades and highlights emerging applications in molecular recognition, medicinal chemistry and catalysis.

  6. A procedure to find thermodynamic equilibrium constants for CO2 and CH4 adsorption on activated carbon.

    Science.gov (United States)

    Trinh, T T; van Erp, T S; Bedeaux, D; Kjelstrup, S; Grande, C A

    2015-03-28

    Thermodynamic equilibrium for adsorption means that the chemical potential of gas and adsorbed phase are equal. A precise knowledge of the chemical potential is, however, often lacking, because the activity coefficient of the adsorbate is not known. Adsorption isotherms are therefore commonly fitted to ideal models such as the Langmuir, Sips or Henry models. We propose here a new procedure to find the activity coefficient and the equilibrium constant for adsorption which uses the thermodynamic factor. Instead of fitting the data to a model, we calculate the thermodynamic factor and use this to find first the activity coefficient. We show, using published molecular simulation data, how this procedure gives the thermodynamic equilibrium constant and enthalpies of adsorption for CO2(g) on graphite. We also use published experimental data to find similar thermodynamic properties of CO2(g) and of CH4(g) adsorbed on activated carbon. The procedure gives a higher accuracy in the determination of enthalpies of adsorption than ideal models do.

  7. Advanced classical thermodynamics

    International Nuclear Information System (INIS)

    Emanuel, G.

    1987-01-01

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

  8. A facilitated diffusion model constrained by the probability isotherm: a pedagogical exercise in intuitive non-equilibrium thermodynamics.

    Science.gov (United States)

    Chapman, Brian

    2017-06-01

    This paper seeks to develop a more thermodynamically sound pedagogy for students of biological transport than is currently available from either of the competing schools of linear non-equilibrium thermodynamics (LNET) or Michaelis-Menten kinetics (MMK). To this end, a minimal model of facilitated diffusion was constructed comprising four reversible steps: cis- substrate binding, cis → trans bound enzyme shuttling, trans -substrate dissociation and trans → cis free enzyme shuttling. All model parameters were subject to the second law constraint of the probability isotherm, which determined the unidirectional and net rates for each step and for the overall reaction through the law of mass action. Rapid equilibration scenarios require sensitive 'tuning' of the thermodynamic binding parameters to the equilibrium substrate concentration. All non-equilibrium scenarios show sigmoidal force-flux relations, with only a minority of cases having their quasi -linear portions close to equilibrium. Few cases fulfil the expectations of MMK relating reaction rates to enzyme saturation. This new approach illuminates and extends the concept of rate-limiting steps by focusing on the free energy dissipation associated with each reaction step and thereby deducing its respective relative chemical impedance. The crucial importance of an enzyme's being thermodynamically 'tuned' to its particular task, dependent on the cis- and trans- substrate concentrations with which it deals, is consistent with the occurrence of numerous isoforms for enzymes that transport a given substrate in physiologically different circumstances. This approach to kinetic modelling, being aligned with neither MMK nor LNET, is best described as intuitive non-equilibrium thermodynamics, and is recommended as a useful adjunct to the design and interpretation of experiments in biotransport.

  9. Thermodynamic equilibrium model to predict the cobalt distribution coefficient in the CoCl2--HCl--H2O--TBP liquid--liquid extraction system

    International Nuclear Information System (INIS)

    Nevarez, M.; Bautista, R.G.

    1976-01-01

    The development of a thermodynamic equilibrium model to predict the cobalt distribution coefficient in the CoCl 2 -HCl-H 2 O-TBP system is described. The model makes use of the various aqueous phase cobaltous chloride complexes stoichiometric stability constants expressed as their degree of formation, their mechanism of extraction into the organic phase, and the equilibrium constant for the extraction reaction. The model was verified by the good agreement between the calculated cobalt distribution coefficients and those obtained experimentally both in the present study and published by other investigators. The optimum extraction of cobalt by the TBP occurred at an HCl equilibrium aqueous place concentration between 8.5 and 9.5M. The development of efficient procedures for the separation and concentration of important industrial metals from their aqueous solutions by liquid-liquid extraction has recently been given impetus by the realization of an impending shortage of energy and mineral resources. Liquid-liquid extraction is one of the few methods by which it is possible to quantitatively separate elements which are similar in properties. The use of liquid-liquid extraction to separate cobalt and nickel, which very frequently occur in nature together, is an important separation problem in nonferrous metallurgy. There is some fundamental information available in the chemical literature regarding the mechanism and equilibrium thermodynamic properties of selected liquid-liquid extraction systems. This research effort shows how this available information can be utilized to improve existing separation and concentration theory and technique. The development and application of a thermodynamic equilibrium model for describing the liquid-liquid extraction of cobaltous chloride from aqueous HCl solutions by tributyl phosphate (TBP) using experimental data obtained in this investigation and from the literature are presented

  10. Superstring thermodynamics and its application to cosmology

    International Nuclear Information System (INIS)

    Matsuo, N.

    1987-01-01

    The thermodynamics of superstring theories (SST-I, SST-II) and heterotic string theory and its application to the cosmology are studied. The free energy of superstring gas is calculated in the one-loop approximation and the stability of the extra torus dimensions is discussed. Assuming that the Einstein equation dictates the evolution of the universe, we show that matter dominated universe filled with massive particles would never be realized at the beginning of the universe, contrary to the naive expectation in the superstring cosmology. (orig.)

  11. A NON-LOCAL THERMODYNAMIC EQUILIBRIUM ANALYSIS OF BORON ABUNDANCES IN METAL-POOR STARS

    International Nuclear Information System (INIS)

    Tan Kefeng; Shi Jianrong; Zhao Gang

    2010-01-01

    The non-local thermodynamic equilibrium (NLTE) line formation of neutral boron in the atmospheres of cool stars are investigated. Our results confirm that NLTE effects for the B I resonance lines, which are due to a combination of overionization and optical pumping effects, are most important for hot, metal-poor, and low-gravity stars; however, the amplitude of departures from local thermodynamic equilibrium (LTE) found by this work is smaller than that of previous studies. In addition, our calculation shows that the line formation of B I will get closer to LTE if the strength of collisions with neutral hydrogen increases, which is contrary to the result of previous studies. The NLTE line formation results are applied to the determination of boron abundances for a sample of 16 metal-poor stars with the method of spectrum synthesis of the B I 2497 A resonance lines using the archived HST/GHRS spectra. Beryllium and oxygen abundances are also determined for these stars with the published equivalent widths of the Be II 3131 A resonance and O I 7774 A triplet lines, respectively. The abundances of the nine stars which are not depleted in Be or B show that, no matter what the strength of collisions with neutral hydrogen may be, both Be and B increase with O quasilinearly in the logarithmic plane, which confirms the conclusions that Be and B are mainly produced by the primary process in the early Galaxy. The most noteworthy result of this work is that B increases with Fe or O at a very similar speed as, or a bit faster than, Be does, which is in accord with the theoretical models. The B/Be ratios remain almost constant over the metallicity range investigated here. Our average B/Be ratio falls in the interval [13 ± 4, 17 ± 4], which is consistent with the predictions of the spallation process. The contribution of B from the ν-process may be required if the 11 B/ 10 B isotopic ratios in metal-poor stars are the same as the meteoric value. An accurate measurement of the

  12. Effect of heavy ion irradiation on thermodynamically equilibrium Zr-Excel alloy

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Hongbing [Department of Mechanical and Materials Engineering, Queen' s University, Kingston, ON, K7L 3N6 (Canada); Liang, Jianlie [Department of Mechanical and Materials Engineering, Queen' s University, Kingston, ON, K7L 3N6 (Canada); College of Science, Guangxi University for Nationalities, 188, East Da Xue Rd., Nanning, Guangxi, 530006 P.R.C (China); Yao, Zhongwen, E-mail: yaoz@queensu.ca [Department of Mechanical and Materials Engineering, Queen' s University, Kingston, ON, K7L 3N6 (Canada); Kirk, Mark A. [Material Science Division Argonne National Laboratory, Argonne, IL 60439 (United States); Daymond, Mark R., E-mail: mark.daymond@queensu.ca [Department of Mechanical and Materials Engineering, Queen' s University, Kingston, ON, K7L 3N6 (Canada)

    2017-05-15

    The thermodynamically equilibrium state was achieved in a Zr-Sn-Nb-Mo alloy by long-term annealing at an intermediate temperature. The fcc intermetallic Zr(Mo, Nb){sub 2} enriched with Fe was observed at the equilibrium state. In-situ 1 MeV Kr{sup 2+} heavy ion irradiation was performed in a TEM to study the stability of the intermetallic particles under irradiation and the effects of the intermetallic particle on the evolution of type dislocation loops at different temperatures from 80 to 550 °C. Chemi-STEM elemental maps were made at the same particles before and after irradiation up to 10 dpa. It was found that no elemental redistribution occurs at 200 °C and below. Selective depletion of Fe was observed from some precipitates under irradiation at higher temperatures. No change in the morphology of particles and no evidence showing a crystalline to amorphous transformation were observed at all irradiation temperatures. The formation of type dislocation loops was observed under irradiation at 80 and 200 °C, but not at 450 and 550 °C. The loops were non-uniformly distributed; a localized high density of type dislocation loops were observed near the second phase particles; we suggest that loop nucleation is favored as a result of the stress induced by the particles, rather than by elemental redistribution. The stability of the second phase particles and the formation of the type loops under heavy ion irradiation are discussed.

  13. A thermodynamic analysis of non-equilibrium heat conduction in a semi-infinite medium subjected to a step change in temperature

    Energy Technology Data Exchange (ETDEWEB)

    Hussain, A.K.; Hussain, T.A.; Shahad, Haroun A.K. [Babylon Univ., Dept. of Mechanical Engineering, Babylon (Iraq)

    2003-05-01

    The problem of non-equilibrium heat conduction in a semi-infinite medium subjected to a step change in temperature is analyzed thermodynamically using the extended irreversible thermodynamic approach. The results show clearly the wave nature of the dimensionless temperature distribution, Stanton number and the dimensionless entropy change profiles. The non-equilibrium profiles approach the equilibrium profiles as the speed of wave propagation is increased. The results also show that the non-equilibrium temperature is higher than the equilibrium temperature but the difference decreases as the wave propagation speed increases. (Author)

  14. A pseudo-equilibrium thermodynamic model of information processing in nonlinear brain dynamics.

    Science.gov (United States)

    Freeman, Walter J

    2008-01-01

    Computational models of brain dynamics fall short of performance in speed and robustness of pattern recognition in detecting minute but highly significant pattern fragments. A novel model employs the properties of thermodynamic systems operating far from equilibrium, which is analyzed by linearization near adaptive operating points using root locus techniques. Such systems construct order by dissipating energy. Reinforcement learning of conditioned stimuli creates a landscape of attractors and their basins in each sensory cortex by forming nerve cell assemblies in cortical connectivity. Retrieval of a selected category of stored knowledge is by a phase transition that is induced by a conditioned stimulus, and that leads to pattern self-organization. Near self-regulated criticality the cortical background activity displays aperiodic null spikes at which analytic amplitude nears zero, and which constitute a form of Rayleigh noise. Phase transitions in recognition and recall are initiated at null spikes in the presence of an input signal, owing to the high signal-to-noise ratio that facilitates capture of cortex by an attractor, even by very weak activity that is typically evoked by a conditioned stimulus.

  15. Equilibrium, kinetic and thermodynamic studies on the adsorption of phenol onto graphene

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yanhui, E-mail: liyanhui@tsinghua.org.cn [Laboratory of Fiber Materials and Modern Textile, The Growing Base for State Key Laboratory, College of Electromechanical Engineering, Qingdao University, 308 Ningxia Road, Qingdao 266071 (China); Du, Qiuju; Liu, Tonghao; Sun, Jiankun; Jiao, Yuqin [Laboratory of Fiber Materials and Modern Textile, The Growing Base for State Key Laboratory, College of Electromechanical Engineering, Qingdao University, 308 Ningxia Road, Qingdao 266071 (China); Xia, Yanzhi, E-mail: xiayzh@qdu.edu.cn [Laboratory of Fiber Materials and Modern Textile, The Growing Base for State Key Laboratory, College of Electromechanical Engineering, Qingdao University, 308 Ningxia Road, Qingdao 266071 (China); Xia, Linhua; Wang, Zonghua [Laboratory of Fiber Materials and Modern Textile, The Growing Base for State Key Laboratory, College of Electromechanical Engineering, Qingdao University, 308 Ningxia Road, Qingdao 266071 (China); Zhang, Wei; Wang, Kunlin; Zhu, Hongwei; Wu, Dehai [Key Laboratory for Advanced Manufacturing by Material Processing Technology, Department of Mechanical Engineering, Tsinghua University, Beijing 100084 (China)

    2012-08-15

    Graphical abstract: The effect of temperature on phenol adsorbed by graphene shows that the equilibrium adsorption capacity of phenol increases with the increase in temperature from 285 to 333 K. Increasing adsorption capacities with temperature indicates that the adsorption of phenol is controlled by an endothermic reaction. Highlights: ► The graphene has high phenol adsorption capacity. ► The graphene has a high specific surface area of 305 m{sup 2}/g. ► The adsorption capacity is high at acidic pH range. ► The graphene has rapid phenol adsorption rate. ► Phenol adsorption is a spontaneous and endothermic process. -- Abstract: Graphene, a new member of carbon family, has been prepared, characterized and used as adsorbent to remove phenol from aqueous solution. The effect parameters including pH, dosage, contact time, and temperature on the adsorption properties of phenol onto graphene were investigated. The results showed that the maximum adsorption capacity can reach 28.26 mg/g at the conditions of initial phenol concentration of 50 mg/L, pH 6.3 and 285 K. Adsorption data were well described by both Freundlich and Langmuir models. The kinetic study illustrated that the adsorption of phenol onto graphene fit the pseudo second-order model. The thermodynamic parameters indicated that the adsorption of phenol onto graphene was endothermic and spontaneous.

  16. Equilibrium, kinetic and thermodynamic studies on the adsorption of phenol onto graphene

    International Nuclear Information System (INIS)

    Li, Yanhui; Du, Qiuju; Liu, Tonghao; Sun, Jiankun; Jiao, Yuqin; Xia, Yanzhi; Xia, Linhua; Wang, Zonghua; Zhang, Wei; Wang, Kunlin; Zhu, Hongwei; Wu, Dehai

    2012-01-01

    Graphical abstract: The effect of temperature on phenol adsorbed by graphene shows that the equilibrium adsorption capacity of phenol increases with the increase in temperature from 285 to 333 K. Increasing adsorption capacities with temperature indicates that the adsorption of phenol is controlled by an endothermic reaction. Highlights: ► The graphene has high phenol adsorption capacity. ► The graphene has a high specific surface area of 305 m 2 /g. ► The adsorption capacity is high at acidic pH range. ► The graphene has rapid phenol adsorption rate. ► Phenol adsorption is a spontaneous and endothermic process. -- Abstract: Graphene, a new member of carbon family, has been prepared, characterized and used as adsorbent to remove phenol from aqueous solution. The effect parameters including pH, dosage, contact time, and temperature on the adsorption properties of phenol onto graphene were investigated. The results showed that the maximum adsorption capacity can reach 28.26 mg/g at the conditions of initial phenol concentration of 50 mg/L, pH 6.3 and 285 K. Adsorption data were well described by both Freundlich and Langmuir models. The kinetic study illustrated that the adsorption of phenol onto graphene fit the pseudo second-order model. The thermodynamic parameters indicated that the adsorption of phenol onto graphene was endothermic and spontaneous.

  17. Modeling of thermodynamic non-equilibrium flows around cylinders and in channels

    Science.gov (United States)

    Sinha, Avick; Gopalakrishnan, Shiva

    2017-11-01

    Numerical simulations for two different types of flash-boiling flows, namely shear flow (flow through a de-Laval nozzle) and free shear flow (flow past a cylinder) are carried out in the present study. The Homogenous Relaxation Model (HRM) is used to model the thermodynamic non-equilibrium process. It was observed that the vaporization of the fluid stream, which was initially maintained at a sub-cooled state, originates at the nozzle throat. This is because the fluid accelerates at the vena-contracta and subsequently the pressure falls below the saturation vapor pressure, generating a two-phase mixture in the diverging section of the nozzle. The mass flow rate at the nozzle was found to decrease with the increase in fluid inlet temperature. A similar phenomenon also occurs for the free shear case due to boundary layer separation, causing a drop in pressure behind the cylinder. The mass fraction of vapor is maximum at rear end of the cylinder, where the size of the wake is highest. As the back pressure is reduced, severe flashing behavior was observed. The numerical simulations were validated against available experimental data. The authors gratefully acknowledge funding from the public-private partnership between DST, Confederation of Indian Industry and General Electric Pvt. Ltd.

  18. A non-equilibrium thermodynamics model of reconstituted Ca(2+)-ATPase.

    Science.gov (United States)

    Waldeck, A R; van Dam, K; Berden, J; Kuchel, P W

    1998-01-01

    A non-equilibrium thermodynamics (NET) model describing the action of completely coupled or 'slipping' reconstituted Ca(2+)-ATPase is presented. Variation of the coupling stoichiometries with the magnitude of the electrochemical gradients, as the ATPase hydrolyzes ATP, is an indication of molecular slip. However, the Ca2+ and H+ membrane-leak conductances may also be a function of their respective gradients. Such non-ohmic leak typically yields 'flow-force' relationships that are similar to those that are obtained when the pump slips; hence, caution needs to be exercised when interpreting data of Ca(2+)-ATPase-mediated fluxes that display a non-linear dependence on the electrochemical proton (delta mu H) and/or calcium gradients (delta mu Ca). To address this issue, three experimentally verifiable relationships differentiating between membrane leak and enzymic slip were derived. First, by measuring delta mu H as a function of the rate of ATP hydrolysis by the enzyme. Second, by measuring the overall 'efficiency' of the pump as a function of delta mu H. Third, by measuring the proton ejection rate by the pump as a function of its ATP hydrolysis rate.

  19. Towards understanding how surface life can affect interior geological processes: a non-equilibrium thermodynamics approach

    Directory of Open Access Journals (Sweden)

    J. G. Dyke

    2011-06-01

    Full Text Available Life has significantly altered the Earth's atmosphere, oceans and crust. To what extent has it also affected interior geological processes? To address this question, three models of geological processes are formulated: mantle convection, continental crust uplift and erosion and oceanic crust recycling. These processes are characterised as non-equilibrium thermodynamic systems. Their states of disequilibrium are maintained by the power generated from the dissipation of energy from the interior of the Earth. Altering the thickness of continental crust via weathering and erosion affects the upper mantle temperature which leads to changes in rates of oceanic crust recycling and consequently rates of outgassing of carbon dioxide into the atmosphere. Estimates for the power generated by various elements in the Earth system are shown. This includes, inter alia, surface life generation of 264 TW of power, much greater than those of geological processes such as mantle convection at 12 TW. This high power results from life's ability to harvest energy directly from the sun. Life need only utilise a small fraction of the generated free chemical energy for geochemical transformations at the surface, such as affecting rates of weathering and erosion of continental rocks, in order to affect interior, geological processes. Consequently when assessing the effects of life on Earth, and potentially any planet with a significant biosphere, dynamical models may be required that better capture the coupled nature of biologically-mediated surface and interior processes.

  20. Equilibrium Kinetics and Thermodynamic Studies of the Adsorption of Tartrazine and Sunset Yellow

    Directory of Open Access Journals (Sweden)

    F. O. Okeola

    2017-04-01

    Full Text Available Batch adsorption experiment was carried out on freema (combination of Tartrazine and Sunset Yellow an adsorbent prepared from moringa pod. The adsorption capacity of the adsorbent was determined. Effect of such factors as initial concentration of the adsorbate solution, contact time with the adsorbent, pH of the dye solution, and temperature of the dye solution on the adsorption capacity of the absorbent was determined. The result showed that the optimum adsorption was attained at pH of 3, adsorption equilibrium was attained within 60 min. The adsorption capacity increases with increase in initial concentration of the dye solution. The result of the kinetics study showed that the adsorption process was better described by the pseudo-second order rate equation. The adsorption process fitted well with both Freundlich (R2 = 0.983 and Langmuir (R2 = 0.933 models. Thermodynamic result showed ΔH and ΔS were all negative. Gibbs free energy change (ΔG increases with increase in temperature of the dye solution.

  1. Biosorption of Cr(VI from AqueousSolution Using New Adsorbent: Equilibrium and Thermodynamic Study

    Directory of Open Access Journals (Sweden)

    Israa G. Zainal

    2010-01-01

    Full Text Available Biosorption is one such emerging technology which utilized naturally occurring waste materials to sequester heavy metals from polluted water. In the present study cinnamon was utilized for Cr(VI removal from aqueous solutions.It was found that a time of two hours was sufficient for sorption to attain equilibrium. The optimum pH was 2 for Cr(VI removal. Temprature has little influence on the biosorption process. The Cr(VI removal decreased with increase in temperature. The biosorption data was well fitted to Dubinin - Radushkevich (D-R, Freundlich and Tempkin adsorption isotherm models, although the correlation coefficient of Langmuir model was high but the calculated adsorption capacity did not agree with the experimental. The thermodynamic study reveals that the biosorption process is spontaneous and the spontaneity decreased with temperature increase and the process is exothermic accompanied by highly ordered adsorbate at the solid liquid interface. ΔH° values were negative and lie in the range of physical adsorption.

  2. Model uncertainties of local-thermodynamic-equilibrium K-shell spectroscopy

    Science.gov (United States)

    Nagayama, T.; Bailey, J. E.; Mancini, R. C.; Iglesias, C. A.; Hansen, S. B.; Blancard, C.; Chung, H. K.; Colgan, J.; Cosse, Ph.; Faussurier, G.; Florido, R.; Fontes, C. J.; Gilleron, F.; Golovkin, I. E.; Kilcrease, D. P.; Loisel, G.; MacFarlane, J. J.; Pain, J.-C.; Rochau, G. A.; Sherrill, M. E.; Lee, R. W.

    2016-09-01

    Local-thermodynamic-equilibrium (LTE) K-shell spectroscopy is a common tool to diagnose electron density, ne, and electron temperature, Te, of high-energy-density (HED) plasmas. Knowing the accuracy of such diagnostics is important to provide quantitative conclusions of many HED-plasma research efforts. For example, Fe opacities were recently measured at multiple conditions at the Sandia National Laboratories Z machine (Bailey et al., 2015), showing significant disagreement with modeled opacities. Since the plasma conditions were measured using K-shell spectroscopy of tracer Mg (Nagayama et al., 2014), one concern is the accuracy of the inferred Fe conditions. In this article, we investigate the K-shell spectroscopy model uncertainties by analyzing the Mg spectra computed with 11 different models at the same conditions. We find that the inferred conditions differ by ±20-30% in ne and ±2-4% in Te depending on the choice of spectral model. Also, we find that half of the Te uncertainty comes from ne uncertainty. To refine the accuracy of the K-shell spectroscopy, it is important to scrutinize and experimentally validate line-shape theory. We investigate the impact of the inferred ne and Te model uncertainty on the Fe opacity measurements. Its impact is small and does not explain the reported discrepancies.

  3. Kinetics, Equilibrium, and Thermodynamic Studies on Adsorption of Methylene Blue by Carbonized Plant Leaf Powder

    Directory of Open Access Journals (Sweden)

    V. Gunasekar

    2013-01-01

    Full Text Available Carbon synthesized from plant leaf powder was employed for the adsorption of methylene blue from aqueous effluent. Effects of pH (2, 4, 6, 8, and 9, dye concentration (50, 100, 150, and 200 mg/dm3, adsorbent dosage (0.5, 1.0, 1.5, and 2.0 g/dm3, and temperature (303, 313, and 323 K were studied. The process followed pseudo-second-order kinetics. Equilibrium data was examined with Langmuir and Freundlich isotherm models and Langmuir model was found to be the best fitting model with high R2 and low chi2 values. Langmuir monolayer adsorption capacity of the adsorbent was found to be 61.22 mg/g. From the thermodynamic analysis, ΔH, ΔG, and ΔS values for the adsorption of MB onto the plant leaf carbon were found out. From the values of free energy change, the process was found out to be feasible process. From the magnitude of ΔH, the process was found to be endothermic physisorption.

  4. Thermodynamics for the practicing engineer

    CERN Document Server

    Theodore, Louis; Vanvliet, Timothy

    2009-01-01

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

  5. Computer program for calculation of complex chemical equilibrium compositions and applications. Part 1: Analysis

    Science.gov (United States)

    Gordon, Sanford; Mcbride, Bonnie J.

    1994-01-01

    This report presents the latest in a number of versions of chemical equilibrium and applications programs developed at the NASA Lewis Research Center over more than 40 years. These programs have changed over the years to include additional features and improved calculation techniques and to take advantage of constantly improving computer capabilities. The minimization-of-free-energy approach to chemical equilibrium calculations has been used in all versions of the program since 1967. The two principal purposes of this report are presented in two parts. The first purpose, which is accomplished here in part 1, is to present in detail a number of topics of general interest in complex equilibrium calculations. These topics include mathematical analyses and techniques for obtaining chemical equilibrium; formulas for obtaining thermodynamic and transport mixture properties and thermodynamic derivatives; criteria for inclusion of condensed phases; calculations at a triple point; inclusion of ionized species; and various applications, such as constant-pressure or constant-volume combustion, rocket performance based on either a finite- or infinite-chamber-area model, shock wave calculations, and Chapman-Jouguet detonations. The second purpose of this report, to facilitate the use of the computer code, is accomplished in part 2, entitled 'Users Manual and Program Description'. Various aspects of the computer code are discussed, and a number of examples are given to illustrate its versatility.

  6. Direct evidence of departure from local thermodynamic equilibrium in a free-burning arc-discharge plasma

    International Nuclear Information System (INIS)

    Snyder, S.C.; Lassahn, G.D.; Reynolds, L.D.

    1993-01-01

    Radial profiles of gas temperature, electron temperature, and electron density were measured in a free-burning atmospheric-pressure argon arc-discharge plasma using line-shape analysis of scattered laser light. This method yields gas temperature, electron temperature, and electron density directly, with no reliance on the assumption of local thermodynamic equilibrium (LTE). Our results show a significant departure from LTE in the center of the discharge, contrary to expectations

  7. Particle creation and non-equilibrium thermodynamical prescription of dark fluids for universe bounded by an event horizon

    OpenAIRE

    Saha, Subhajit; Biswas, Atreyee; Chakraborty, Subenoy

    2015-01-01

    In the present work, flat FRW model of the universe is considered to be an isolated open thermodynamical system where non-equilibrium prescription has been studied using the mechanism of particle creation. In the perspective of recent observational evidences, the matter distribution in the universe is assumed to be dominated by dark matter and dark energy. The dark matter is chosen as dust while for dark energy, the following choices are considered: (i) Perfect fluid with constant equation of...

  8. Equilibrium, kinetic and thermodynamic studies on the adsorption of the toxins of Bacillus thuringiensis subsp. kurstaki by clay minerals

    Energy Technology Data Exchange (ETDEWEB)

    Fu Qingling; Deng Yali; Li Huishu; Liu Jie [Key Laboratory of Subtropical Agricultural Resource and Environment, Ministry of Agriculture, Huazhong Agricultural University, Wuhan, 430070 (China); Hu Hongqing, E-mail: hqhu@mail.hzau.edu.cn [Key Laboratory of Subtropical Agricultural Resource and Environment, Ministry of Agriculture, Huazhong Agricultural University, Wuhan, 430070 (China); Chen Shouwen [Key Laboratory of Subtropical Agricultural Resource and Environment, Ministry of Agriculture, Huazhong Agricultural University, Wuhan, 430070 (China); Sa Tongmin [Department of Agricultural Chemistry, College of Agriculture, Chungbuk National University, Cheongju, 361-763 (Korea, Republic of)

    2009-02-01

    The persistence of Bacillus thuringiensis (Bt) toxins in soil is further enhanced through association with soil particles. Such persistence may improve the effectiveness of controlling target pests, but impose a hazard to non-target organisms in soil ecosystems. In this study, the equilibrium adsorption of the Bt toxin by four clay minerals (montmorillonite, kaolinite, goethite, and silicon dioxide) was investigated, and the kinetic and thermodynamic parameters were calculated. The results showed that Bt toxin could be adsorbed easily by minerals, and the adsorption was much easier at low temperature than at high temperature at the initial concentration varying from 0 to 1000 mg L{sup -1}. The adsorption fitted well to both Langmuir and Freundlich isotherm models, but the Freundlich equation was more suitable. The pseudo-second-order (PSO) was the best application model to describe the adsorption kinetic. The adsorption process appeared to be controlled by chemical process, and the intra-particle diffusion was not the only rate-controlling step. The negative standard free energy ({Delta}{sub r}G{sub m}{sup {theta}}) values of the adsorption indicated that the adsorption of the Bt toxin by the minerals was spontaneous, and the changes of the standard enthalpy ({Delta}{sub r}H{sub m}{sup {theta}}) showed that the adsorption of the Bt toxin by montmorillonite was endothermic while the adsorption by the other three minerals was exothermic.

  9. Equilibrium, kinetic and thermodynamic studies on the adsorption of the toxins of Bacillus thuringiensis subsp. kurstaki by clay minerals

    International Nuclear Information System (INIS)

    Fu Qingling; Deng Yali; Li Huishu; Liu Jie; Hu Hongqing; Chen Shouwen; Sa Tongmin

    2009-01-01

    The persistence of Bacillus thuringiensis (Bt) toxins in soil is further enhanced through association with soil particles. Such persistence may improve the effectiveness of controlling target pests, but impose a hazard to non-target organisms in soil ecosystems. In this study, the equilibrium adsorption of the Bt toxin by four clay minerals (montmorillonite, kaolinite, goethite, and silicon dioxide) was investigated, and the kinetic and thermodynamic parameters were calculated. The results showed that Bt toxin could be adsorbed easily by minerals, and the adsorption was much easier at low temperature than at high temperature at the initial concentration varying from 0 to 1000 mg L -1 . The adsorption fitted well to both Langmuir and Freundlich isotherm models, but the Freundlich equation was more suitable. The pseudo-second-order (PSO) was the best application model to describe the adsorption kinetic. The adsorption process appeared to be controlled by chemical process, and the intra-particle diffusion was not the only rate-controlling step. The negative standard free energy (Δ r G m θ ) values of the adsorption indicated that the adsorption of the Bt toxin by the minerals was spontaneous, and the changes of the standard enthalpy (Δ r H m θ ) showed that the adsorption of the Bt toxin by montmorillonite was endothermic while the adsorption by the other three minerals was exothermic.

  10. Statistical thermodynamics

    International Nuclear Information System (INIS)

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

    1987-01-01

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

  11. Biosorption studies on waste cotton seed for cationic dyes sequestration: equilibrium and thermodynamics

    Science.gov (United States)

    Sivarajasekar, N.; Baskar, R.; Ragu, T.; Sarika, K.; Preethi, N.; Radhika, T.

    2017-07-01

    The immature Gossypium hirsutum seeds—an agricultural waste was converted into a novel adsorbent and its effectiveness for cationic dyes removal was discussed in this study. Characterization revealed that sulfuric acid activated waste Gossypium hirsutum seed (WGSAB) contains surface area 496 m2 g-1. The ability of WGSAB to adsorb basic red 2 (BR2) and basic violet 3 (BV3) from aqueous solutions has been studied. Batch adsorption studies were carried out at different initial dye concentrations (100-300 mg l-1), contact time (1-5 h), pH (2-12) and temperature (293-323 K) to understand the adsorption mechanism. Adsorption data were modeled using Langmuir, Freundlich and Toth adsorption isotherms. Equilibrium data of the adsorption process fitted very well to the Toth model for both dyes. The Langmuir maximum adsorption capacity was 66.69 mg g-1 for BV3 and 50.11 mg g-1 for BR2 at optimum conditions. The near unity value of Toth isotherm constant (BR2: 0.999 and BV3: 1.0) indicates that WGSAB surface is heterogeneous in nature. The maximum adsorption capacity predicted by Toth isotherm of BV3 (66.699 mg g-1) is higher than BR2 (50.310 mg g-1). The kinetic investigation revealed that the BR2 and BV3 were chemisorbed on WGSAB surface following Avrami fractional order kinetics. Further, the fractional order and rate constant values are almost similar for every concentration in both the dyes. The thermodynamic parameters such as Δ H 0, Δ S 0 and Δ G 0 were evaluated. The dye adsorption process was found to be spontaneous and endothermic for the two dyes. Regeneration of WGSAB exhausted by the two dyes could be possible via acetic acid as elutant.

  12. Phase equilibrium data and thermodynamic modeling of the system (CO2 + biodiesel + methanol) at high pressures

    International Nuclear Information System (INIS)

    Pinto, Leandro F.; Segalen da Silva, Diogo Italo; Rosa da Silva, Fabiano; Ramos, Luiz P.; Ndiaye, Papa M.; Corazza, Marcos L.

    2012-01-01

    Highlights: → We measured phase behavior for the system involving {CO 2 + biodiesel + methanol}. → 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 {CO 2 (1) + methanol(2)} and {CO 2 (1) + soybean methyl esters (biodiesel)(2)} and the ternary system {CO 2 (1) + biodiesel(2) + methanol(3)} 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 {CO 2 (1) + methanol(2)}; (0.4201 to 0.9931) for the binary system {CO 2 (1) + biodiesel(2)}; (0.4864 to 0.9767) for the ternary system {CO 2 (1) + biodiesel(2) + methanol(3)} with a biodiesel to methanol molar ratio of (1:3); and (0.3732 to 0.9630) for the system {CO 2 + biodiesel + methanol} 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.

  13. Experimental benchmark of non-local-thermodynamic-equilibrium plasma atomic physics codes

    International Nuclear Information System (INIS)

    Nagels-Silvert, V.

    2004-09-01

    The main purpose of this thesis is to get experimental data for the testing and validation of atomic physics codes dealing with non-local-thermodynamical-equilibrium plasmas. The first part is dedicated to the spectroscopic study of xenon and krypton plasmas that have been produced by a nanosecond laser pulse interacting with a gas jet. A Thomson scattering diagnostic has allowed us to measure independently plasma parameters such as electron temperature, electron density and the average ionisation state. We have obtained time integrated spectra in the range between 5 and 10 angstroms. We have identified about one hundred xenon rays between 8.6 and 9.6 angstroms via the use of the Relac code. We have discovered unknown rays for the krypton between 5.2 and 7.5 angstroms. In a second experiment we have extended the wavelength range to the X UV domain. The Averroes/Transpec code has been tested in the ranges from 9 to 15 angstroms and from 10 to 130 angstroms, the first range has been well reproduced while the second range requires a more complex data analysis. The second part is dedicated to the spectroscopic study of aluminium, selenium and samarium plasmas in femtosecond operating rate. We have designed an interferometry diagnostic in the frequency domain that has allowed us to measure the expanding speed of the target's backside. Via the use of an adequate isothermal model this parameter has led us to know the plasma electron temperature. Spectra and emission times of various rays from the aluminium and selenium plasmas have been computed satisfactorily with the Averroes/Transpec code coupled with Film and Multif hydrodynamical codes. (A.C.)

  14. Insight into biosorption equilibrium, kinetics and thermodynamics of crystal violet onto Ananas comosus (pineapple) leaf powder

    Science.gov (United States)

    Chakraborty, Sagnik; Chowdhury, Shamik; Saha, Papita Das

    2012-06-01

    Biosorption performance of pineapple leaf powder (PLP) for removal of crystal violet (CV) from its aqueous solutions was investigated. To this end, the influence of operational parameters such as pH, biosorbent dose, initial dye concentration and temperature were studied employing a batch experimental setup. The biosorption process followed the Langmuir isotherm model with high correlation coefficients ( R 2 > 0.99) at different temperatures. The maximum monolayer biosorption capacity was found to be 78.22 mg g-1 at 293 K. The kinetic data conformed to the pseudo-second-order kinetic model. The activation energy of the system was calculated as 58.96 kJ mol- 1 , indicating chemisorption nature of the ongoing biosorption process. A thermodynamic study showed spontaneous and exothermic nature of the biosorption process. Owing to its low cost and high dye uptake capacity, PLP has potential for application as biosorbent for removal of CV from aqueous solutions.

  15. General method and thermodynamic tables for computation of equilibrium composition and temperature of chemical reactions

    Science.gov (United States)

    Huff, Vearl N; Gordon, Sanford; Morrell, Virginia E

    1951-01-01

    A rapidly convergent successive approximation process is described that simultaneously determines both composition and temperature resulting from a chemical reaction. This method is suitable for use with any set of reactants over the complete range of mixture ratios as long as the products of reaction are ideal gases. An approximate treatment of limited amounts of liquids and solids is also included. This method is particularly suited to problems having a large number of products of reaction and to problems that require determination of such properties as specific heat or velocity of sound of a dissociating mixture. The method presented is applicable to a wide variety of problems that include (1) combustion at constant pressure or volume; and (2) isentropic expansion to an assigned pressure, temperature, or Mach number. Tables of thermodynamic functions needed with this method are included for 42 substances for convenience in numerical computations.

  16. GEODAT. Development of thermodynamic data for the thermodynamic equilibrium modeling of processes in deep geothermal formations. Combined report; GEODAT. Entwicklung von thermodynamischen Daten zur thermodynamischen Gleichgewichtsmodellierung von Prozessen in tiefen, geothermalen Schichten. Synthesebericht

    Energy Technology Data Exchange (ETDEWEB)

    Moog, Helge C. [Gesellschaft fuer Anlagen- und Reaktorsicherheit mbH (GRS), Koeln (Germany); Regenspurg, Simona [GeoForschungsZentrum Potsdam (Germany); Voigt, Wolfgang [Technische Univ. Bergakademie Freiberg (Germany). Inst. fuer Anorganische Chemie

    2015-02-15

    The concept for geothermal energy application for electricity generation can be differentiated into three compartments: In the geologic compartment cooled fluid is pressed into a porous or fractured rock formation, in the borehole compartment a hot fluid is pumped to the surface and back into the geothermal reservoir, in the aboveground facility the energy is extracted from the geothermal fluid by heat exchangers. Pressure and temperature changes influence the thermodynamic equilibrium of a system. The modeling of a geothermal system has therefore to consider besides the mass transport the heat transport and consequently changing solution compositions and the pressure/temperature effected chemical equilibrium. The GEODAT project is aimed to simulate the reactive mass transport in a geothermal reservoir in the North German basin (Gross Schoenebeck). The project was performed by the cooperation of three partners: Geoforschungsinstitut Potsdam, Bergakademie Freiberg and GRS.

  17. Game-theoretic equilibrium analysis applications to deregulated electricity markets

    Science.gov (United States)

    Joung, Manho

    This dissertation examines game-theoretic equilibrium analysis applications to deregulated electricity markets. In particular, three specific applications are discussed: analyzing the competitive effects of ownership of financial transmission rights, developing a dynamic game model considering the ramp rate constraints of generators, and analyzing strategic behavior in electricity capacity markets. In the financial transmission right application, an investigation is made of how generators' ownership of financial transmission rights may influence the effects of the transmission lines on competition. In the second application, the ramp rate constraints of generators are explicitly modeled using a dynamic game framework, and the equilibrium is characterized as the Markov perfect equilibrium. Finally, the strategic behavior of market participants in electricity capacity markets is analyzed and it is shown that the market participants may exaggerate their available capacity in a Nash equilibrium. It is also shown that the more conservative the independent system operator's capacity procurement, the higher the risk of exaggerated capacity offers.

  18. Irreversible thermodynamic analysis and application for molecular heat engines

    Science.gov (United States)

    Lucia, Umberto; Açıkkalp, Emin

    2017-09-01

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

  19. Relativistic thermodynamics and kinetic theory, with applications to cosmology

    International Nuclear Information System (INIS)

    Stewart, J.M.

    1973-01-01

    The discussion of relativistic thermodynamics and kinetic theory with applications to cosmology also covers the fundamentals and nonequilibrium relativistic kinetic theory and applications to cosmology and astrophysics. (U.S.)

  20. Precise Control of Quantum Confinement in Cesium Lead Halide Perovskite Quantum Dots via Thermodynamic Equilibrium.

    Science.gov (United States)

    Dong, Yitong; Qiao, Tian; Kim, Doyun; Parobek, David; Rossi, Daniel; Son, Dong Hee

    2018-05-09

    Cesium lead halide (CsPbX 3 ) nanocrystals have emerged as a new family of materials that can outperform the existing semiconductor nanocrystals due to their superb optical and charge-transport properties. However, the lack of a robust method for producing quantum dots with controlled size and high ensemble uniformity has been one of the major obstacles in exploring the useful properties of excitons in zero-dimensional nanostructures of CsPbX 3 . Here, we report a new synthesis approach that enables the precise control of the size based on the equilibrium rather than kinetics, producing CsPbX 3 quantum dots nearly free of heterogeneous broadening in their exciton luminescence. The high level of size control and ensemble uniformity achieved here will open the door to harnessing the benefits of excitons in CsPbX 3 quantum dots for photonic and energy-harvesting applications.

  1. Some applications of equilibrium thermodynamic properties to continuum gasdynamics

    Science.gov (United States)

    1976-01-01

    The speed of sound for the propagation of isentropic disturbances in a gas is developed, including corrections for chemical reaction. The term zero frequency is used to describe this isentropic limit sound speed; the term signifies that change in the gasdynamic variables are all very slow compared with the chemical rate changes in the gas. A faster, nonisentropic speed of propagation occurs for disturbances where the changes in gasdynamic variables are fast compared with the chemical rate changes. In the limit, this is known as the infinite frequency or frozen sound speed - the former term calling attention to the very high frequency of the disturbance, the latter term calling attention to the frozen character of the chemical reactions under such rapid changes of state. The true sound speed for a disturbance of finite frequency is shown to be between these two limits and is expressed in terms of the chemical relaxation time. The Riemann invariants that are useful in determining the changes in flow speed along characteristic directions in supersonic flow are derived in terms of integrations of acoustic impedance, and example results are given for air.

  2. Application of Statistical Thermodynamics in Refrigeration

    International Nuclear Information System (INIS)

    Avsec, J.; Marcic, M.

    1999-01-01

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

  3. Measurements and non-local thermodynamic equilibrium modeling of mid-Z plasma emission

    International Nuclear Information System (INIS)

    Jacquet, L.; Primout, M.; Kaiser, P.; Clouët, J. F.; Girard, F.; Villette, B.; Reverdin, C.; Oudot, G.

    2015-01-01

    The x-ray yields from laser-irradiated thin foils of iron, copper, zinc, and germanium have been measured in the soft and multi-keV x-ray ranges at the OMEGA laser at the Laboratory for Laser Energetics. The incident laser power had a pre-pulse to enhance the x-ray emission of a 1 ns flat-top main pulse. The experimental results have been compared with post-shot simulations performed with the two-dimensional radiation-hydrodynamics code FCI2. A new non-local thermodynamic equilibrium model, NOO-RAD, have been incorporated into FCI2. In this approach, the plasma ionization state is in-line calculated by the atomic physics NOHEL package. In the soft x-ray bands, both simulations using RADIOM [M. Busquet, Phys. Fluids B 5, 4191 (1993)] and NOO-RAD clearly over-predict the powers and energies measured by a broad-band spectrometer. In one case (the iron foil), the discrepancy between the measured and simulated x-ray output is nevertheless significantly reduced when NOO-RAD is used in the simulations. In the multi-keV x-ray bands, the simulations display a strong sensitivity to the coupling between the electron thermal conductivity and the NLTE models, and for some particular combinations of these, provide a close match to the measured emission. The comparison between the measured and simulated H-like to He-like line-intensity ratios deduced from high-resolution spectra indicates higher experimental electron temperatures were achieved, compared to the simulated ones. Measurements of the plasma conditions have been achieved using the Thomson-scattering diagnostic. The electron temperatures are found to range from 3 to 5 keV at the end of the laser pulse and are greater than predicted by the simulations. The measured flow velocities are in reasonable agreement with the calculated ones. This last finding gives us confidence in our numerical predictions for the plasma parameters, which are over that time mainly determined by hydrodynamics, such as the mass densities and

  4. Measurements and non-local thermodynamic equilibrium modeling of mid-Z plasma emission

    Science.gov (United States)

    Jacquet, L.; Primout, M.; Kaiser, P.; Clouët, J. F.; Girard, F.; Villette, B.; Reverdin, C.; Oudot, G.

    2015-12-01

    The x-ray yields from laser-irradiated thin foils of iron, copper, zinc, and germanium have been measured in the soft and multi-keV x-ray ranges at the OMEGA laser at the Laboratory for Laser Energetics. The incident laser power had a pre-pulse to enhance the x-ray emission of a 1 ns flat-top main pulse. The experimental results have been compared with post-shot simulations performed with the two-dimensional radiation-hydrodynamics code FCI2. A new non-local thermodynamic equilibrium model, NOO-RAD, have been incorporated into FCI2. In this approach, the plasma ionization state is in-line calculated by the atomic physics NOHEL package. In the soft x-ray bands, both simulations using RADIOM [M. Busquet, Phys. Fluids B 5, 4191 (1993)] and NOO-RAD clearly over-predict the powers and energies measured by a broad-band spectrometer. In one case (the iron foil), the discrepancy between the measured and simulated x-ray output is nevertheless significantly reduced when NOO-RAD is used in the simulations. In the multi-keV x-ray bands, the simulations display a strong sensitivity to the coupling between the electron thermal conductivity and the NLTE models, and for some particular combinations of these, provide a close match to the measured emission. The comparison between the measured and simulated H-like to He-like line-intensity ratios deduced from high-resolution spectra indicates higher experimental electron temperatures were achieved, compared to the simulated ones. Measurements of the plasma conditions have been achieved using the Thomson-scattering diagnostic. The electron temperatures are found to range from 3 to 5 keV at the end of the laser pulse and are greater than predicted by the simulations. The measured flow velocities are in reasonable agreement with the calculated ones. This last finding gives us confidence in our numerical predictions for the plasma parameters, which are over that time mainly determined by hydrodynamics, such as the mass densities and the

  5. Measurements and non-local thermodynamic equilibrium modeling of mid-Z plasma emission

    Energy Technology Data Exchange (ETDEWEB)

    Jacquet, L., E-mail: laurent.jacquet@cea.fr; Primout, M.; Kaiser, P.; Clouët, J. F.; Girard, F.; Villette, B.; Reverdin, C.; Oudot, G. [CEA, DAM, DIF, F-91297 Arpajon (France)

    2015-12-15

    The x-ray yields from laser-irradiated thin foils of iron, copper, zinc, and germanium have been measured in the soft and multi-keV x-ray ranges at the OMEGA laser at the Laboratory for Laser Energetics. The incident laser power had a pre-pulse to enhance the x-ray emission of a 1 ns flat-top main pulse. The experimental results have been compared with post-shot simulations performed with the two-dimensional radiation-hydrodynamics code FCI2. A new non-local thermodynamic equilibrium model, NOO-RAD, have been incorporated into FCI2. In this approach, the plasma ionization state is in-line calculated by the atomic physics NOHEL package. In the soft x-ray bands, both simulations using RADIOM [M. Busquet, Phys. Fluids B 5, 4191 (1993)] and NOO-RAD clearly over-predict the powers and energies measured by a broad-band spectrometer. In one case (the iron foil), the discrepancy between the measured and simulated x-ray output is nevertheless significantly reduced when NOO-RAD is used in the simulations. In the multi-keV x-ray bands, the simulations display a strong sensitivity to the coupling between the electron thermal conductivity and the NLTE models, and for some particular combinations of these, provide a close match to the measured emission. The comparison between the measured and simulated H-like to He-like line-intensity ratios deduced from high-resolution spectra indicates higher experimental electron temperatures were achieved, compared to the simulated ones. Measurements of the plasma conditions have been achieved using the Thomson-scattering diagnostic. The electron temperatures are found to range from 3 to 5 keV at the end of the laser pulse and are greater than predicted by the simulations. The measured flow velocities are in reasonable agreement with the calculated ones. This last finding gives us confidence in our numerical predictions for the plasma parameters, which are over that time mainly determined by hydrodynamics, such as the mass densities and

  6. Thermodynamic versus non-equilibrium stability of palmitic acid monolayers in calcium-enriched sea spray aerosol proxy systems.

    Science.gov (United States)

    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.

  7. Analysis of the Range of Applicability of Thermodynamic Calculations in the Engineering of Nitride Fuel Elements

    Science.gov (United States)

    Ivanov, A. S.; Rusinkevich, A. A.; Belov, G. V.; Ivanov, Yu. A.

    2017-12-01

    The domains of applicability of thermodynamic calculations in the engineering of nitride fuel are analyzed. Characteristic values of the following parameters, which affect directly the concentration equilibration time, are estimated: nuclide production rate; characteristic times to local equilibrium in the considered temperature range; characteristic time needed for a stationary temperature profile to be established; characteristic time needed for a quasi-stationary concentration field to be established on a scale comparable to the size of a fuel pellet. It is demonstrated that equilibrium thermodynamic calculations are suitable for estimating the chemical and phase composition of fuel. However, a two-layer kinetic model should be developed in order to characterize the transport processes in condensed and gaseous phases. The process of diffusive transport needs to be taken into account in order to determine the composition in the hot region at the center of a fuel element.

  8. The applicability of equilibrium calculations to dichlorosilane CVD

    International Nuclear Information System (INIS)

    Medernach, J.W.; Ho, P.

    1987-01-01

    Equilibrium calculations were made for the chlorosilane (Si-H-Cl) system over a wide range of temperatures, pressures and Si/Cl ratios. The Si/Cl ratios are presented as a function of the Cl/H ratio, temperature and pressure. Three-dimensional contour plots of the equilibrium Si/Cl also give a qualitative picture. Comparison of observed and equilibrium deposition rates indicate the range of applicability for the chlorosilane system. Results of this study indicate that equilibrium calculations can serve as a useful guide for silicon deposition from dichlorosilane at temperatures > 1000 0 C and pressures between 625 and 80 Torr. An application related to the silicon-on insulator (SOI) technology is presented

  9. Thermodynamic Analysis of Ionic Compounds: Synthetic Applications.

    Science.gov (United States)

    Yoder, Claude H.

    1986-01-01

    Shows how thermodynamic cycles can be used to understand trends in heats of formation and aqueous solubilities and, most importantly, how they may be used to choose synthetic routes to new ionic compounds. (JN)

  10. Friction-induced vibrations and self-organization mechanics and non-equilibrium thermodynamics of sliding contact

    CERN Document Server

    Nosonovsky, Michael

    2013-01-01

    Many scientists and engineers do not realize that, under certain conditions, friction can lead to the formation of new structures at the interface, including in situ tribofilms and various patterns. In turn, these structures-usually formed by destabilization of the stationary sliding regime-can lead to the reduction of friction and wear. Friction-Induced Vibrations and Self-Organization: Mechanics and Non-Equilibrium Thermodynamics of Sliding Contact combines the mechanical and thermodynamic methods in tribology, thus extending the field of mechanical friction-induced vibrations to non-mechanical instabilities and self-organization processes at the frictional interface. The book also relates friction-induced self-organization to novel biomimetic materials, such as self-lubricating, self-cleaning, and self-healing materials. Explore Friction from a Different Angle-as a Fundamental Force of Nature The book begins with an exploration of friction as a fundamental force of nature throughout the history of science....

  11. Towards the unified non-classical physics: account for quantum fluctuations in equilibrium thermodynamics via the effective temperature

    Directory of Open Access Journals (Sweden)

    Yu.G.Rudoy

    2005-01-01

    Full Text Available The concept of effective temperature (ET T*(T0, T is used in order to approximately "quantize" the thermodynamic functions of the dynamical object which is in the thermal equilibrium with thermal bath being at constant temperature T (T0=E0/kB, where E0 is the ground-state energy, kB - Boltzmann constant, is the characteristic ``quantum'' temperature of the system itself. On these grounds the extensive comparative investigation is carried out for the ``standard model'' of statistical mechanics - the one-dimensional harmonic oscillator (HO. Three well-known approaches are considered and their thermodynamic consequences thoroughly studied. These are: the exact quantum, or non-classical Planck-Einstein approach, intermediate, or semiclassical Bloch-Wigner approach and, finally, the pure classical, or Maxwell-Boltzmann approach.

  12. Particle creation and non-equilibrium thermodynamical prescription of dark fluids for universe bounded by an event horizon

    Science.gov (United States)

    Saha, Subhajit; Biswas, Atreyee; Chakraborty, Subenoy

    2015-03-01

    In the present work, flat FRW model of the universe is considered to be an isolated open thermodynamical system where non-equilibrium prescription has been studied using the mechanism of particle creation. In the perspective of recent observational evidences, the matter distribution in the universe is assumed to be dominated by dark matter and dark energy. The dark matter is chosen as dust while for dark energy, the following choices are considered: (i) Perfect fluid with constant equation of state and (ii) Holographic dark energy. In both the cases, the validity of generalized second law of thermodynamics (GSLT) which states that the total entropy of the fluid as well as that of the horizon should not decrease with the evolution of the universe, has been examined graphically for universe bounded by the event horizon. It is found that GSLT holds in both the cases with some restrictions on the interacting coupling parameter.

  13. Fixed Points in Grassmannians with Applications to Economic Equilibrium

    DEFF Research Database (Denmark)

    Keiding, Hans

    2017-01-01

    In some applications of equilibrium theory, the fixed point involves not only a state and a value of a parameter in the dual of the state space, but also a particular subspace of the state space. Since the set of all subspaces of a finite-dimensional Euclidean space has a structure which does...... not allow immediate application of fixed point theorems, the problem must be reformulated using a suitable parametrization of subspaces. One such parametrization, the Plücker coordinates, is used here to prove a general equilibrium existence theorem. Applications to economic problems involving hierarchies...... of consumers or incomplete markets with real assets are outlined....

  14. Retention of phosphorous ions on natural and engineered waste pumice: Characterization, equilibrium, competing ions, regeneration, kinetic, equilibrium and thermodynamic study

    Energy Technology Data Exchange (ETDEWEB)

    Karimaian, Kamal Aldin [Department of Environmental Health Engineering, Faculty of Health, Kurdistan University of Medical Sciences, Sannandaj (Iran, Islamic Republic of); Amrane, Abdeltif [Ecole Nationale Supérieure de Chimie de Rennes, Université Rennes 1, CNRS, UMR 6226, Avenue du Général Leclerc, CS 50837, 35708 Rennes Cedex 7 (France); Kazemian, Hossein [Department of Chemical and Biochemical Engineering, Western University, London, ON, Canada N6A 5B9 (Canada); Panahi, Reza [Department of Biotechnology, Faculty of Chemical Engineering, Tarbiat Modares University, Tehran (Iran, Islamic Republic of); Zarrabi, Mansur, E-mail: mansor62@gmail.com [Department of Environmental Health Engineering, Faculty of Health, Alborz University of Medical Sciences, Karaj (Iran, Islamic Republic of)

    2013-11-01

    Natural and Mg{sup 2+} modified pumice were used for the removal of phosphorous. The adsorbents were characterized using XRF, XRD, SEM and FTIR instrumental techniques. In the optimal conditions, namely at equilibrium time (30 min), for a phosphorus concentration of 15 mg/L and pH 6, 69 and 97% phosphorus removals were achieved using 10 g/L of natural and modified pumice adsorbents, respectively. Maximum adsorption capacities were 11.88 and 17.71 mg/g by natural and modified pumice, respectively. Pseudo-second order kinetic model was the most relevant to describe the kinetic of phosphorus adsorption. External mass transfer coefficient decreased for increasing phosphorous concentration and film diffusion was found to be the rate-controlling step. Only a very low dissolution of the adsorbent was observed, leading to a low increase in conductivity and turbidity. Removal efficiency decreased for increasing ionic strength. It also decreased in the presence of competing ions; however modified pumice remained effective, since 67% of phosphorus was removed, versus only 17% for the natural pumice. The efficiency of the modified pumice was confirmed during the regeneration tests, since 96% regeneration yield was obtained after 510 min experiment, while only 22% was observed for the raw pumice.

  15. 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

  16. Removal of ibuprofen, naproxen and carbamazepine in aqueous solution onto natural clay: equilibrium, kinetics, and thermodynamic study

    Science.gov (United States)

    Khazri, Hassen; Ghorbel-Abid, Ibtissem; Kalfat, Rafik; Trabelsi-Ayadi, Malika

    2017-10-01

    This study aimed to describe the adsorption of three pharmaceuticals compounds (ibuprofen, naproxen and carbamazepine) onto natural clay on the basis of equilibrium parameters such as a function of time, effect of pH, varying of the concentration and the temperature. Adsorption kinetic data were modeled using the Lagergren's first-order and the pseudo-second-order kinetic equations. The kinetic results of adsorption are described better using the pseudo-second order model. The isotherm results were tested in the Langmuir, Freundlich and Dubinin-Radushkevich models. The thermodynamic parameters obtained indicate that the adsorption of pharmaceuticals on the clay is a spontaneous and endothermic process.

  17. The Use of VMD Data/Model to Test Different Thermodynamic Models for Vapour-Liquid Equilibrium

    DEFF Research Database (Denmark)

    Abildskov, Jens; Azquierdo-Gil, M.A.; Jonsson, Gunnar Eigil

    2004-01-01

    Vacuum membrane distillation (VMD) has been studied as a separation process to remove volatile organic compounds from aqueous streams. A vapour pressure difference across a microporous hydrophobic membrane is the driving force for the mass transport through the membrane pores (this transport take...... place in vapour phase). The vapour pressure difference is obtained in VMD processes by applying a vacuum on one side of the membrane. The membrane acts as a mere support for the liquid-vapour equilibrium. The evaporation of the liquid stream takes place on the feed side of the membrane...... values; membrane type: PTFE/PP/PVDF; feed flow rate; feed temperature. A comparison is made between different thermodynamic models for calculating the vapour-liquid equilibrium at the membrane/pore interface. (C) 2004 Elsevier B.V. All rights reserved....

  18. Catalytic supercritical water gasification of primary paper sludge using a homogeneous and heterogeneous catalyst: Experimental vs thermodynamic equilibrium results.

    Science.gov (United States)

    Louw, Jeanne; Schwarz, Cara E; Burger, Andries J

    2016-02-01

    H2, CH4, CO and CO2 yields were measured during supercritical water gasification (SCWG) of primary paper waste sludge (PWS) at 450°C. Comparing these yields with calculated thermodynamic equilibrium values offer an improved understanding of conditions required to produce near-equilibrium yields. Experiments were conducted at different catalyst loads (0-1g/gPWS) and different reaction times (15-120min) in a batch reactor, using either K2CO3 or Ni/Al2O3-SiO2 as catalyst. K2CO3 up to 1g/gPWS increased the H2 yield significantly to 7.5mol/kgPWS. However, these yields and composition were far from equilibrium values, with carbon efficiency (CE) and energy recovery (ER) of only 29% and 20%, respectively. Addition of 0.5-1g/gPWS Ni/Al2O3-SiO2 resulted in high H2 and CH4 yields (6.8 and 14.8mol/kgPWS), CE of 84-90%, ER of 83% and a gas composition relatively close to the equilibrium values (at hold times of 60-120min). Copyright © 2015 Elsevier Ltd. All rights reserved.

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

    Directory of Open Access Journals (Sweden)

    Samson Abramsky

    2015-11-01

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

  20. Efficient removal of cadmium using magnetic multiwalled carbon nanotube nanoadsorbents: equilibrium, kinetic, and thermodynamic study

    Energy Technology Data Exchange (ETDEWEB)

    Pashai Gatabi, Maliheh; Milani Moghaddam, Hossain, E-mail: Milani@umz.ac.ir [University of Mazandaran, Soid State Physics Department (Iran, Islamic Republic of); Ghorbani, Mohsen [Babol Noshirvani University of Technology, Chemical Engineering Department (Iran, Islamic Republic of)

    2016-07-15

    Adsorptive potential of maghemite decorated multiwalled carbon nanotubes (MWCNTs) for the removal of cadmium ions from aqueous solution was investigated. The magnetic nanoadsorbent was synthesized using a versatile and cost effective chemical route. Structural, magnetic and surface charge properties of the adsorbent were characterized using FTIR, XRD, TEM, VSM analysis and pH{sub PZC} determination. Batch adsorption experiments were performed under varied system parameters such as pH, contact time, initial cadmium concentration and temperature. Highest cadmium adsorption was obtained at pH 8.0 and contact time of 30 min. Adsorption behavior was kinetically studied using pseudo first-order, pseudo second-order, and Weber–Morris intra particle diffusion models among which data were mostly correlated to pseudo second-order model. Adsorbate-adsorbent interactions as a function of temperature was assessed by Langmuir, Freundlich, Dubinin–Radushkevich (D-R) and Temkin isotherm models from which Freundlich model had the highest consistency with the data. The adsorption capacity increased with increasing temperature and maximum Langmuir’s adsorption capacity was found to be 78.81 mg g{sup −1} at 298 K. Thermodynamic parameters and activation energy value suggest that the process of cadmium removal was spontaneous and physical in nature, which lead to fast kinetics and high regeneration capability of the nanoadsorbent. Results of this work are of great significance for environmental applications of magnetic MWCNTs as promising adsorbent for heavy metals removal from aqueous solutions.Graphical Abstract.

  1. Modelling reactive material transport in the near field of a repository for radioactive waste. Coupling the EMOS near field modules CLAYPOS and LOPOS with thermodynamic equilibrium calculations

    International Nuclear Information System (INIS)

    Moog, H.C.; Keesmann, S.M.

    2007-02-01

    This paper reports on the project ''Coupling transport models with thermodynamic equilibrium calculations'' - short title EQLINK, promotion code number 02 E 9723 - in the which the scope for coupling thermodynamic equilibrium model calculations with EMOS was expanded and improved. The first step was to inquire into the current state of research on radiolytic processes. It transpired that there is currently no conclusive description of radiolytic processes. The existing descriptions are too complex and too narrowly geared to specific scenarios to allow a general view on radiolytic processes, which would be a prerequisite for creating suitable long-term geochemical safety analysis modules. It appears that the approximation calculations implemented in EMOS tend to overestimate rather than underestimate radiolytic gas formation. The thermodynamic database which is used at GRS (Society for Plant and Reactor Safety) as a basis for coupled transport calculations has been updated. For this purpose the radionuclide database of the Institut fuer Nukleare Entsorgung (INE = Institute for Nuclear Disposal) was converted to an in-house format which permits creating parameter files for specific requirements. The data of the INE comprise thermodynamic parameters such as equilibrium constants, Gibbs free enthalpies of formation, enthalpies and entropies of formation and Pitzer parameters, which are required for model calculations on high-saline solutions. The database for low-saline solutions which had been developed by PSI/NAGRA for calculations with CLAYPOS was also adopted. Both parameter sets were subjected to test calculations to detect any errors that might have occurred during the data transfer. It is thus now possible to perform coupled transport calculations with the EMOS modules LOPOS and CLAYPOS according to the state of the art of geochemical research. The EQLINK interface which had been developed in an earlier project, titled ''Development of a model for describing the

  2. Experimental determination and thermodynamic modeling of phase equilibrium and protein partitioning in aqueous two-phase systems containing biodegradable salts

    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.

  3. Application of dhurrin for kinetics and thermodynamic ...

    African Journals Online (AJOL)

    The entropy change (ΔS) increased with enzyme purity from 0.588 J/mol.deg. to 1.4625Jmol degree. The enthalpy change KJ/mol followed the same pattern whereby increases influenced by enzyme purity ranged from 1892 KJ/mol to 13104KJ/mol. Keywords: kinetics, thermodynamic, characterization, dhurrin, genetically ...

  4. Biogenic methane potential of marine sediments. Application of chemical thermodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Arning, E.T.; Schulz, H.M. [Helmholtz Centre Potsdam GFZ, Potsdam (Germany); Berk, W. van [Technical Univ. of Clausthal (Germany). Dept. of Hydrogeology

    2013-08-01

    Accumulations of biogenic methane-dominated gas are widespread and occur in a variety of depositional settings and rock types. However, the potential of biogenic methane remains underexplored. This is mainly due to the fact that quantitative assessments applying numerical modeling techniques for exploration purposes are generally lacking to date. Biogenic methane formation starts in relatively shallow marine sediments below the sulfate reduction zone. When sulfate is exhausted, methanogenesis via the CO{sub 2} reduction pathway is often the dominant biogenic methane formation process in marine sediments (Claypool and Kaplan, 1974). The process can be simplified by the reaction: 2CH{sub 2}O + Ca{sup 2+} + H{sub 2}O {yields} CH{sub 4} + CaCO{sub 3} + 2H{sup +}. The products of early diagenetic reactions initiate coupled equilibrium reactions that induce a new state of chemical equilibrium among minerals, pore water and gas. The driving force of the complex biogeochemical reactions in sedimentary environments during early diagenesis is the irreversible redox-conversion of organic matter. Early diagenetic formation of biogenic methane shortly after deposition ('early diagenesis') was retraced using PHREEQC computer code that is applied to calculate homogenous and heterogeneous mass-action equations in combination with one-dimensional diffusion driven transport (Parkhurst and Appelo, 1999). Our modeling approach incorporates interdependent diagenetic reactions evolving into a diffusive multi-component and multiphase system by means of thermodynamic equilibrium calculations of species distribution (Arning et al., 2011, 2012, 2013). Reaction kinetics of organic carbon conversion is integrated into the set of equilibrium reactions by defining type and amount of converted organic matter in a certain time step. It is the aim (1) to calculate quantitatively thermodynamic equilibrium conditions (composition of pore water, mineral phase and gas phase assemblage) in

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

    Science.gov (United States)

    Popovas, A.; Jørgensen, U. G.

    2016-11-01

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

  6. Thermodynamic Simulation of Equilibrium Composition of Reaction Products at Dehydration of a Technological Channel in a Uranium-Graphite Reactor

    Science.gov (United States)

    Pavliuk, A. O.; Zagumennov, V. S.; Kotlyarevskiy, S. G.; Bespala, E. V.

    2018-01-01

    The problems of accumulation of nuclear fuel spills in the graphite stack in the course of operation of uranium-graphite nuclear reactors are considered. The results of thermodynamic analysis of the processes in the graphite stack at dehydration of a technological channel, fuel element shell unsealing and migration of fission products, and activation of stable nuclides in structural elements of the reactor and actinides inside the graphite moderator are given. The main chemical reactions and compounds that are produced in these modes in the reactor channel during its operation and that may be hazardous after its shutdown and decommissioning are presented. Thermodynamic simulation of the equilibrium composition is performed using the specialized code TERRA. The results of thermodynamic simulation of the equilibrium composition in different cases of technological channel dehydration in the course of the reactor operation show that, if the temperature inside the active core of the nuclear reactor increases to the melting temperature of the fuel element, oxides and carbides of nuclear fuel are produced. The mathematical model of the nonstationary heat transfer in a graphite stack of a uranium-graphite reactor in the case of the technological channel dehydration is presented. The results of calculated temperature evolution at the center of the fuel element, the replaceable graphite element, the air gap, and in the surface layer of the block graphite are given. The numerical results show that, in the case of dehydration of the technological channel in the uranium-graphite reactor with metallic uranium, the main reaction product is uranium dioxide UO2 in the condensed phase. Low probability of production of pyrophoric uranium compounds (UH3) in the graphite stack is proven, which allows one to disassemble the graphite stack without the risk of spontaneous graphite ignition in the course of decommissioning of the uranium-graphite nuclear reactor.

  7. Non-local thermodynamic equilibrium effects on isentropic coefficient in argon and helium thermal plasmas

    International Nuclear Information System (INIS)

    Sharma, Rohit; Singh, Kuldip

    2014-01-01

    In the present work, two cases of thermal plasma have been considered; the ground state plasma in which all the atoms and ions are assumed to be in the ground state and the excited state plasma in which atoms and ions are distributed over various possible excited states. The variation of Zγ, frozen isentropic coefficient and the isentropic coefficient with degree of ionization and non-equilibrium parameter θ(= T e /T h ) has been investigated for the ground and excited state helium and argon plasmas at pressures 1 atm, 10 atm, and 100 atm in the temperature range from 6000 K to 60 000 K. For a given value of non-equilibrium parameter, the relationship of Zγ with degree of ionization does not show any dependence on electronically excited states in helium plasma whereas in case of argon plasma this dependence is not appreciable till degree of ionization approaches 2. The minima of frozen isentropic coefficient shifts toward lower temperature with increase of non-equilibrium parameter for both the helium and argon plasmas. The lowering of non-equilibrium parameter decreases the frozen isentropic coefficient more emphatically in helium plasma at high pressures in comparison to argon plasma. The increase of pressure slightly reduces the ionization range over which isentropic coefficient almost remains constant and it does not affect appreciably the dependence of isentropic coefficient on non-equilibrium parameter

  8. Self-assembled materials and supramolecular chemistry within microfluidic environments: from common thermodynamic states to non-equilibrium structures.

    Science.gov (United States)

    Sevim, S; Sorrenti, A; Franco, C; Furukawa, S; Pané, S; deMello, A J; Puigmartí-Luis, J

    2018-05-01

    Self-assembly is a crucial component in the bottom-up fabrication of hierarchical supramolecular structures and advanced functional materials. Control has traditionally relied on the use of encoded building blocks bearing suitable moieties for recognition and interaction, with targeting of the thermodynamic equilibrium state. On the other hand, nature leverages the control of reaction-diffusion processes to create hierarchically organized materials with surprisingly complex biological functions. Indeed, under non-equilibrium conditions (kinetic control), the spatio-temporal command of chemical gradients and reactant mixing during self-assembly (the creation of non-uniform chemical environments for example) can strongly affect the outcome of the self-assembly process. This directly enables a precise control over material properties and functions. In this tutorial review, we show how the unique physical conditions offered by microfluidic technologies can be advantageously used to control the self-assembly of materials and of supramolecular aggregates in solution, making possible the isolation of intermediate states and unprecedented non-equilibrium structures, as well as the emergence of novel functions. Selected examples from the literature will be used to confirm that microfluidic devices are an invaluable toolbox technology for unveiling, understanding and steering self-assembly pathways to desired structures, properties and functions, as well as advanced processing tools for device fabrication and integration.

  9. Understanding of surface pit formation mechanism of GaN grown in MOCVD based on local thermodynamic equilibrium assumption

    International Nuclear Information System (INIS)

    Gao Zhi-Yuan; Xue Xiao-Wei; Li Jiang-Jiang; Wang Xun; Xing Yan-Hui; Cui Bi-Feng; Zou De-Shu

    2016-01-01

    Frank’s theory describes that a screw dislocation will produce a pit on the surface, and has been evidenced in many material systems including GaN. However, the size of the pit calculated from the theory deviates significantly from experimental result. Through a careful observation of the variations of surface pits and local surface morphology with growing temperature and V/III ratio for c -plane GaN, we believe that Frank’s model is valid only in a small local surface area where thermodynamic equilibrium state can be assumed to stay the same. If the kinetic process is too vigorous or too slow to reach a balance, the local equilibrium range will be too small for the center and edge of the screw dislocation spiral to be kept in the same equilibrium state. When the curvature at the center of the dislocation core reaches the critical value 1/ r 0 , at the edge of the spiral, the accelerating rate of the curvature may not fall to zero, so the pit cannot reach a stationary shape and will keep enlarging under the control of minimization of surface energy to result in a large-sized surface pit. (paper)

  10. Understanding of surface pit formation mechanism of GaN grown in MOCVD based on local thermodynamic equilibrium assumption

    Science.gov (United States)

    Zhi-Yuan, Gao; Xiao-Wei, Xue; Jiang-Jiang, Li; Xun, Wang; Yan-Hui, Xing; Bi-Feng, Cui; De-Shu, Zou

    2016-06-01

    Frank’s theory describes that a screw dislocation will produce a pit on the surface, and has been evidenced in many material systems including GaN. However, the size of the pit calculated from the theory deviates significantly from experimental result. Through a careful observation of the variations of surface pits and local surface morphology with growing temperature and V/III ratio for c-plane GaN, we believe that Frank’s model is valid only in a small local surface area where thermodynamic equilibrium state can be assumed to stay the same. If the kinetic process is too vigorous or too slow to reach a balance, the local equilibrium range will be too small for the center and edge of the screw dislocation spiral to be kept in the same equilibrium state. When the curvature at the center of the dislocation core reaches the critical value 1/r 0, at the edge of the spiral, the accelerating rate of the curvature may not fall to zero, so the pit cannot reach a stationary shape and will keep enlarging under the control of minimization of surface energy to result in a large-sized surface pit. Project supported by the National Natural Science Foundation of China (Grant Nos. 11204009 and 61204011) and the Beijing Municipal Natural Science Foundation, China (Grant No. 4142005).

  11. Adsorption of uranium(VI) from sulphate solutions using Amberlite IRA-402 resin: Equilibrium, kinetics and thermodynamics study

    International Nuclear Information System (INIS)

    Solgy, Mostafa; Taghizadeh, Majid; Ghoddocynejad, Davood

    2015-01-01

    Highlights: • Adsorption of uranium from sulphate solutions by an anion exchange resin. • The effects of pH, contact time and adsorbent dosage were investigated. • The adsorption equilibrium is well described by the Freundlich isotherm model. • The adsorption kinetics can be predicted by the pseudo second-order model. • The adsorption is a physical, spontaneous and endothermic process. - Abstract: In the present study, adsorption of uranium from sulphate solutions was evaluated using Amberlite IRA-402 resin. The variation of adsorption process was investigated in batch sorption mode. The parameters studied were pH, contact time and adsorbent dosage. Langmuir and Freundlich isotherm models were used in order to present a mathematical description of the equilibrium data at three different temperatures (25 °C, 35 °C and 45 °C). The final results confirmed that the equilibrium data tend to follow Freundlich isotherm model. The maximum adsorption capacity of Amberlite IRA-402 for uranium(VI) was evaluated to be 213 mg/g for the Langmuir model at 25 °C. The adsorption of uranium on the mentioned anion exchange resin was found to follow the pseudo-second order kinetic model, indicating that chemical adsorption was the rate limiting-step. The values of thermodynamic parameters proved that adsorption process of uranium onto Amberlite IRA-402 resin could be considered endothermic (ΔH > 0) and spontaneous (ΔG < 0)

  12. New insights for mesospheric OH: multi-quantum vibrational relaxation as a driver for non-local thermodynamic equilibrium

    Directory of Open Access Journals (Sweden)

    K. S. Kalogerakis

    2018-01-01

    Full Text Available The question of whether mesospheric OH(v rotational population distributions are in equilibrium with the local kinetic temperature has been debated over several decades. Despite several indications for the existence of non-equilibrium effects, the general consensus has been that emissions originating from low rotational levels are thermalized. Sky spectra simultaneously observing several vibrational levels demonstrated reproducible trends in the extracted OH(v rotational temperatures as a function of vibrational excitation. Laboratory experiments provided information on rotational energy transfer and direct evidence for fast multi-quantum OH(high-v vibrational relaxation by O atoms. We examine the relationship of the new relaxation pathways with the behavior exhibited by OH(v rotational population distributions. Rapid OH(high-v + O multi-quantum vibrational relaxation connects high and low vibrational levels and enhances the hot tail of the OH(low-v rotational distributions. The effective rotational temperatures of mesospheric OH(v are found to deviate from local thermodynamic equilibrium for all observed vibrational levels. Dedicated to Tom G. Slanger in celebration of his 5 decades of research in aeronomy.

  13. Equilibrium, Kinetic and Thermodynamic Study of Removal of Eosin Yellow from Aqueous Solution Using Teak Leaf Litter Powder.

    Science.gov (United States)

    Oyelude, Emmanuel O; Awudza, Johannes A M; Twumasi, Sylvester K

    2017-09-22

    Low-cost teak leaf litter powder (TLLP) was prepared as possible substitute for activated carbon. The feasibility of using the adsorbent to remove eosin yellow (EY) dye from aqueous solution was investigated through equilibrium adsorption, kinetic and thermodynamic studies. The removal of dye from aqueous solution was feasible but influenced by temperature, pH, adsorbent dosage and contact time. Variation in the initial concentration of dye did not influence the equilibrium contact time. Optimum adsorption of dye occurred at low adsorbent dosages, alkaline pH and high temperatures. Langmuir isotherm model best fit the equilibrium adsorption data and the maximum monolayer capacity of the adsorbent was 31.64 mg g -1 at 303 K. The adsorption process was best described by pseudo-second order kinetic model at 303 K. Boundary layer diffusion played a key role in the adsorption process. The mechanism of uptake of EY by TLLP was controlled by both liquid film diffusion and intraparticle diffusion. The values of mean adsorption free energy, E (7.91 kJ mol -1 ), and standard enthalpy, ΔH° (+13.34 kJ mol -1 ), suggest physical adsorption. The adsorption process was endothermic and spontaneous. Teak leaf litter powder is a promising low-cost adsorbent for treating wastewaters containing eosin yellow.

  14. Thermodynamic database for proteins: features and applications.

    Science.gov (United States)

    Gromiha, M Michael; Sarai, Akinori

    2010-01-01

    We have developed a thermodynamic database for proteins and mutants, ProTherm, which is a collection of a large number of thermodynamic data on protein stability along with the sequence and structure information, experimental methods and conditions, and literature information. This is a valuable resource for understanding/predicting the stability of proteins, and it can be accessible at http://www.gibk26.bse.kyutech.ac.jp/jouhou/Protherm/protherm.html . ProTherm has several features including various search, display, and sorting options and visualization tools. We have analyzed the data in ProTherm to examine the relationship among thermodynamics, structure, and function of proteins. We describe the progress on the development of methods for understanding/predicting protein stability, such as (i) relationship between the stability of protein mutants and amino acid properties, (ii) average assignment method, (iii) empirical energy functions, (iv) torsion, distance, and contact potentials, and (v) machine learning techniques. The list of online resources for predicting protein stability has also been provided.

  15. Parallel application of plasma equilibrium fitting based on inhomogeneous platforms

    International Nuclear Information System (INIS)

    Liao Min; Zhang Jinhua; Chen Liaoyuan; Li Yongge; Pan Wei; Pan Li

    2008-01-01

    An online analysis and online display platform EFIT, which is based on the equilibrium-fitting mode, is inducted in this paper. This application can realize large data transportation between inhomogeneous platforms by designing a communication mechanism using sockets. It spends approximately one minute to complete the equilibrium fitting reconstruction by using a finite state machine to describe the management node and several node computers of cluster system to fulfill the parallel computation, this satisfies the online display during the discharge interval. An effective communication model between inhomogeneous platforms is provided, which could transport the computing results from Linux platform to Windows platform for online analysis and display. (authors)

  16. 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.

  17. Statistical thermodynamics of association colloids : the equilibrium structure of micelles, vesicles, and bilayer membranes

    NARCIS (Netherlands)

    Leermakers, F.A.M.

    1988-01-01

    The aim of the present study was to unravel the general equilibrium physical properties of lipid bilayer membranes. We consider four major questions:
    1. What determines the morphology of the association colloids (micelles, membranes, vesicles) in general?
    2. Do the

  18. Nonlocal effects in nonisothermal hydrodynamics from the perspective of beyond-equilibrium thermodynamics

    OpenAIRE

    Hütter, Markus; Brader, Joseph M.

    2009-01-01

    We examine the origins of nonlocality in a nonisothermal hydrodynamic formulation of a one-component fluid of particles that exhibit long-range correlations, e.g., due to a spherically symmetric, long-range interaction potential. In order to furnish the continuum modeling with physical understanding of the microscopic interactions and dynamics, we make use of systematic coarse graining from the microscopic to the continuum level. We thus arrive at a thermodynamically admissible and closed set...

  19. Interpreting equilibrium-conductivity and conductivity-relaxation measurements to establish thermodynamic and transport properties for multiple charged defect conducting ceramics.

    Science.gov (United States)

    Zhu, Huayang; Ricote, Sandrine; Coors, W Grover; Kee, Robert J

    2015-01-01

    A model-based interpretation of measured equilibrium conductivity and conductivity relaxation is developed to establish thermodynamic, transport, and kinetics parameters for multiple charged defect conducting (MCDC) ceramic materials. The present study focuses on 10% yttrium-doped barium zirconate (BZY10). In principle, using the Nernst-Einstein relationship, equilibrium conductivity measurements are sufficient to establish thermodynamic and transport properties. However, in practice it is difficult to establish unique sets of properties using equilibrium conductivity alone. Combining equilibrium and conductivity-relaxation measurements serves to significantly improve the quantitative fidelity of the derived material properties. The models are developed using a Nernst-Planck-Poisson (NPP) formulation, which enables the quantitative representation of conductivity relaxations caused by very large changes in oxygen partial pressure.

  20. Effect of temperature on equilibrium and thermodynamic parameters of Cd (II) adsorption onto turmeric powder

    International Nuclear Information System (INIS)

    Qayoom, A.

    2012-01-01

    Summary: Batch adsorption of Cd (II) onto turmeric powder was conducted as a function of temperature. Nonlinear Langmuir, Freundlich, Dubinin-Radushkevish (D-R) and Temkin equilibrium models were employed. In addition to R 2, five different error functions were used to determine best fit equilibrium isotherm model. It was found that Freundlich isotherm model provided better fit for adsorption data at 298 and 303 K and Langmuir model was suitable for the experimental data obtained at 310 and 313 K. It was found that increase in temperature decreased maximum adsorption capacities, showing that the adsorption of Cd (II) onto turmeric powder is exothermic. Enthalpy values also confirmed the same trend. Entropy values were negative which means that randomness decreased on increasing temperature. Gibbs free energies were non spontaneous at all the temperatures studied. E values were in the range of 2.73-3.23 kJ mol/sup -1/ which indicated that adsorption mechanism is essentially physical. (author)

  1. Thermodynamic Modeling and Optimization of the Copper Flash Converting Process Using the Equilibrium Constant Method

    Science.gov (United States)

    Li, Ming-zhou; Zhou, Jie-min; Tong, Chang-ren; Zhang, Wen-hai; Chen, Zhuo; Wang, Jin-liang

    2018-05-01

    Based on the principle of multiphase equilibrium, a mathematical model of the copper flash converting process was established by the equilibrium constant method, and a computational system was developed with the use of MetCal software platform. The mathematical model was validated by comparing simulated outputs, industrial data, and published data. To obtain high-quality blister copper, a low copper content in slag, and increased impurity removal rate, the model was then applied to investigate the effects of the operational parameters [oxygen/feed ratio (R OF), flux rate (R F), and converting temperature (T)] on the product weights, compositions, and the distribution behaviors of impurity elements. The optimized results showed that R OF, R F, and T should be controlled at approximately 156 Nm3/t, within 3.0 pct, and at approximately 1523 K (1250 °C), respectively.

  2. Equilibrium and Thermodynamic Studies of Methane Adsorption on Multi-Walled Carbon Nanotube

    OpenAIRE

    Sanaz. Monemtabary; Mojtaba Shariati Niasar; Mohsen Jahanshahi; Ali Asghar Ghoreyshi

    2013-01-01

    In this work, The adsorption of methane onto multi-walled carbon nanotubes (MWCNTs) was studied, in which the influences of temperatureand pressure were investigated. The physical properties of the MWCNT were systematically characterised by Scanning Electron Microscopy (SEM) and Brunauere-Emmette-Teller (BET) surface area measurements. The equilibrium adsorption data were analyzed using threecommon adsorption models: Langmuir, Freundlich and Sips. All of the models fit the experimental result...

  3. Adsorption of Benzaldehyde on Granular Activated Carbon: Kinetics, Equilibrium, and Thermodynamic

    OpenAIRE

    Rajoriya, R.K.; Prasad, B.; Mishra, I.M.; Wasewar, K.L.

    2007-01-01

    Adsorption isotherms of benzaldehyde from aqueous solutions onto granular activated carbon have been determined and studied the effect of dosage of granular activated carbon, contact time, and temperature on adsorption. Optimum conditions for benzaldehyde removal were found adsorbent dose 4 g l–1 of solution and equilibrium time t 4 h. Percent removal of benzaldehyde increases with the increase in adsorbent dose for activated carbon, however, it decreases with increase in benzaldehyde m...

  4. Continuum Thermodynamics - Part II: Applications and Examples

    Science.gov (United States)

    Albers, Bettina; Wilmanski, Krzysztof

    The intention by writing Part II of the book on continuum thermodynamics was the deepening of some issues covered in Part I as well as a development of certain skills in dealing with practical problems of oscopic processes. However, the main motivation for this part is the presentation of main facets of thermodynamics which appear when interdisciplinary problems are considered. There are many monographs on the subjects of solid mechanics and thermomechanics, on fluid mechanics and on coupled fields but most of them cover only special problems in great details which are characteristic for the chosen field. It is rather seldom that relations between these fields are discussed. This concerns, for instance, large deformations of the skeleton of porous materials with diffusion (e.g. lungs), couplings of deformable particles with the fluid motion in suspensions, couplings of adsorption processes and chemical reactions in immiscible mixtures with diffusion, various multi-component aspects of the motion, e.g. of avalanches, such as segregation processes, etc...

  5. Thermodynamic behavior of poly(3-alkyl thiophene) blends: Equilibrium cocrystal formation and phase segregation.

    Science.gov (United States)

    Pal, Susmita; Nandi, Arun K

    2005-02-24

    The equilibrium cocrystal formation of poly(3-alkyl thiophene) (P3AT) blends has been studied by isothermal cocrystallization in a differential scanning calorimeter (DSC-7). The equilibrium melting points (T(m)0) of the cocrystals are measured using the Hoffman-Weeks extrapolation procedure. The equilibrium phase diagrams are of three different types: (a) concave upward, (b) linear, and (c) linear with phase separation at higher content of lower melting component. The phase diagram nature depends on the regioregularity difference and also on the difference in the number of carbon atoms in the pendent alkyl group of the components. The origin of biphasic nature of type "c" phase diagram has been explored from the glass transition temperature (Tg) measurement using a dynamic mechanical analyzer. The biphasic compositions show two glass transition temperatures (Tg) as well as two beta transition temperatures (T beta). The T(g)s of phase-separated regions correspond to almost the component values but the T(beta)s correspond to that of a lower (T beta) component value, and the other is higher than that of the higher (T beta) component value. Possible reasons are discussed from the interchain lamella thickness in the P3AT blends and molecular modeling using molecular mechanics program.

  6. Nonequilibrium thermodynamics and maximum entropy production in the Earth system: applications and implications.

    Science.gov (United States)

    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.

  7. A theoretical view on the thermodynamic cis-trans equilibrium of dihalo ruthenium olefin metathesis (pre-)catalysts

    KAUST Repository

    Pump, Eva

    2015-02-24

    Abstract: This work was conducted to provide an overview on the position of the thermodynamic cis–trans equilibrium of 85 conventional and X-chelated alkylidene-ruthenium complexes (X=O, S, Se, N, P, Cl, I, Br). The reported energies (ΔE) were obtained through single-point calculations with M06 functional and TZVP basis set from BP86/SVP-optimized cis- and trans-dichloro geometries and using the polarizable continuum model to simulate the influence of the solvent. Dichloromethane and toluene were selected as examples for solvents with high and low dielectric constants. The obtained relative stabilities of the cis- and trans-dihalo derivatives of the respective alkylidene complexes will serve for a better explanation of their catalytic activity as has been disclosed herein with selected examples.Graphical abstract: [Figure not available: see fulltext.

  8. Biosorption of bovine serum albumin by Ulva lactuca biomass from industrial wastewater: Equilibrium, kinetic and thermodynamic study

    Energy Technology Data Exchange (ETDEWEB)

    Rathinam, Aravindhan [Chemical Laboratory, Central Leather Research Institute, Adyar, Chennai 600020 (India); Zou, Linda, E-mail: linda.zou@unisa.edu.au [SA Water Centre for Water Management and Reuse, University of South Australia, Mawson Lakes Campus, Adelaide, SA 5095 (Australia)

    2010-12-15

    Batch biosorption experiments have been carried out for the removal of bovine serum albumin (BSA) from simulated industrial wastewater onto Ulva lactuca seaweed. Various vital parameters influencing the biosorption process such as initial concentration of BSA, pH of the solution, adsorbent dosage and temperature have been determined. The biosorption kinetics follows a pseudo-second order kinetic model. Equilibrium isotherm studies demonstrate that the biosorption followed the Freundlich isotherm model, which implies a heterogeneous sorption phenomenon. Various thermodynamic parameters such as changes in enthalpy, free energy and entropy have been calculated. The positive value of {Delta}H{sup o} and the negative value of {Delta}G{sup o} show that the sorption process is endothermic and spontaneous. The positive value of change in entropy {Delta}S{sup o} shows increased randomness at the solid-liquid interface during the biosorption of BSA onto U. lactuca seaweed.

  9. Effects of deviations from local thermodynamic equilibrium in the atmospheres of F supergiants. I. Overionization of Fe I atoms

    International Nuclear Information System (INIS)

    Boyarchuk, A.A.; Lyubimkov, L.S.; Sakhibullin, N.A.

    1985-01-01

    For a number of class F supergiants and dwarfs, non-LTE calculations have been made of the Fe I-Fe II ionization balance. It is shown that deviations from local thermodynamic equilibrium lead to a strong overionization of the Fe I atoms in the upper layers of the atmosphere. This confirms the conclusion obtained by Lyubimkov and Boyarchuk on the basis of an investigation of microturbulence in F supergiants. The reason for the overionization (compared with LTE) is the nonequality of the recombination and photoionization temperatures: To recombination processes there corresponds a local temperature T(/tau/), whereas the photoionization takes place under the influence of ultraviolet radiation from deeper and hotter layers of the atmosphere. The equivalent widths of some Fe I lines have been calculated. It is shown that neglect of the overionization in the analysis of sufficiently strong lines may lead to an underestimation of the iron abundance by an order of magnitude

  10. Adsorptioin performance of modified nkalagu bentonite in dye removal: kinetics, equilibrium, thermodynamics and structureal properties of the modified samples

    International Nuclear Information System (INIS)

    Ajemba, R.O.

    2015-01-01

    The adsorption performance of modified Nkalagu bentonite in removing Congo red (CR) from solution was investigated. The raw bentonite was modified by three different physicochemical methods: thermal activation (TA), acid activation (AA), and combined acid and thermal activation (ATA). The Congo red adsorption increased with increase in contact time, initial dye concentration, adsorbent dosage, temperature, and pH change. The results of the kinetics analysis of the adsorption data revealed that adsorption follows pseudo second-order kinetics. Analysis of the equilibrium data showed that Langmuir isotherm provided a better fit to the data. Evaluation of the thermodynamic parameters revealed that adsorption process is spontaneous and endothermic. The results from this study suggest that a combination of thermal and acid activation is an effective modification method to improve adsorption capacity of bentonite and makes the bentonite as low-cost adsorbent for removal of water pollutants. (author)

  11. A thermodynamic data base for Tc to calculate equilibrium solubilities at temperatures up to 300 deg C

    International Nuclear Information System (INIS)

    Puigdomenech, I.; Bruno, J.

    1995-04-01

    Thermodynamic data has been selected for solids and aqueous species of technetium. Equilibrium constants have been calculated in the temperature range 0 to 300 deg C at a pressure of 1 bar for T r Cdeg pm values for mononuclear hydrolysis reactions. The formation constants for chloro complexes of Tc(V) and Tc(IV), whose existence is well established, have been estimated. The majority of entropy and heat capacity values in the data base have also been estimated, and therefore temperature extrapolations are largely based on estimations. The uncertainties derived from these calculations are described. Using the data base developed in this work, technetium solubilities have been calculated as a function of temperature for different chemical conditions. The implications for the mobility of Tc under nuclear repository conditions are discussed. 70 refs

  12. Biosorption of bovine serum albumin by Ulva lactuca biomass from industrial wastewater: equilibrium, kinetic and thermodynamic study.

    Science.gov (United States)

    Rathinam, Aravindhan; Zou, Linda

    2010-12-15

    Batch biosorption experiments have been carried out for the removal of bovine serum albumin (BSA) from simulated industrial wastewater onto Ulva lactuca seaweed. Various vital parameters influencing the biosorption process such as initial concentration of BSA, pH of the solution, adsorbent dosage and temperature have been determined. The biosorption kinetics follows a pseudo-second order kinetic model. Equilibrium isotherm studies demonstrate that the biosorption followed the Freundlich isotherm model, which implies a heterogeneous sorption phenomenon. Various thermodynamic parameters such as changes in enthalpy, free energy and entropy have been calculated. The positive value of ΔH° and the negative value of ΔG° show that the sorption process is endothermic and spontaneous. The positive value of change in entropy ΔS° shows increased randomness at the solid-liquid interface during the biosorption of BSA onto U. lactuca seaweed. Copyright © 2010 Elsevier B.V. All rights reserved.

  13. Biosorption of bovine serum albumin by Ulva lactuca biomass from industrial wastewater: Equilibrium, kinetic and thermodynamic study

    International Nuclear Information System (INIS)

    Rathinam, Aravindhan; Zou, Linda

    2010-01-01

    Batch biosorption experiments have been carried out for the removal of bovine serum albumin (BSA) from simulated industrial wastewater onto Ulva lactuca seaweed. Various vital parameters influencing the biosorption process such as initial concentration of BSA, pH of the solution, adsorbent dosage and temperature have been determined. The biosorption kinetics follows a pseudo-second order kinetic model. Equilibrium isotherm studies demonstrate that the biosorption followed the Freundlich isotherm model, which implies a heterogeneous sorption phenomenon. Various thermodynamic parameters such as changes in enthalpy, free energy and entropy have been calculated. The positive value of ΔH o and the negative value of ΔG o show that the sorption process is endothermic and spontaneous. The positive value of change in entropy ΔS o shows increased randomness at the solid-liquid interface during the biosorption of BSA onto U. lactuca seaweed.

  14. Advanced thermodynamics engineering

    CERN Document Server

    Annamalai, Kalyan; Jog, Milind A

    2011-01-01

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

  15. Equilibrium, kinetic and thermodynamic studies of the biosorption of textile dye (Reactive Red 195) onto Pinus sylvestris L

    International Nuclear Information System (INIS)

    Aksakal, Ozkan; Ucun, Handan

    2010-01-01

    This study investigated the biosorption of Reactive Red 195 (RR 195), an azo dye, from aqueous solution by using cone biomass of Pinus sylvestris Linneo. To this end, pH, initial dye concentration, biomass dosage and contact time were studied in a batch biosorption system. Maximum pH for efficient RR 195 biosorption was found to be 1.0 and the initial RR 195 concentration increased with decreasing percentage removal. Biosorption capacity increased from 6.69 mg/g at 20 deg. C to 7.38 mg/g at 50 deg. C for 200 mg/L dye concentration. Kinetics of the interactions was tested by pseudo-first-order and pseudo-second-order kinetics, the Elovich equation and intraparticle diffusion mechanism. Pseudo-second-order kinetic model provided a better correlation for the experimental data studied in comparison to the pseudo-first-order kinetic model and intraparticle diffusion mechanism. Moreover, the Elovich equation also showed a good fit to the experimental data. Freundlich and Langmuir adsorption isotherms were used for the mathematical description of the biosorption equilibrium data. The activation energy of biosorption (Ea) was found to be 8.904 kJ/mol by using the Arrhenius equation. Using the thermodynamic equilibrium coefficients obtained at different temperatures, the study also evaluated the thermodynamic constants of biosorption (ΔG o , ΔH o and ΔS). The results indicate that cone biomass can be used as an effective and low-cost biosorbent to remove reactive dyes from aqueous solution.

  16. The applications of chemical thermodynamics and chemical kinetics to planetary atmospheres research

    Science.gov (United States)

    Fegley, Bruce, Jr.

    1990-01-01

    A review of the applications of chemical thermodynamics and chemical kinetics to planetary atmospheres research during the past four decades is presented with an emphasis on chemical equilibrium models and thermochemical kinetics. Several current problems in planetary atmospheres research such as the origin of the atmospheres of the terrestrial planets, atmosphere-surface interactions on Venus and Mars, deep mixing in the atmospheres of the gas giant planets, and the origin of the atmospheres of outer planet satellites all require laboratory data on the kinetics of thermochemical reactions for their solution.

  17. Numerical implementation and oceanographic application of the Gibbs thermodynamic potential of seawater

    Directory of Open Access Journals (Sweden)

    R. Feistel

    2005-01-01

    Full Text Available The 2003 Gibbs thermodynamic potential function represents a very accurate, compact, consistent and comprehensive formulation of equilibrium properties of seawater. It is expressed in the International Temperature Scale ITS-90 and is fully consistent with the current scientific pure water standard, IAPWS-95. Source code examples in FORTRAN, C++ and Visual Basic are presented for the numerical implementation of the potential function and its partial derivatives, as well as for potential temperature. A collection of thermodynamic formulas and relations is given for possible applications in oceanography, from density and chemical potential over entropy and potential density to mixing heat and entropy production. For colligative properties like vapour pressure, freezing points, and for a Gibbs potential of sea ice, the equations relating the Gibbs function of seawater to those of vapour and ice are presented.

  18. Acid-base equilibrium. A thermodynamic study of formation and stability of the Bi-2223 phase

    International Nuclear Information System (INIS)

    Xi, Z.; Zhou, L.

    1993-01-01

    A general acid-base equilibrium theory was proposed to explain the formation and stability of the Bi-2223 phase based on the Lewis acid base theory and principle of metallurgical physical chemistry. The acid-base nature of oxide was defined according to the electrostatic force between cation and oxygen anion. A series of experimental facts were systematically explained based on the theory: substitution of Bi for Ca in the Pb-free 2223 phase, and the effect of substitution of the high-valent cation for Bi 3+ ; oxygen-pressure atmosphere, and the heat-schocking technique on the formation and stability of the 2223 phase. 14 refs., 2 tabs

  19. Equilibrium, kinetic and thermodynamic studies of adsorption of Pb(II) from aqueous solution onto Turkish kaolinite clay

    International Nuclear Information System (INIS)

    Sari, Ahmet; Tuzen, Mustafa; Citak, Demirhan; Soylak, Mustafa

    2007-01-01

    The adsorption of Pb(II) onto Turkish (Bandirma region) kaolinite clay was examined in aqueous solution with respect to the pH, adsorbent dosage, contact time, and temperature. The linear Langmuir and Freundlich models were applied to describe equilibrium isotherms and both models fitted well. The monolayer adsorption capacity was found as 31.75 mg/g at pH 5 and 20 deg. C. Dubinin-Radushkevich (D-R) isotherm model was also applied to the equilibrium data. The mean free energy of adsorption (13.78 kJ/mol) indicated that the adsorption of Pb(II) onto kaolinite clay may be carried out via chemical ion-exchange mechanism. Thermodynamic parameters, free energy (ΔG o ), enthalpy (ΔH o ) and entropy (ΔS o ) of adsorption were also calculated. These parameters showed that the adsorption of Pb(II) onto kaolinite clay was feasible, spontaneous and exothermic process in nature. Furthermore, the Lagergren-first-order, pseudo-second-order and the intraparticle diffusion models were used to describe the kinetic data. The experimental data fitted well the pseudo-second-order kinetics

  20. Adsorption of basic dye on high-surface-area activated carbon prepared from coconut husk: Equilibrium, kinetic and thermodynamic studies

    Energy Technology Data Exchange (ETDEWEB)

    Tan, I.A.W.; Ahmad, A.L. [School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, 14300 Nibong Tebal, Penang (Malaysia); Hameed, B.H. [School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, 14300 Nibong Tebal, Penang (Malaysia)], E-mail: chbassim@eng.usm.my

    2008-06-15

    Adsorption isotherm and kinetics of methylene blue on activated carbon prepared from coconut husk were determined from batch tests. The effects of contact time (1-30 h), initial dye concentration (50-500 mg/l) and solution temperature (30-50 {sup o}C) were investigated. Equilibrium data were fitted to Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherm models. The equilibrium data were best represented by Langmuir isotherm model, showing maximum monolayer adsorption capacity of 434.78 mg/g. The kinetic data were fitted to pseudo-first-order, pseudo-second-order and intraparticle diffusion models, and was found to follow closely the pseudo-second-order kinetic model. Thermodynamic parameters such as standard enthalpy ({delta}H{sup o}), standard entropy ({delta}S{sup o}) and standard free energy ({delta}G{sup o}) were evaluated. The adsorption interaction was found to be exothermic in nature. Coconut husk-based activated carbon was shown to be a promising adsorbent for removal of methylene blue from aqueous solutions.

  1. Cluster emission at pre-equilibrium stage in Heavy Nuclear Reactions. A Model considering the Thermodynamics of Small Systems

    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)

  2. Elimination of carbon vacancies in 4H-SiC employing thermodynamic equilibrium conditions at moderate temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Ayedh, H. M.; Svensson, B. G. [University of Oslo, Department of Physics/Center for Materials Science and Nanotechnology, P.O. Box 1048 Blindern, N-0316 Oslo (Norway); Nipoti, R. [Consiglio Nazionale delle Ricerche, Istituto di Microelettronica e Microsistemi, Sezione di Bologna (CNR-IMM of Bologna), I-40129 Bologna (Italy); Hallén, A. [Royal Institute of Technology, School of Information and Communication Technology (ICT), SE-164 40 Kista-Stockholm (Sweden)

    2015-12-21

    The carbon vacancy (V{sub C}) is a major point defect in high-purity 4H-SiC epitaxial layers limiting the minority charge carrier lifetime. In layers grown by chemical vapor deposition techniques, the V{sub C} concentration is typically in the range of 10{sup 12 }cm{sup −3}, and after device processing at temperatures approaching 2000 °C, it can be enhanced by several orders of magnitude. In the present study, both as-grown layers and a high-temperature processed one have been annealed at 1500 °C and the V{sub C} concentration is demonstrated to be strongly reduced, exhibiting a value of only a few times 10{sup 11 }cm{sup −3} as determined by deep-level transient spectroscopy measurements. The value is reached already after annealing times on the order of 1 h and is evidenced to reflect thermodynamic equilibrium under C-rich ambient conditions. The physical processes controlling the kinetics for establishment of the V{sub C} equilibrium are estimated to have an activation energy below ∼3 eV and both in-diffusion of carbon interstitials and out-diffusion of V{sub C}'s are discussed as candidates. This concept of V{sub C} elimination is flexible and readily integrated in a materials and device processing sequence.

  3. Equilibrium, kinetics and thermodynamics studies of chitosan-based solid phase nanoparticles as sorbent for lead (II) cations from aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Shaker, Medhat A., E-mail: drmashaker@yahoo.com [Current address: Chemistry Department, Faculty of Science, University of Jeddah, Jeddah (Saudi Arabia); Permanent address: Chemistry Department, Faculty of Science, Damanhour University, Damanhour (Egypt)

    2015-07-15

    Ternary nanoparticles of chitosan, non-viable biomass (Pseudomonas sp.) and gelatin, CPG were synthesized by chemical crosslinking method and applied as a novel and cost-effective solid phase to adsorb Pb(II) cations from aqueous solution. Characterization of the fabricated CPG nanoparticles and their complexation behavior were extensively interrogated by dynamic light scattering (DLS), FTIR, TGA, XRD and SEM techniques. The extent of adsorption was found to be a function of medium pH, contact time, initial Pb(II) concentration and temperature. The Langmuir, Freundlich, Dubinin–Radushkevich and Redlich–Peterson models were used to illustrate the isotherms of the adsorption system. The adsorption of Pb(II) cations onto CPG best-fits the Langmuir isotherm model which predicts two stoichiometric temperature-independent adsorption sites, A and B with variable capacities, 35.4 and 91.1 mg g{sup −1}, respectively and removal capacity above 90%. Thermodynamic studies revealed that the adsorption process was physical, spontaneous, and endothermic. The adsorption rate is influenced by temperature and the adsorption kinetic is well confirmed with pseudo-second-order equation compared with three other investigated kinetic models. Present study indicated potential applications of CPG nanoparticles as excellent natural and promising solid phase for Pb(II) extraction in wastewater treatment. - Graphical abstract: Display Omitted - Highlights: • Kinetics and thermodynamics of Pb{sup 2+} biosorption onto CPG nanoparticles are studied. • Adsorption kinetic data are best modeled using second-order rate equations. • The Pb{sup 2}adsorption onto CPG was physical diffusion controlled reaction. • The experimental equilibrium results well fit the Langmuir model. • The thermodynamics show endothermic, favorable and spontaneous adsorption processes.

  4. Adsorption of Malachite Green Dye by Acid Activated Carbon - Kinetic, Thermodynamic and Equilibrium Studies

    Directory of Open Access Journals (Sweden)

    P. K. Baskaran

    2011-01-01

    Full Text Available The ability of zea mays dust carbon to remove malachite green from aqueous solutions has been studied for different adsorbate concentrations by varying the amount of adsorbent, temperature, pH and shaking time. Thermodynamic parameters such as ΔH°,ΔS° and ΔG°, were calculated from the slope and intercept of the linear plots. Analysis of adsorption results obtained at 303, 313, 323 and 333 K showed that the adsorption pattern on zea mays dust carbon seems to follow the Langmuir and Freundlich. The numerical values of sorption free energy indicate physical adsorption. The kinetic data indicated an intra-particle diffusion process with sorption being first order. The concentration of malachite green oxalate was measured before and after adsorption by using UV-visible spectrophotometer.

  5. A breakthrough biosorbent in removing heavy metals: Equilibrium, kinetic, thermodynamic and mechanism analyses in a lab-scale study

    Energy Technology Data Exchange (ETDEWEB)

    Abdolali, Atefeh [Centre for Technology in Water and Wastewater, School of Civil and Environmental Engineering, University of Technology Sydney, Broadway, NSW 2007 (Australia); Ngo, Huu Hao, E-mail: h.ngo@uts.edu.au [Centre for Technology in Water and Wastewater, School of Civil and Environmental Engineering, University of Technology Sydney, Broadway, NSW 2007 (Australia); Guo, Wenshan [Centre for Technology in Water and Wastewater, School of Civil and Environmental Engineering, University of Technology Sydney, Broadway, NSW 2007 (Australia); Lu, Shaoyong [Chinese Research Academy of Environmental Science, Beijing 100012 (China); Chen, Shiao-Shing; Nguyen, Nguyen Cong [Institute of Environmental Engineering and Management, National Taipei University of Technology, No. 1, Sec. 3, Chung-Hsiao E. Rd, Taipei 106, Taiwan (China); Zhang, Xinbo [Department of Environmental and Municipal Engineering, Tianjin Key Laboratory of Aquatic Science and Technology, Tianjin Chengjian University, Jinjing Road 26, Tianjin 300384 (China); Wang, Jie; Wu, Yun [School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387 (China)

    2016-01-15

    A breakthrough biosorbent namely multi-metal binding biosorbent (MMBB) made from a combination of tea wastes, maple leaves and mandarin peels, was prepared to evaluate their biosorptive potential for removal of Cd(II), Cu(II), Pb(II) and Zn(II) from multi-metal aqueous solutions. FTIR and SEM were conducted, before and after biosorption, to explore the intensity and position of the available functional groups and changes in adsorbent surface morphology. Carboxylic, hydroxyl and amine groups were found to be the principal functional groups for the sorption of metals. MMBB exhibited best performance at pH 5.5 with maximum sorption capacities of 31.73, 41.06, 76.25 and 26.63 mg/g for Cd(II), Cu(II), Pb(II) and Zn(II), respectively. Pseudo-first and pseudo-second-order models represented the kinetic experimental data in different initial metal concentrations very well. Among two-parameter adsorption isotherm models, the Langmuir equation gave a better fit of the equilibrium data. For Cu(II) and Zn(II), the Khan isotherm describes better biosorption conditions while for Cd(II) and Pb(II), the Sips model was found to provide the best correlation of the biosorption equilibrium data. The calculated thermodynamic parameters indicated feasible, spontaneous and exothermic biosorption process. Overall, this novel MMBB can effectively be utilized as an adsorbent to remove heavy metal ions from aqueous solutions. - Highlights: • A novel multi-metal binding biosorbent (MMBB) was studied. • The biosorption of Cd{sup 2+}, Cu{sup 2+}, Pb{sup 2+} and Zn{sup 2+} on MMBB was evaluated. • Hydroxyl, carbonyl and amine groups are involved in metal binding of MMBB. • Equilibrium data were presented and the best fitting models were identified. • The obtained results recommend this MMBB as potentially low-cost biosorbent.

  6. Do all ecosystems maximise their distance with respect to thermodynamic equilibrium? A comment on the Ecological Law of Thermodynamics (ELT, proposed by Sven Erik Jørgensen

    Directory of Open Access Journals (Sweden)

    Rutger de Wit

    2005-09-01

    Full Text Available Sven Erik Jørgensen has boldly proposed a “Fourth Law of Thermodynamics” which he also advocates as the “Ecological Law of Thermodynamics” or ELT (Integration of Ecosystem Theories: A Pattern, Kluwer Academic Publisher. This Law is still a hypothesis and can be tested. I disagree with the generalised way he uses the term “exergy” in his approach. Exergy is commonly defined as a measure of the work capacity of a system. According to the physicists Boltzmann information embodies energy. Jørgensen takes this into account when considering the “exergy” stored in ecosystems; hence, according to his way of calculating the genetic information of the organisms is the mayor contribution to “exergy”. I argue that energy has been embodied in the information during a historical process and that because of fundamental irreversibility this energy cannot be extracted again for work capacity. Moreover, other phenomena mentioned earlier by Ramon Margalef, demonstrate that proliferating information in biota shows uncoupling with respect to its embodied energy content according to the Boltzmann formula. In spite of these objections, some of Sven Erik Jørgensen’s core ideas are exiting and worthwhile testing. I place these within the context of the non-equilibrium thermodynamic theories on “dissipative systems” developed by the physicist Ilya Prigogine.

  7. Thermodynamics of Micellar Systems : Comparison of Mass Action and Phase Equilibrium Models for the Calculation of Standard Gibbs Energies of Micelle Formation

    NARCIS (Netherlands)

    Blandamer, Michael J.; Cullis, Paul M.; Soldi, L. Giorgio; Engberts, Jan B.F.N.; Kacperska, Anna; Os, Nico M. van

    1995-01-01

    Micellar colloids are distinguished from other colloids by their association-dissociation equilibrium in solution between monomers, counter-ions and micelles. According to classical thermodynamics, the standard Gibbs energy of formation of micelles at fixed temperature and pressure can be related to

  8. Non-local thermodynamic equilibrium stellar spectroscopy with 1D and 3D models - II. Chemical properties of the Galactic metal-poor disk and the halo

    DEFF Research Database (Denmark)

    Bergemann, Maria; Collet, Remo; Schönrich, Ralph

    2016-01-01

    We have analysed high-resolution spectra of 328 stars and derived Mg abundances using non-local thermodynamic equilibrium (NLTE) spectral line formation calculations and plane-parallel model stellar atmospheres derived from the mean stratification of 3D hydrodynamical surface convection simulations...

  9. Aeroacoustic and aerodynamic applications of the theory of nonequilibrium thermodynamics

    Science.gov (United States)

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

    1991-01-01

    Recent developments in the field of nonequilibrium thermodynamics associated with viscous flows are examined and related to developments to the understanding of specific phenomena in aerodynamics and aeroacoustics. A key element of the nonequilibrium theory is the principle of minimum entropy production rate for steady dissipative processes near equilibrium, and variational calculus is used to apply this principle to several examples of viscous flow. A review of nonequilibrium thermodynamics and its role in fluid motion are presented. Several formulations are presented of the local entropy production rate and the local energy dissipation rate, two quantities that are of central importance to the theory. These expressions and the principle of minimum entropy production rate for steady viscous flows are used to identify parallel-wall channel flow and irrotational flow as having minimally dissipative velocity distributions. Features of irrotational, steady, viscous flow near an airfoil, such as the effect of trailing-edge radius on circulation, are also found to be compatible with the minimum principle. Finally, the minimum principle is used to interpret the stability of infinitesimal and finite amplitude disturbances in an initially laminar, parallel shear flow, with results that are consistent with experiment and linearized hydrodynamic stability theory. These results suggest that a thermodynamic approach may be useful in unifying the understanding of many diverse phenomena in aerodynamics and aeroacoustics.

  10. Modeling the Non-Equilibrium Process of the Chemical Adsorption of Ammonia on GaN(0001) Reconstructed Surfaces Based on Steepest-Entropy-Ascent Quantum Thermodynamics.

    Science.gov (United States)

    Kusaba, Akira; Li, Guanchen; von Spakovsky, Michael R; Kangawa, Yoshihiro; Kakimoto, Koichi

    2017-08-15

    Clearly understanding elementary growth processes that depend on surface reconstruction is essential to controlling vapor-phase epitaxy more precisely. In this study, ammonia chemical adsorption on GaN(0001) reconstructed surfaces under metalorganic vapor phase epitaxy (MOVPE) conditions (3Ga-H and N ad -H + Ga-H on a 2 × 2 unit cell) is investigated using steepest-entropy-ascent quantum thermodynamics (SEAQT). SEAQT is a thermodynamic-ensemble based, first-principles framework that can predict the behavior of non-equilibrium processes, even those far from equilibrium where the state evolution is a combination of reversible and irreversible dynamics. SEAQT is an ideal choice to handle this problem on a first-principles basis since the chemical adsorption process starts from a highly non-equilibrium state. A result of the analysis shows that the probability of adsorption on 3Ga-H is significantly higher than that on N ad -H + Ga-H. Additionally, the growth temperature dependence of these adsorption probabilities and the temperature increase due to the heat of reaction is determined. The non-equilibrium thermodynamic modeling applied can lead to better control of the MOVPE process through the selection of preferable reconstructed surfaces. The modeling also demonstrates the efficacy of DFT-SEAQT coupling for determining detailed non-equilibrium process characteristics with a much smaller computational burden than would be entailed with mechanics-based, microscopic-mesoscopic approaches.

  11. Equilibrium, kinetic and thermodynamic studies for adsorption of BTEX onto Ordered Mesoporous Carbon (OMC).

    Science.gov (United States)

    Konggidinata, Mas Iwan; Chao, Bing; Lian, Qiyu; Subramaniam, Ramalingam; Zappi, Mark; Gang, Daniel Dianchen

    2017-08-15

    Chemical and petrochemical industries produce substantial amounts of wastewater everyday. This wastewater contains organic pollutants such as benzene, toluene, ethylbenzene and xylenes (BTEX) that are toxic to human and aquatic life. Ordered Mesoporous Carbon (OMC), the adsorbent that possesses the characteristics of an ideal adsorbent was investigated to understand its properties and suitability for BTEX removal. Adsorption isotherms, adsorption kinetics, the effects of initial BTEX concentrations and temperatures on the adsorption process were studied. The OMCs were characterized using surface area and pore size analyzer, transmission electron microscopy (TEM), elemental analysis, thermogravimetric analysis (TGA) and fourier transform infrared spectroscopy (FTIR). The results suggested that the Langmuir Isotherm and Pseudo-Second-Order Models described the experimental data well. The thermodynamic parameters, Gibbs free energy (ΔG°), the enthalpy change (ΔH°) and the entropy change (ΔS°) of adsorption indicated that the adsorption processes were physical, endothermic, and spontaneous. In addition, OMC had 27% higher overall adsorption capacities compared to granular activated carbon (GAC). Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Abnormal grain growth: a non-equilibrium thermodynamic model for multi-grain binary systems

    International Nuclear Information System (INIS)

    Svoboda, J; Fischer, F D

    2014-01-01

    Abnormal grain growth as the abrupt growth of a group of the largest grains in a multi-grain system is treated within the context of unequal retardation of grain growth due to the segregation of solute atoms from the bulk of the grains into the grain boundaries. During grain boundary migration, the segregated solute atoms are dragged under a small driving force or left behind the migrating grain boundary under a large driving force. Thus, the solute atoms in the grain boundaries of large grains, exhibiting a large driving force, can be released from the grain boundary. The mobility of these grain boundaries becomes significantly higher and abnormal grain growth is spontaneously provoked. The mean-field model presented here assumes that each grain is described by its grain radius and by its individual segregation parameter. The thermodynamic extremal principle is engaged to obtain explicit evolution equations for the radius and segregation parameter of each grain. Simulations of grain growth kinetics for various conditions of segregation with the same initial setting (100 000 grains with a given radius distribution) are presented. Depending on the diffusion coefficients of the solute in the grain boundaries, abnormal grain growth may be strongly or marginally pronounced. Solute segregation and drag can also significantly contribute to the stabilization of the grain structure. Qualitative agreement with several experimental results is reported. (paper)

  13. Phase equilibrium, crystallization behavior and thermodynamic studies of (m-dinitrobenzene + vanillin) eutectic system

    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

  14. Nonlocal effects in nonisothermal hydrodynamics from the perspective of beyond-equilibrium thermodynamics.

    Science.gov (United States)

    Hütter, Markus; Brader, Joseph M

    2009-06-07

    We examine the origins of nonlocality in a nonisothermal hydrodynamic formulation of a one-component fluid of particles that exhibit long-range correlations, e.g., due to a spherically symmetric, long-range interaction potential. In order to furnish the continuum modeling with physical understanding of the microscopic interactions and dynamics, we make use of systematic coarse graining from the microscopic to the continuum level. We thus arrive at a thermodynamically admissible and closed set of evolution equations for the densities of momentum, mass, and internal energy. From the consideration of an illustrative special case, the following main conclusions emerge. There are two different source terms in the momentum balance. The first is a body force, which in special circumstances can be related to the functional derivative of a nonlocal Helmholtz free energy density with respect to the mass density. The second source term is proportional to the temperature gradient, multiplied by the nonlocal entropy density. These two source terms combine into a pressure gradient only in the absence of long-range effects. In the irreversible contributions to the time evolution, the nonlocal contributions arise since the self-correlations of the stress tensor and heat flux, respectively, are nonlocal as a result of the microscopic nonlocal correlations. Finally, we point out specific points that warrant further discussions.

  15. Adsorption Properties of Doxorubicin Hydrochloride onto Graphene Oxide: Equilibrium, Kinetic and Thermodynamic Studies

    Directory of Open Access Journals (Sweden)

    Zonghua Wang

    2013-05-01

    Full Text Available Doxorubicin hydrochloride (DOX is an effective anticancer agent for leukemia chemotherapy, although its clinical use has been limited because of its side effects such as cardiotoxicity, alopecia, vomiting, and leucopenia. Attention has been focussed on developing new drug carriers with high adsorption capacity and rapid adsorption rate in order to minimize the side effects of DOX. Graphene oxide (GO, a new type of nanomaterial in the carbon family, was prepared by Hummers method and used as adsorbent for DOX from aqueous solution. The physico-chemical properties of GO were characterized by transmission electron microscope (TEM, Fourier transform infrared spectroscopy (FTIR, zeta potential, and element analysis. The adsorption properties of DOX on GO were studied as a function of contact time, adsorbent dosage, temperature and pH value. The results showed that GO had a maximum adsorption capacity of 1428.57 mg/g and the adsorption isotherm data fitted the Langmuir model. The kinetics of adsorption fits a pseudo-second-order model. The thermodynamic studies indicate that the adsorption of DOX on GO is spontaneous and endothermic in nature.

  16. Thermodynamic equilibrium of hydroxyacetic acid in pure and binary solvent systems

    International Nuclear Information System (INIS)

    Huang, Qiaoyin; Xie, Chuang; Li, Yang; Su, Nannan; Lou, Yajing; Hu, Xiaoxue; Wang, Yongli; Bao, Ying; Hou, Baohong

    2017-01-01

    Highlights: • Solubility of hydroxyacetic acid in mono-solvents and binary solvent mixtures was measured. • Modified Apelblat, NRTL and Wilson model were used to correlate the solubility data in pure solvents. • CNIBS/R-K and Jouyban-Acree model were used to correlate the solubility in binary solvent mixtures. • The mixing properties were calculated based on the NRTL model. - Abstract: The solubility of hydroxyacetic acid in five pure organic solvents and two binary solvent mixtures were experimentally measured from 273.15 K to 313.15 K at atmospheric pressure (p = 0.1 MPa) by using a dynamic method. The order of solubility in pure organic solvents is ethanol > isopropanol > n-butanol > acetonitrile > ethyl acetate within the investigated temperature range, except for temperature lower than 278 K where the solubility of HA in ethyl acetate is slightly larger than that in acetonitrile. Furthermore, the solubility data in pure solvents were correlated with the modified Apelblat model, NRTL model, and Wilson model and that in the binary solvents mixtures were fitted to the CNIBS/R-K model and Jouyban-Acree model. Finally, the mixing thermodynamic properties of hydroxyacetic acid in pure and binary solvent systems were calculated and discussed.

  17. Removal of Pb from Water by Adsorption on Apple Pomace: Equilibrium, Kinetics, and Thermodynamics Studies

    Directory of Open Access Journals (Sweden)

    Piar Chand

    2013-01-01

    Full Text Available The adsorption-influencing factors such as pH, dose, and time were optimized by batch adsorption study. A 0.8 g dose, 4.0 pH, and 80 min of contact time were optimized for maximum adsorption of Pb on AP. The adsorption isotherms (Langmuir and Freundlich were well fitted to the data obtained with values of qmax (16.39 mg/g; r2=0.985 and K (16.14 mg/g; r2=0.998, respectively. The kinetics study showed that lead adsorption follows the pseudo-second-order kinetics with correlation coefficient (r2 of 0.999 for all of the concentration range. FTIR spectra also showed that the major functional groups like polyphenols (–OH and carbonyl (–CO were responsible for Pb binding on AP. The thermodynamic parameters as ΔG, ΔH (33.54 J/mol, and ΔS (1.08 J/mol/K were also studied and indicate that the reaction is feasible, endothermic, and spontaneous in nature.

  18. Applicability of the theory of thermodynamic similarity to predict the enthalpies of vaporization of aliphatic aldehydes

    Science.gov (United States)

    Esina, Z. N.; Korchuganova, M. R.

    2015-06-01

    The theory of thermodynamic similarity is used to predict the enthalpies of vaporization of aliphatic aldehydes. The predicted data allow us to calculate the phase diagrams of liquid-vapor equilibrium in a binary water-aliphatic aldehyde system.

  19. Adsorption of rhodamine B by acid activated carbon-Kinetic, thermodynamic and equilibrium studies

    Directory of Open Access Journals (Sweden)

    Shanmugam Arivoli

    2009-08-01

    Full Text Available A carbonaceous adsorbent prepared from an indigenous waste by acid treatment was tested for its efficiency in removing Rhodamine B (RDB. The parameters studied include agitation time, initial dye concentration, carbon dose, pH and temperature. The adsorption followed first order kinetics and the rate is mainly controlled by intra-particle diffusion. Freundlich and Langmuir isotherm models were applied to the equilibrium data. The adsorption capacity (Qm obtained from the Langmuir isotherm plots were 40.161, 35.700, 38.462 and 37.979 mg/g respectively at an initial pH of 7.0 at 30, 40, 50 and 60 0C. The temperature variation study showed that the RDB adsorption is endothermic and spontaneous with increased randomness at the solid solution interface. Significant effect on adsorption was observed on varying the pH of the RDB solutions. Almost 85% removal of RDB was observed at 60 0C. The Langmuir and Freundlich isotherms obtained, positive ?H0 value, pH dependent results and desorption of dye in mineral acid suggest that the adsorption of RDB by Banana bark carbon involves physisorption mechanism.

  20. Comments on the compatibility of thermodynamic equilibrium conditions with lattice propagators

    Science.gov (United States)

    Canfora, Fabrizio; Giacomini, Alex; Pais, Pablo; Rosa, Luigi; Zerwekh, Alfonso

    2016-08-01

    In this paper the compatibility is analyzed of the non-perturbative equations of state of quarks and gluons arising from the lattice with some natural requirements for self-gravitating objects at equilibrium: the existence of an equation of state (namely, the possibility to define the pressure as a function of the energy density), the absence of superluminal propagation and Le Chatelier's principle. It is discussed under which conditions it is possible to extract an equation of state (in the above sense) from the non-perturbative propagators arising from the fits of the latest lattice data. In the quark case, there is a small but non-vanishing range of temperatures in which it is not possible to define a single-valued functional relation between density and pressure. Interestingly enough, a small change of the parameters appearing in the fit of the lattice quark propagator (of around 10 %) could guarantee the fulfillment of all the three conditions (keeping alive, at the same time, the violation of positivity of the spectral representation, which is the expected signal of confinement). As far as gluons are concerned, the analysis shows very similar results. Whether or not the non-perturbative quark and gluon propagators satisfy these conditions can have a strong impact on the estimate of the maximal mass of quark stars.

  1. Comments on the compatibility of thermodynamic equilibrium conditions with lattice propagators

    Energy Technology Data Exchange (ETDEWEB)

    Canfora, Fabrizio [Centro de Estudios Cientificos (CECs), Valdivia (Chile); Giacomini, Alex [Universidad Austral de Chile, Instituto de Ciencias Fisicas y Matematicas, Valdivia (Chile); Pais, Pablo [Centro de Estudios Cientificos (CECs), Valdivia (Chile); Universite Libre de Bruxelles and International Solvay Institutes, Physique Theorique et Mathematique, Brussels (Belgium); Rosa, Luigi [Universita di Napoli Federico II, Complesso Universitario di Monte S. Angelo, Dipartimento di Fisica, Naples (Italy); Complesso Universitario di Monte S. Angelo, Naples (Italy); INFN, Sezione di Napoli, Naples (Italy); Zerwekh, Alfonso [Universidad Tecnica Federico Santa Maria, Departamento de Fisica and Centro Cientifico-Tecnologico de Valparaiso, Valparaiso (Chile)

    2016-08-15

    In this paper the compatibility is analyzed of the non-perturbative equations of state of quarks and gluons arising from the lattice with some natural requirements for self-gravitating objects at equilibrium: the existence of an equation of state (namely, the possibility to define the pressure as a function of the energy density), the absence of superluminal propagation and Le Chatelier's principle. It is discussed under which conditions it is possible to extract an equation of state (in the above sense) from the non-perturbative propagators arising from the fits of the latest lattice data. In the quark case, there is a small but non-vanishing range of temperatures in which it is not possible to define a single-valued functional relation between density and pressure. Interestingly enough, a small change of the parameters appearing in the fit of the lattice quark propagator (of around 10 %) could guarantee the fulfillment of all the three conditions (keeping alive, at the same time, the violation of positivity of the spectral representation, which is the expected signal of confinement). As far as gluons are concerned, the analysis shows very similar results. Whether or not the non-perturbative quark and gluon propagators satisfy these conditions can have a strong impact on the estimate of the maximal mass of quark stars. (orig.)

  2. Comments on the compatibility of thermodynamic equilibrium conditions with lattice propagators

    International Nuclear Information System (INIS)

    Canfora, Fabrizio; Giacomini, Alex; Pais, Pablo; Rosa, Luigi; Zerwekh, Alfonso

    2016-01-01

    In this paper the compatibility is analyzed of the non-perturbative equations of state of quarks and gluons arising from the lattice with some natural requirements for self-gravitating objects at equilibrium: the existence of an equation of state (namely, the possibility to define the pressure as a function of the energy density), the absence of superluminal propagation and Le Chatelier's principle. It is discussed under which conditions it is possible to extract an equation of state (in the above sense) from the non-perturbative propagators arising from the fits of the latest lattice data. In the quark case, there is a small but non-vanishing range of temperatures in which it is not possible to define a single-valued functional relation between density and pressure. Interestingly enough, a small change of the parameters appearing in the fit of the lattice quark propagator (of around 10 %) could guarantee the fulfillment of all the three conditions (keeping alive, at the same time, the violation of positivity of the spectral representation, which is the expected signal of confinement). As far as gluons are concerned, the analysis shows very similar results. Whether or not the non-perturbative quark and gluon propagators satisfy these conditions can have a strong impact on the estimate of the maximal mass of quark stars. (orig.)

  3. Thermodynamic modeling of phases equilibrium in aqueous systems to recover potassium chloride from natural brines

    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.

  4. Equilibrium, kinetic and thermodynamic studies on the adsorption of m-cresol onto micro- and mesoporous carbon

    International Nuclear Information System (INIS)

    Kennedy, L. John; Vijaya, J. Judith; Sekaran, G.; Kayalvizhi, K.

    2007-01-01

    Investigations were conducted in batch mode to study the adsorption behaviour of m-cresol on a porous carbon prepared from rice husk (RHAC) by varying the parameters such as agitation time, m-cresol concentration (50-300 mg/l), pH (2.5-10) and temperature (293-323 K). Studies showed that the adsorption decreased with increase in pH and temperature. The isotherm data were fitted to Langmuir, Freundlich, and Dubinin-Radushkevic (D-R) models. The kinetic models such as pseudo-first-order, pseudo-second-order and intraparticle diffusion models were selected to understand the reaction pathways and mechanism of adsorption process. The thermodynamic equilibrium coefficients obtained at different temperatures were used to evaluate the thermodynamic constants ΔG o , ΔH o and ΔS o . The sorption process was found to be exothermic in nature (ΔH o : -23.46 to -25.40 kJ/mol) with a decrease in entropy (ΔS o : -19.44 to -35.87 J/(mol K)). The negative value of Gibbs free energy, ΔG o indicates that the adsorption occurs via a spontaneous process. The decrease in the value of -ΔG o from 17.70 to 13.54 kJ/mol with increase in pH and temperature indicates that the adsorption of m-cresol onto activated carbon is less favourable at higher temperature and pH range. The influence of mesopore and a possible mechanism of adsorption is also suggested

  5. Adsorption of Pb(II) ions from aqueous solution by native and activated bentonite: Kinetic, equilibrium and thermodynamic study

    Energy Technology Data Exchange (ETDEWEB)

    Kul, Ali Riza [Yuzuncu Yil University, Faculty of Art and Science, Department of Chemistry, 65080 Van (Turkey); Koyuncu, Huelya, E-mail: hkoyuncu@yyu.edu.tr [Forensic Medicine Foundation, Felek Street No. 45, 06300 Kecioren, Ankara (Turkey)

    2010-07-15

    In this study, the adsorption kinetics, equilibrium and thermodynamics of Pb(II) ions on native (NB) and acid activated (AAB) bentonites were examined. The specific surface areas, pore size and pore-size distributions of the samples were fully characterized. The adsorption efficiency of Pb(II) onto the NB and AAB was increased with increasing temperature. The kinetics of adsorption of Pb(II) ions was discussed using three kinetic models, the pseudo-first-order, the pseudo-second-order and the intra-particle diffusion model. The experimental data fitted very well the pseudo-second-order kinetic model. The initial sorption rate and the activation energy were also calculated. The activation energy of the sorption was calculated as 16.51 and 13.66 kJ mol{sup -1} for NB and AAB, respectively. Experimental results were also analysed by the Langmuir, Freundlich and Dubinin-Redushkevich (D-R) isotherm equations at different temperatures. R{sub L} separation factor for Langmuir and the n value for Freundlich isotherm show that Pb(II) ions are favorably adsorbed by NB and AAB. Thermodynamic quantities such as Gibbs free energy ({Delta}G), the enthalpy ({Delta}H) and the entropy change of sorption ({Delta}S) were determined as about -5.06, 10.29 and 0.017 kJ mol{sup -1} K{sup -1}, respectively for AAB. It was shown that the sorption processes were an endothermic reactions, controlled by physical mechanisms and spontaneously.

  6. Calculation of thermodynamic equilibrium between bcc disordered solid solutions U and Mo

    International Nuclear Information System (INIS)

    Alonso, Paula R.; Rubiolo, Gerardo H.

    2003-01-01

    There is actually an interest to develop a new fuel with higher density for research reactors. Fuel plates would be obtained by dispersion, a method that requires both a very dense fuel dispersant (>15.0 g U/cm 3 ) and a very high volume loading of the dispersant (>55%). Dispersants based in gamma (BCC) stabilized uranium alloys are being investigated, as they are able to reach uranium densities of 17.0 g U/cm 3 . Among them, we focus in U(Mo) bcc solid solutions with the addition of ternary elements to stabilize gamma phase. Transition metals, 4d and 5d, of groups VII and VIII are good candidates for the ternary alloy U - Mo - X. Their relative power to stabilize gamma phase seems to be in close relation with bonding energies between atoms in the alloy. A first approach to the calculation of these energies has been performed by the semi empiric method of Miedema where only bonds between pairs are considered, neglecting ternary and quaternary bonds. There is also a lack of information concerning solubilities of the ternary elements in the ternary cubic phase. In this work we aim to calculate bonding energies between atoms in the alloy using a cluster expansion of the formation energy (T=0 K) of a series of bcc ordered compounds in the systems U-Mo-X. Then the calculation of the equilibrium phase diagram by the Cluster Variation Method will be done (CVM). We show here the first part of the investigation devoted to calculation of phases equilibria in the U Mo system Formation energies of the ordered compounds were obtained by the first principles methods TB-LMTO-ASA and FP-LAPW. Another set of bonding energies was calculated in order to fit the known experimental diagram and new formation energies for the ordered compounds were derived from them. Discrepancies between both sets are discussed. (author)

  7. Local thermodynamic equilibrium and related metrological issues involving collisional-radiative model in laser-induced aluminum plasmas

    International Nuclear Information System (INIS)

    Travaille, G.; Peyrusse, O.; Bousquet, B.; Canioni, L.; Pierres, K. Michel-Le; Roy, S.

    2009-01-01

    We present a collisional-radiative approach of the theoretical analysis of laser-induced breakdown spectroscopy (LIBS) plasmas. This model, which relies on an optimized effective potential atomic structure code, was used to simulate a pure aluminum plasma. The description of aluminum involved a set of 220 atomic levels representative of three different stages of ionization (Al 0 , Al + and Al ++ ). The calculations were carried for stationary plasmas, with input parameters (n e and T e ) ranging respectively between 10 13-18 cm -3 and 0.3-2 eV. A comparison of our atomic data with some existing databases is made. The code was mainly developed to address the validity of the local thermodynamic equilibrium (LTE) assumption. For usual LIBS plasma parameters, we did not reveal a sizeable discrepancy of the radiative equilibrium of the plasma towards LTE. For cases where LTE was firmly believed to stand, the Boltzmann plot outputs of this code were used to check the physical accuracy of the Boltzmann temperature, as it is currently exploited in several calibration-free laser-induced breakdown spectroscopy (CF-LIBS) studies. In this paper, a deviation ranging between 10 and 30% of the measured Boltzmann temperature to the real excitation temperature is reported. This may be due to the huge dispersion induced on the line emissivities, on which the Boltzmann plots are based to extract this parameter. Consequences of this fact on the CF-LIBS procedure are discussed and further insights to be considered for the future are introduced.

  8. 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.

  9. Thermodynamics

    International Nuclear Information System (INIS)

    Zanchini, E.

    1988-01-01

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

  10. Statistical thermodynamics

    International Nuclear Information System (INIS)

    Lim, Gyeong Hui

    2008-03-01

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

  11. Adsorptive removal of phenol from aqueous solutions on activated carbon prepared from tobacco residues: Equilibrium, kinetics and thermodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Kilic, Murat; Apaydin-Varol, Esin [Department of Chemical Engineering, Anadolu University, Eskisehir 26470 (Turkey); Puetuen, Ayse E., E-mail: aeputun@anadolu.edu.tr [Department of Chemical Engineering, Anadolu University, Eskisehir 26470 (Turkey)

    2011-05-15

    This study consists of producing high surface area activated carbon from tobacco residues by chemical activation and its behavior of phenol removal from aqueous solutions. K{sub 2}CO{sub 3} and KOH were used as chemical activation agents and three impregnation ratios (50, 75 and 100 wt.%) were applied on biomass. Maximum BET surface areas of activated carbons were obtained from impregnation with 75 wt.% of K{sub 2}CO{sub 3} and 75 wt.% of KOH as 1635 and 1474 m{sup 2}/g, respectively. Optimum adsorption conditions were determined as a function of pH, adsorbent dosage, initial phenol concentration, contact time and temperature of solution for phenol removal. To describe the equilibrium isotherms the experimental data were analyzed by the Langmuir, Freundlich, Dubinin-Radushkevich (D-R) and Temkin isotherm models. Pseudo-first order, pseudo-second order and intraparticle diffusion kinetic models were used to find out the kinetic parameters and mechanism of adsorption process. The thermodynamic parameters such as {Delta}G{sup o}, {Delta}H{sup o} and {Delta}S{sup o} were calculated for predicting the nature of adsorption. According to the experimental results, activated carbon prepared from tobacco residue seems to be an effective, low-cost and alternative adsorbent precursor for the removal of phenol from aqueous solutions.

  12. On the biosorption, by brown seaweed, Lobophora variegata, of Ni(II) from aqueous solutions: equilibrium and thermodynamic studies.

    Science.gov (United States)

    Basha, Shaik; Jaiswar, Santlal; Jha, Bhavanath

    2010-09-01

    The biosorption equilibrium isotherms of Ni(II) onto marine brown algae Lobophora variegata, which was chemically-modified by CaCl(2) were studied and modeled. To predict the biosorption isotherms and to determine the characteristic parameters for process design, twenty-three one-, two-, three-, four- and five-parameter isotherm models were applied to experimental data. The interaction among biosorbed molecules is attractive and biosorption is carried out on energetically different sites and is an endothermic process. The five-parameter Fritz-Schluender model gives the most accurate fit with high regression coefficient, R (2) (0.9911-0.9975) and F-ratio (118.03-179.96), and low standard error, SE (0.0902-0.0.1556) and the residual or sum of square error, SSE (0.0012-0.1789) values to all experimental data in comparison to other models. The biosorption isotherm models fitted the experimental data in the order: Fritz-Schluender (five-parameter) > Freundlich (two-parameter) > Langmuir (two-parameter) > Khan (three-parameter) > Fritz-Schluender (four-parameter). The thermodynamic parameters such as DeltaG (0), DeltaH (0) and DeltaS (0) have been determined, which indicates the sorption of Ni(II) onto L. variegata was spontaneous and endothermic in nature.

  13. Kinetics, equilibrium and thermodynamic studies on biosorption of Ag(I) from aqueous solution by macrofungus Pleurotus platypus.

    Science.gov (United States)

    Das, Devlina; Das, Nilanjana; Mathew, Lazar

    2010-12-15

    Reports are available on silver binding capacity of some microorganisms. However, reports on the equilibrium studies on biosorption of silver by macrofungi are seldom known. The present study was carried out in a batch system using dead biomass of macrofungus Pleurotus platypus for the sorption of Ag(I). P. platypus exhibited the highest silver uptake of 46.7 mg g(-1) of biomass at pH 6.0 in the presence of 200 mg L(-1) Ag(I) at 20°C. Kinetic studies based on fractional power, zero order, first order, pseudo-first order, Elovich, second order and pseudo-second order rate expressions have been carried out. The results showed a very good compliance with the pseudo-first order model. The experimental data were analyzed using two parameter isotherms (Langmuir, Freundlich, Dubinin-Radushkevich, Temkin and Halsey), three parameter isotherms (Redlich-Peterson, Sips, Khan, Koble-Corrigan, Hill, Toth, Radke-Prausmitz, Jossens, Langmuir-Freundlich), four parameter isotherms (Weber-van Vliet, Fritz-Schlunder, Baudu) and five parameter isotherm (Fritz-Schlunder). Thermodynamic parameters of the biosorption (ΔG, ΔH and ΔS) were also determined. The present study confirmed that macrofungus P. platypus may be used as a cost effective efficient biosorbent for the removal of Ag(I) ions from aqueous solution. Copyright © 2010 Elsevier B.V. All rights reserved.

  14. Adsorption capacity of Curcuma longa for the removal of basic green 1 dye--equilibrium, kinetics and thermodynamic study.

    Science.gov (United States)

    Roopavathi, K V; Shanthakumar, S

    2016-09-01

    In the present study, Curcuma longa (turmeric plant) was used as an adsorbent to remove Basic Green 1 (BG) dye. Batch study was carried out to evaluate the adsorption potential of C. longa and influencing factors such as pH (4-10), adsorbent dose (0.2-5 g l-1), initial dye concentration (50-250 mg l-1) and temperature (30-50°C) on dye removal were analysed. The characterisation of adsorbent was carried out using fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and Brunauer, Emmett and Teller (BET) method. Isotherm models that included Langmuir, Freundlich, Tempkin and Dubinin-Radushkevich, and kinetic models such as pseudo first order, pseudo second-order, Elovich and intraparticle diffusion models were studied. A maximum removal percentage (82.76%) of BG dye from aqueous solution was obtained with optimum conditions of pH 7, 1g l-1 adsorbent dose and 30°C temperature, for 100 mg l-1 initial dye concentration. The equilibrium and kinetic study revealed that the experimental data fitted suitably the Freundlich isotherm and Pseudo second order kinetic model. Thermodynamic analysis proved that adsorption system in this study was spontaneous, feasible and endothermic in nature.

  15. Roles of bulk viscosity on Rayleigh-Taylor instability: Non-equilibrium thermodynamics due to spatio-temporal pressure fronts

    Energy Technology Data Exchange (ETDEWEB)

    Sengupta, Tapan K., E-mail: tksen@iitk.ac.in; Bhole, Ashish; Shruti, K. S. [HPCL, Department of Aerospace Engineering, IIT Kanpur, Kanpur, UP (India); Sengupta, Aditi [Department of Engineering, University of Cambridge, Cambridge (United Kingdom); Sharma, Nidhi [Graduate Student, HPCL, Department of Aerospace Engineering, IIT Kanpur, Kanpur, UP (India); Sengupta, Soumyo [Department of Mechanical and Aerospace Engineering, Ohio State University, Columbus, Ohio 43210 (United States)

    2016-09-15

    Direct numerical simulations of Rayleigh-Taylor instability (RTI) between two air masses with a temperature difference of 70 K is presented using compressible Navier-Stokes formulation in a non-equilibrium thermodynamic framework. The two-dimensional flow is studied in an isolated box with non-periodic walls in both vertical and horizontal directions. The non-conducting interface separating the two air masses is impulsively removed at t = 0 (depicting a heaviside function). No external perturbation has been used at the interface to instigate the instability at the onset. Computations have been carried out for rectangular and square cross sections. The formulation is free of Boussinesq approximation commonly used in many Navier-Stokes formulations for RTI. Effect of Stokes’ hypothesis is quantified, by using models from acoustic attenuation measurement for the second coefficient of viscosity from two experiments. Effects of Stokes’ hypothesis on growth of mixing layer and evolution of total entropy for the Rayleigh-Taylor system are reported. The initial rate of growth is observed to be independent of Stokes’ hypothesis and the geometry of the box. Following this stage, growth rate is dependent on the geometry of the box and is sensitive to the model used. As a consequence of compressible formulation, we capture pressure wave-packets with associated reflection and rarefaction from the non-periodic walls. The pattern and frequency of reflections of pressure waves noted specifically at the initial stages are reflected in entropy variation of the system.

  16. A thermodynamic data base for Tc to calculate equilibrium solubilities at temperatures up to 300 deg C

    Energy Technology Data Exchange (ETDEWEB)

    Puigdomenech, I [Studsvik AB, Nykoeping (Sweden); Bruno, J [Intera Information Technologies SL, Cerdanyola (Spain)

    1995-04-01

    Thermodynamic data has been selected for solids and aqueous species of technetium. Equilibrium constants have been calculated in the temperature range 0 to 300 deg C at a pressure of 1 bar for T<100 deg C and at the steam saturated pressure at higher temperatures. For aqueous species, the revised Helgeson-Kirkham-Flowers model is used for temperature extrapolations. The data base contains a large amount of estimated data, and the methods used for these estimations are described in detail. A new equation is presented that allows the estimation of {Delta}{sub r}Cdeg{sub pm} values for mononuclear hydrolysis reactions. The formation constants for chloro complexes of Tc(V) and Tc(IV), whose existence is well established, have been estimated. The majority of entropy and heat capacity values in the data base have also been estimated, and therefore temperature extrapolations are largely based on estimations. The uncertainties derived from these calculations are described. Using the data base developed in this work, technetium solubilities have been calculated as a function of temperature for different chemical conditions. The implications for the mobility of Tc under nuclear repository conditions are discussed. 70 refs.

  17. Removal of phenol from aqueous solutions by adsorption onto organomodified Tirebolu bentonite: Equilibrium, kinetic and thermodynamic study

    Energy Technology Data Exchange (ETDEWEB)

    Senturk, Hasan Basri; Ozdes, Duygu; Gundogdu, Ali; Duran, Celal [Department of Chemistry, Karadeniz Technical University, Faculty of Arts and Sciences, 61080 Trabzon (Turkey); Soylak, Mustafa, E-mail: soylak@erciyes.edu.tr [Department of Chemistry, Erciyes University, Faculty of Arts and Sciences, 38039 Kayseri (Turkey)

    2009-12-15

    A natural bentonite modified with a cationic surfactant, cetyl trimethylammonium bromide (CTAB), was used as an adsorbent for removal of phenol from aqueous solutions. The natural and modified bentonites (organobentonite) were characterized with some instrumental techniques (FTIR, XRD and SEM). Adsorption studies were performed in a batch system, and the effects of various experimental parameters such as solution pH, contact time, initial phenol concentration, organobentonite concentration, and temperature, etc. were evaluated upon the phenol adsorption onto organobentonite. Maximum phenol removal was observed at pH 9.0. Equilibrium was attained after contact of 1 h only. The adsorption isotherms were described by Langmuir and Freundlich isotherm models, and both model fitted well. The monolayer adsorption capacity of organobentonite was found to be 333 mg g{sup -1}. Desorption of phenol from the loaded adsorbent was achieved by using 20% acetone solution. The kinetic studies indicated that the adsorption process was best described by the pseudo-second-order kinetics (R{sup 2} > 0.99). Thermodynamic parameters including the Gibbs free energy ({Delta}G{sup o}), enthalpy ({Delta}H{sup o}), and entropy ({Delta}S{sup o}) were also calculated. These parameters indicated that adsorption of phenol onto organobentonite was feasible, spontaneous and exothermic in the temperature range of 0-40 {sup o}C.

  18. Removal of phenol from aqueous solutions by adsorption onto organomodified Tirebolu bentonite: Equilibrium, kinetic and thermodynamic study

    International Nuclear Information System (INIS)

    Senturk, Hasan Basri; Ozdes, Duygu; Gundogdu, Ali; Duran, Celal; Soylak, Mustafa

    2009-01-01

    A natural bentonite modified with a cationic surfactant, cetyl trimethylammonium bromide (CTAB), was used as an adsorbent for removal of phenol from aqueous solutions. The natural and modified bentonites (organobentonite) were characterized with some instrumental techniques (FTIR, XRD and SEM). Adsorption studies were performed in a batch system, and the effects of various experimental parameters such as solution pH, contact time, initial phenol concentration, organobentonite concentration, and temperature, etc. were evaluated upon the phenol adsorption onto organobentonite. Maximum phenol removal was observed at pH 9.0. Equilibrium was attained after contact of 1 h only. The adsorption isotherms were described by Langmuir and Freundlich isotherm models, and both model fitted well. The monolayer adsorption capacity of organobentonite was found to be 333 mg g -1 . Desorption of phenol from the loaded adsorbent was achieved by using 20% acetone solution. The kinetic studies indicated that the adsorption process was best described by the pseudo-second-order kinetics (R 2 > 0.99). Thermodynamic parameters including the Gibbs free energy (ΔG o ), enthalpy (ΔH o ), and entropy (ΔS o ) were also calculated. These parameters indicated that adsorption of phenol onto organobentonite was feasible, spontaneous and exothermic in the temperature range of 0-40 o C.

  19. The Zr-Pt system. Experimental determination of the phase equilibrium conditions, and obtention of the diagram by thermodynamical modeling

    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)

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

    DEFF Research Database (Denmark)

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

    2010-01-01

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

  1. Use of the SSF equations in the Kojima-Moon-Ochi thermodynamic consistency test of isothermal vapour-liquid equilibrium data

    Directory of Open Access Journals (Sweden)

    SLOBODAN P. SERBANOVIC

    2000-12-01

    Full Text Available The Kojima-Moon-Ochi (KMO thermodynamic consistency test of vapour–liquid equilibrium (VLE measurements for 32 isothermal data sets of binary systems of various complexity was applied using two fitting equations: the Redlich-Kister equation and the Sum of Symmetrical Functions. It was shown that the enhanced reliability of the fitting of the experimental data can change the conclusions drawn on their thermodynamic consistency in those cases of VLE data sets that are estimated to be near the border of consistency.

  2. Kinetic, equilibrium and thermodynamic studies on sorption of uranium and thorium from aqueous solutions by a selective impregnated resin containing carminic acid

    International Nuclear Information System (INIS)

    Rahmani-Sani, Abolfazl; Hosseini-Bandegharaei, Ahmad; Hosseini, Seyyed-Hossein; Kharghani, Keivan; Zarei, Hossein; Rastegar, Ayoob

    2015-01-01

    Highlights: • The objective of the study is to investigate the potential application of a selective EIR for sorption of U(VI) and Th(IV) ions. • The effects of several physiochemical parameters were investigated. • The sorption kinetics and sorption isotherms were used to explain the sorption mechanism. • The thermodynamic studies showed the feasibility of sorption process. • The EIR beads showed a great potential for effective removal of U(VI) and Th(IV) ions. - Abstract: In this work, the removal of uranium and thorium ions from aqueous solutions was studied by solid–liquid extraction using an advantageous extractant-impregnated resin (EIR) prepared by loading carminic acid (CA) onto Amberlite XAD-16 resin beads. Batch sorption experiments using CA/XAD-16 beads for the removal of U(VI) and Th(IV) ions were carried out as a function of several parameters, like equilibration time, metal ion concentration, etc. The equilibrium data obtained from the sorption experiments were adjusted to the Langmuir isotherm model and the calculated maximum sorption capacities in terms of monolayer sorption were in agreement with those obtained from the experiments. The experimental data on the sorption behavior of both metal ions onto the EIR beads fitted well in both Bangham and intra-particle diffusion kinetic models, indicating that the intra-particle diffusion is the rate-controlling step. The thermodynamic studies at different temperatures revealed the feasibility and the spontaneous nature of the sorption process for both uranium and thorium ions

  3. Removal of malathion from aqueous solution using De-Acidite FF-IP resin and determination by UPLC-MS/MS: equilibrium, kinetics and thermodynamics studies.

    Science.gov (United States)

    Naushad, Mu; Alothman, Z A; Khan, M R

    2013-10-15

    In the present study, De-Acidite FF-IP resin was used to remove a highly toxic and persistent organophosphorus pesticide (malathion) from the aqueous solution. Batch experiments were performed as a function of various experimental parameters such as effect of pH (2-10), contact time (10-120 min), resin dose (0.05-0.5 g), initial malathion concentration (0.5-2.5 µg mL(-1)) and temperature (25-65°C). The concentration of malathion was determined using a sensitive, selective and rapid ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method. The uptake rate of malathion on De-Acidite FF-IP resin was rapid and equilibrium established within 40 min. Kinetics studies showed better applicability for pseudo-second-order model. The equilibrium data was fitted to Langmuir and Freundlich isotherm models and the isotherm constants were calculated for malathion. The values of thermodynamic parameters (ΔG(0), ΔH(0) and ΔS(0)) were computed from the Van't Hoff plot of lnKC vs. 1/T which showed that the adsorption of malathion was feasible, endothermic and spontaneous. The regeneration studies were carried out which demonstrated a decrease in the recovery of malathion from 95% to 68% after five consecutive cycles. Breakthrough and exhaustive capacities of malathion were found to be 1.25 mg g(-1) and 3.5 mg g(-1), respectively. © 2013 Elsevier B.V. All rights reserved.

  4. Investigations on application of multigrid method to MHD equilibrium analysis

    International Nuclear Information System (INIS)

    Ikuno, Soichiro

    2000-01-01

    The potentiality of application for Multi-grid method to MHD equilibrium analysis is investigated. The nonlinear eigenvalue problem often appears when the MHD equilibria are determined by solving the Grad-Shafranov equation numerically. After linearization of the equation, the problem is solved by use of the iterative method. Although the Red-Black SOR method or Gauss-Seidel method is often used for the solution of the linearized equation, it takes much CPU time to solve the problem. The Multi-grid method is compared with the SOR method for the Poisson Problem. The results of computations show that the CPU time required for the Multi-grid method is about 1000 times as small as that for the SOR method. (author)

  5. Thermodynamic design of natural gas liquefaction cycles for offshore application

    Science.gov (United States)

    Chang, Ho-Myung; Lim, Hye Su; Choe, Kun Hyung

    2014-09-01

    A thermodynamic study is carried out for natural gas liquefaction cycles applicable to offshore floating plants, as partial efforts of an ongoing governmental project in Korea. For offshore liquefaction, the most suitable cycle may be different from the on-land LNG processes under operation, because compactness and simple operation are important as well as thermodynamic efficiency. As a turbine-based cycle, closed Claude cycle is proposed to use NG (natural gas) itself as refrigerant. The optimal condition for NG Claude cycle is determined with a process simulator (Aspen HYSYS), and the results are compared with fully-developed C3-MR (propane pre-cooled mixed refrigerant) JT cycles and various N2 (nitrogen) Brayton cycles in terms of efficiency and compactness. The newly proposed NG Claude cycle could be a good candidate for offshore LNG processes.

  6. An experimental and thermodynamic equilibrium investigation of the Pb, Zn, Cr, Cu, Mn and Ni partitioning during sewage sludge incineration.

    Science.gov (United States)

    Liu, Jingyong; Fu, Jiewen; Ning, Xun'an; Sun, Shuiyu; Wang, Yujie; Xie, Wuming; Huang, Shaosong; Zhong, Sheng

    2015-09-01

    The effects of different chlorides and operational conditions on the distribution and speciation of six heavy metals (Pb, Zn, Cr, Cu, Mn and Ni) during sludge incineration were investigated using a simulated laboratory tubular-furnace reactor. A thermodynamic equilibrium investigation using the FactSage software was performed to compare the experimental results. The results indicate that the volatility of the target metals was enhanced as the chlorine concentration increased. Inorganic-Cl influenced the volatilization of heavy metals in the order of Pb>Zn>Cr>Cu>Mn>Ni. However, the effects of organic-Cl on the volatility of Mn, Pb and Cu were greater than the effects on Zn, Cr and Ni. With increasing combustion temperature, the presence of organic-Cl (PVC) and inorganic-Cl (NaCl) improved the transfer of Pb and Zn from bottom ash to fly ash or fuse gas. However, the presence of chloride had no obvious influence on Mn, Cu and Ni. Increased retention time could increase the volatilization rate of heavy metals; however, this effect was insignificant. During the incineration process, Pb readily formed PbSiO4 and remained in the bottom ash. Different Pb compounds, primarily the volatile PbCl2, were found in the gas phase after the addition of NaCl; the dominant Pb compounds in the gas phase after the addition of PVC were PbCl2, Pb(ClO4)2 and PbCl2O4. Copyright © 2015. Published by Elsevier B.V.

  7. Statistical Thermodynamics and Microscale Thermophysics

    Science.gov (United States)

    Carey, Van P.

    1999-08-01

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

  8. Thermodynamic models for determination of solid–liquid equilibrium of the 6-benzyladenine in pure and binary organic solvents

    International Nuclear Information System (INIS)

    Li, Tao; Deng, Renlun; Wu, Gang; Gu, Pengfei; Hu, Yonghong; Yang, Wenge; Yu, Yemin; Zhang, Yuhao; Yang, Chen

    2017-01-01

    Highlights: • The solubility increased with increasing temperature. • Data were fitted using the modified Apelblat equation and other models in pure solvents. • Data were fitted using the modified Apelblat equation and other models in binary solvent mixture. - Abstract: Data on corresponding solid–liquid equilibrium of 6-benzyladenine in different solvents are essential for a preliminary study of industrial applications. In this paper, the solid–liquid equilibrium of 6-benzyladenine in methanol, ethanol, 1-butanol, acetone, acetonitrile, ethyl acetate, dimethyl formamide and tetrahydrofuran pure solvents and (dimethyl formamide + actone) mixture solvents was explored within the temperature range from (278.15 to 333.15) K under 0.1 MPa. For the temperature range investigated, the solubility of 6-benzyladenine in the solvents increased with increasing temperature. The solubility of 6-benzyladenine in dimethyl formamide is superior to other selected pure solvents. The modified Apelblat model, the Buchowski-Ksiazaczak λh model, and the ideal model were adopted to describe and predict the change tendency of solubility. Computational results showed that the modified Apelblat model has more advantages than the other two models. The solubility results were fitted using a modified Apelblat equation, a variant of the combined nearly ideal binary solvent/Redich-Kister (CNIBS/R-K) model, Jouyban-Acree model and Ma model in (dimethyl formamide + acetone) binary solvent mixture. Computational results showed that the modified Apelblat model is superior to the other equations.

  9. Thermodynamics for scientists and engineers

    International Nuclear Information System (INIS)

    Lim, Gyeong Hui

    2011-02-01

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

  10. Thermodynamic nonequilibrium phase change behavior and thermal properties of biological solutions for cryobiology applications.

    Science.gov (United States)

    Han, Bumsoo; Bischof, John C

    2004-04-01

    Understanding the phase change behavior of biomaterials during freezing/thawing including their thermal properties at low temperatures is essential to design and improve cryobiology applications such as cryopreservation and cryosurgery. However, knowledge of phase change behavior and thermal properties of various biomaterials is still incomplete, especially at cryogenic temperatures (solutions--either water-NaCl or phosphate buffered saline (PBS)--with various chemical additives were investigated. The chemical additives studied are glycerol and raffinose as CPAs, an AFP (Type III, molecular weight = 6500), and NaCl as a cryosurgical adjuvant. The phase change behavior was investigated using a differential scanning calorimeter (DSC) and a cryomicroscope. The specific and latent heat of these solutions were also measured with the DSC. The saline solutions have two distinct phase changes--water/ice and eutectic phase changes. During freezing, eutectic solidification of both water-NaCl and PBS are significantly supercooled below their thermodynamic equilibrium eutectic temperatures. However, their melting temperatures are close to thermodynamic equilibrium during thawing. These eutectic phase changes disappear when even a small amount (0.1 M glycerol) of CPA was added, but they are still observed after the addition of an AFP. The specific heats of these solutions are close to that of ice at very low temperatures (< or = -100 degrees C) regardless of the additives, but they increase between -100 degrees C and -30 degrees C with the addition of CPAs. The amount of latent heat, which is evaluated with sample weight, generally decreases with the addition of the additives, but can be normalized to approximately 300 J/g based on the weight of water which participates in the phase change. This illustrates that thermal properties, especially latent heat, of a biomaterial should be evaluated based on the understanding of its phase change behavior. The results of the present

  11. Thermodynamic properties and transport coefficients of a two-temperature polytetrafluoroethylene vapor plasma for ablation-controlled discharge applications

    Science.gov (United States)

    Wang, Haiyan; Wang, Weizong; Yan, Joseph D.; Qi, Haiyang; Geng, Jinyue; Wu, Yaowu

    2017-10-01

    Ablation-controlled plasmas have been used in a range of technical applications where local thermodynamic equilibrium (LTE) is often violated near the wall due to the strong cooling effect caused by the ablation of wall materials. The thermodynamic and transport properties of ablated polytetrafluoroethylene (PTFE) vapor, which determine the flowing plasma behavior in such applications, are calculated based on a two-temperature model at atmospheric pressure. To our knowledge, no data for PTFE have been reported in the literature. The species composition and thermodynamic properties are numerically determined using the two-temperature Saha equation and the Guldberg-Waage equation according to van de Sanden et al’s derivation. The transport coefficients, including viscosity, thermal conductivity and electrical conductivity, are calculated with the most recent collision interaction potentials using Devoto’s electron and heavy-particle decoupling approach but expanded to the third-order approximation (second-order for viscosity) in the frame of the Chapman-Enskog method. Results are computed for different degrees of thermal non-equilibrium, i.e. the ratio of electron to heavy-particle temperatures, from 1 to 10, with electron temperature ranging from 300 to 40 000 K. Plasma transport properties in the LTE state obtained from the present work are compared with existing published results and the causes for the discrepancy analyzed. The two-temperature plasma properties calculated in the present work enable the modeling of wall ablation-controlled plasma processes.

  12. Thermodynamic properties and transport coefficients of a two-temperature polytetrafluoroethylene vapor plasma for ablation-controlled discharge applications

    International Nuclear Information System (INIS)

    Wang, Haiyan; Qi, Haiyang; Wang, Weizong; Yan, Joseph D; Geng, Jinyue; Wu, Yaowu

    2017-01-01

    Ablation-controlled plasmas have been used in a range of technical applications where local thermodynamic equilibrium (LTE) is often violated near the wall due to the strong cooling effect caused by the ablation of wall materials. The thermodynamic and transport properties of ablated polytetrafluoroethylene (PTFE) vapor, which determine the flowing plasma behavior in such applications, are calculated based on a two-temperature model at atmospheric pressure. To our knowledge, no data for PTFE have been reported in the literature. The species composition and thermodynamic properties are numerically determined using the two-temperature Saha equation and the Guldberg–Waage equation according to van de Sanden et al ’s derivation. The transport coefficients, including viscosity, thermal conductivity and electrical conductivity, are calculated with the most recent collision interaction potentials using Devoto’s electron and heavy-particle decoupling approach but expanded to the third-order approximation (second-order for viscosity) in the frame of the Chapman–Enskog method. Results are computed for different degrees of thermal non-equilibrium, i.e. the ratio of electron to heavy-particle temperatures, from 1 to 10, with electron temperature ranging from 300 to 40 000 K. Plasma transport properties in the LTE state obtained from the present work are compared with existing published results and the causes for the discrepancy analyzed. The two-temperature plasma properties calculated in the present work enable the modeling of wall ablation-controlled plasma processes. (paper)

  13. Phase equilibrium data and thermodynamic modeling of the system (CO{sub 2} + biodiesel + methanol) at high pressures

    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.

  14. Application of exergy as thermodynamic indicator in ecology

    International Nuclear Information System (INIS)

    Jorgensen, S.E.; Nors Nielsen, Soren

    2007-01-01

    We introduce a modified form of exergy named eco-exergy as an ecological indicator. Exergy of detritus and of various organisms are found based upon the definition of eco-exergy. Eco-exergy measures a system's deviation from chemical equilibrium. It is, therefore, crucial to find the concentration of detritus and the various organisms at chemical equilibrium which is possible by the calculation of the probability to form detritus and the various organisms by chemical equilibrium. It implies that the probability to form proteins with the right amino acid sequence must be determined by the use of the amount of coding genes. It is stressed that what we determine by this method of exergy calculation is a relative eco-exergy index. It is not possible to find the eco-exergy of entire ecosystems, because they are far too complex to allow us to know all the details of an ecosystem. The eco-exergy indices have been found in a few cases to demonstrate the usefulness of the method and to show how the exergy indices can be translated to applicable ecological information

  15. Extended Irreversible Thermodynamics

    CERN Document Server

    Jou, David

    2010-01-01

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

  16. Eggshell Powder as an Adsorbent for Removal of Fluoride from Aqueous Solution: Equilibrium, Kinetic and Thermodynamic Studies

    Directory of Open Access Journals (Sweden)

    R. Bhaumik

    2012-01-01

    Full Text Available A new medium, eggshell powder has been developed for fluoride removal from aqueous solution. Fluoride adsorption was studied in a batch system where adsorption was found to be pH dependent with maximum removal efficiency at 6.0. The experimental data was more satisfactorily fitted with Langmuir isotherm model. The kinetics and the factor controlling adsorption process fully accepted by pseudo-second-order model were also discussed. Ea was found to be 45.98 kJmol-1 by using Arrhenius equation, indicating chemisorption nature of fluoride onto eggshell powder. Thermodynamic study showed spontaneous nature and feasibility of the adsorption process with negative enthalpy (∆H0 value also supported the exothermic nature. Batch experiments were performed to study the applicability of the adsorbent by using fluoride contaminated water collected from affected areas. These results indicate that eggshell powder can be used as an effective, low-cost adsorbent to remove fluoride from aqueous solution as well as groundwater.

  17. Enhancing adsorption capacity of toxic malachite green dye through chemically modified breadnut peel: equilibrium, thermodynamics, kinetics and regeneration studies.

    Science.gov (United States)

    Chieng, Hei Ing; Lim, Linda B L; Priyantha, Namal

    2015-01-01

    Breadnut skin, in both its unmodified (KS) and base-modified (BM-KS) forms, was investigated for its potential use as a low-cost adsorbent for the removal of toxic dye, malachite green (MG). Characterization of the adsorbents was carried out using scanning electron microscope, X-ray fluorescence and Fourier transform infra-red spectroscopy. Batch adsorption experiments, carried out under optimized conditions, for the adsorption of MG were fitted using five isotherm models (Langmuir, Freundlich, Dubinin-Radushkevich, Temkin and Sips) and six error functions to determine the best-fit model. The adsorption capacity was greatly enhanced when breadnut skin was chemically modified with NaOH, leading to an adsorption capacity of 353.0 mg g(-1), that was far superior to most reported adsorbents for the removal of MG. Thermodynamics studies indicated that the adsorption of MG was spontaneous on KS and BM-KS, and the reactions were endothermic and exothermic, respectively. Kinetics studies showed that both followed the pseudo-second order. Regeneration experiments on BM-KS indicated that its adsorption capacity was still maintained at>90% even after five cycles. It can be concluded that NaOH-modified breadfruit skin has great potential to be utilized in real-life application as a low-cost adsorbent for the removal of MG in wastewater treatment.

  18. Green Synthesis of Zinc Oxide Nanoparticles for Enhanced Adsorption of Lead Ions from Aqueous Solutions: Equilibrium, Kinetic and Thermodynamic Studies

    Directory of Open Access Journals (Sweden)

    Susan Azizi

    2017-06-01

    Full Text Available In the present study, ZnO nanoparticles (NPs were synthesized in zerumbone solution by a green approach and appraised for their ability to absorb Pb(II ions from aqueous solution. The formation of as-synthesized NPs was established by X-ray diffraction (XRD, Transmission Electron Microscopy (TEM, and UV–visible studies. The XRD and TEM analyses revealed high purity and wurtzite hexagonal structure of ZnO NPs with a mean size of 10.01 ± 2.6 nm. Batch experiments were performed to investigate the impact of process parameters viz. Pb(II concentration, pH of solution, adsorbent mass, solution temperature, and contact time variations on the removal efficiency of Pb(II. The adsorption isotherm data provided that the adsorption process was mainly monolayer on ZnO NPs. The adsorption process follows pseudo-second-order reaction kinetic. The maximum removal efficiencies were 93% at pH 5. Thermodynamic parameters such as enthalpy change (ΔH0, free energy change (ΔG0, and entropy change (ΔS0 were calculated; the adsorption process was spontaneous and endothermic. The good efficiency of the as-synthesized NPs makes them attractive for applications in water treatment, for removal of heavy metals from aqueous system.

  19. Application of Enzyme Coupling Reactions to Shift Thermodynamically Limited Biocatalytic Reactions

    DEFF Research Database (Denmark)

    Abu, Rohana; Woodley, John M.

    2015-01-01

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

  20. DISCRETE FIXED POINT THEOREMS AND THEIR APPLICATION TO NASH EQUILIBRIUM

    OpenAIRE

    Sato, Junichi; Kawasaki, Hidefumi

    2007-01-01

    Fixed point theorems are powerful tools in not only mathematics but also economic. In some economic problems, we need not real-valued but integer-valued equilibriums. However, classical fixed point theorems guarantee only real-valued equilibria. So we need discrete fixed point theorems in order to get discrete equilibria. In this paper, we first provide discrete fixed point theorems, next apply them to a non-cooperative game and prove the existence of a Nash equilibrium of pure strategies.

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

    Science.gov (United States)

    Grossman, B.; Cinella, P.

    1988-01-01

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

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

    International Nuclear Information System (INIS)

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

    1999-04-01

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

  3. Equilibrium Crystal Shape of BaZrO{sub 3} and Space Charge Formation in the (011) Surface by Using Ab-Initio Thermodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Ji-Su; Kim, Yeong-Cheol [Korea University of Technology and Education, Cheonan (Korea, Republic of)

    2017-01-15

    We investigated the equilibrium crystal shape of BaZrO{sub 3} and the space charge formation in an O-terminated (011) surface by using ab-initio thermodynamics. Twenty-two low-indexed (001), (011), and (111) surfaces were calculated to analyze their surface Gibbs-free energy under the stable condition of BaZrO{sub 3}. Based on the Gibbs-Wulff theorem, the equilibrium crystal shape of BaZrO{sub 3} changed from cubic to decaoctahedral with decreasing Ba chemical potential. The dominant facets of BaZrO{sub 3} were {001} and {011}, which were well consistent with experimental observations. The space charge formation in the (011) surface was evaluated using the space-charge model. We found that the (011) surface was even more resistive than the (001) surface.

  4. Departures from local thermodynamic equilibrium in cutting arc plasmas derived from electron and gas density measurements using a two-wavelength quantitative Schlieren technique

    International Nuclear Information System (INIS)

    Prevosto, L.; Mancinelli, B.; Artana, G.; Kelly, H.

    2011-01-01

    A two-wavelength quantitative Schlieren technique that allows inferring the electron and gas densities of axisymmetric arc plasmas without imposing any assumption regarding statistical equilibrium models is reported. This technique was applied to the study of local thermodynamic equilibrium (LTE) departures within the core of a 30 A high-energy density cutting arc. In order to derive the electron and heavy particle temperatures from the inferred density profiles, a generalized two-temperature Saha equation together with the plasma equation of state and the quasineutrality condition were employed. Factors such as arc fluctuations that influence the accuracy of the measurements and the validity of the assumptions used to derive the plasma species temperature were considered. Significant deviations from chemical equilibrium as well as kinetic equilibrium were found at elevated electron temperatures and gas densities toward the arc core edge. An electron temperature profile nearly constant through the arc core with a value of about 14000-15000 K, well decoupled from the heavy particle temperature of about 1500 K at the arc core edge, was inferred.

  5. Thermodynamical Description of Running Discontinuities: Application to Friction and Wear

    Directory of Open Access Journals (Sweden)

    Claude Stolz

    2010-06-01

    Full Text Available The friction and wear phenomena appear due to contact and relative motion between two solids. The evolution of contact conditions depends on loading conditions and mechanical behaviours. The wear phenomena are essentially characterized by a matter loss. Wear and friction are in interaction due to the fact that particles are detached from the solids. A complex medium appears as an interface having a strong effect on the friction condition. The purpose of this paper is to describe such phenomena taking account of different scales of modelization in order to derive some macroscopic laws. A thermodynamical approach is proposed and models of wear are analysed in this framework where the separation between the dissipation due to friction and that due to wear is made. Applications on different cases are presented.

  6. The rational expectations equilibrium inventory model theory and applications

    CERN Document Server

    1989-01-01

    This volume consists of six essays that develop and/or apply "rational expectations equilibrium inventory models" to study the time series behavior of production, sales, prices, and inventories at the industry level. By "rational expectations equilibrium inventory model" I mean the extension of the inventory model of Holt, Modigliani, Muth, and Simon (1960) to account for: (i) discounting, (ii) infinite horizon planning, (iii) observed and unobserved by the "econometrician" stochastic shocks in the production, factor adjustment, storage, and backorders management processes of firms, as well as in the demand they face for their products; and (iv) rational expectations. As is well known according to the Holt et al. model firms hold inventories in order to: (a) smooth production, (b) smooth production changes, and (c) avoid stockouts. Following the work of Zabel (1972), Maccini (1976), Reagan (1982), and Reagan and Weitzman (1982), Blinder (1982) laid the foundations of the rational expectations equilibrium inve...

  7. Applications of non-equilibrium plasma in chemical processes

    International Nuclear Information System (INIS)

    Patino, P.; Castro, A.

    2003-01-01

    By means of optical emission spectroscopy the population of O( 3 P) in a non-equilibrium, high voltage, oxygen plasma, and O( 3 P), H and OH in another of steam in radio frequency, have been followed. Reactions of both plasmas with liquid hydrocarbons have produced oxidation and/or hydrogenation, depending on the conditions of each one. (Author)

  8. Application of frequency spectrum analysis in the rotator moving equilibrium

    International Nuclear Information System (INIS)

    Liu Ruilan; Su Guanghui; Shang Zhi; Jia Dounan

    2001-01-01

    The experimental equipment is developed to simulate the rotator vibration. The running state of machine is simulated by using different running conditions. The vibration caused by non-equilibrium mass is analyzed and discussed for first order with focus load. The effective method is found out by using frequency spectrum analysis

  9. A New Multimedia Application for Teaching and Learning Chemical Equilibrium

    Science.gov (United States)

    Ollino, Mario; Aldoney, Jenny; Domínguez, Ana M.; Merino, Cristian

    2018-01-01

    This study presents a method for teaching the subject of chemical equilibrium in which students engage in self-learning mediated by the use of a new multimedia animation (SEQ-alfa©). This method is presented together with evidence supporting its advantages. At a microscopic level, the simulator shows the mutual transformation of A molecules into B…

  10. Modified NASA-Lewis chemical equilibrium code for MHD applications

    Science.gov (United States)

    Sacks, R. A.; Geyer, H. K.; Grammel, S. J.; Doss, E. D.

    1979-01-01

    A substantially modified version of the NASA-Lewis Chemical Equilibrium Code was recently developed. The modifications were designed to extend the power and convenience of the Code as a tool for performing combustor analysis for MHD systems studies. The effect of the programming details is described from a user point of view.

  11. The physical basis of thermodynamics with applications to chemistry

    CERN Document Server

    Richet, Pascal

    2001-01-01

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

  12. UAV applications for thermodynamic profiling: Emphasis on ice fog research

    Science.gov (United States)

    Gultepe, Ismail; Heymsfield, Andrew J.; Fernando, Harindra J. S.; Hoch, Sebastian W.; Ware, Randolph

    2016-04-01

    Ice fog occurs often over the Arctic, cold climatic, and mountainous regions for about 30% of time where temperature (T) can go down to -10°C or below. Ice Nucleation (IN) and cooling processes play an important role by the controlling the intensity of ice fog conditions that affect aviation application, transportation, and local climate. Ice fog can also occur at T above -10°C but close to 0°C it occurs due to freezing of supercooled droplets that include an IN. To better document ice fog conditions, observations from the ice fog events of the Indirect and Semi-Direct Aerosol effects on Climate (ISDAC) project, Barrow, Alaska, Fog Remote Sensing And Modeling (FRAM) project Yellowknife, Northwest Territories, and the Mountain Terrain Atmospheric Modeling and Observations (MATERHORN) project, Heber City, Utah, were analyzed.. Measurements difficulties of small ice fog particles at cold temperatures and low-level flying restrictions prevent observations from aircraft within the surface boundary layer. However, unmanned Aerial Vehicles (UAVs) can be operated safely to measure IN number concentration, Relative Humidity with respect to ice (RHi), T, horizontal wind speed (Uh) and direction, and ice crystal spectra less than about 500 micron. Thermodynamic profiling by a Radiometrics Profiling Microwave Radiometer (PMWR) and Vaisala CL51 ceilometer was used to describe ice fog conditions in the vertical and its time development. In this presentation, ice fog characteristics and its thermodynamic environment will be presented using both ground-based and airborne platforms such as a UAV with new sensors. Some examples of measurements from the UAV for future research, and challenges related to both ice fog measurements and visibility parameterization will also be presented.

  13. A sub-grid, mixture-fraction-based thermodynamic equilibrium model for gas phase combustion in FIRETEC: development and results

    Science.gov (United States)

    M. M. Clark; T. H. Fletcher; R. R. Linn

    2010-01-01

    The chemical processes of gas phase combustion in wildland fires are complex and occur at length-scales that are not resolved in computational fluid dynamics (CFD) models of landscape-scale wildland fire. A new approach for modelling fire chemistry in HIGRAD/FIRETEC (a landscape-scale CFD wildfire model) applies a mixture– fraction model relying on thermodynamic...

  14. An Introduction to Equilibrium Thermodynamics. A Rational Approach to Its Teaching. Part 2: Internal Energy, Entropy, and Temperature.

    Science.gov (United States)

    Williams, Donald F.; Glasser, David

    1991-01-01

    An approach that may be used to introduce the fundamental ideas of thermodynamics using a mathematical background with the knowledge of the behavior of matter is described. The physical background, conservation of energy, predicting the behavior of a system, and solving problems are topics of discussion. (KR)

  15. Non-equilibrium statistical physics with application to disordered systems

    CERN Document Server

    Cáceres, Manuel Osvaldo

    2017-01-01

    This textbook is the result of the enhancement of several courses on non-equilibrium statistics, stochastic processes, stochastic differential equations, anomalous diffusion and disorder. The target audience includes students of physics, mathematics, biology, chemistry, and engineering at undergraduate and graduate level with a grasp of the basic elements of mathematics and physics of the fourth year of a typical undergraduate course. The little-known physical and mathematical concepts are described in sections and specific exercises throughout the text, as well as in appendices. Physical-mathematical motivation is the main driving force for the development of this text. It presents the academic topics of probability theory and stochastic processes as well as new educational aspects in the presentation of non-equilibrium statistical theory and stochastic differential equations.. In particular it discusses the problem of irreversibility in that context and the dynamics of Fokker-Planck. An introduction on fluc...

  16. Thermodynamics of binary mixtures of N-methyl-2-pyrrolidinone and ketone. Experimental results and modelling of the (solid + liquid) equilibrium and the (vapour + liquid) equilibrium. The modified UNIFAC (Do) model characterization

    International Nuclear Information System (INIS)

    Domanska, Urszula; Lachwa, Joanna

    2005-01-01

    The (solid + liquid) equilibrium (SLE) of eight binary systems containing N-methyl-2-pyrrolidinone (NMP) with (2-propanone, or 2-butanone, or 2-pentanone, or 3-pentanone, or cyclopentanone, or 2-hexanone, or 4-methyl-2-pentanone, or 3-heptanone) were carried out by using a dynamic method from T = 200 K to the melting point of the NMP. The isothermal (vapour + liquid) equilibrium data (VLE) have been measured for three binary mixtures of NMP with 2-propanone, 3-pentanone and 2-hexanone at pressure range from p = 0 kPa to p = 115 kPa. Data were obtained at the temperature T = 333.15 K for the first system and at T = 373.15 K for the second two systems. The experimental results of SLE have been correlated using the binary parameters Wilson, UNIQUAC ASM and two modified NRTL equations. The root-mean-square deviations of the solubility temperatures for all the calculated values vary from (0.32 K to 0.68 K) and depend on the particular equation used. The data of VLE were correlated with one to three parameters in the Redlich-Kister expansion. Binary mixtures of NMP with (2-propanone, or 2-butanone, or 2-pentanone, or 3-pentanone, or cyclopentanone, or 2-hexanone, or 4-methyl-2-pentanone, or 3-heptanone) have been investigated in the framework of the modified UNIFAC (Do) model. The reported new interaction parameters for NMP-group (c-CONCH 3 ) and carbonyl group ( C=O) let the model consistently described a set of thermodynamic properties, including (solid + liquid) equilibrium (vapour + liquid) equilibrium, excess Gibbs energy and molar excess enthalpies of mixing. Our experimental and literature data of binary mixtures containing NMP and ketones were compared with the results of prediction with the modified UNIFAC (Do) model

  17. Contact symmetries and Hamiltonian thermodynamics

    International Nuclear Information System (INIS)

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

    2015-01-01

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

  18. REMOVAL OF AN ACID DYE FROM AQUEOUS SOLUTIONS BY ADSORPTION ON A COMMERCIAL GRANULAR ACTIVATED CARBON: EQUILIBRIUM, KINETIC AND THERMODYNAMIC STUDY

    Directory of Open Access Journals (Sweden)

    Marius Sebastian Secula

    2011-12-01

    Full Text Available The present paper approaches the study of the adsorption of an acid dye on a commercial granular activated carbon (GAC. Batch experiments were conducted to study the equilibrium isotherms and kinetics of Indigo Carmine on GAC. The kinetic data were analyzed using the Lagargren, Ho, Elovich, Weber-Morris and Bangham models in order to establish the most adequate model that describes this process, and to investigate the rate of IC adsorption. Equilibrium data were fitted to Langmuir and Freundlich isotherms. Langmuir isotherm equilibrium model and Ho kinetic model fitted best the experimental data.The effects of temperature (25 – 45 °C, initial concentration of dye (7.5 – 150 mg•L−1, GAC dose (0.02 – 1 g•L-1, particle size (2 – 7 mm in diameter, solution pH (3 – 11 on GAC adsorption capacity were established. The adsorption process is found to be favored by a neutral pH, high values of temperature and small particle sizes. The highest adsorption capacity (133.8 mg•g-1 of the GAC is obtained at 45 °C. The removal efficiency increases with GAC dose at relatively low initial concentrations of dye. Thermodynamic parameters such as standard enthalpy (H, standard entropy (S and standard free energy (G were evaluated. The adsorption of Indigo Carmine onto GAC is an endothermic process.

  19. Le Chatelier Principle for Out-of-Equilibrium and Boundary-Driven Systems: Application to Dynamical Phase Transitions

    Science.gov (United States)

    Shpielberg, O.; Akkermans, E.

    2016-06-01

    A stability analysis is presented for boundary-driven and out-of-equilibrium systems in the framework of the hydrodynamic macroscopic fluctuation theory. A Hamiltonian description is proposed which allows us to thermodynamically interpret the additivity principle. A necessary and sufficient condition for the validity of the additivity principle is obtained as an extension of the Le Chatelier principle. These stability conditions result from a diagonal quadratic form obtained using the cumulant generating function. This approach allows us to provide a proof for the stability of the weakly asymmetric exclusion process and to reduce the search for stability to the solution of two coupled linear ordinary differential equations instead of nonlinear partial differential equations. Additional potential applications of these results are discussed in the realm of classical and quantum systems.

  20. Le Chatelier Principle for Out-of-Equilibrium and Boundary-Driven Systems: Application to Dynamical Phase Transitions.

    Science.gov (United States)

    Shpielberg, O; Akkermans, E

    2016-06-17

    A stability analysis is presented for boundary-driven and out-of-equilibrium systems in the framework of the hydrodynamic macroscopic fluctuation theory. A Hamiltonian description is proposed which allows us to thermodynamically interpret the additivity principle. A necessary and sufficient condition for the validity of the additivity principle is obtained as an extension of the Le Chatelier principle. These stability conditions result from a diagonal quadratic form obtained using the cumulant generating function. This approach allows us to provide a proof for the stability of the weakly asymmetric exclusion process and to reduce the search for stability to the solution of two coupled linear ordinary differential equations instead of nonlinear partial differential equations. Additional potential applications of these results are discussed in the realm of classical and quantum systems.

  1. Entransy loss in thermodynamic processes and its application

    International Nuclear Information System (INIS)

    Cheng, Xuetao; Liang, Xingang

    2012-01-01

    The entransy theory has been developed for heat transfer optimization. This paper extends it to optimize thermodynamic processes. The entransy balance equation of thermodynamic processes is introduced, with which the concept of entransy loss is developed. For the Carnot cycle and the irreversible thermodynamic processes where the working fluid is heated by the streams with prescribed inlet temperatures and specific capacity flow rates, we find that the maximum entransy loss leads to the maximum output work, which is the maximum principle of entransy loss in thermodynamic processes. However, the entropy generation cannot describe the change of the output work for the Carnot cycle. Therefore, the concept of entransy loss could describe the performance of thermodynamic processes. Then, the principle is used to optimize the thermodynamic processes of heat exchanger groups and the design of the irreversible Brayton cycle. For these problems, the operation parameters are optimized to get the maximum output work by calculating the maximum entransy loss when the entransy loss induced by dumping the used streams into the environment is considered. The analysis of the air conditioning system for room heating with heat–work conversion processes demonstrates the entransy loss has a direct relation with the input heat. -- Highlights: ► The entransy balance equation of thermodynamic processes is introduced. ► The concept of entransy loss is developed. ► The maximum entransy loss corresponds to the maximum output work. ► Examples show that entransy loss can be used to optimize heat–work conversion.

  2. Thermodynamic modelling of phase equilibrium in system Ti-B-Si-C, synthesis and phases composition of borides and carbides layers on titanic alloyVT-1 at electron beam treatment in vacuum

    Science.gov (United States)

    Smirnyagina, N. N.; Khaltanova, V. M.; Lapina, A. E.; Dasheev, D. E.

    2017-01-01

    Composite layers on the basis of carbides and borides the titan and silicon on titanic alloy VT-1 are generated at diffused saturation in vacuum. Formation in a composite of MAX phase Ti3SiC2 is shown. Thermodynamic research of phase equilibrium in systems Ti-Si-C and Ti-B-C in the conditions of high vacuum is executed. The thermodynamics, formation mechanisms of superfirm layers borides and carbides of the titan and silicon are investigated.

  3. A Virtual Mixture Approach to the Study of Multistate Equilibrium: Application to Constant pH Simulation in Explicit Water

    Science.gov (United States)

    Wu, Xiongwu; Brooks, Bernard R.

    2015-01-01

    Chemical and thermodynamic equilibrium of multiple states is a fundamental phenomenon in biology systems and has been the focus of many experimental and computational studies. This work presents a simulation method to directly study the equilibrium of multiple states. This method constructs a virtual mixture of multiple states (VMMS) to sample the conformational space of all chemical states simultaneously. The VMMS system consists of multiple subsystems, one for each state. The subsystem contains a solute and a solvent environment. The solute molecules in all subsystems share the same conformation but have their own solvent environments. Transition between states is implicated by the change of their molar fractions. Simulation of a VMMS system allows efficient calculation of relative free energies of all states, which in turn determine their equilibrium molar fractions. For systems with a large number of state transition sites, an implicit site approximation is introduced to minimize the cost of simulation. A direct application of the VMMS method is for constant pH simulation to study protonation equilibrium. Applying the VMMS method to a heptapeptide of 3 ionizable residues, we calculated the pKas of those residues both with all explicit states and with implicit sites and obtained consistent results. For mouse epidermal growth factor of 9 ionizable groups, our VMMS simulations with implicit sites produced pKas of all 9 ionizable groups and the results agree qualitatively with NMR measurement. This example demonstrates the VMMS method can be applied to systems of a large number of ionizable groups and the computational cost scales linearly with the number of ionizable groups. For one of the most challenging systems in constant pH calculation, SNase Δ+PHS/V66K, our VMMS simulation shows that it is the state-dependent water penetration that causes the large deviation in lysine66’s pKa. PMID:26506245

  4. A Virtual Mixture Approach to the Study of Multistate Equilibrium: Application to Constant pH Simulation in Explicit Water.

    Directory of Open Access Journals (Sweden)

    Xiongwu Wu

    2015-10-01

    Full Text Available Chemical and thermodynamic equilibrium of multiple states is a fundamental phenomenon in biology systems and has been the focus of many experimental and computational studies. This work presents a simulation method to directly study the equilibrium of multiple states. This method constructs a virtual mixture of multiple states (VMMS to sample the conformational space of all chemical states simultaneously. The VMMS system consists of multiple subsystems, one for each state. The subsystem contains a solute and a solvent environment. The solute molecules in all subsystems share the same conformation but have their own solvent environments. Transition between states is implicated by the change of their molar fractions. Simulation of a VMMS system allows efficient calculation of relative free energies of all states, which in turn determine their equilibrium molar fractions. For systems with a large number of state transition sites, an implicit site approximation is introduced to minimize the cost of simulation. A direct application of the VMMS method is for constant pH simulation to study protonation equilibrium. Applying the VMMS method to a heptapeptide of 3 ionizable residues, we calculated the pKas of those residues both with all explicit states and with implicit sites and obtained consistent results. For mouse epidermal growth factor of 9 ionizable groups, our VMMS simulations with implicit sites produced pKas of all 9 ionizable groups and the results agree qualitatively with NMR measurement. This example demonstrates the VMMS method can be applied to systems of a large number of ionizable groups and the computational cost scales linearly with the number of ionizable groups. For one of the most challenging systems in constant pH calculation, SNase Δ+PHS/V66K, our VMMS simulation shows that it is the state-dependent water penetration that causes the large deviation in lysine66's pKa.

  5. A Virtual Mixture Approach to the Study of Multistate Equilibrium: Application to Constant pH Simulation in Explicit Water.

    Science.gov (United States)

    Wu, Xiongwu; Brooks, Bernard R

    2015-10-01

    Chemical and thermodynamic equilibrium of multiple states is a fundamental phenomenon in biology systems and has been the focus of many experimental and computational studies. This work presents a simulation method to directly study the equilibrium of multiple states. This method constructs a virtual mixture of multiple states (VMMS) to sample the conformational space of all chemical states simultaneously. The VMMS system consists of multiple subsystems, one for each state. The subsystem contains a solute and a solvent environment. The solute molecules in all subsystems share the same conformation but have their own solvent environments. Transition between states is implicated by the change of their molar fractions. Simulation of a VMMS system allows efficient calculation of relative free energies of all states, which in turn determine their equilibrium molar fractions. For systems with a large number of state transition sites, an implicit site approximation is introduced to minimize the cost of simulation. A direct application of the VMMS method is for constant pH simulation to study protonation equilibrium. Applying the VMMS method to a heptapeptide of 3 ionizable residues, we calculated the pKas of those residues both with all explicit states and with implicit sites and obtained consistent results. For mouse epidermal growth factor of 9 ionizable groups, our VMMS simulations with implicit sites produced pKas of all 9 ionizable groups and the results agree qualitatively with NMR measurement. This example demonstrates the VMMS method can be applied to systems of a large number of ionizable groups and the computational cost scales linearly with the number of ionizable groups. For one of the most challenging systems in constant pH calculation, SNase Δ+PHS/V66K, our VMMS simulation shows that it is the state-dependent water penetration that causes the large deviation in lysine66's pKa.

  6. Thermodynamic properties for applications in chemical industry via classical force fields.

    Science.gov (United States)

    Guevara-Carrion, Gabriela; Hasse, Hans; Vrabec, Jadran

    2012-01-01

    Thermodynamic properties of fluids are of key importance for the chemical industry. Presently, the fluid property models used in process design and optimization are mostly equations of state or G (E) models, which are parameterized using experimental data. Molecular modeling and simulation based on classical force fields is a promising alternative route, which in many cases reasonably complements the well established methods. This chapter gives an introduction to the state-of-the-art in this field regarding molecular models, simulation methods, and tools. Attention is given to the way modeling and simulation on the scale of molecular force fields interact with other scales, which is mainly by parameter inheritance. Parameters for molecular force fields are determined both bottom-up from quantum chemistry and top-down from experimental data. Commonly used functional forms for describing the intra- and intermolecular interactions are presented. Several approaches for ab initio to empirical force field parameterization are discussed. Some transferable force field families, which are frequently used in chemical engineering applications, are described. Furthermore, some examples of force fields that were parameterized for specific molecules are given. Molecular dynamics and Monte Carlo methods for the calculation of transport properties and vapor-liquid equilibria are introduced. Two case studies are presented. First, using liquid ammonia as an example, the capabilities of semi-empirical force fields, parameterized on the basis of quantum chemical information and experimental data, are discussed with respect to thermodynamic properties that are relevant for the chemical industry. Second, the ability of molecular simulation methods to describe accurately vapor-liquid equilibrium properties of binary mixtures containing CO(2) is shown.

  7. Experimental measurement of phase equilibrium for gas hydrates of refrigerants, and thermodynamic modeling by SRK, VPT and CPA EOSs

    International Nuclear Information System (INIS)

    Karamoddin, Maryam; Varaminian, Farshad

    2013-01-01

    Highlights: • Three-phase equilibrium data, (VL W H), were measured for HCFC22 and HFC134a hydrates. • The pressures were evaluated by simple EoSs (modified mixing rule) and CPA EOS. • The Kihara potential parameters were obtained by optimizing scheme for refrigerants. -- Abstract: In this study, three-phase equilibrium conditions of hydrate-liquid–vapor, (VL W H), were experimentally determined for chlorodifluoromethane and 1,1,1,2-tetrafluoroethane gas hydrates at temperatures ranging from (278 to 290) K and (280 to 285) K respectively, at pressures ranging from (0.2 to 0.8) MPa. Then the different models were presented for estimating of the hydrate dissociation conditions of chlorodifluoromethane, 1,1,1,2-tetrafluoroethane and 1,1-difluoroethane refrigerants. The cubic simple equations of state (SRK and VPT) and the cubic plus association equation of state (CPA) were employed for modeling the vapor and liquid phases, also van der Waals–Platteeuw statistical model was used for the solid hydrate phase. In this paper, the binary interaction parameters of classic and modified mixing rules were optimized by using two-phase equilibrium data (VL W H). The Kihara potential parameters in each refrigerant were estimated using obtained experimental equilibrium data (VL W H) and based on the optimization scheme by the Nelder Mead optimization method. The agreement between the experimental and the predicted pressure is acceptable by using these models. The average deviation of models for chlorodifluoromethane, 1,1,1,2-tetrafluoroethane, and 1,1-difluoroethane hydrates is about 3%, 4.3%, and 3.6%, respectively

  8. Thermodynamic and Quantum Thermodynamic Analyses of Brownian Movement

    OpenAIRE

    Gyftopoulos, Elias P.

    2006-01-01

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

  9. Removal of Direct Red 12B by garlic peel as a cheap adsorbent: Kinetics, thermodynamic and equilibrium isotherms study of removal

    Science.gov (United States)

    Asfaram, A.; Fathi, M. R.; Khodadoust, S.; Naraki, M.

    2014-06-01

    The removal of dyes from industrial waste is very important from health and hygiene point of view and for environmental protection. In this work, efficiency and performance of garlic peel (GP) adsorbent for the removal of Direct Red 12B (DR12B) from wastewater was investigated. The influence of variables including pH, concentration of the dye and amount of adsorbent, particle size, contact time and temperature on the dye removal has been investigated. It was observed that the pseudo-second-order kinetic model fits better with good correlation coefficient and the equilibrium data fitted well with the Langmuir model. More than 99% removal efficiency was obtained within 25 min at adsorbent dose of 0.2 g per 50 ml for initial dye concentration of 50 mg L-1. Calculation of various thermodynamic parameters such as, Gibb's free energy, entropy and enthalpy of the on-going adsorption process indicate feasibility and endothermic nature of DR12B adsorption.

  10. Equilibrium, thermodynamic and kinetic studies for the biosorption of aqueous lead(II), cadmium(II) and nickel(II) ions on Spirulina platensis

    Energy Technology Data Exchange (ETDEWEB)

    Seker, Ayseguel [Department of Chemistry, Izmir Institute of Technology, Urla 35430, Izmir (Turkey)], E-mail: aysegulseker@iyte.edu.tr; Shahwan, Talal [Department of Chemistry, Izmir Institute of Technology, Urla 35430, Izmir (Turkey)], E-mail: talalshahwan@iyte.edu.tr; Eroglu, Ahmet E. [Department of Chemistry, Izmir Institute of Technology, Urla 35430, Izmir (Turkey)], E-mail: ahmeteroglu@iyte.edu.tr; Yilmaz, Sinan [Department of Chemistry, Izmir Institute of Technology, Urla 35430, Izmir (Turkey)], E-mail: sinanyilmaz@iyte.edu.tr; Demirel, Zeliha [Department of Biology, Ege University, Bornova 35100, Izmir (Turkey)], E-mail: zelihademirel@gmail.com; Dalay, Meltem Conk [Department of Bioengineering, Ege University, Bornova 35100, Izmir (Turkey)], E-mail: meltemconkdalay@gmail.com

    2008-06-15

    The biosorption of lead(II), cadmium(II) and nickel(II) ions from aqueous solution by Spirulina platensis was studied as a function of time, concentration, temperature, repetitive reactivity, and ionic competition. The kinetic results obeyed well the pseudo second-order model. Freundlich, Dubinin Radushkevich and Temkin isotherm models were applied in describing the equilibrium partition of the ions. Freundlich isotherm was applied to describe the design of a single-stage batch sorption system. According to the thermodynamic parameters such as {delta}G{sup o}, {delta}H{sup o}and {delta}S{sup o} calculated, the sorption process was endothermic and largely driven towards the products. Sorption activities in a three metal ion system were studied which indicated that there is a relative selectivity of the biosorbent towards Pb{sup 2+} ions. The measurements of the repetitive reusability of S. platensis indicated a large capacity towards the three metal ions.

  11. Equilibrium thermodynamics of the partitioning of non-steroidal anti-inflammatory drugs into human erythrocyte ghost membranes

    International Nuclear Information System (INIS)

    Omran, Ahmed A.

    2013-01-01

    Graphical abstract: Bar diagram representing thermodynamic parameters obtained for the partitioning of NSAIDs into human erythrocyte ghost membranes at physiological pH; 7.4. Highlights: • Partition coefficients of NSAIDs into HEG membranes were determined. • Thermodynamic parameters were evaluated and successfully analyzed. • Partitioning of NSAIDs into HEG membranes was exothermic. • Partitioning of NSAIDs into HEG is spontaneous with negative free energy values. • Identical partitioning enthalpy–entropy driven compensation mechanism was shown. -- Abstract: In this work,second derivative spectrophotometry was applied for determining the partition coefficients (K p s) of four non-steroidal anti-inflammatory drugs (NSAIDs; flufenamic, meclofenamic, mefenamic and niflumic acids) into human erythrocyte ghost (HEG) membranes over a temperature range from (283.2 to 313.2) K. The proposed method allowed the evaluation and direct analyses of thermodynamic parameters; enthalpy (ΔH W→M ), Gibbs energy (ΔG W→M ) and entropy (ΔS W→M ) changes of the partitioning of NSAIDs into HEG membranes. The partitioning of NSAIDs between polar aqueous phase and non-polar lipid bilayer HEG membrane phase was exothermic with negative (ΔH W→M ) which compensated for the changes in (ΔS W→M ). The negative values of (ΔG W→M ) revealed that the partitioning of NSAIDs into HEG, owing to their transfer from polar aqueous phase and non-polar HEG phase is spontaneous. The enthalpy–entropy correlation analysis resulted in a good linearity that suggests an identical partitioning enthalpy–entropy driven compensation mechanism for the studied NSAIDs

  12. Molecular-Level Thermodynamic Switch Controls Chemical Equilibrium in Sequence-Specific Hydrophobic Interaction of 35 Dipeptide Pairs

    OpenAIRE

    Chun, Paul W.

    2003-01-01

    Applying the Planck-Benzinger methodology, the sequence-specific hydrophobic interactions of 35 dipeptide pairs were examined over a temperature range of 273–333 K, based on data reported by Nemethy and Scheraga in 1962. The hydrophobic interaction in these sequence-specific dipeptide pairs is highly similar in its thermodynamic behavior to that of other biological systems. The results imply that the negative Gibbs free energy change minimum at a well-defined stable temperature, 〈Ts〉, where t...

  13. Thermodynamics of Radiation Modes

    Science.gov (United States)

    Pina, Eduardo; de la Selva, Sara Maria Teresa

    2010-01-01

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

  14. Higher adsorption capacity of Spirulina platensis alga for Cr(VI) ions removal: parameter optimisation, equilibrium, kinetic and thermodynamic predictions.

    Science.gov (United States)

    Gunasundari, Elumalai; Senthil Kumar, Ponnusamy

    2017-04-01

    This study discusses about the biosorption of Cr(VI) ion from aqueous solution using ultrasonic assisted Spirulina platensis (UASP). The prepared UASP biosorbent was characterised by Fourier transform infrared spectroscopy, X-ray diffraction, Brunauer-Emmet-Teller, scanning electron spectroscopy and energy dispersive X-ray and thermogravimetric analyses. The optimum condition for the maximum removal of Cr(VI) ions for an initial concentration of 50 mg/l by UASP was measured as: adsorbent dose of 1 g/l, pH of 3.0, contact time of 30 min and temperature of 303 K. Adsorption isotherm, kinetics and thermodynamic parameters were calculated. Freundlich model provided the best results for the removal of Cr(VI) ions by UASP. The adsorption kinetics of Cr(VI) ions onto UASP showed that the pseudo-first-order model was well in line with the experimental data. In the thermodynamic study, the parameters like Gibb's free energy, enthalpy and entropy changes were evaluated. This result explains that the adsorption of Cr(VI) ions onto the UASP was exothermic and spontaneous in nature. Desorption of the biosorbent was done using different desorbing agents in which NaOH gave the best result. The prepared material showed higher affinity for the removal of Cr(VI) ions and this may be an alternative material to the existing commercial adsorbents.

  15. Thermodynamic, Kinetic, and Equilibrium Parameters for the Removal of Lead and Cadmium from Aqueous Solutions with Calcium Alginate Beads

    Directory of Open Access Journals (Sweden)

    Ruth Alfaro-Cuevas-Villanueva

    2014-01-01

    Full Text Available The sorption of cadmium (Cd and lead (Pb by calcium alginate beads (CAB from aqueous solutions in batch systems was investigated. The kinetic and thermodynamic parameters, as well as the sorption capacities of CAB in each system at different temperatures, were evaluated. The rate of sorption for both metals was rapid in the first 10 minutes and reached a maximum in 50 minutes. Sorption kinetic data were fitted to Lagergren, pseudo-second-order and Elovich models and it was found that the second-order kinetic model describes these data for the two metals; comparing kinetic parameters for Cd and Pb sorption a higher kinetic rate (K2 for Pb was observed, indicating that the interaction between lead cations and alginate beads was faster than for cadmium. Similarly, isotherm data were fitted to different models reported in literature and it was found that the Langmuir-Freundlich (L-F and Dubinin-Radushkevich (D-R models describe the isotherms in all cases. CAB sorption capacity for cadmium was 27.4 mg/g and 150.4 mg/g for lead, at 25°C. Sorption capacities of Cd and Pb increase as temperature rises. According to the thermodynamic parameters, the cadmium and lead adsorption process was spontaneous and endothermic. It was also found that pH has an important effect on the adsorption of these metals by CAB, as more were removed at pH values between 6 and 7.

  16. The Adsorption of Pb, Zn, Cu, Ni, and Cd by Modified Ligand in a Single Component Aqueous Solution: Equilibrium, Kinetic, Thermodynamic, and Desorption Studies

    Directory of Open Access Journals (Sweden)

    E. Igberase

    2017-01-01

    Full Text Available In this investigation, an amino functionalized adsorbent was developed by grafting 4-aminobenzoic acid onto the backbone of cross-linked chitosan beads. The 3 sets of beads including chitosan (CX, glutaraldehyde cross-linked chitosan (CCX, and 4-aminobenzoic acid grafted cross-linked chitosan (FGCX were characterized by FTIR, XRD, SEM, and TGA. The water content and amine concentration of FGCX were determined. The effect of adsorption parameters was studied and the optimum was used for further studies. Equilibrium data was obtained from the adsorption experiment carried out at different initial concentration; the data were applied in isotherm, thermodynamics, and kinetic studies. The Langmuir and Dubinin-Kaganer-Radushkevich (DKR models were successful in describing the isotherm data for the considered metal ions while the Freundlich and Temkin model fit some of the considered metal ions. Pseudo-second-order and intraparticle model described the kinetic data quite well. Thermodynamic parameters such as Gibb’s free energy change (ΔGo, enthalpy change (ΔHo, and entropy change (ΔSo were calculated and the results showed that the adsorption of Pb, Cu, Ni, Zn, and Cd ions onto FGCX is spontaneous and endothermic in nature. Regeneration of the spent adsorbent was efficient for the considered metal ions.

  17. Thermodynamic investigation of the phase equilibrium boundary between TiO2 rutile and its α-PbO2-type high-pressure polymorph

    Science.gov (United States)

    Kojitani, Hiroshi; Yamazaki, Monami; Kojima, Meiko; Inaguma, Yoshiyuki; Mori, Daisuke; Akaogi, Masaki

    2018-06-01

    Heat capacity (C P) of rutile and α-PbO2 type TiO2 (TiO2-II) were measured by the differential scanning calorimetry and thermal relaxation method. Using the results, standard entropies at 1 atm and 298.15 K of rutile and TiO2-II were determined to be 50.04(4) and 46.54(2) J/mol K, respectively. Furthermore, thermal expansivity (α) determined by high-temperature X-ray diffraction measurement and mode Grüneisen parameters obtained by high-pressure Raman spectroscopy suggested the thermal Grüneisen parameter (γ th) for TiO2-II of 1.7(1). By applying the obtained low-temperature C P and γ th, the measured C P and α data of TiO2-II were extrapolated to higher temperature region using a lattice vibrational model calculation, as well as rutile. Internally consistent thermodynamic data sets of both rutile and TiO2-II assessed in this study were used to thermodynamically calculate the rutile‒TiO2-II phase equilibrium boundary. The most plausible boundary was obtained to be P (GPa) = 0.0074T (K) - 1.7. Our boundary suggests that the crystal growth of TiO2-II observed below 5.5 GPa and 900 K in previous studies advanced in its stability field. The phase boundary calculation also suggested small, exothermic phase transition enthalpy from rutile to TiO2-II at 1 atm and 298.15 K of - 0.5 to - 1.1 kJ/mol. This implies that the thermodynamic stability of rutile at 1 atm above room temperature is due to larger contribution of entropy term.

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

    International Nuclear Information System (INIS)

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

    2009-01-01

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

  19. Non-equilibrium plasma chemistry at high pressure and its applications

    International Nuclear Information System (INIS)

    Bai Xiyao; Zhang Zhitao; Bai Mindong; Zhu Qiaoying

    2000-01-01

    A review is presented of research and development of gas discharge and non-equilibrium plasma including, new ideas of non-equilibrium plasma at high gas pressure. With special technology, strong electric fields (>400 Td) can be achieved by which electrons are accelerated suddenly, becoming high energy electrons (> 10 eV) at high pressure. On impact with the electrons, the gas molecules dissociate into ions, atomic ions, atoms and free radicals, and new substances or molecules can be synthesized through custom design. Chemical reaction difficult to achieve by conventional method can be realized or accelerated. Non-equilibrium plasma chemistry at high pressure has wide application prospects

  20. Aluminium fumarate and CPO-27(Ni) MOFs: Characterization and thermodynamic analysis for adsorption heat pump applications

    International Nuclear Information System (INIS)

    Elsayed, Eman; AL-Dadah, Raya; Mahmoud, Saad; Elsayed, Ahmed; Anderson, Paul A.

    2016-01-01

    Highlights: • CPO-27(Ni) and aluminium fumarate were investigated for adsorption heating, cooling and desalination applications. • Both MOFs have high potential in adsorption applications. • The optimum desorption temperature for the CPO-27(Ni) is higher than 90 °C, and for aluminium fumarate, it is 55–70 °C. • CPO-27(Ni) outperforms aluminium fumarate at low evaporation temperature (5 °C). • Aluminium fumarate outperforms CPO-27(Ni) at high evaporation temperature (20 °C). - Abstract: Metal-organic framework (MOF) materials are new porous materials with high surface area, pore size and volume, and tunable pore geometry thus providing high adsorption capacity. Currently, limited MOF materials with high water adsorption capabilities and hydrothermal stability are available on a large scale. Two MOF materials, namely CPO-27(Ni) and aluminium fumarate, have been identified to have a high hydrothermal stability, high water uptake of 0.47 g_H_2_O_.g_a_d_s"−"1 and 0.53 g_H_2_O_.g_a_d_s"−"1 at a relative pressure of 0.9 and are commercially available. This work aims to measure the water adsorption characteristics of these two MOF materials in terms of isotherms, kinetics and cyclic stability. Also the thermodynamic cycle performance of such materials based on their equilibrium adsorption data was investigated under different operating conditions for various adsorption applications such as heating, cooling and water desalination. Results showed that the CPO-27(Ni)/water pair outperformed the aluminium fumarate/water pair at low evaporation temperatures (5 °C) and high desorption temperatures (≥90 °C), while the aluminium fumarate/water pair was more suitable for applications requiring high evaporation temperature (20 °C) and/or low desorption temperature (70 °C).

  1. Development of a multi-species mass transport model for concrete with account to thermodynamic phase equilibriums

    DEFF Research Database (Denmark)

    Hosokawa, Yoshifumi; Yamada, Kazuo; Johannesson, Björn

    2011-01-01

    different types of cements. For example, the physicochemical evaluation of steel corrosion initiation can be studied by calculating the molar ratio of chloride ion to hydroxide ion in the pore solution. The model can, further, for example, calculate changes of solid-phase composition caused......) theory alone, not involving chemical processes, have no real practical interest since the chemical action is very dominant for cement based materials. Coupled mass transport and chemical equilibrium models can be used to calculate the variation in pore solution and solid-phase composition when using...

  2. Thermodynamic modelling of phase equilibrium for water + poly(Ethylene glycol + salt aqueous two-phase systems

    Directory of Open Access Journals (Sweden)

    R.A.G. Sé

    2002-04-01

    Full Text Available The NRTL (nonrandom, two-liquid model, expressed in mass fraction instead of mole fraction, was used to correlate liquid-liquid equilibria for aqueous two-phase polymer-salt solutions. New interaction energy parameters for this model were determined using reported data on the water + poly(ethylene glycol + salt systems, with different molecular masses for PEG and the salts potassium phosphate, sodium sulfate, sodium carbonate and magnesium sulfate. The correlation of liquid-liquid equilibrium is quite satisfactory.

  3. Fundamentals of thermodynamics and applications with historical annotations and many citations from Avogadro to Zermelo

    CERN Document Server

    Müller, Ingo

    2009-01-01

    Here is a systematic introduction into the fundamental ideas of thermodynamics at a somewhat advanced level. The book details many applications of the theory in the fields of engineering, physics, chemistry, physical chemistry, and materials science.

  4. New fundamental equations of thermodynamics for systems in chemical equilibrium at a specified partial pressure of a reactant and the standard transformed formation properties of reactants

    International Nuclear Information System (INIS)

    Alberty, R.A.; Oppenheim, I.

    1993-01-01

    When temperature, pressure, and the partial pressure of a reactant are fixed, the criterion of chemical equilibrium can be expressed in terms of the transformed Gibbs energy G' that is obtained by using a Legendre transform involving the chemical potential of the reactant that is fixed. For reactions of ideal gases, the most natural variables to use in the fundamental equation are T, P', and P B , where P' is the partial pressure of the reactants other than the one that is fixed and P B is the partial pressure of the reactant that is fixed. The fundamental equation for G' yields the expression for the transformed entropy S', and a transformed enthalpy can be defined by the additional Legendre transform H'=G'+TS'. This leads to an additional form of the fundamental equation. The calculation of transformed thermodynamic properties and equilibrium compositions is discussed for a simple system and for a general multireaction system. The change, in a reaction, of the binding of the reactant that is at a specified pressure can be calculated using one of the six Maxwell equations of the fundamental equation in G'

  5. Pyridine sorption from aqueous solution by rice husk ash (RHA) and granular activated carbon (GAC): Parametric, kinetic, equilibrium and thermodynamic aspects

    International Nuclear Information System (INIS)

    Lataye, D.H.; Mishra, I.M.; Mall, I.D.

    2008-01-01

    The present study deals with the adsorption of pyridine (Py) from synthetic aqueous solutions by rice husk ash (RHA) and commercial grade granular activated carbon (GAC) and reports on the kinetic, equilibrium and thermodynamic aspects of Py sorption. Batch sorption studies were carried out to evaluate the effect of various parameters, such as adsorbent dose (m), initial pH (pH 0 ), contact time (t), initial concentration (C 0 ) and temperature (T) on the removal of Py. The maximum removal of Py is found to be ∼96% and ∼97% at lower concentrations ( -3 ) and ∼79.5% and ∼84% at higher concentrations (600 mg dm -3 ) using 50 kg m -3 and 30 kg m -3 of RHA and GAC dosage, respectively, at 30 ± 1 o C. Adsorption of Py is found to be endothermic in nature and the equilibrium data can be adequately represented by Toth and Redlich-Peterson isotherm equations. Py can be recovered from the spent adsorbents by using acidic water and 0.1 N H 2 SO 4 . The overall adsorption of Py on RHA and GAC is found to be in the order of GAC > RHA. Comparative assessment of adsorbents used by various investigators available in literature showed the effectiveness of BFA and RHA over other adsorbents. Spent RHA can simply be filtered, dried and used in the boiler furnaces/incinerators. Thus, its heating value can be recovered

  6. Synthesis of a new low-cost activated carbon from activated sludge for the removal of Cr (Ⅵ) from aqueous solution: Equilibrium, kinetics, thermodynamics and desorption studies

    Energy Technology Data Exchange (ETDEWEB)

    Gorzin, Fatemeh; Ghoreyshi, Ali Asghar [Babol University of Technology, Babol (Iran, Islamic Republic of)

    2013-08-15

    Elimination of Cr (Ⅵ) from aqueous solution was investigated by a new low cost activated carbon developed from aerobically digested activated sludge (ADAS). The adsorbent demonstrated remarkable characteristics such as high surface area of 760m{sup 2}·g{sup −1} and large total pore volume of 0.8383 cm{sup 3}·g{sup −1}. The maximum equilibrium uptake of Cr (Ⅵ) was 70.15 mg·g{sup −1} at optimum pH 2.0. Interpretation of equilibrium data revealed that the best description was provided by the Freundlich isotherm. The kinetics of Cr (Ⅵ) adsorption was well described by the pseudo-second order equation. Calculation of thermodynamic parameters revealed that the adsorption process was endothermic, spontaneous and feasible.. The adsorbent was regenerated using NaOH and it was found to be suitable for reuse in successive adsorption-desorption cycles. The desorption efficiency of Cr (Ⅵ) ion was up to 78%. Finally, comparison of Cr (Ⅵ) adsorption capacity of the developed adsorbent with commercial activated carbon demonstrated its higher performance.

  7. Thermodynamic considerations in the application of reverse mode gasification to the destruction of hazardous substances

    Energy Technology Data Exchange (ETDEWEB)

    Larsen, D.W.; Washington, M.D.; Manahan, S.E.; Medcalf, B.; Stary, F.E. [University of Missouri-St. Louis, St. Louis, MO (United States). Dept. of Chemistry

    1999-09-01

    Previous studies by the authors have demonstrated the effectiveness of reverse mode gasification using a granular coal char matrix for treatment of hazardous wastes. Calculations pertaining to this gasification are presented, including a one-dimensional temperature profile and a thermodynamic analysis. Equilibrium compositions were calculated by free energy minimization using commercially available software. The calculated results were compared with experimental data for gasification of mixtures containing water, selected hydrocarbons, and used motor oil. Batch and continuous feed reactors were used with optimized operating parameters to generate the data. The dry gas product obtained from gasification of water and selected hydrocarbons contains carbon dioxide, carbon monoxide, methane, and hydrogen, in agreement with thermodynamic predictions, and the compositions agree well with predictions obtained assuming that chemical equilibrium is attained at a temperature of 650{degree}C. The dry gas product from gasification of motor oil contains small amounts of low molecular weight hydrocarbons, which are not thermodynamically stable, but the composition of the major products generally agrees with the thermodynamic predictions. Under optimized conditions, the aqueous condensate contains between 1 and 100 ppm organics. Heat balance terms for the process were also calculated, and these demonstrate the efficiency of gasification as a treatment method. 21 refs., 4 figs., 1 tab.

  8. Focus on adsorptive equilibrium, kinetics and thermodynamic components of petroleum produced water biocoagulation using novel Tympanotonos Fuscatus extract

    Directory of Open Access Journals (Sweden)

    Matthew Menkiti

    2018-03-01

    Full Text Available Adsorptive component of produced water (PW coagulation using Tympanotonos Fuscatus coagulant (TFC was studied. Influence of the following parameters: pH, coagulant dose, settling time, and temperature were investigated. The functional group, crystalline nature, morphological observation and thermal characteristics of the sample were evaluated. Equilibrium data were analyzed using Langmuir, Freundlich, Temkin, Frumkin, and Dubinin-Radushkevich (D-R adsorption isotherms. The kinetics data were fitted to reversible first order, pseudo-first-order, pseudo-second-order, elovich, intra-particle diffusion and Boyd kinetic models. Adsorption Gibbs energy, enthalpy and entropy were evaluated. Equilibrium data best fitted the Langmuir isotherm (R2 > 0.99; X2 < 1.6; SSE < 1.6. Reversible first order model correlated best to the kinetics data. The values of process average Gibb's free energy, enthalpy and entropy were 30.35, 27.88 and 0.1891 kJ/mol, respectively. The process was spontaneous, feasible and endothermic in nature. The maximum efficiency of 83.1% was favored at pH 2.0. This study indicated significant adsorptive component, while using Tympanotonos Fuscatus extract as readily available, renewable, ecofriendly bio – coagulant for efficient treatments of PW.

  9. Adsorption equilibrium and thermodynamics of CO{sub 2} and CH{sub 4} on carbon molecular sieves

    Energy Technology Data Exchange (ETDEWEB)

    Song, Xue [College of Resource and Environmental Science, Chongqing University, Chongqing, 400044 (China); State key laboratory of coal and disaster and control, Chongqing University, Chongqing University, Chongqing, 400044 (China); Wang, Li’ao, E-mail: wangliao@cqu.edu.cn [College of Resource and Environmental Science, Chongqing University, Chongqing, 400044 (China); State key laboratory of coal and disaster and control, Chongqing University, Chongqing University, Chongqing, 400044 (China); Ma, Xu; Zeng, Yunmin [College of Resource and Environmental Science, Chongqing University, Chongqing, 400044 (China); State key laboratory of coal and disaster and control, Chongqing University, Chongqing University, Chongqing, 400044 (China)

    2017-02-28

    Highlights: • Impacts of pore structure on adsorption capacity of CO{sub 2} and CH{sub 4} on CMS were studied. • Thermodynamic properties of CO{sub 2} and CH{sub 4} at zero surface coverage were analyzed. • Variation of entropy change and Gibbs free energy with surface loading was explored. - Abstract: Carbon molecular sieves (CMS) are widely used in the separation of dioxide carbon and methane. In this research, three commercial CMS were utilized to analyze the pore structure and chemical properties. The adsorption isotherms of CO{sub 2} and CH{sub 4} were studied at 298 K, 308 K and 318 K over the pressure range of 0–1 MPa by an Intelligent Gravimetric analysis (IGA-100B, UK). Langmuir model was adopted to fit the experimental data. The working capacity and selectivity were employed to evaluate the adsorbents. The adsorption thermodynamics were discussed. The adsorbed amounts of both CO{sub 2} and CH{sub 4} are found to be highly related with the BET specific surface area and the volume of micropores, and also are interrelated with the total pore volume and micropore surface area. The standard enthalpy change (ΔH{sup Θ}), standard Gibbs free energy (ΔG{sup Θ}) and standard entropy change (ΔS{sup Θ}) at zero surface loading are negative, manifesting the adsorption process is exothermic and spontaneous, and the system tends to be ordered. With the increasing surface coverage, the absolute values of Gibbs free energy (ΔG) decrease whereas the absolute values of enthalpy change (ΔH) and entropy change(ΔS) increase. This indicates that as the adsorbed amount increases, the degree of the spontaneity reduces, the intermolecular forces among the adsorbate molecules increase, the orderliness of the system improves and the adsorbed amount approaches the maximum adsorbed capacity.

  10. Thermodynamics of dilute gases: application to submonolayer He films

    International Nuclear Information System (INIS)

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

    1979-01-01

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

  11. Thermodynamic database of multi-component Mg alloys and its application to solidification and heat treatment

    Directory of Open Access Journals (Sweden)

    Guanglong Xu

    2016-12-01

    Full Text Available An overview about one thermodynamic database of multi-component Mg alloys is given in this work. This thermodynamic database includes thermodynamic descriptions for 145 binary systems and 48 ternary systems in 23-component (Mg–Ag–Al–Ca–Ce–Cu–Fe–Gd–K–La–Li–Mn–Na–Nd–Ni–Pr–Si–Sn–Sr–Th–Y–Zn–Zr system. First, the major computational and experimental tools to establish the thermodynamic database of Mg alloys are briefly described. Subsequently, among the investigated binary and ternary systems, representative binary and ternary systems are shown to demonstrate the major feature of the database. Finally, application of the thermodynamic database to solidification simulation and selection of heat treatment schedule is described.

  12. Kinetic, Thermodynamic and Equilibrium Studies on Uptake of Rhodamine B onto ZnCl2 Activated Low Cost Carbon

    Directory of Open Access Journals (Sweden)

    N. Bhadusha

    2012-01-01

    Full Text Available A carbonaceous adsorbent prepared from biomass waste like wood apple outer shell (Limonia acidissima by ZnCl2 treatment was investigated for its efficiency in removing Rhodamine B (RDB. Influence of agitation time, adsorbent dose, dye concentration, pH and temperature were explored. Two theoretical adsorption isotherms namely Langmuir and Freundlich were used to describe the experimental results. The Langmuir adsorption capacity (Qo was found to be 46.7 mg/g and the equilibrium parameter (RL values indicate favourable adsorption. The experimental data were well fitted with Langmuir isotherm model and pseudo second order kinetic model. Desorption studies showed that ion exchange mechanism might be involved in the adsorption process.

  13. Para-equilibrium phase diagrams

    International Nuclear Information System (INIS)

    Pelton, Arthur D.; Koukkari, Pertti; Pajarre, Risto; Eriksson, Gunnar

    2014-01-01

    Highlights: • A rapidly cooled system may attain a state of para-equilibrium. • In this state rapidly diffusing elements reach equilibrium but others are immobile. • Application of the Phase Rule to para-equilibrium phase diagrams is discussed. • A general algorithm to calculate para-equilibrium phase diagrams is described. - Abstract: If an initially homogeneous system at high temperature is rapidly cooled, a temporary para-equilibrium state may result in which rapidly diffusing elements have reached equilibrium but more slowly diffusing elements have remained essentially immobile. The best known example occurs when homogeneous austenite is quenched. A para-equilibrium phase assemblage may be calculated thermodynamically by Gibbs free energy minimization under the constraint that the ratios of the slowly diffusing elements are the same in all phases. Several examples of calculated para-equilibrium phase diagram sections are presented and the application of the Phase Rule is discussed. Although the rules governing the geometry of these diagrams may appear at first to be somewhat different from those for full equilibrium phase diagrams, it is shown that in fact they obey exactly the same rules with the following provision. Since the molar ratios of non-diffusing elements are the same in all phases at para-equilibrium, these ratios act, as far as the geometry of the diagram is concerned, like “potential” variables (such as T, pressure or chemical potentials) rather than like “normal” composition variables which need not be the same in all phases. A general algorithm to calculate para-equilibrium phase diagrams is presented. In the limit, if a para-equilibrium calculation is performed under the constraint that no elements diffuse, then the resultant phase diagram shows the single phase with the minimum Gibbs free energy at any point on the diagram; such calculations are of interest in physical vapor deposition when deposition is so rapid that phase

  14. Entropy equilibrium equation and dynamic entropy production in environment liquid

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The entropy equilibrium equation is the basis of the nonequilibrium state thermodynamics. But the internal energy implies the kinetic energy of the fluid micelle relative to mass center in the classical entropy equilibrium equation at present. This internal energy is not the mean kinetic energy of molecular movement in thermodynamics. Here a modified entropy equilibrium equation is deduced, based on the concept that the internal energy is just the mean kinetic energy of the molecular movement. A dynamic entropy production is introduced into the entropy equilibrium equation to describe the dynamic process distinctly. This modified entropy equilibrium equation can describe not only the entropy variation of the irreversible processes but also the reversible processes in a thermodynamic system. It is more reasonable and suitable for wider applications.

  15. Effective Remediation of Lead Ions from Aqueous Solution by Chemically Carbonized Rubber Wood Sawdust: Equilibrium, Kinetics, and Thermodynamic Study

    Directory of Open Access Journals (Sweden)

    Swarup Biswas

    2015-01-01

    Full Text Available Rubber wood sawdust was carbonized into charcoal by chemical treatment which was used for removal of lead ion from aqueous solution. The work involves batch experiments to investigate the pH effect, initial concentration of adsorbate, contact time, and adsorbent dose. Experimental data confirmed that the adsorption capacities increased with increasing inlet concentration and bed height and decreased with increasing flow rate. Adsorption results showed a maximum adsorption capacity of 37 mg/g at 308 K. Langmuir, Freundlich, and Temkin model adsorption isotherm models were applied to analyze the process where Temkin was found as a best fitted model for present study. Simultaneously kinetics of adsorption like pseudo-first-order, pseudo-second-order, and intraparticle diffusion models were investigated. Thermodynamic parameters were used to analyze the adsorption experiment. Fourier transform infrared spectroscopy, scanning electron microscope, and energy dispersive X-ray spectroscopy confirmed the batch adsorption of lead ion onto chemically carbonized rubber wood sawdust.

  16. Breadnut peel as a highly effective low-cost biosorbent for methylene blue: Equilibrium, thermodynamic and kinetic studies

    Directory of Open Access Journals (Sweden)

    Linda B.L. Lim

    2017-05-01

    Full Text Available This work reports the potential use of peel of breadnut, Artocarpus camansi, as an effective low-cost biosorbent for the removal of methylene blue (MB. Oven dried A. camansi peel (ACP, which had a point of zero charge at pH = 4.8, showed maximum biosorption capacity which was far superior to most literature reported fruit biomasses, including samples that have been activated. Isotherm studies on biosorption of MB onto ACP gave a maximum biosorption capacity of 409 mg g−1. The Langmuir model was found to give the best fit among various isotherm models investigated and error analyses performed. Kinetics studies were fast with 50% dye being removed in less than 8 min from a 50 mg L−1 dye solution and further, kinetics followed the pseudo second order. Thermodynamic studies indicated that the biosorption process was both spontaneous and exothermic. Fourier transform infrared (FT-IR of ACP before and after MB adsorption was investigated. It can be concluded that oven dried breadnut peel is a highly promising low-cost biosorbent with great potential for the removal of MB.

  17. Equilibrium isotherms, kinetics, and thermodynamics studies for congo red adsorption using calcium alginate beads impregnated with nano-goethite.

    Science.gov (United States)

    Munagapati, Venkata Subbaiah; Kim, Dong-Su

    2017-07-01

    The present study is concerned with the batch adsorption of congo red (CR) from an aqueous solution using calcium alginate beads impregnated with nano-goethite (CABI nano-goethite) as an adsorbent. The optimum conditions for CR removal were determined by studying operational variables viz. pH, adsorbent dose, contact time, initial dye ion concentration and temperature. The CABI nano-goethite was characterized by Fourier transform infrared spectroscopy (FTIR), X- ray diffraction (XRD) and Scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) analysis. The CR sorption data onto CABI nano-goethite were described using Langmuir, Freundlich, Dubinin-Radushkevich and Temkin isotherm models. The results show that the best fit was achieved with the Langmuir isotherm model. The maximum adsorption capacity (181.1mg/g) of CR was occurred at pH 3.0. Kinetic studies showed that the adsorption followed a pseudo-second-order model. Desorption experiments were carried out to explore the feasibility of regenerating the adsorbent and the adsorbed CR from CABI nano-goethite. The best desorbing agent was 0.1M NaOH with an efficiency of 94% recovery. The thermodynamic parameters ΔG°, ΔH°, and ΔS° for the CR adsorption were determined by using adsorption capacities at five different temperatures (293, 303, 313, 323 and 303K). Results show that the adsorption process was endothermic and favoured at high temperature. Copyright © 2017 Elsevier Inc. All rights reserved.

  18. The removal of Tartrazine dye by modified Alumina with sodium dodecyl sulfate from aqueous solutions: equilibrium and thermodynamic studies

    Directory of Open Access Journals (Sweden)

    A. Parchebaf Jadid

    2017-11-01

    Full Text Available Edible colors are materials which in the case of adding to food and drinks cause transferring color to them. Most of these colors are not acceptable in terms of applying in human food and underlies various diseases like gastrointestinal disorders, renal, liver and blood toxicity. The goal of this study was investigating the efficiency of improved alumina by sodium dodecyl sulfate (SDS in eliminating Tartrazine from aqueous environments. In this research, the impact of effective parameters such as initial concentration of Tartrazine, time, pH, alumina dose and SDS value were studied in order to approach an optimal condition for eliminating the color. Also, absorption behavior was evaluated by Freundlich and Langmuir isotherms. The highest efficiency of Tartrazine elimination in the solution resulted in optimal pH of 2, the amount of adsorbent 1.5 g/L, 16 min duration and value 0.04 SDS g/l which was obtained for dye concentration 5 mg/L about 94.13%. Also, results suggested that Tartrazine absorption follows Langmuir isotherm (R2 = 0.9867. Obtained results from thermodynamic studies such as Gibbs free energy (-5.728 Kj/mol and enthalpy (-85.86 Kj/mol and entropy (-271.102 J/mol.K also suggested that the absorption process was exothermic. The results of this research suggested that improved alumina by sodium dodecyl sulfate had a relative good capability in Tartrazine elimination from aqueous environments. Thus

  19. Solid–liquid equilibrium and thermodynamic research of 3-Thiophenecarboxylic acid in (water + acetic acid) binary solvent mixtures

    International Nuclear Information System (INIS)

    Liu, Xiang; Liang, Mengmeng; Hu, Yonghong; Yang, Wenge; Shi, Ying; Yin, Jingjing; Liu, Yan

    2014-01-01

    Highlights: • The solubility was measured in (water + acetic acid) from 283.15 to 338.15 K. • The solubility increased with increasing temperature and water contents. • The modified Apelblat equation was more accurate than the λh equation. - Abstract: In this study, the solubility of 3-thiophenecarboxylic acid was measured in (water + acetic acid) binary solvent mixtures in the temperature ranging from 283.15 to 338.15 K by the analytical stirred-flask method under atmospheric pressure. The experimental data were well-correlated with the modified Apelblat equation and the λh equation. In addition, the calculated solubilities showed good agreement with the experimental results. It was found that the modified Apelblat equation could obtain the better correlation results than the λh equation. The experiment results indicated that the solubility of 3-thiophenecarboxylic acid in the binary solvents increased with increasing temperature, increases with increasing water contents, but the increments with temperature differed from different water contents. In addition, the thermodynamic properties of the solution process, including the Gibbs energy, enthalpy, and entropy were calculated by the van’t Hoff analysis. The experimental data and model parameters would be useful for optimizing the process of purification of 3-thiophenecarboxylic acid in industry

  20. Models of supply function equilibrium with applications to the electricity industry

    Science.gov (United States)

    Aromi, J. Daniel

    Electricity market design requires tools that result in a better understanding of incentives of generators and consumers. Chapter 1 and 2 provide tools and applications of these tools to analyze incentive problems in electricity markets. In chapter 1, models of supply function equilibrium (SFE) with asymmetric bidders are studied. I prove the existence and uniqueness of equilibrium in an asymmetric SFE model. In addition, I propose a simple algorithm to calculate numerically the unique equilibrium. As an application, a model of investment decisions is considered that uses the asymmetric SFE as an input. In this model, firms can invest in different technologies, each characterized by distinct variable and fixed costs. In chapter 2, option contracts are introduced to a supply function equilibrium (SFE) model. The uniqueness of the equilibrium in the spot market is established. Comparative statics results on the effect of option contracts on the equilibrium price are presented. A multi-stage game where option contracts are traded before the spot market stage is considered. When contracts are optimally procured by a central authority, the selected profile of option contracts is such that the spot market price equals marginal cost for any load level resulting in a significant reduction in cost. If load serving entities (LSEs) are price takers, in equilibrium, there is no trade of option contracts. Even when LSEs have market power, the central authority's solution cannot be implemented in equilibrium. In chapter 3, we consider a game in which a buyer must repeatedly procure an input from a set of firms. In our model, the buyer is able to sign long term contracts that establish the likelihood with which the next period contract is awarded to an entrant or the incumbent. We find that the buyer finds it optimal to favor the incumbent, this generates more intense competition between suppliers. In a two period model we are able to completely characterize the optimal mechanism.

  1. Generalization of Gibbs Entropy and Thermodynamic Relation

    OpenAIRE

    Park, Jun Chul

    2010-01-01

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

  2. Kinetics, equilibrium, and thermodynamics investigation on the adsorption of lead(II) by coal-based activated carbon.

    Science.gov (United States)

    Yi, Zhengji; Yao, Jun; Zhu, Mijia; Chen, Huilun; Wang, Fei; Liu, Xing

    2016-01-01

    The goal of this research is to investigate the feasibility of using activated coal-based activated carbon (CBAC) to adsorb Pb(II) from aqueous solutions through batch tests. Effects of contact time, pH, temperature and initial Pb(II) concentration on the Pb(II) adsorption were examined. The Pb(II) adsorption is strongly dependent on pH, but insensitive to temperature. The best pH for Pb(II) removal is in the range of 5.0-5.5 with more than 90 % of Pb(II) removed. The equilibrium time was found to be 60 min and the adsorption data followed the pseudo-second-order kinetics. Isotherm data followed Langmuir isotherm model with a maximum adsorption capacity of 162.33 mg/g. The adsorption was exothermic and spontaneous in nature. The Fourier transform infrared spectroscopy and scanning electron microscopy analysis suggested that CBAC possessed a porous structure and was rich in carboxyl and hydroxyl groups on its surface, which might play a major role in Pb(II) adsorption. These findings indicated that CBAC has great potential as an alternative adsorbent for Pb(II) removal.

  3. Non-Equilibrium Thermodynamic Analysis of Double Diffusive, Nanofluid Forced Convection in Catalytic Microreactors with Radiation Effects

    Directory of Open Access Journals (Sweden)

    Lilian Govone

    2017-12-01

    Full Text Available This paper presents a theoretical investigation of the second law performance of double diffusive forced convection in microreactors with the inclusion of nanofluid and radiation effects. The investigated microreactors consist of a single microchannel, fully filled by a porous medium. The transport of heat and mass are analysed by including the thick walls and a first order, catalytic chemical reaction on the internal surfaces of the microchannel. Two sets of thermal boundary conditions are considered on the external surfaces of the microchannel; (1 constant temperature and (2 constant heat flux boundary condition on the lower wall and convective boundary condition on the upper wall. The local thermal non-equilibrium approach is taken to thermally analyse the porous section of the system. The mass dispersion equation is coupled with the transport of heat in the nanofluid flow through consideration of Soret effect. The problem is analytically solved and illustrations of the temperature fields, Nusselt number, total entropy generation rate and performance evaluation criterion (PEC are provided. It is shown that the radiation effect tends to modify the thermal behaviour within the porous section of the system. The radiation parameter also reduces the overall temperature of the system. It is further demonstrated that, expectedly, the nanoparticles reduce the temperature of the system and increase the Nusselt number. The total entropy generation rate and consequently PEC shows a strong relation with radiation parameter and volumetric concentration of nanoparticles.

  4. Theoretical calculation of reorganization energy for electron self-exchange reaction by constrained density functional theory and constrained equilibrium thermodynamics.

    Science.gov (United States)

    Ren, Hai-Sheng; Ming, Mei-Jun; Ma, Jian-Yi; Li, Xiang-Yuan

    2013-08-22

    Within the framework of constrained density functional theory (CDFT), the diabatic or charge localized states of electron transfer (ET) have been constructed. Based on the diabatic states, inner reorganization energy λin has been directly calculated. For solvent reorganization energy λs, a novel and reasonable nonequilibrium solvation model is established by introducing a constrained equilibrium manipulation, and a new expression of λs has been formulated. It is found that λs is actually the cost of maintaining the residual polarization, which equilibrates with the extra electric field. On the basis of diabatic states constructed by CDFT, a numerical algorithm using the new formulations with the dielectric polarizable continuum model (D-PCM) has been implemented. As typical test cases, self-exchange ET reactions between tetracyanoethylene (TCNE) and tetrathiafulvalene (TTF) and their corresponding ionic radicals in acetonitrile are investigated. The calculated reorganization energies λ are 7293 cm(-1) for TCNE/TCNE(-) and 5939 cm(-1) for TTF/TTF(+) reactions, agreeing well with available experimental results of 7250 cm(-1) and 5810 cm(-1), respectively.

  5. Thermodynamic aspects of dynamical calibration of microbarometers used for IMS applications

    International Nuclear Information System (INIS)

    Starovojt, Yu.O.; Martysevich, P.N.; Kunakov, A.V.

    2006-01-01

    This paper describes the method of dynamical calibration of a microbarometer using the chamber with variable volume. The physics of this method is based on the thermodynamic process occurring inside the closed volume and on the corresponding relationships between pressure, volume and temperature changes caused by the movement of the piston attached to the inlet of the chamber. The method has been already used in several applications, however we consider essential to analyze its physical details. The paper gives the description of thermodynamic processes inside the calibration volume, the discussion of thermodynamics need and its effect on the calibration accuracy. (author)

  6. Application of mathematical experimental planning in the investigation of thermodynamic properties of three- component alloys

    International Nuclear Information System (INIS)

    Sokolovskaya, E.M.; Guzej, L.S.; Tikhankin, G.A.; Meshkov, L.L.

    1977-01-01

    Thermodynamic properties of solid solutions of niobium and tungsten in nickel have been investigated by the method of electromotive forces with the use of simplex-matrix experiment planning techniques. The planning matrix and the results of investigating the thermodynamic properties of alloys of the nickel-niobium-tungsten system at 1250 deg are presented. The application of experiment planning has made it possible to obtain sufficient information concerning the thermodynamics of solid solutions of niobium and tungsten in nickel from the experimental data for six ternary alloys only

  7. Application of calorimetry and thermodynamics to critical problems in materials science

    International Nuclear Information System (INIS)

    Atake, Tooru

    2009-01-01

    Calorimetry and thermodynamic studies have long been playing a very important role in the research fields of fundamental science and technology. Some topics and examples of thermodynamics studies are given, and the details are explained on the basis of the present author's experience, focusing attention to application of adiabatic calorimetry and thermodynamics to solve critical problems in materials science: (1) condensed gas calorimetry and third law entropy, (2) phase transition and polymorphism in simple molecular crystals, (3) incommensurate phase transitions, (4) particle size effects on the phase transitions in ferroelectric/ferroelastic crystals, (5) relaxor ferroelectrics and multi-ferroics, and some other topics in materials science and technology

  8. Fine-particle pH for Beijing winter haze as inferred from different thermodynamic equilibrium models

    Directory of Open Access Journals (Sweden)

    S. Song

    2018-05-01

    Full Text Available pH is an important property of aerosol particles but is difficult to measure directly. Several studies have estimated the pH values for fine particles in northern China winter haze using thermodynamic models (i.e., E-AIM and ISORROPIA and ambient measurements. The reported pH values differ widely, ranging from close to 0 (highly acidic to as high as 7 (neutral. In order to understand the reason for this discrepancy, we calculated pH values using these models with different assumptions with regard to model inputs and particle phase states. We find that the large discrepancy is due primarily to differences in the model assumptions adopted in previous studies. Calculations using only aerosol-phase composition as inputs (i.e., reverse mode are sensitive to the measurement errors of ionic species, and inferred pH values exhibit a bimodal distribution, with peaks between −2 and 2 and between 7 and 10, depending on whether anions or cations are in excess. Calculations using total (gas plus aerosol phase measurements as inputs (i.e., forward mode are affected much less by these measurement errors. In future studies, the reverse mode should be avoided whereas the forward mode should be used. Forward-mode calculations in this and previous studies collectively indicate a moderately acidic condition (pH from about 4 to about 5 for fine particles in northern China winter haze, indicating further that ammonia plays an important role in determining this property. The assumed particle phase state, either stable (solid plus liquid or metastable (only liquid, does not significantly impact pH predictions. The unrealistic pH values of about 7 in a few previous studies (using the standard ISORROPIA model and stable state assumption resulted from coding errors in the model, which have been identified and fixed in this study.

  9. Mathematical foundations of thermodynamics

    CERN Document Server

    Giles, R; Stark, M; Ulam, S

    2013-01-01

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

  10. Non-local Thermodynamic Equilibrium Abundance Analyses of the Extreme Helium Stars V652 Her and HD 144941

    International Nuclear Information System (INIS)

    Pandey, Gajendra; Lambert, David L.

    2017-01-01

    Optical high-resolution spectra of V652 Her and HD 144941, the two extreme helium stars with exceptionally low C/He ratios, have been subjected to a non-LTE abundance analysis using the tools TLUSTY and SYNSPEC. Defining atmospheric parameters were obtained from a grid of non-LTE atmospheres and a variety of spectroscopic indicators including He i and He ii line profiles, and the ionization equilibrium of ion pairs such as C ii/C iii and N ii/N iii. The various indicators provide a consistent set of atmospheric parameters: T eff = 25,000 ± 300 K, log g = 3.10 ± 0.12(cgs), and ξ = 13 ± 2 km s −1 are provided for V652 Her, and T eff = 22,000 ± 600 K, log g = 3.45 ± 0.15 (cgs), and ξ = 10 km s −1 are provided for HD 144941. In contrast to the non-LTE analyses, the LTE analyses—LTE atmospheres and an LTE line analysis—with the available indicators do not provide a consistent set of atmospheric parameters. The principal non-LTE effect on the elemental abundances is on the neon abundance. It is generally considered that these extreme helium stars with their very low C/He ratio result from the merger of two helium white dwarfs. Indeed, the derived composition of V652 Her is in excellent agreement with predictions by Zhang and Jeffery, who model the slow merger of helium white dwarfs; a slow merger results in the merged star having the composition of the accreted white dwarf. In the case of HD 144941, which appears to have evolved from metal-poor stars, a slow merger is incompatible with the observed composition but variations of the merger rate may account for the observed composition. More detailed theoretical studies of the merger of a pair of helium white dwarfs are to be encouraged.

  11. A thermodynamic approach to obtain materials properties for engineering applications

    Science.gov (United States)

    Chang, Y. Austin

    1993-01-01

    With the ever increases in the capabilities of computers for numerical computations, we are on the verge of using these tools to model manufacturing processes for improving the efficiency of these processes as well as the quality of the products. One such process is casting for the production of metals. However, in order to model metal casting processes in a meaningful way it is essential to have the basic properties of these materials in their molten state, solid state as well as in the mixed state of solid and liquid. Some of the properties needed may be considered as intrinsic such as the density, heat capacity or enthalpy of freezing of a pure metal, while others are not. For instance, the enthalpy of solidification of an alloy is not a defined thermodynamic quantity. Its value depends on the micro-segregation of the phases during the course of solidification. The objective of the present study is to present a thermodynamic approach to obtain some of the intrinsic properties and combining thermodynamics with kinetic models to estimate such quantities as the enthalpy of solidification of an alloy.

  12. Neutron scattering on equilibrium and nonequilibrium phonons, excitons and polaritons

    International Nuclear Information System (INIS)

    Broude, V.L.; Sheka, E.F.

    1978-01-01

    A number of problems of solid-state physics representing interest for neutron spectroscopy of future is considered. The development of the neutron inelastic scattering spectroscopy (neutron spectroscopy of equilibrium phonons) is discussed with application to nuclear dynamics of crystals in the thermodynamic equilibrium. The results of high-flux neutron source experiments on molecular crystals are presented. The advantages of neutron inelastic scattering over optical spectroscopy are discussed. The spectroscopy of quasi-equilibrium and non-equilibrium quasi-particles is discussed. In particular, the neutron scattering on polaritons, excitons in thermal equilibrium and production of light-excitons are considered. The problem of the possibility of such experiments is elucidated

  13. Study of the coupling of geochemical models based on thermodynamic equilibrium with models of component transfer as solutions in porous media or fractures

    International Nuclear Information System (INIS)

    Coudrain-Ribstein, A.

    1985-01-01

    This study is a contribution of analyses possibilities of modelling the transfer of components in the underground taking into account complexes geochemical phenomena. In the first part, the aim and the methodology of existing codes are presented. The transfer codes describe with a great precision the physical phenomena of transport but they are based on a very simple conceptualisation of the geochemical phenomena of retention by the rock. The geochemical models are interested by a stable unity of volume. They allow to compute the equilibrium distribution of the components between the chemical species of the solution, and the solid and gaseous phases. They use important thermodynamic data bases corresponding to each possible reaction. To sum up the situation about the geochemical codes in Europe and United States, a list of about thirty codes describe their method and potentialities. The mathematical analysis of the different methods used in both types of codes is presented. Then, the principles of a modelisation associating the potentialities of the transport codes and the geochemical codes are discussed. It is not possible to think of a simple coupling. A general code must be established on the bases of the existing codes but also on new concepts and under new constraints. In such studies one must always deal with the problem of the reactions kinetics. When the velocity of the reactions is big enough versus the velocity of transport processes, the assumption of local geochemical equilibrium can be retained. A general code would be very cumbersome, expensive and difficult to use. The results would be difficult to analyse and exploit. On the other hand, for each case study, a detailed analysis can point out many computing simplifications without simplifying the concepts [fr

  14. Phase equilibrium measurements and thermodynamic modelling for the system (CO2 + ethyl palmitate + ethanol) at high pressures

    International Nuclear Information System (INIS)

    Gaschi, Priscilla S.; Mafra, Marcos R.; Ndiaye, Papa M.; Corazza, Marcos L.

    2013-01-01

    Graphical abstract: Ethyl palmitate and biodiesel comparison in a pressure–composition diagram for the systems (CO 2 + ethyl palmitate + biodiesel), at different temperatures. Highlights: ► We measured VLE, LLE, and VLLE for the system (CO 2 + ethyl palmitate + ethanol). ► The saturation pressures were obtained using a variable-volume view cell. ► Phase envelope of (CO 2 + ethyl palmitate) is different that (CO 2 + soybean oil biodiesel). ► The experimental data were modeled using PR-vdW2 and PR–WS equations of state. - Abstract: This work reports phase equilibrium measurements for the binary {CO 2 (1) + ethyl palmitate(2)} and ternary {CO 2 (1) + ethyl palmitate(2) + ethanol(3)} systems at high pressures. There is currently great interest in biodiesel production processes involving supercritical and/or pressurized solvents, such as non-catalytic supercritical biodiesel production and enzyme-catalysed biodiesel production. Also, supercritical CO 2 can offer an interesting alternative for glycerol separation in the biodiesel purification step in a water-free process. In this context, the main goal of this work was to investigate the phase behaviour of binary and ternary systems involving CO 2 , a pure constituent of biodiesel ethyl palmitate and ethanol. Experiments were carried out in a high-pressure variable-volume view cell with operating temperatures ranging from (303.15 to 353.15) K and pressures up to 21 MPa. The CO 2 mole fraction ranged from 0.5033 to 0.9913 for the binary {CO 2 (1) + ethyl palmitate(2)} system and from 0.4436 to 0.9712 for ternary system {CO 2 (1) + ethyl palmitate(2) + ethanol(3)} system with ethyl ester to ethanol molar ratios of (1:6), (1:3), and (1:1). For the systems investigated, vapour–liquid (VL), liquid–liquid (LL) and vapour–liquid–liquid (VLL) phase transitions were observed. The experimental data sets were successfully modeled using the Peng–Robinson equation of state with the classical van der Waals

  15. Non-local Thermodynamic Equilibrium Abundance Analyses of the Extreme Helium Stars V652 Her and HD 144941

    Energy Technology Data Exchange (ETDEWEB)

    Pandey, Gajendra [Indian Institute of Astrophysics, Bangalore, 560034 (India); Lambert, David L., E-mail: pandey@iiap.res.in, E-mail: dll@astro.as.utexas.edu [The W.J. McDonald Observatory and Department of Astronomy, University of Texas at Austin, Austin, TX 78712-1083 (United States)

    2017-10-01

    Optical high-resolution spectra of V652 Her and HD 144941, the two extreme helium stars with exceptionally low C/He ratios, have been subjected to a non-LTE abundance analysis using the tools TLUSTY and SYNSPEC. Defining atmospheric parameters were obtained from a grid of non-LTE atmospheres and a variety of spectroscopic indicators including He i and He ii line profiles, and the ionization equilibrium of ion pairs such as C ii/C iii and N ii/N iii. The various indicators provide a consistent set of atmospheric parameters: T {sub eff} = 25,000 ± 300 K, log g = 3.10 ± 0.12(cgs), and ξ = 13 ± 2 km s{sup −1} are provided for V652 Her, and T {sub eff} = 22,000 ± 600 K, log g = 3.45 ± 0.15 (cgs), and ξ = 10 km s{sup −1} are provided for HD 144941. In contrast to the non-LTE analyses, the LTE analyses—LTE atmospheres and an LTE line analysis—with the available indicators do not provide a consistent set of atmospheric parameters. The principal non-LTE effect on the elemental abundances is on the neon abundance. It is generally considered that these extreme helium stars with their very low C/He ratio result from the merger of two helium white dwarfs. Indeed, the derived composition of V652 Her is in excellent agreement with predictions by Zhang and Jeffery, who model the slow merger of helium white dwarfs; a slow merger results in the merged star having the composition of the accreted white dwarf. In the case of HD 144941, which appears to have evolved from metal-poor stars, a slow merger is incompatible with the observed composition but variations of the merger rate may account for the observed composition. More detailed theoretical studies of the merger of a pair of helium white dwarfs are to be encouraged.

  16. Thermodynamics of nanoadsorption from solution: Theoretical and experimental research

    International Nuclear Information System (INIS)

    Wen, Yan-Zhen; Xue, Yong-Qiang; Cui, Zi-Xiang; Wang, Yan

    2015-01-01

    Highlights: • The thermodynamic theory of nanoadsorption was proposed. • The thermodynamic relations of nanoadsorption were derived. • The results of the experiments are accord with the theory. - Abstract: In this study, the effect of nanoparticle size on adsorption thermodynamics was investigated. The results of theoretical and experimental studies show that particle size significantly affects the equilibrium constant and thermodynamic properties of nanoadsorption. Relationships between the equilibrium constant, thermodynamic properties and particle size were derived using the thermodynamic theory of nanoadsorption. The equilibrium constant and thermodynamic properties were obtained by investigating the adsorption of Cu 2+ onto different sizes of nano-ZnO and the adsorption of Ag + onto different sizes of nano-TiO 2 . Good agreement was achieved between results obtained by experiments and predicted by theoretical analyses. The equilibrium constant and the molar Gibbs free energy of nanoadsorption were found to increase with smaller nanoparticle size. However, the effects of particle size on the molar enthalpy and the molar entropy are uncertain. In addition, the molar Gibbs free energy, the molar enthalpy, the molar entropy and the logarithm of the equilibrium constant are linearly related to the reciprocal of the diameter of the nanoparticle. The thermodynamic properties revealed in this study may provide important guidelines for research and application in the field of nanoadsorption

  17. Study of Thermal Equilibrium in Heavy Ion Collisions via the Ma Coincidence Method - Test of Applicability

    International Nuclear Information System (INIS)

    Kirejczyk, M.

    2002-01-01

    The coincidence method of judging whether a system reached thermal equilibrium is shortly presented. It is used on the model data to test, whether it is applicable in the low-relativistic energy range. Also, the cuts corresponding to real detectors are introduced and their influence is briefly discussed. (author)

  18. Teaching the Concept of Gibbs Energy Minimization through Its Application to Phase-Equilibrium Calculation

    Science.gov (United States)

    Privat, Romain; Jaubert, Jean-Noe¨l; Berger, Etienne; Coniglio, Lucie; Lemaitre, Ce´cile; Meimaroglou, Dimitrios; Warth, Vale´rie

    2016-01-01

    Robust and fast methods for chemical or multiphase equilibrium calculation are routinely needed by chemical-process engineers working on sizing or simulation aspects. Yet, while industrial applications essentially require calculation tools capable of discriminating between stable and nonstable states and converging to nontrivial solutions,…

  19. Rapid computation of chemical equilibrium composition - An application to hydrocarbon combustion

    Science.gov (United States)

    Erickson, W. D.; Prabhu, R. K.

    1986-01-01

    A scheme for rapidly computing the chemical equilibrium composition of hydrocarbon combustion products is derived. A set of ten governing equations is reduced to a single equation that is solved by the Newton iteration method. Computation speeds are approximately 80 times faster than the often used free-energy minimization method. The general approach also has application to many other chemical systems.

  20. Removal of Pb(II) ions from aqueous solution by a waste mud from copper mine industry: equilibrium, kinetic and thermodynamic study.

    Science.gov (United States)

    Ozdes, Duygu; Gundogdu, Ali; Kemer, Baris; Duran, Celal; Senturk, Hasan Basri; Soylak, Mustafa

    2009-07-30

    The objective of this study was to assess the adsorption potential of a waste mud (WM) for the removal of lead (Pb(II)) ions from aqueous solutions. The WM was activated with NaOH in order to increase its adsorption capacity. Adsorption studies were conducted in a batch system as a function of solution pH, contact time, initial Pb(II) concentration, activated-waste mud (a-WM) concentration, temperature, etc. Optimum pH was specified as 4.0. The adsorption kinetic studies indicated that the overall adsorption process was best described by pseudo-second-order kinetics. The equilibrium adsorption capacity of a-WM was obtained by using Langmuir and Freundlich isotherm models and both models fitted well. Adsorption capacity for Pb(II) was found to be 24.4 mg g(-1) for 10 g L(-1) of a-WM concentration. Thermodynamic parameters including the Gibbs free energy (Delta G degrees), enthalpy (Delta H degrees), and entropy (DeltaS degrees) indicated that the adsorption of Pb(II) ions on the a-WM was feasible, spontaneous and endothermic, at temperature range of 0-40 degrees C. Desorption studies were carried out successfully with diluted HCl solutions. The results indicate that a-WM can be used as an effective and no-cost adsorbent for the treatment of industrial wastewaters contaminated with Pb(II) ions.

  1. Removal of Pb(II) ions from aqueous solution by a waste mud from copper mine industry: Equilibrium, kinetic and thermodynamic study

    International Nuclear Information System (INIS)

    Ozdes, Duygu; Gundogdu, Ali; Kemer, Baris; Duran, Celal; Senturk, Hasan Basri; Soylak, Mustafa

    2009-01-01

    The objective of this study was to assess the adsorption potential of a waste mud (WM) for the removal of lead (Pb(II)) ions from aqueous solutions. The WM was activated with NaOH in order to increase its adsorption capacity. Adsorption studies were conducted in a batch system as a function of solution pH, contact time, initial Pb(II) concentration, activated-waste mud (a-WM) concentration, temperature, etc. Optimum pH was specified as 4.0. The adsorption kinetic studies indicated that the overall adsorption process was best described by pseudo-second-order kinetics. The equilibrium adsorption capacity of a-WM was obtained by using Langmuir and Freundlich isotherm models and both models fitted well. Adsorption capacity for Pb(II) was found to be 24.4 mg g -1 for 10 g L -1 of a-WM concentration. Thermodynamic parameters including the Gibbs free energy (ΔG o ), enthalpy (ΔH o ), and entropy (ΔS o ) indicated that the adsorption of Pb(II) ions on the a-WM was feasible, spontaneous and endothermic, at temperature range of 0-40 o C. Desorption studies were carried out successfully with diluted HCl solutions. The results indicate that a-WM can be used as an effective and no-cost adsorbent for the treatment of industrial wastewaters contaminated with Pb(II) ions.

  2. Removal of Pb(II) ions from aqueous solution by a waste mud from copper mine industry: Equilibrium, kinetic and thermodynamic study

    Energy Technology Data Exchange (ETDEWEB)

    Ozdes, Duygu; Gundogdu, Ali; Kemer, Baris; Duran, Celal; Senturk, Hasan Basri [Department of Chemistry, Karadeniz Technical University, Faculty of Arts and Sciences, 61080 Trabzon (Turkey); Soylak, Mustafa, E-mail: soylak@erciyes.edu.tr [Department of Chemistry, Erciyes University, Faculty of Arts and Sciences, 38039 Kayseri (Turkey)

    2009-07-30

    The objective of this study was to assess the adsorption potential of a waste mud (WM) for the removal of lead (Pb(II)) ions from aqueous solutions. The WM was activated with NaOH in order to increase its adsorption capacity. Adsorption studies were conducted in a batch system as a function of solution pH, contact time, initial Pb(II) concentration, activated-waste mud (a-WM) concentration, temperature, etc. Optimum pH was specified as 4.0. The adsorption kinetic studies indicated that the overall adsorption process was best described by pseudo-second-order kinetics. The equilibrium adsorption capacity of a-WM was obtained by using Langmuir and Freundlich isotherm models and both models fitted well. Adsorption capacity for Pb(II) was found to be 24.4 mg g{sup -1} for 10 g L{sup -1} of a-WM concentration. Thermodynamic parameters including the Gibbs free energy ({Delta}G{sup o}), enthalpy ({Delta}H{sup o}), and entropy ({Delta}S{sup o}) indicated that the adsorption of Pb(II) ions on the a-WM was feasible, spontaneous and endothermic, at temperature range of 0-40 {sup o}C. Desorption studies were carried out successfully with diluted HCl solutions. The results indicate that a-WM can be used as an effective and no-cost adsorbent for the treatment of industrial wastewaters contaminated with Pb(II) ions.

  3. Measurement of Stark width of some Ar I transitions and the investigation of local thermodynamic equilibrium (LTE) in an atmospheric d.c. argon plasma jet

    International Nuclear Information System (INIS)

    Bakshi, V.

    1988-01-01

    The Stark widths of seven Ar I transitions are reported. Axial line shape data from an atmospheric d.c. argon plasma jet were Abel-inverted to obtain radial line shapes. The electron-density was determined by Stark width measurements of the hydrogen H β transition. In the electron-density region of ≤6 x 10 22 m -3 the experimental Ar I Stark widths are fitted to a linear dependence on the electron-density. Values of Stark width extrapolated to other electron densities are compared to measurements reported in the literature on the 4s-4p array. Experimental values are up to 45% smaller than those predicted by Griem's theory of Stark broadening. Conditions for local thermodynamic equilibrium (LTE) to exist in an atmospheric argon plasma jet were studied. The experiment measures the emission coefficient of seven Ar I transitions and the line shape of the hydrogen H beta transition. After transforming the side-on data into radial space the excited neutral argon atom-density and the electron-density are determined. It is found LTE does not exist below an electron-density of 6 x 10 33 m -3 in the experimental conditions

  4. Retrieval of Kinetic Temperature and Carbon Dioxide Abundance from Non-Local Thermodynamic Equilibrium Limb Emission Measurements made by the SABER Experiment on the TIMED Satellite

    Science.gov (United States)

    Mertens, Christopher J.; Mlynczak, Martin G.; Lopez-Puertas, Manuel; Wintersteiner, Peter P.; Picard, Richard H.; Winick, Jeremy R.; Gordley, Larry L.; Russell, James M., III

    2002-01-01

    The Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) experiment was launched onboard the TIMED satellite in December, 2001. SABER is designed to provide measurements of the key radiative and chemical sources and sinks of energy in the mesosphere and lower thermosphere (MLT). SABER measures Earth limb emission in 10 broadband radiometer channels ranging from 1.27 micrometers to 17 micrometers. Measurements are made both day and night over the latitude range from 54 deg. S to 87 deg. N with alternating hemisphere coverage every 60 days. In this paper we concentrate on retrieved profiles of kinetic temperature (T(sub k)) and CO2 volume mixing ratio (vmr), inferred from SABER-observed 15 micrometer and 4.3 micrometer limb emissions, respectively. SABER-measured limb radiances are in non-local thermodynamic equilibrium (non-LTE) in the MLT region. The complexity of non-LTE radiation transfer combined with the large volume of data measured by SABER requires new retrieval approaches and radiative transfer techniques to accurately and efficiently retrieve the data products. In this paper we present the salient features of the coupled non-LTE T(sub k)/CO2 retrieval algorithm, along with preliminary results.

  5. Assessment of solubility and speciation of U, Pu, Np, and Th in natural groundwaters: theory, thermodynamic data, and primary applications

    Energy Technology Data Exchange (ETDEWEB)

    Schweingruber, M

    1981-11-01

    The computer code MINEQL was adapted and extended to assess the solubility and speciation of radioactive waste nuclides in groundwaters under conditions which are expected to exist in the surroundings of planned underground repositories. By means of an additional data base including standard reaction enthalpies and heat capacities at 25/sup 0/C, the relevant equilibrium constants at 25/sup 0/C can be converted to other temperatures using Ulich's formulae. The activitiy coefficients for dissolved species are modelled with a temperature dependent function of the Davies' approximation type. The report is segmented in three main parts: (1) a review of the MINEQL fundamentals and a summary of the theory needed for the extensions; (2) an outline of the general program structure and of criteria applied to the selection of thermodynamic data; (3) a discussion of the results from first model applications to evaluate the solubility and speciation of U, Pu, Np and Th in two Swiss groundwaters, based either on the approach of negligible chemical disturbance or on a solid/solution titration concept. All thermodynamic data involved in this study are collected in an appendix, together with a compilation of references.

  6. Modern thermodynamics

    CERN Document Server

    Ben-Naim, Arieh

    2017-01-01

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

  7. Stochastic thermodynamics

    Science.gov (United States)

    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

  8. Thermodynamic Calculations for Systems Biocatalysis

    DEFF Research Database (Denmark)

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

    2015-01-01

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

  9. Choice of the thermodynamic variables

    International Nuclear Information System (INIS)

    Balian, R.

    1985-09-01

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

  10. Computer Program for Calculation of Complex Chemical Equilibrium Compositions and Applications II. Users Manual and Program Description. 2; Users Manual and Program Description

    Science.gov (United States)

    McBride, Bonnie J.; Gordon, Sanford

    1996-01-01

    This users manual is the second part of a two-part report describing the NASA Lewis CEA (Chemical Equilibrium with Applications) program. The program obtains chemical equilibrium compositions of complex mixtures with applications to several types of problems. The topics presented in this manual are: (1) details for preparing input data sets; (2) a description of output tables for various types of problems; (3) the overall modular organization of the program with information on how to make modifications; (4) a description of the function of each subroutine; (5) error messages and their significance; and (6) a number of examples that illustrate various types of problems handled by CEA and that cover many of the options available in both input and output. Seven appendixes give information on the thermodynamic and thermal transport data used in CEA; some information on common variables used in or generated by the equilibrium module; and output tables for 14 example problems. The CEA program was written in ANSI standard FORTRAN 77. CEA should work on any system with sufficient storage. There are about 6300 lines in the source code, which uses about 225 kilobytes of memory. The compiled program takes about 975 kilobytes.

  11. Determination of Ni{sup 2+} using an equilibrium ion exchange technique: Important chemical factors and applicability to environmental samples

    Energy Technology Data Exchange (ETDEWEB)

    Worms, Isabelle A.M. [CABE - Analytical and Biophysical Environmental Chemistry, University of Geneva, 30 quai Ernest Ansermet 1211 Geneva 4 (Switzerland); Wilkinson, Kevin J. [Department of Chemistry, University of Montreal C.P. 6128, succursale Centre-ville Montreal, H3C 3J7 (Canada)], E-mail: KJ.Wilkinson@umontreal.ca

    2008-05-26

    In natural waters, the determination of free metal concentrations is a key parameter for studying bioavailability. Unfortunately, few analytical tools are available for determining Ni speciation at the low concentrations found in natural waters. In this paper, an ion exchange technique (IET) that employs a Dowex resin is evaluated for its applicability to measure [Ni{sup 2+}] in freshwaters. The presence of major cations (e.g. Na, Ca and Mg) reduced both the times that were required for equilibration and the partition coefficient to the resin ({lambda}{sup '}{sub Ni}). IET measurements of [Ni{sup 2+}] in the presence of known ligands (citrate, diglycolate, sulfoxine, oxine and diethyldithiocarbamate) were verified by thermodynamic speciation models (MINEQL{sup +} and VisualMINTEQ). Results indicated that the presence of hydrophobic complexes (e.g. Ni(DDC){sub 2}{sup 0}) lead to an overestimation of the Ni{sup 2+} fraction. On the other hand, [Ni{sup 2+}] measurements that were made in the presence of amphiphilic complexes formed with humic substances (standard aquatic humic acid (SRHA) and standard aquatic fulvic acid (SRFA)) were well correlated to free ion concentrations that were calculated using a NICA-DONNAN model. An analytical method is also presented here to reduce the complexity of the calibration (due to the presence of many other cations) for the use of Dowex equilibrium ion exchange technique in natural waters.

  12. Experimental benchmark of non-local-thermodynamic-equilibrium plasma atomic physics codes; Validation experimentale des codes de physique atomique des plasmas hors equilibre thermodynamique local

    Energy Technology Data Exchange (ETDEWEB)

    Nagels-Silvert, V

    2004-09-15

    The main purpose of this thesis is to get experimental data for the testing and validation of atomic physics codes dealing with non-local-thermodynamical-equilibrium plasmas. The first part is dedicated to the spectroscopic study of xenon and krypton plasmas that have been produced by a nanosecond laser pulse interacting with a gas jet. A Thomson scattering diagnostic has allowed us to measure independently plasma parameters such as electron temperature, electron density and the average ionisation state. We have obtained time integrated spectra in the range between 5 and 10 angstroms. We have identified about one hundred xenon rays between 8.6 and 9.6 angstroms via the use of the Relac code. We have discovered unknown rays for the krypton between 5.2 and 7.5 angstroms. In a second experiment we have extended the wavelength range to the X UV domain. The Averroes/Transpec code has been tested in the ranges from 9 to 15 angstroms and from 10 to 130 angstroms, the first range has been well reproduced while the second range requires a more complex data analysis. The second part is dedicated to the spectroscopic study of aluminium, selenium and samarium plasmas in femtosecond operating rate. We have designed an interferometry diagnostic in the frequency domain that has allowed us to measure the expanding speed of the target's backside. Via the use of an adequate isothermal model this parameter has led us to know the plasma electron temperature. Spectra and emission times of various rays from the aluminium and selenium plasmas have been computed satisfactorily with the Averroes/Transpec code coupled with Film and Multif hydrodynamical codes. (A.C.)

  13. Errors in Sounding of the Atmosphere Using Broadband Emission Radiometry (SABER) Kinetic Temperature Caused by Non-Local Thermodynamic Equilibrium Model Parameters

    Science.gov (United States)

    Garcia-Comas, Maya; Lopez-Puertas, M.; Funke, B.; Bermejo-Pantaleon, D.; Marshall, Benjamin T.; Mertens, Christopher J.; Remsberg, Ellis E.; Mlynczak, Martin G.; Gordley, L. L.; Russell, James M.

    2008-01-01

    The vast set of near global and continuous atmospheric measurements made by the SABER instrument since 2002, including daytime and nighttime kinetic temperature (T(sub k)) from 20 to 105 km, is available to the scientific community. The temperature is retrieved from SABER measurements of the atmospheric 15 micron CO2 limb emission. This emission separates from local thermodynamic equilibrium (LTE) conditions in the rarefied mesosphere and thermosphere, making it necessary to consider the CO2 vibrational state non-LTE populations in the retrieval algorithm above 70 km. Those populations depend on kinetic parameters describing the rate at which energy exchange between atmospheric molecules take place, but some of these collisional rates are not well known. We consider current uncertainties in the rates of quenching of CO2 (v2 ) by N2 , O2 and O, and the CO2 (v2 ) vibrational-vibrational exchange to estimate their impact on SABER T(sub k) for different atmospheric conditions. The T(sub k) is more sensitive to the uncertainty in the latter two and their effects depend on altitude. The T(sub k) combined systematic error due to non-LTE kinetic parameters does not exceed +/- 1.5 K below 95 km and +/- 4-5 K at 100 km for most latitudes and seasons (except for polar summer) if the Tk profile does not have pronounced vertical structure. The error is +/- 3 K at 80 km, +/- 6 K at 84 km and +/- 18 K at 100 km under the less favourable polar summer conditions. For strong temperature inversion layers, the errors reach +/- 3 K at 82 km and +/- 8 K at 90 km. This particularly affects tide amplitude estimates, with errors of up to +/- 3 K.

  14. Experimental benchmark of non-local-thermodynamic-equilibrium plasma atomic physics codes; Validation experimentale des codes de physique atomique des plasmas hors equilibre thermodynamique local

    Energy Technology Data Exchange (ETDEWEB)

    Nagels-Silvert, V

    2004-09-15

    The main purpose of this thesis is to get experimental data for the testing and validation of atomic physics codes dealing with non-local-thermodynamical-equilibrium plasmas. The first part is dedicated to the spectroscopic study of xenon and krypton plasmas that have been produced by a nanosecond laser pulse interacting with a gas jet. A Thomson scattering diagnostic has allowed us to measure independently plasma parameters such as electron temperature, electron density and the average ionisation state. We have obtained time integrated spectra in the range between 5 and 10 angstroms. We have identified about one hundred xenon rays between 8.6 and 9.6 angstroms via the use of the Relac code. We have discovered unknown rays for the krypton between 5.2 and 7.5 angstroms. In a second experiment we have extended the wavelength range to the X UV domain. The Averroes/Transpec code has been tested in the ranges from 9 to 15 angstroms and from 10 to 130 angstroms, the first range has been well reproduced while the second range requires a more complex data analysis. The second part is dedicated to the spectroscopic study of aluminium, selenium and samarium plasmas in femtosecond operating rate. We have designed an interferometry diagnostic in the frequency domain that has allowed us to measure the expanding speed of the target's backside. Via the use of an adequate isothermal model this parameter has led us to know the plasma electron temperature. Spectra and emission times of various rays from the aluminium and selenium plasmas have been computed satisfactorily with the Averroes/Transpec code coupled with Film and Multif hydrodynamical codes. (A.C.)

  15. A non-local thermodynamical equilibrium line formation for neutral and singly ionized titanium in model atmospheres of reference A-K stars

    Science.gov (United States)

    Sitnova, T. M.; Mashonkina, L. I.; Ryabchikova, T. A.

    2016-09-01

    We construct a model atom for Ti I-II using more than 3600 measured and predicted energy levels of Ti I and 1800 energy levels of Ti II, and quantum mechanical photoionization cross-sections. Non-local thermodynamical equilibrium (NLTE) line formation for Ti I and Ti II is treated through a wide range of spectral types from A to K, including metal-poor stars with [Fe/H] down to -2.6 dex. NLTE leads to weakened Ti I lines and positive abundance corrections. The magnitude of NLTE corrections is smaller compared to the literature data for FGK atmospheres. NLTE leads to strengthened Ti II lines and negative NLTE abundance corrections. For the first time, we have performed NLTE calculations for Ti I-II in the 6500 ≤ Teff ≤ 13 000 K range. For four A-type stars, we derived in LTE an abundance discrepancy of up to 0.22 dex between Ti I and Ti II, which vanishes in NLTE. For four other A-B stars, with only Ti II lines observed, NLTE leads to a decrease of line-to-line scatter. An efficiency of inelastic Ti I + H I collisions was estimated from an analysis of Ti I and Ti II lines in 17 cool stars with -2.6 ≤ [Fe/H] ≤ 0.0. Consistent NLTE abundances from Ti I and Ti II were obtained by applying classical Drawinian rates for the stars with log g ≥ 4.1, and neglecting inelastic collisions with H I for the very metal-poor (VMP) giant HD 122563. For the VMP turn-off stars ([Fe/H] ≤ -2 and log g ≤ 4.1), we obtained the positive abundance difference Ti I-II already in LTE, which increases in NLTE. Accurate collisional data for Ti I and Ti II are necessary to help solve this problem.

  16. Quantum reference frames and their applications to thermodynamics.

    Science.gov (United States)

    Popescu, Sandu; Sainz, Ana Belén; Short, Anthony J; Winter, Andreas

    2018-07-13

    We construct a quantum reference frame, which can be used to approximately implement arbitrary unitary transformations on a system in the presence of any number of extensive conserved quantities, by absorbing any back action provided by the conservation laws. Thus, the reference frame at the same time acts as a battery for the conserved quantities. Our construction features a physically intuitive, clear and implementation-friendly realization. Indeed, the reference system is composed of the same types of subsystems as the original system and is finite for any desired accuracy. In addition, the interaction with the reference frame can be broken down into two-body terms coupling the system to one of the reference frame subsystems at a time. We apply this construction to quantum thermodynamic set-ups with multiple, possibly non-commuting conserved quantities, which allows for the definition of explicit batteries in such cases.This article is part of a discussion meeting issue 'Foundations of quantum mechanics and their impact on contemporary society'. © 2018 The Author(s).

  17. The thermodynamics of quantum Yang–Mills theory theory and applications

    CERN Document Server

    Hofmann, Ralf

    2012-01-01

    This book aims to provide advanced students and researchers with the text on a nonperturbative, thermodynamically grounded, and largely analytical approach to four-dimensional Quantum Gauge Theory. The terrestrial, astrophysical, and cosmological applications, mostly within the realm of low-temperature photon physics, are treated.

  18. Application of thermodynamic data from THEREDA with THROUHREACT; Anwendung thermodynamischer Daten aus THEREDA mit TOUGHREACT

    Energy Technology Data Exchange (ETDEWEB)

    Seher, Holger; Weyand, Torben; Bracke, Guido

    2017-02-15

    Codes from the TOUGH family are used by GRS for many issues of the final radioactive waste disposal. For geochemical modeling in highly saline solutions the project THEREDA offers qualified thermodynamic data sets with Pitzer parameters that can be used as input data for specific systems and geochemical codes. For the application of thermodynamic data base from THEREDA in model calculations with THROUGHREACT a tool for the reformatting of the data sets was developed. THROUGHREACT will be used in the future for modeling of reactive transport in final radioactive waste repositories including complex processes.

  19. A Tightly Coupled Non-Equilibrium Magneto-Hydrodynamic Model for Inductively Coupled RF Plasmas

    Science.gov (United States)

    2016-02-29

    development a tightly coupled magneto-hydrodynamic model for Inductively Coupled Radio- Frequency (RF) Plasmas. Non Local Thermodynamic Equilibrium (NLTE...for Inductively Coupled Radio-Frequency (RF) Plasmas. Non Local Thermodynamic Equilibrium (NLTE) effects are described based on a hybrid State-to-State...Inductively Coupled Plasma (ICP) torches have wide range of possible applications which include deposition of metal coatings, synthesis of ultra-fine powders

  20. Applications of thermodynamic calculations to Mg alloy design: Mg-Sn based alloy development

    International Nuclear Information System (INIS)

    Jung, In-Ho; Park, Woo-Jin; Ahn, Sang Ho; Kang, Dae Hoon; Kim, Nack J.

    2007-01-01

    Recently an Mg-Sn based alloy system has been investigated actively in order to develop new magnesium alloys which have a stable structure and good mechanical properties at high temperatures. Thermodynamic modeling of the Mg-Al-Mn-Sb-Si-Sn-Zn system was performed based on available thermodynamic, phase equilibria and phase diagram data. Using the optimized database, the phase relationships of the Mg-Sn-Al-Zn alloys with additions of Si and Sb were calculated and compared with their experimental microstructures. It is shown that the calculated results are in good agreement with experimental microstructures, which proves the applicability of thermodynamic calculations for new Mg alloy design. All calculations were performed using FactSage thermochemical software. (orig.)

  1. Ecosystem thermodynamics

    International Nuclear Information System (INIS)

    Gomez Palacio, German Rau

    1998-01-01

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

  2. An Application of Context- and Problem-Based Learning (C-PBL) into Teaching Thermodynamics

    Science.gov (United States)

    Baran, Mukadder; Sozbilir, Mustafa

    2017-05-01

    This study aims to investigate the applicability of context- and problem-based learning (C-PBL) into teaching thermodynamics and to examine its influence on the students' achievements in chemistry, retention of knowledge, students' attitudes, motivation and interest towards chemistry. The embedded mixed method design was utilized with a group of 13 chemistry students in a 2-year program of "Medical Laboratory and Techniques" at a state university in an underdeveloped city at the southeastern region of Turkey. The research data were collected via questionnaires regarding the students' attitudes, motivation and interest in chemistry, an achievement test on "thermodynamics" and interviews utilized to find out the applicability of C-PBL into thermodynamics. The findings demonstrated that C-PBL led a statistically significant increase in the students' achievement in thermodynamics and their interest in chemistry, while no statistically significant difference was observed in the students' attitudes and motivation towards chemistry before and after the intervention. The interviews revealed that C-PBL developed not only the students' communication skills but also their skills in using time effectively, making presentations, reporting research results and using technology. It was also found to increase their self-confidence together with the positive attitudes towards C-PBL and being able to associate chemistry with daily life. In light of these findings, it could be stated that it will be beneficial to increase the use of C-PBL in teaching chemistry.

  3. Extraction of 2-Phenylethanol (PEA) from Aqueous Solution Using Ionic Liquids: Synthesis, Phase Equilibrium Investigation, Selectivity in Separation, and Thermodynamic Models.

    Science.gov (United States)

    Domańska, Urszula; Okuniewska, Patrycja; Paduszyński, Kamil; Królikowska, Marta; Zawadzki, Maciej; Więckowski, Mikołaj

    2017-08-17

    This study assessed the effect of ionic liquids (ILs) on extraction of 2-phenylethanol (PEA) from aqueous phase. It consists the synthesis of four new ILs, their physicochemical properties, and experimental solubility measurements in water as well as liquid-liquid phase equilibrium in ternary systems. ILs are an important new media for imaging and sensing applications because of their solvation property, thermal stability, and negligible vapor pressure. However, complex procedures and nonmiscibility with water are often required in PEA extraction. Herein, a facile and general strategy using four ILs as extraction media including the synthesis of new bis(fluorosulfonyl)imide-based ILs, 1-hexyl-methylmorpholinium bis(fluorosulfonyl)imide, [HMMOR][FSI], N-octylisoquinolinium bis(fluorosulfonyl)imide, [OiQuin][FSI], 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide, [BMPYR][FSI], and N-triethyl-N-octylammonium bis(fluorosulfonyl)imide, [N 2228 ][FSI], were investigated. The thermal properties, density, viscosity, and surface tension of new ILs were measured. Calorimetric measurements (DSC) were used to determine the melting point and the enthalpy of melting as well as the glass transition temperature and heat capacity at glass transition of the ILs. The phase equilibrium in binary systems (IL + PEA, or water) and in ternary systems {IL (1) + PEA (2) + water (3)} at temperature T = 308.15 K and ambient pressure are reported. All systems present liquid-liquid equilibrium with the upper critical solution temperature (UCST). All ILs revealed complete miscibility with PEA. In all ternary systems immiscibility gap was observed, which classified measured systems as Treybal's type II. The two partially miscible binaries (IL + water) and (PEA + water) exist in these systems. The discussion contains the specific selectivity and the solute distribution ratio of separation for the used ILs. The commonly used NRTL model was used for the correlation of the experimental binary

  4. Small Systems and Limitations on the Use of Chemical Thermodynamics

    Science.gov (United States)

    Tovbin, Yu. K.

    2018-01-01

    Limitations on using chemical thermodynamics to describe small systems are formulated. These limitations follow from statistical mechanics for equilibrium and nonequilibrium processes and reflect (1) differences between characteristic relaxation times in momentum, energy, and mass transfer in different aggregate states of investigated systems; (2) achievements of statistical mechanics that allow us to determine criteria for the size of smallest region in which thermodynamics can be applied and the scale of the emergence of a new phase, along with criteria for the conditions of violating a local equilibrium. Based on this analysis, the main thermodynamic results are clarified: the phase rule for distorted interfaces, the sense and area of applicability of Gibbs's concept of passive forces, and the artificiality of Kelvin's equation as a result of limitations on the thermodynamic approach to considering small bodies. The wrongness of introducing molecular parameters into thermodynamic derivations, and the activity coefficient for an activated complex into the expression for a reaction rate constant, is demonstrated.

  5. Thermodynamics and energy conversion

    CERN Document Server

    Struchtrup, Henning

    2014-01-01

    This textbook gives a thorough treatment of engineering thermodynamics with applications to classical and modern energy conversion devices.   Some emphasis lies on the description of irreversible processes, such as friction, heat transfer and mixing, and the evaluation of the related work losses. Better use of resources requires high efficiencies, therefore the reduction of irreversible losses should be seen as one of the main goals of a thermal engineer. This book provides the necessary tools.   Topics include: car and aircraft engines,  including Otto, Diesel and Atkinson cycles, by-pass turbofan engines, ramjet and scramjet;  steam and gas power plants, including advanced regenerative systems, solar tower, and compressed air energy storage; mixing and separation, including reverse osmosis, osmotic powerplants, and carbon sequestration; phase equilibrium and chemical equilibrium, distillation, chemical reactors, combustion processes, and fuel cells; the microscopic definition of entropy.    The book i...

  6. Braun-Le Chatelier principle in dissipative thermodynamics

    OpenAIRE

    Pavelka, Michal; Grmela, Miroslav

    2016-01-01

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

  7. Out-of-equilibrium body potential measurements in pseudo-MOSFET for sensing applications

    Science.gov (United States)

    Benea, Licinius; Bawedin, Maryline; Delacour, Cécile; Ionica, Irina

    2018-05-01

    The aim of this paper is to present the out-of-equilibrium body potential behaviour in the Ψ-MOSFET configuration. Consistent measurements in this experimental setup succeeded in providing a substantial understanding of its characteristics in the depletion region. The final objective of this work is to envision this new measurement technique for biochemical sensor applications. Among its advantages, the most important are its simplicity, the good sensitivity, the measurement of a potential instead of a current and the low bias needed for detection compared to the conventional drain current measurements.

  8. The use of computational thermodynamics to predict properties of multicomponent materials for nuclear applications

    International Nuclear Information System (INIS)

    Sundman, B.; Gueneau, C.

    2013-01-01

    Computational Thermodynamics is based on physically realistic models to describe metallic and oxide crystalline phases as well as the liquid and gas in a consistent manner. The models are used to assess experimental and theoretical data for many different materials and several thermodynamic databases has been developed for steels, ceramics, semiconductor materials as well as materials for nuclear applications. Within CEA a long term work is ongoing to develop a database for the properties of nuclear fuels and structural materials. An overview of the modelling technique will be given and several examples of the application of the database to different problems, both for traditional phase diagram calculations and its use in simulating phase transformations. The following diagrams (Fig. 1, Fig. 2 and Fig.3) show calculations in the U-Pu-O system. (authors)

  9. Application of a Thermodynamic Concept for the Analysis of Structural Degradation of Soap Thickened Lubricating Greases

    Directory of Open Access Journals (Sweden)

    Erik Kuhn

    2018-01-01

    Full Text Available Lubricating greases are special lubricants with a wide range of application. The tribologically stressed grease is used as tribological system and finally modeled as an open thermodynamic system. This study investigated the phenomenon of self-optimization and applied to the process of shearing a grease. The conditions for self-optimization and the consequences of created dissipative structures are investigated according to the interpreted literature.

  10. Nanofluidics thermodynamic and transport properties

    CERN Document Server

    Michaelides, Efstathios E (Stathis)

    2014-01-01

    This volume offers a comprehensive examination of the subject of heat and mass transfer with nanofluids as well as a critical review of the past and recent research projects in this area. Emphasis is placed on the fundamentals of the transport processes using particle-fluid suspensions, such as nanofluids. The nanofluid research is examined and presented in a holistic way using a great deal of our experience with the subjects of continuum mechanics, statistical thermodynamics, and non-equilibrium thermodynamics of transport processes. Using a thorough database, the experimental, analytical, and numerical advances of recent research in nanofluids are critically examined and connected to past research with medium and fine particles as well as to functional engineering systems. Promising applications and technological issues of heat/mass transfer system design with nanofluids are also discussed. This book also: Provides a deep scientific analysis of nanofluids using classical thermodynamics and statistical therm...

  11. Elements of chemical thermodynamics

    CERN Document Server

    Nash, Leonard K

    2005-01-01

    This survey of purely thermal data in calculating the position of equilibrium in a chemical reaction highlights the physical content of thermodynamics, as distinct from purely mathematical aspects. 1970 edition.

  12. 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

  13. Modeling the Non-Equilibrium Process of the Chemical Adsorption of Ammonia on GaN(0001) Reconstructed Surfaces Based on Steepest-Entropy-Ascent Quantum Thermodynamics

    OpenAIRE

    Kusaba, Akira; Li, Guanchen; von Spakovsky, Michael R.; Kangawa, Yoshihiro; Kakimoto, Koichi

    2017-01-01

    Clearly understanding elementary growth processes that depend on surface reconstruction is essential to controlling vapor-phase epitaxy more precisely. In this study, ammonia chemical adsorption on GaN(0001) reconstructed surfaces under metalorganic vapor phase epitaxy (MOVPE) conditions (3Ga-H and Nad-H + Ga-H on a 2 × 2 unit cell) is investigated using steepest-entropy-ascent quantum thermodynamics (SEAQT). SEAQT is a thermodynamic-ensemble based, first-principles framework that can predict...

  14. Reply to 'Photon emission from sputtered atoms - the observation of apparent local thermodynamic equilibrium in the excitation' by R.J. MacDonald, R.F. Garrett and P.J. Martin

    International Nuclear Information System (INIS)

    Tsong, I.S.T.

    1978-01-01

    MacDonald, Garrett and Martin have measured the intensities of spectral lines of Fe and Ni in alloy samples to study the problem of local thermodynamic equilibrium (LTE) in sputtering by plotting log(Ilambda 3 /gf) versus E. The measurements were made using a spectrometer with good resolution, 0.4 A, and great care was exercised in selecting only the lines free from interference or overlap. While the author agrees that their experimental approach is superior to the one attempted earlier and their experimental data are therefore more accurate, he does not agree with their data analysis. (Auth.)

  15. Statistical mechanics and the foundations of thermodynamics

    International Nuclear Information System (INIS)

    Martin-Loef, A.

    1979-01-01

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

  16. Application potential of grapefruit peel as dye sorbent: Kinetics, equilibrium and mechanism of crystal violet adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Saeed, Asma, E-mail: asmadr@wol.net.pk [Environmental Biotechnology Group, Biotechnology and Food Research Centre, PCSIR Laboratories Complex, Ferozepur Road, Lahore 54600 (Pakistan); Sharif, Mehwish [School of Biological Sciences, University of the Punjab, Lahore 54590 (Pakistan); Iqbal, Muhammad [Environmental Biotechnology Group, Biotechnology and Food Research Centre, PCSIR Laboratories Complex, Ferozepur Road, Lahore 54600 (Pakistan)

    2010-07-15

    This study reports the sorption of crystal violet (CV) dye by grapefruit peel (GFP), which has application potential in the remediation of dye-contaminated wastewaters using a solid waste generated by the citrus fruit juice industry. Batch adsorption of CV was conducted to evaluate the effect of initial pH, contact time, temperature, initial dye concentration, GFP adsorbent dose, and removal of the adsorbate CV dye from aqueous solution to understand the mechanism of sorption involved. Sorption equilibrium reached rapidly with 96% CV removal in 60 min. Fit of the sorption experimental data was tested on the pseudo-first and pseudo-second-order kinetics mathematical equations, which was noted to follow the pseudo-second-order kinetics better, with coefficient of correlation {>=}0.992. The equilibrium process was well described by the Langmuir isotherm model, with maximum sorption capacity of 254.16 mg g{sup -1}. The GFP was regenerated using 1 M NaOH, with up to 98.25% recovery of CV and could be reused as a dye sorbent in repeated cycles. GFP was also shown to be highly effective in removing CV from aqueous solution in continuous-flow fixed-bed column reactors. The study shows that GFP has the potential of application as an efficient sorbent for the removal of CV from aqueous solutions.

  17. Application potential of grapefruit peel as dye sorbent: Kinetics, equilibrium and mechanism of crystal violet adsorption

    International Nuclear Information System (INIS)

    Saeed, Asma; Sharif, Mehwish; Iqbal, Muhammad

    2010-01-01

    This study reports the sorption of crystal violet (CV) dye by grapefruit peel (GFP), which has application potential in the remediation of dye-contaminated wastewaters using a solid waste generated by the citrus fruit juice industry. Batch adsorption of CV was conducted to evaluate the effect of initial pH, contact time, temperature, initial dye concentration, GFP adsorbent dose, and removal of the adsorbate CV dye from aqueous solution to understand the mechanism of sorption involved. Sorption equilibrium reached rapidly with 96% CV removal in 60 min. Fit of the sorption experimental data was tested on the pseudo-first and pseudo-second-order kinetics mathematical equations, which was noted to follow the pseudo-second-order kinetics better, with coefficient of correlation ≥0.992. The equilibrium process was well described by the Langmuir isotherm model, with maximum sorption capacity of 254.16 mg g -1 . The GFP was regenerated using 1 M NaOH, with up to 98.25% recovery of CV and could be reused as a dye sorbent in repeated cycles. GFP was also shown to be highly effective in removing CV from aqueous solution in continuous-flow fixed-bed column reactors. The study shows that GFP has the potential of application as an efficient sorbent for the removal of CV from aqueous solutions.

  18. Application potential of grapefruit peel as dye sorbent: kinetics, equilibrium and mechanism of crystal violet adsorption.

    Science.gov (United States)

    Saeed, Asma; Sharif, Mehwish; Iqbal, Muhammad

    2010-07-15

    This study reports the sorption of crystal violet (CV) dye by grapefruit peel (GFP), which has application potential in the remediation of dye-contaminated wastewaters using a solid waste generated by the citrus fruit juice industry. Batch adsorption of CV was conducted to evaluate the effect of initial pH, contact time, temperature, initial dye concentration, GFP adsorbent dose, and removal of the adsorbate CV dye from aqueous solution to understand the mechanism of sorption involved. Sorption equilibrium reached rapidly with 96% CV removal in 60 min. Fit of the sorption experimental data was tested on the pseudo-first and pseudo-second-order kinetics mathematical equations, which was noted to follow the pseudo-second-order kinetics better, with coefficient of correlation > or = 0.992. The equilibrium process was well described by the Langmuir isotherm model, with maximum sorption capacity of 254.16 mg g(-1). The GFP was regenerated using 1 M NaOH, with up to 98.25% recovery of CV and could be reused as a dye sorbent in repeated cycles. GFP was also shown to be highly effective in removing CV from aqueous solution in continuous-flow fixed-bed column reactors. The study shows that GFP has the potential of application as an efficient sorbent for the removal of CV from aqueous solutions. 2010 Elsevier B.V. All rights reserved.

  19. Information-theoretic equilibrium and observable thermalization

    OpenAIRE

    Anza, Fabio; Vedral, Vlatko

    2015-01-01

    To understand under which conditions thermodynamics emerges from the microscopic dynamics is the ultimate goal of statistical mechanics. Despite the fact that the theory is more than 100 years old, we are still discussing its foundations and its regime of applicability. A point of crucial importance is the definition of the notion of thermal equilibrium, which is given as the state that maximises the von Neumann entropy. Here we argue that it is necessary to propose a new way of describing th...

  20. Derivation of the Second Law of Thermodynamics from Boltzmann's Distribution Law.

    Science.gov (United States)

    Nelson, P. G.

    1988-01-01

    Shows how the thermodynamic condition for equilibrium in an isolated system can be derived by the application of Boltzmann's law to a simple physical system. States that this derivation could be included in an introductory course on chemical equilibrium to help prepare students for a statistical mechanical treatment presented in the curriculum.…

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

    International Nuclear Information System (INIS)

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

    2011-01-01

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

  2. Time-Depending Parametric Variational Approach for an Economic General Equilibrium Problem of Pure Exchange with Application

    International Nuclear Information System (INIS)

    Scaramuzzino, F.

    2009-01-01

    This paper considers a qualitative analysis of the solution of a pure exchange general economic equilibrium problem according to two independent parameters. Some recently results obtained by the author in the static and the dynamic case have been collected. Such results have been applied in a particular parametric case: it has been focused the attention on a numerical application for which the existence of the solution of time-depending parametric variational inequality that describes the equilibrium conditions has been proved by means of the direct method. By using MatLab computation after a linear interpolation, the curves of equilibrium have been visualized.

  3. Applicability of thermodynamic database of radioactive elements developed for the Japanese performance assessment of HLW repository

    International Nuclear Information System (INIS)

    Yui, Mikazu; Shibata, Masahiro; Rai, Dhanpat; Ochs, Michael

    2003-01-01

    In 1999 Japan Nuclear Cycle Development Institute (JNC) published a second progress report (also known as H12 report) on high-level radioactive waste (HLW) disposal in Japan (JNC 1999). This report helped to develop confidence in the selected HLW disposal system and to establish the implementation body in 2000 for the disposal of HLW. JNC developed an in-house thermodynamic database for radioactive elements for performance analysis of the engineered barrier system (EBS) and the geosphere for H12 report. This paper briefly presents the status of the JNC's thermodynamic database and its applicability to perform realistic analyses of the solubilities of radioactive elements, evolution of solubility-limiting solid phases, predictions of the redox state of Pu in the neutral pH range under reducing conditions, and to estimate solubilities of radioactive elements in cementitious conditions. (author)

  4. Equilibrium Dialysis

    African Journals Online (AJOL)

    context of antimicrobial therapy in malnutrition. Dialysis has in the past presented technical problems, being complicated and time-consuming. A new dialysis system based on the equilibrium technique has now become available, and it is the principles and practical application of this apparatus (Kontron Diapack; Kontron.

  5. Application of solution-mineral equilibrium chemistry to solution mining of uranium ores

    International Nuclear Information System (INIS)

    Riese, A.C.; Propp, C.J.

    1980-01-01

    Modern methods of uranium solution mining are typically accompanied by gains and losses of mass through reagent consumption by rock-forming minerals, with subsequent formation of clay minerals, gypsum, carbonates, and iron oxyhydroxides. A systematic approach to alleviate such problems involves the application of leach solutions that are in equilibrium with the host-rock minerals but in disequilibrium with the ore-forming minerals. This partial equilibrium can be approximated by solution-composition adjustments within the systems K 2 O-Al 2 O 3 SiO 2 -H 2 O and Na 2 O 3 -Al 2 O 3 SiO 2 -H 2 O. Uranium ore containing 0.15 percent U 3 O 8 from the Gulf Mineral Resources Corporation's Mariano Lake mine, the Smith Lake district of the Grants mineral belt, was collected for investigation. Presented are a theoretical evaluation of leachate data and an experimental treatment of the ore, which contained mainly K-feldspar, plagioclase feldspar, and quartz (with lesser amounts of micas, clay minerals, and organic carbonaceous material). Small-scale (less than or equal to 1 kg) column-leaching experiments were conducted to model the results of conventional leaching operations and to provide leachate solutions that could be compared with solutions calculated to be in equilibrium with the matrix minerals. Leach solutions employed include: 1) sulfuric acid, 2) sodium bicarbonate, and 3) sulfuric acid with 1.0 molal potassium chloride. The uranium concentrations in the sodium-bicarbonate leach solution and the acid-leach solution were about a gram per liter at the termination of the tests. However, the permeability of the ore in the acid leach was greatly reduced, owing to the formation of clay minerals. Uranium solubility in the leach column stabilized with the potassium-chloride solution was calculated from leachate compositions to be limited by the solubility of carnotite

  6. On Thermodynamic Interpretation of Transfer Entropy

    Directory of Open Access Journals (Sweden)

    Don C. Price

    2013-02-01

    Full Text Available We propose a thermodynamic interpretation of transfer entropy near equilibrium, using a specialised Boltzmann’s principle. The approach relates conditional probabilities to the probabilities of the corresponding state transitions. This in turn characterises transfer entropy as a difference of two entropy rates: the rate for a resultant transition and another rate for a possibly irreversible transition within the system affected by an additional source. We then show that this difference, the local transfer entropy, is proportional to the external entropy production, possibly due to irreversibility. Near equilibrium, transfer entropy is also interpreted as the difference in equilibrium stabilities with respect to two scenarios: a default case and the case with an additional source. Finally, we demonstrated that such a thermodynamic treatment is not applicable to information flow, a measure of causal effect.

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

    International Nuclear Information System (INIS)

    Cheng, XueTao; Liang, XinGang

    2013-01-01

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

  8. ISORROPIA II: a computationally efficient thermodynamic equilibrium model for K+─Ca²+─Mg²+─NH4+─Na+─SO4²-─NO3-─Cl-─H2O aerosols

    Directory of Open Access Journals (Sweden)

    C. Fountoukis

    2007-09-01

    Full Text Available This study presents ISORROPIA II, a thermodynamic equilibrium model for the K+–Ca2+–Mg2+–NH4+–Na+–SO42−–NO3−–Cl−–H2O aerosol system. A comprehensive evaluation of its performance is conducted against water uptake measurements for laboratory aerosol and predictions of the SCAPE2 thermodynamic module over a wide range of atmospherically relevant conditions. The two models agree well, to within 13% for aerosol water content and total PM mass, 16% for aerosol nitrate and 6% for aerosol chloride and ammonium. Largest discrepancies were found under conditions of low RH, primarily from differences in the treatment of water uptake and solid state composition. In terms of computational speed, ISORROPIA II was more than an order of magnitude faster than SCAPE2, with robust and rapid convergence under all conditions. The addition of crustal species does not slow down the thermodynamic calculations (compared to the older ISORROPIA code because of optimizations in the activity coefficient calculation algorithm. Based on its computational rigor and performance, ISORROPIA II appears to be a highly attractive alternative for use in large scale air quality and atmospheric transport models.

  9. Equilibrium statistical mechanics

    CERN Document Server

    Mayer, J E

    1968-01-01

    The International Encyclopedia of Physical Chemistry and Chemical Physics, Volume 1: Equilibrium Statistical Mechanics covers the fundamental principles and the development of theoretical aspects of equilibrium statistical mechanics. Statistical mechanical is the study of the connection between the macroscopic behavior of bulk matter and the microscopic properties of its constituent atoms and molecules. This book contains eight chapters, and begins with a presentation of the master equation used for the calculation of the fundamental thermodynamic functions. The succeeding chapters highlight t

  10. Computing Equilibrium Chemical Compositions

    Science.gov (United States)

    Mcbride, Bonnie J.; Gordon, Sanford

    1995-01-01

    Chemical Equilibrium With Transport Properties, 1993 (CET93) computer program provides data on chemical-equilibrium compositions. Aids calculation of thermodynamic properties of chemical systems. Information essential in design and analysis of such equipment as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical-processing equipment. CET93/PC is version of CET93 specifically designed to run within 640K memory limit of MS-DOS operating system. CET93/PC written in FORTRAN.

  11. Fundamental Research in Engineering Education. Development of Concept Questions and Inquiry-Based Activities in Thermodynamics and Heat Transfer: An Example for Equilibrium vs. Steady-State

    Science.gov (United States)

    Vigeant, Margot; Prince, Michael; Nottis, Katharyn

    2011-01-01

    This study examines the use of inquiry-based instruction to promote the understanding of critical concepts in thermodynamics and heat transfer. Significant research shows that students frequently enter our courses with tightly held misconceptions about the physical world that are not effectively addressed through traditional instruction. Students'…

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  13. Application of computational chemistry methods to obtain thermodynamic data for hydrogen production from liquefied petroleum gas

    Directory of Open Access Journals (Sweden)

    J. A. Sousa

    2013-03-01

    Full Text Available The objective of this study was to estimate thermodynamic data, such as standard enthalpy, entropy and Gibbs free energy changes of reaction and, consequently, chemical equilibrium constants, for a reaction system describing the hydrogen production from Liquefied Petroleum Gas (LPG. The acquisition of those properties was made using computational chemistry methods and the results were compared with experimental data reported in the literature. The reaction system of steam reforming of LPG was reported as a set of seven independent reactions involving the chemical species n-C4H10, C3H8, C2H6, C2H4, CH4, CO2, CO, H2O, H2 and solid carbon. Six computational approaches were used: Density Functional Theory (DFT employing Becke's three parameter hybrid exchange functional, and the Lee-Yang-Parr correlation functional (B3LYP using the 6-31G++(d,p basis set and the composite methods CBS-QB3, Gaussian-1 (G1, Gaussian-2 (G2, Gaussian-3 (G3 and Gaussian-4 (G4. Mole fractions of the system components were also determined between 873.15 and 1173.15 K, at 1 atm and a feed with a stoichiometric amount of water. Results showed that the hybrid functional B3LYP/6-31G++(d,p, G3 and G4 theories were the most appropriated methods to predict the properties of interest. Gaussian-3 and Gaussian-4 theories are expected to be good thermodynamic data predictors and the known efficient prediction of vibrational frequencies by B3LYP is probably the source of the good agreement found in this study. This last methodology is of special interest since it presents low computational cost, which is important when more complex molecular systems are considered.

  14. Liquid-liquid equilibrium of water + PEG 8000 + magnesium sulfate or sodium sulfate aqueous two-phase systems at 35°C: experimental determination and thermodynamic modeling

    Directory of Open Access Journals (Sweden)

    B. D. Castro

    2005-09-01

    Full Text Available Liquid-liquid extraction using aqueous two-phase systems is a highly efficient technique for separation and purification of biomolecules due to the mild properties of both liquid phases. Reliable data on the phase behavior of these systems are essential for the design and operation of new separation processes; several authors reported phase diagrams for polymer-polymer systems, but data on polymer-salt systems are still relatively scarce. In this work, experimental liquid-liquid equilibrium data on water + polyethylene glycol 8000 + magnesium sulfate and water + polyethylene glycol 8000 + sodium sulfate aqueous two-phase systems were obtained at 35°C. Both equilibrium phases were analyzed by lyophilization and ashing. Experimental results were correlated with a mass-fraction-based NRTL activity coefficient model. New interaction parameters were estimated with the Simplex method. The mean deviations between the experimental and calculated compositions in both equilibrium phases is about 2%.

  15. Atmospheric thermodynamics

    CERN Document Server

    Iribarne, J V

    1973-01-01

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

  16. Thermodynamic holography

    Science.gov (United States)

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

    2015-01-01

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

  17. Determination and thermodynamic modeling of solid–liquid phase equilibrium for 3,5-dichloroaniline in pure solvents and ternary 3,5-dichloroaniline + 1,3,5-trichlorobenzene + toluene system

    International Nuclear Information System (INIS)

    Li, Rongrong; Du, Cunbin; Meng, Long; Han, Shuo; Wang, Jian; Zhao, Hongkun

    2016-01-01

    Highlights: • Solubility of 3,5-dichloroaniline in seven organic solvents were determined. • Solid–liquid phase equilibrium for ternary system was measured. • The binary and ternary phase diagrams were constructed. • The phase diagrams were correlated with thermodynamic models. - Abstract: The solid–liquid phase equilibrium data for 3,5-dichloroaniline in n-propanol, isopropanol, n-butanol, isobutanol, toluene, ethyl acetate and acetone at (283.15 to 308.15) K were determined experimentally by gas chromatography under 101.3 kPa. The solubility of 3,5-dichloroaniline in these solvents decreased according to the following order: ethyl acetate > (acetone, toluene) for the solvents of ethyl acetate, acetone, and toluene; and for the other solvents, (isopropanol, n-butanol) > n-propanol > isobutanol. According to the solubility of 3,5-dichloroaniline in pure solvents, the solid–liquid phase equilibrium for the ternary mixture of 3,5-dichloroaniline + 1,3,5-trichlorobenzene + toluene were measured by using an isothermal saturation method at three temperatures of 283.15, 293.15, and 303.15 K under 101.3 kPa, and the corresponding isothermal phase diagrams were constructed. Two pure solids were formed in the ternary system at a fixed temperature, which were pure 3,5-dichloroaniline and pure 1,3,5-trichlorobenzene and were identified by Schreinemakers’ method of wet residue. The temperature dependence of 3,5-dichloroaniline solubility in pure solvents was correlated by the modified Apelblat equation, λh equation, Wilson model and NRTL model; and the ternary solid–liquid phase equilibrium of 3,5-dichloroaniline + 1,3,5-trichlorobenzene + toluene were described by the Wilson model and NRTL model. Results showed that calculated solubility values with these models agreed well with the experimental ones for the studied binary and ternary systems. The solid–liquid equilibrium and the thermodynamic models for the binary and ternary systems can offer the

  18. Non equilibrium atomic processes and plasma spectroscopy

    International Nuclear Information System (INIS)

    Kato, Takako

    2003-01-01

    Along with the technical progress in plasma spectroscopy, non equilibrium ionization processes have been recently observed. We study non local thermodynamic equilibrium and non ionization equilibrium for various kinds of plasmas. Specifically we discuss non equilibrium atomic processes in magnetically confined plasmas, solar flares and laser produced plasmas using a collisional radiative model based on plasma spectroscopic data. (author)

  19. Application of exergy analysis to the thermodynamical study of operation cycles of diesel engines

    Energy Technology Data Exchange (ETDEWEB)

    Zellat, M

    1987-01-01

    To simulate the operation cycle of a diesel engine a general methodology is proposed, called as exergy theory, based on the simultaneous application of the first and second principles of thermodynamics. This analysis accounts for the exergy losses in function of what can be recovered from the second principle and give a more fruitful representation than the pure energy analysis which takes into account only the first principle. The concept of a recovery power turbine RPT, linked to the driving shaft and declutchable is described. The yield increase in nominal power and at half-charge when the RPT is disconnected, is explained by exergy analysis.

  20. Introduction into thermodynamics. From elements to technical applications. 12. rev. ed.

    International Nuclear Information System (INIS)

    Cerbe, G.; Hoffmann, H.J.

    1999-01-01

    This textbook has been proved for more than 30 years and has been regularly revised and updated. Thus, recent developments in energy conversion and environmental protection have constantly been taken into account. Tabulated values and standards reflect the current state of things. The book's basic concept was maintained without change from the first to the twelfth edition: leading over from well-founded thermodynamic theory to technical applications, closeness to practice because of many examples with solutions and tasks with solution results, the opportunity for self-study with 124 examples, 132 tasks and 170 control questions with answers, and high usability because of many tables and direct-information diagrams. (orig.) [de

  1. Statistical equilibrium equations for trace elements in stellar atmospheres

    OpenAIRE

    Kubat, Jiri

    2010-01-01

    The conditions of thermodynamic equilibrium, local thermodynamic equilibrium, and statistical equilibrium are discussed in detail. The equations of statistical equilibrium and the supplementary equations are shown together with the expressions for radiative and collisional rates with the emphasize on the solution for trace elements.

  2. Thermodynamic model for predicting equilibrium conditions of clathrate hydrates of noble gases + light hydrocarbons: Combination of Van der Waals–Platteeuw model and sPC-SAFT EoS

    International Nuclear Information System (INIS)

    Abolala, Mostafa; Varaminian, Farshad

    2015-01-01

    Highlights: • Applying sPC-SAFT for phase equilibrium calculations. • Determining Kihara potential parameters for hydrate formers. • Successful usage of the model for systems with hydrate azeotropes. - Abstract: In this communication, equilibrium conditions of clathrate hydrates containing mixtures of noble gases (Argon, Krypton and Xenon) and light hydrocarbons (C 1 –C 3 ), which form structure I and II, are modeled. The thermodynamic model is based on the solid solution theory of Van der Waals–Platteeuw combined with the simplified Perturbed-Chain Statistical Association Fluid Theory equation of state (sPC-SAFT EoS). In dispersion term of sPC-SAFT EoS, the temperature dependent binary interaction parameters (k ij ) are adjusted; taking advantage of the well described (vapor + liquid) phase equilibria. Furthermore, the Kihara potential parameters are optimized based on the P–T data of pure hydrate former. Subsequently, these obtained parameters are used to predict the binary gas hydrate dissociation conditions. The equilibrium conditions of the binary gas hydrates predicted by this model agree well with experimental data (overall AAD P ∼ 2.17)

  3. Chemical Equilibrium Modeling of Hanford Waste Tank Processing: Applications of Fundamental Science

    International Nuclear Information System (INIS)

    Felmy, Andrew R.; Wang, Zheming; Dixon, David A.; Hess, Nancy J.

    2004-01-01

    The development of computational models based upon fundamental science is one means of quantitatively transferring the results of scientific investigations to practical application by engineers in laboratory and field situations. This manuscript describes one example of such efforts, specifically the development and application of chemical equilibrium models to different waste management issues at the U.S. Department of Energy (DOE) Hanford Site. The development of the chemical models is described with an emphasis on the fundamental science investigations that have been undertaken in model development followed by examples of different waste management applications. The waste management issues include the leaching of waste slurries to selective remove non-hazardous components and the separation of Sr90 and transuranics from the waste supernatants. The fundamental science contributions include: molecular simulations of the energetics of different molecular clusters to assist in determining the species present in solution, advanced synchrotron research to determine the chemical form of precipitates, and laser based spectroscopic studies of solutions and solids.

  4. Phases, periphases, and interphases equilibrium by molecular modeling. I. Mass equilibrium by the semianalytical stochastic perturbations method and application to a solution between (120) gypsum faces

    Science.gov (United States)

    Pedesseau, Laurent; Jouanna, Paul

    2004-12-01

    importance for all coupled chemical-mechanical problems dealing with interfaces, and more generally for a wide variety of applications such as phase changes, osmotic equilibrium, surface energy, etc., in complex chemical-physics situations.

  5. Thermodynamics of gas-metal-slag equilibria for applications in in situ and ex situ vitrification melts

    International Nuclear Information System (INIS)

    Miller, R.L.; Reimann, G.A.

    1993-05-01

    An equilibrium thermodynamic model for melting mixed waste was evaluated using the STEPSOL computer code. STEPSOL uses free energy minimization techniques to predict equilibrium composition from input species and user selected species in the output. The model assumes equilibrium between gas, slag, and metallic phases. Input for the model was developed using compositional data from Pit 9 of the Subsurface Disposal Area at the Idaho National Engineering Laboratory. Thermodynamic data were primarily from compilations published by the US Government. The results of model evaluation indicate that the amount of plutonium chloride or plutonium oxyhydroxide that would be evaporated into the vapor phase would be minor. Relatively more uranium chloride and uranium oxyhydroxide would be vaporized. However, a hazards analysis was not part of the present task. Minor amounts of plutonium and uranium would be reduced to the metallic state, but these amounts should alloy with the iron-chromium-nickel metallic phase. The vast majority of the plutonium and uranium are in the slag phase as oxides. Results of the calculations show that silica and silicates dominate the products and that the system is very reducing. The major gases are carbon monoxide and hydrogen, with lesser amounts of carbon dioxide and water. High vapor pressure metals are considered but were not analyzed using STEPSOL. STEPSOL does not make predictions of distribution of species between phases

  6. Accuracy and precision of polar lower stratospheric temperatures from reanalyses evaluated from A-Train CALIOP and MLS, COSMIC GPS RO, and the equilibrium thermodynamics of supercooled ternary solutions and ice clouds

    Science.gov (United States)

    Lambert, Alyn; Santee, Michelle L.

    2018-02-01

    We investigate the accuracy and precision of polar lower stratospheric temperatures (100-10 hPa during 2008-2013) reported in several contemporary reanalysis datasets comprising two versions of the Modern-Era Retrospective analysis for Research and Applications (MERRA and MERRA-2), the Japanese 55-year Reanalysis (JRA-55), the European Centre for Medium-Range Weather Forecasts (ECMWF) interim reanalysis (ERA-I), and the National Oceanic and Atmospheric Administration (NOAA) National Centers for Environmental Prediction (NCEP) Climate Forecast System Reanalysis (NCEP-CFSR). We also include the Goddard Earth Observing System model version 5.9.1 near-real-time analysis (GEOS-5.9.1). Comparisons of these datasets are made with respect to retrieved temperatures from the Aura Microwave Limb Sounder (MLS), Constellation Observing System for Meteorology, Ionosphere and Climate (COSMIC) Global Positioning System (GPS) radio occultation (RO) temperatures, and independent absolute temperature references defined by the equilibrium thermodynamics of supercooled ternary solutions (STSs) and ice clouds. Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) observations of polar stratospheric clouds are used to determine the cloud particle types within the Aura MLS geometric field of view. The thermodynamic calculations for STS and the ice frost point use the colocated MLS gas-phase measurements of HNO3 and H2O. The estimated bias and precision for the STS temperature reference, over the 68 to 21 hPa pressure range, are 0.6-1.5 and 0.3-0.6 K, respectively; for the ice temperature reference, they are 0.4 and 0.3 K, respectively. These uncertainties are smaller than those estimated for the retrieved MLS temperatures and also comparable to GPS RO uncertainties (bias 0.7 K) in the same pressure range. We examine a case study of the time-varying temperature structure associated with layered ice clouds formed by orographic gravity waves forced by flow over the Palmer Peninsula and

  7. 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)

  8. Thermodynamic Study of Solid-Liquid Equilibrium in NaCl-NaBr-H2O System at 288.15 K

    Science.gov (United States)

    Li, Dan; Meng, Ling-zong; Deng, Tian-long; Guo, Ya-fei; Fu, Qing-Tao

    2018-06-01

    The solubility data, composition of the solid solution and refractive indices of the NaCl-NaBr-H2O system at 288.15 K were studied with the isothermal equilibrium dissolution method. The solubility diagram and refractive index diagram of this system were plotted at 288.15 K. The solubility diagram consists of two crystallization zones for solid solution Na(Cl,Br) · 2H2O and Na(Cl,Br), one invariant points cosaturated with two solid solution and two univariant solubility isothermal curves. On the basis of Pitzer and Harvie-Weare (HW) chemical models, the composition equations and solubility equilibrium constant equations of the solid solutions at 288.15 K were acquired using the solubility data, the composition of solid solutions, and binary Pitzer parameters. The solubilities calculated using the new method combining the equations are in good agreement with the experimental data.

  9. Thermodynamic extremal principles for irreversible processes in materials science

    Czech Academy of Sciences Publication Activity Database

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

    2014-01-01

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

  10. Thermodynamic modeling of the insoluble phases in the nuclear waste glasses. Application to the vitrification of molybdenum and of platinoid fission products

    International Nuclear Information System (INIS)

    Bordier, Sebastien

    2015-01-01

    calculations in relation with the industrial vitrification process. The thermodynamic calculations in the ternary oxide System Na_2O-SiO_2-MoO_3 revealed the possible equilibrium of two immiscible liquids. The thermodynamic solubility of the molybdenum in the melt is clearly characterized. These calculations enable to determine the nature and the proportion of the molybdate phases formed when the glass is cooled and allow to calculate the equilibrium vapor pressure of these phases. As an example, some application calculations on the platinoid system at the composition of the industrial fission product flow reveal the formation of metallic and oxide phases. They also evaluate the influence of the introduction of a variable amount of selenium and tellurium on the phases formed. The calculation of the evolution of the proportion and of the composition of the phases at the equilibrium helps to manage the consequences of their formation on the process. (author) [fr

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

    Science.gov (United States)

    Kleidon, Axel

    2010-12-01

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

  12. Thermodynamic Performance Indicators for Offshore Oil and Gas Processing: Application to Four North Sea Facilities

    DEFF Research Database (Denmark)

    Voldsund, Mari; Nguyen, Tuong-Van; Elmegaard, Brian

    2014-01-01

    Well-defined performance indicators can motivate optimal operation of offshore oil and gas platforms. We evaluate several thermodynamic performance indicators presented in the literature according to three criteria: Thermodynamic performance indicators should evaluate the use of technically...

  13. Molecular thermodynamics using fluctuation solution theory

    DEFF Research Database (Denmark)

    Ellegaard, Martin Dela

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

  14. Insight into the SEA amide thioester equilibrium. Application to the synthesis of thioesters at neutral pH.

    Science.gov (United States)

    Pira, S L; El Mahdi, O; Raibaut, L; Drobecq, H; Dheur, J; Boll, E; Melnyk, O

    2016-07-26

    The bis(2-sulfanylethyl)amide (SEA) N,S-acyl shift thioester surrogate has found a variety of useful applications in the field of protein total synthesis. Here we present novel insights into the SEA amide/thioester equilibrium in water which is an essential step in any reaction involving the thioester surrogate properties of the SEA group. We also show that the SEA amide thioester equilibrium can be efficiently displaced at neutral pH for accessing peptide alkylthioesters, i.e. the key components of the native chemical ligation (NCL) reaction.

  15. Use of a Mobile Application to Help Students Develop Skills Needed in Solving Force Equilibrium Problems

    Science.gov (United States)

    Yang, Eunice

    2016-02-01

    This paper discusses the use of a free mobile engineering application (app) called Autodesk® ForceEffect™ to provide students assistance with spatial visualization of forces and more practice in solving/visualizing statics problems compared to the traditional pencil-and-paper method. ForceEffect analyzes static rigid-body systems using free-body diagrams (FBDs) and provides solutions in real time. It is a cost-free software that is available for download on the Internet. The software is supported on the iOS™, Android™, and Google Chrome™ platforms. It is easy to use and the learning curve is approximately two hours using the tutorial provided within the app. The use of ForceEffect has the ability to provide students different problem modalities (textbook, real-world, and design) to help them acquire and improve on skills that are needed to solve force equilibrium problems. Although this paper focuses on the engineering mechanics statics course, the technology discussed is also relevant to the introductory physics course.

  16. Applications of Protein Thermodynamic Database for Understanding Protein Mutant Stability and Designing Stable Mutants.

    Science.gov (United States)

    Gromiha, M Michael; Anoosha, P; Huang, Liang-Tsung

    2016-01-01

    Protein stability is the free energy difference between unfolded and folded states of a protein, which lies in the range of 5-25 kcal/mol. Experimentally, protein stability is measured with circular dichroism, differential scanning calorimetry, and fluorescence spectroscopy using thermal and denaturant denaturation methods. These experimental data have been accumulated in the form of a database, ProTherm, thermodynamic database for proteins and mutants. It also contains sequence and structure information of a protein, experimental methods and conditions, and literature information. Different features such as search, display, and sorting options and visualization tools have been incorporated in the database. ProTherm is a valuable resource for understanding/predicting the stability of proteins and it can be accessed at http://www.abren.net/protherm/ . ProTherm has been effectively used to examine the relationship among thermodynamics, structure, and function of proteins. We describe the recent progress on the development of methods for understanding/predicting protein stability, such as (1) general trends on mutational effects on stability, (2) relationship between the stability of protein mutants and amino acid properties, (3) applications of protein three-dimensional structures for predicting their stability upon point mutations, (4) prediction of protein stability upon single mutations from amino acid sequence, and (5) prediction methods for addressing double mutants. A list of online resources for predicting has also been provided.

  17. Thermodynamic, Environmental and Economic Analyses of Solar Ejector Refrigeration System Application for Cold Storage

    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.

  18. Metronidazole removal in powder-activated carbon and concrete-containing graphene adsorption systems: Estimation of kinetic, equilibrium and thermodynamic parameters and optimization of adsorption by a central composite design.

    Science.gov (United States)

    Manjunath, S V; Kumar, S Mathava; Ngo, Huu Hao; Guo, Wenshan

    2017-12-06

    Metronidazole (MNZ) removal by two adsorbents, i.e., concrete-containing graphene (CG) and powder-activated carbon (PAC), was investigated via batch-mode experiments and the outcomes were used to analyze the kinetics, equilibrium and thermodynamics of MNZ adsorption. MNZ sorption on CG and PAC has followed the pseudo-second-order kinetic model, and the thermodynamic parameters revealed that MNZ adsorption was spontaneous on PAC and non-spontaneous on CG. Subsequently, two-parameter isotherm models, i.e., Langmuir, Freundlich, Temkin, Dubinin-Radushkevich and Elovich models, were applied to evaluate the MNZ adsorption capacity. The maximum MNZ adsorption capacities ([Formula: see text]) of PAC and CG were found to be between 25.5-32.8 mg/g and 0.41-0.002 mg/g, respectively. Subsequently, the effects of pH, temperature and adsorbent dosage on MNZ adsorption were evaluated by a central composite design (CCD) approach. The CCD experiments have pointed out the complete removal of MNZ at a much lower PAC dosage by increasing the system temperature (i.e., from 20°C to 40°C). On the other hand, a desorption experiment has shown 3.5% and 1.7% MNZ removal from the surface of PAC and CG, respectively, which was insignificant compared to the sorbed MNZ on the surface by adsorption. The overall findings indicate that PAC and CG with higher graphene content could be useful in MNZ removal from aqueous systems.

  19. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1999-04-01

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