WorldWideScience

Sample records for thermodynamics governing metal

  1. Investigation of the thermodynamics governing metal hydride synthesis in the molten state process

    International Nuclear Information System (INIS)

    Stowe, Ashley C.; Berseth, Polly A.; Farrell, Thomas P.; Laughlin, Laura; Anton, Donald; Zidan, Ragaiy

    2008-01-01

    This work is aimed at utilizing a new synthetic technique to form novel complex hydrides for hydrogen storage. This technique is based on fusing different complex hydrides at elevated temperatures and pressures to form new species with improved hydrogen storage properties. Under conditions of elevated hydrogen overpressures and temperatures the starting materials can reach melting or near-melting point without decomposing (molten state processing), allowing for enhanced diffusion and exchange of elements among the starting materials. The formation and stabilization of these compounds, using the molten state process, is driven by the thermodynamic and kinetic properties of the starting and resulting compounds. Complex hydrides (e.g. NaK 2 AlH 6 , Mg(AlH 4 ) 2 ) were formed, structurally characterized and their hydrogen desorption properties were tested. In this paper we report on investigations of the thermodynamic aspects governing the process and products. We also report on the role of molar ratio in determining the final products. The effectiveness of the molten state process is compared with chemomechanical synthetic methods (ball milling)

  2. Development of a thermodynamic data base for selected heavy metals

    International Nuclear Information System (INIS)

    Hageman, Sven; Scharge, Tina; Willms, Thomas

    2015-07-01

    The report on the development of a thermodynamic data base for selected heavy metals covers the description of experimental methods, the thermodynamic model for chromate, the thermodynamic model for dichromate, the thermodynamic model for manganese (II), the thermodynamic model for cobalt, the thermodynamic model for nickel, the thermodynamic model for copper (I), the thermodynamic model for copper(II), the thermodynamic model for mercury (0) and mercury (I), the thermodynamic model for mercury (III), the thermodynamic model for arsenate.

  3. Thermodynamic data-base for metal fluorides

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Jae Hyung; Lee, Byung Gik; Kang, Young Ho and others

    2001-05-01

    This study is aimed at collecting useful data of thermodynamic properties of various metal fluorides. Many thermodynamic data for metal fluorides are needed for the effective development, but no report of data-base was published. Accordingly, the objective of this report is to rearrange systematically the existing thermodynamic data based on metal fluorides and is to use it as basic data for the development of pyrochemical process. The physicochemical properties of various metal fluorides and metals were collected from literature and such existing data base as HSC code, TAPP code, FACT code, JANAF table, NEA data-base, CRC handbook. As major contents of the thermodynamic data-base, the physicochemical properties such as formation energy, viscosity, density, vapor pressure, etc. were collected. Especially, some phase diagrams of eutectic molten fluorides are plotted and thermodynamic data of liquid metals are also compiled. In the future, the technical report is to be used as basic data for the development of the pyrochemical process which is being carried out as a long-term nuclear R and D project.

  4. Thermodynamic data-base for metal fluorides

    International Nuclear Information System (INIS)

    Yoo, Jae Hyung; Lee, Byung Gik; Kang, Young Ho and others

    2001-05-01

    This study is aimed at collecting useful data of thermodynamic properties of various metal fluorides. Many thermodynamic data for metal fluorides are needed for the effective development, but no report of data-base was published. Accordingly, the objective of this report is to rearrange systematically the existing thermodynamic data based on metal fluorides and is to use it as basic data for the development of pyrochemical process. The physicochemical properties of various metal fluorides and metals were collected from literature and such existing data base as HSC code, TAPP code, FACT code, JANAF table, NEA data-base, CRC handbook. As major contents of the thermodynamic data-base, the physicochemical properties such as formation energy, viscosity, density, vapor pressure, etc. were collected. Especially, some phase diagrams of eutectic molten fluorides are plotted and thermodynamic data of liquid metals are also compiled. In the future, the technical report is to be used as basic data for the development of the pyrochemical process which is being carried out as a long-term nuclear R and D project

  5. Thermodynamic principles governing metabolic operation : inference, analysis, and prediction

    NARCIS (Netherlands)

    Niebel, Bastian

    2015-01-01

    The principles governing metabolic flux are poorly understood. Because diverse organisms show similar metabolic flux patterns, we hypothesized that fundamental thermodynamic constraints might shape cellular metabolism. We developed a constraint-based model for Saccharomyces cerevisiae that included

  6. Correlation of thermodynamics and grain growth kinetics in nanocrystalline metals

    International Nuclear Information System (INIS)

    Song Xiaoyan; Zhang Jiuxing; Li Lingmei; Yang Keyong; Liu Guoquan

    2006-01-01

    We investigated the correlation of thermodynamics and grain growth kinetics of nanocrystalline metals both theoretically and experimentally. A model was developed to describe the thermodynamic properties of nanograin boundaries, which could give reliable predictions in the destabilization characteristics of nanograin structures and the slowing down of grain growth kinetics at a constant temperature. Both the temperature-varying and isothermal nanograin growth behaviors in pure nanocrystalline Co were studied to verify the thermodynamic predictions. The experimental results showing that discontinuous nanograin growth takes place at a certain temperature and grain growth rate decreases monotonically with time confirm our thermodynamics-based description of nanograin growth characteristics. Therefore, we propose a thermodynamic viewpoint to explain the deviation of grain growth kinetics in nanocrystalline metals from those of polycrystalline materials

  7. Theoretical investigation of the thermodynamic properties of metallic thin films

    International Nuclear Information System (INIS)

    Hung, Vu Van; Phuong, Duong Dai; Hoa, Nguyen Thi; Hieu, Ho Khac

    2015-01-01

    The thermodynamic properties of metallic thin films with face-centered cubic structure at ambient conditions were investigated using the statistical moment method including the anharmonicity effects of thermal lattice vibrations. The analytical expressions of Helmholtz free energy, lattice parameter, linear thermal expansion coefficient, specific heats at the constant volume and constant pressure were derived in terms of the power moments of the atomic displacements. Numerical calculations of thermodynamic properties have been performed for Au and Al thin films and compared with those of bulk metals. This research proposes that thermodynamic quantities of thin films approach the values of bulk when the thickness of thin film is about 70 nm. - Highlights: • Thermodynamic properties of thin films were investigated using the moment method. • Expressions of Helmholtz energy, expansion coefficient, specific heats were derived. • Calculations for Au, Al thin films were performed and compared with those of bulks

  8. Theoretical investigation of the thermodynamic properties of metallic thin films

    Energy Technology Data Exchange (ETDEWEB)

    Hung, Vu Van [Vietnam Education Publishing House, 81 Tran Hung Dao, Hanoi (Viet Nam); Phuong, Duong Dai [Hanoi National University of Education, 136 Xuan Thuy, Hanoi (Viet Nam); Hoa, Nguyen Thi [University of Transport and Communications, Lang Thuong, Dong Da, Hanoi (Viet Nam); Hieu, Ho Khac, E-mail: hieuhk@duytan.edu.vn [Institute of Research and Development, Duy Tan University, K7/25 Quang Trung, Danang (Viet Nam)

    2015-05-29

    The thermodynamic properties of metallic thin films with face-centered cubic structure at ambient conditions were investigated using the statistical moment method including the anharmonicity effects of thermal lattice vibrations. The analytical expressions of Helmholtz free energy, lattice parameter, linear thermal expansion coefficient, specific heats at the constant volume and constant pressure were derived in terms of the power moments of the atomic displacements. Numerical calculations of thermodynamic properties have been performed for Au and Al thin films and compared with those of bulk metals. This research proposes that thermodynamic quantities of thin films approach the values of bulk when the thickness of thin film is about 70 nm. - Highlights: • Thermodynamic properties of thin films were investigated using the moment method. • Expressions of Helmholtz energy, expansion coefficient, specific heats were derived. • Calculations for Au, Al thin films were performed and compared with those of bulks.

  9. The kinetics and thermodynamics of adsorption of heavy metal ions ...

    African Journals Online (AJOL)

    Titanium-Pillared and Un-Pillared bentonite clays were studied in order to evaluate the thermodynamics and kinetics of heavy metal ion removal from aqueous solutions. The results showed that the maximum sorption of Cu, Cd, Hg and Pb ions occurred within 30 minutes. A pseudo-second order kinetic model was used to ...

  10. Development of a thermodynamic data base for selected heavy metals; Entwicklung einer thermodynamischen Datenbasis fuer ausgewaehlte Schwermetalle

    Energy Technology Data Exchange (ETDEWEB)

    Hageman, Sven; Scharge, Tina; Willms, Thomas

    2015-07-15

    The report on the development of a thermodynamic data base for selected heavy metals covers the description of experimental methods, the thermodynamic model for chromate, the thermodynamic model for dichromate, the thermodynamic model for manganese (II), the thermodynamic model for cobalt, the thermodynamic model for nickel, the thermodynamic model for copper (I), the thermodynamic model for copper(II), the thermodynamic model for mercury (0) and mercury (I), the thermodynamic model for mercury (III), the thermodynamic model for arsenate.

  11. Magnetic properties and thermodynamics in a metallic nanotube

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  12. Simulation of Cu-Mg metallic glass: Thermodynamics and structure

    DEFF Research Database (Denmark)

    Bailey, Nicholas; Schiøtz, Jakob; Jacobsen, Karsten Wedel

    2004-01-01

    We have obtained effective medium theory interatomic potential parameters suitable for studying Cu-Mg metallic glasses. We present thermodynamic and structural results from simulations of such glasses over a range of compositions. We have produced low-temperature configurations by cooling from...... the melt at as slow a rate as practical, using constant temperature and pressure molecular dynamics. During the cooling process we have carried out thermodynamic analyses based on the temperature dependence of the enthalpy and its derivative, the specific heat, from which the glass transition temperature...

  13. Equation of state and thermodynamic properties of BCC metals

    Directory of Open Access Journals (Sweden)

    Vu Van Hung, N.T. Hoa

    2017-10-01

    Full Text Available The moment method in statistical dynamics is used to study the equation of state and thermodynamic properties of the bcc metals taking into account the anharmonicity effects of the lattice vibrations and hydrostatic pressures. The explicit expressions of the lattice constant, thermal expansion  oefficient, and the specific heats of the bcc metals are derived within the fourth order moment approximation. The termodynamic quantities of W, Nb, Fe,and Ta metals are calculated as a function of the pressure, and they are in good agreement with the corresponding results obtained from the first principles calculations and experimental results. The effective pair potentials work well for the calculations of bcc metals.

  14. Heavy metal adsorption by modified oak sawdust: Thermodynamics and kinetics

    International Nuclear Information System (INIS)

    Argun, Mehmet Emin; Dursun, Sukru; Ozdemir, Celalettin; Karatas, Mustafa

    2007-01-01

    This paper describes the adsorption of heavy metal ions from aqueous solutions by oak (Quercus coccifera) sawdust modified by means of HCl treatment. Our study tested the removal of three heavy metals: Cu, Ni, and Cr. The optimum shaking speed, adsorbent mass, contact time, and pH were determined, and adsorption isotherms were obtained using concentrations of the metal ions ranging from 0.1 to 100 mg L -1 . The adsorption process follows pseudo-second-order reaction kinetics, as well as Langmuir and D-R adsorption isotherms. The paper discusses the thermodynamic parameters of the adsorption (the Gibbs free energy, entropy, and enthalpy). Our results demonstrate that the adsorption process was spontaneous and endothermic under natural conditions. The maximum removal efficiencies were 93% for Cu(II) at pH 4, 82% for Ni(II) at pH 8, and 84% for Cr(VI) at pH 3

  15. High-Pressure Thermodynamic Properties of f-electron Metals, Transition Metal Oxides, and Half-Metallic Magnets

    International Nuclear Information System (INIS)

    Richard T. Scalettar; Warren E. Pickett

    2005-01-01

    This project involves research into the thermodynamic properties of f-electron metals, transition metal oxides, and half-metallic magnets at high pressure. These materials are ones in which the changing importance of electron-electron interactions as the distance between atoms is varied can tune the system through phase transitions from localized to delocalized electrons, from screened to unscreened magnetic moments, and from normal metal to one in which only a single spin specie can conduct. Three main thrusts are being pursued: (1) Mott transitions in transition metal oxides, (2) magnetism in half-metallic compounds, and (3) large volume-collapse transitions in f-band metals

  16. High-Pressure Thermodynamic Properties of f-electron Metals, Transition Metal Oxides, and Half-Metallic Magnets

    Energy Technology Data Exchange (ETDEWEB)

    Scalettar, Richard T.; Pickett, Warren E.

    2004-07-01

    This project involves research into the thermodynamic properties of f-electron metals, transition metal oxides, and half-metallic magnets at high pressure. These materials are ones in which the changing importance of electron-electron interactions as the distance between atoms is varied can tune the system through phase transitions from localized to delocalized electrons, from screened to unscreened magnetic moments, and from normal metal to one in which only a single spin specie can conduct. Three main thrusts are being pursued: (1) Mott transitions in transition metal oxides, (2) magnetism in half-metallic compounds, and (3) large volume-collapse transitions in f-band metals.

  17. High-Pressure Thermodynamic Properties of f-electron Metals, Transition Metal Oxides, and Half-Metallic Magnets

    Energy Technology Data Exchange (ETDEWEB)

    Richard T. Scalettar; Warren E. Pickett

    2005-08-02

    This project involves research into the thermodynamic properties of f-electron metals, transition metal oxides, and half-metallic magnets at high pressure. These materials are ones in which the changing importance of electron-electron interactions as the distance between atoms is varied can tune the system through phase transitions from localized to delocalized electrons, from screened to unscreened magnetic moments, and from normal metal to one in which only a single spin specie can conduct. Three main thrusts are being pursued: (i) Mott transitions in transition metal oxides, (ii) magnetism in half-metallic compounds, and (iii) large volume-collapse transitions in f-band metals.

  18. Thermodynamics of carbon deoxidation and aluminium deoxidation of refractory metals

    International Nuclear Information System (INIS)

    Garg, S.P.; Sundaram, C.V.

    1975-01-01

    Carbon has been used for removing the last traces of oxygen from many refractory metals by evaporation of CO at high temperature and vacuum. Similar purification can also be achieved employing aluminium deoxidation by evaporation of Al 2 Osub(g). In the present paper a theoretical thermodynamic approach has been attempted to evaluate the deoxidation tendencies of refractory metals of groups IV to VI by these two processes. Expressions have been theoretically derived, relating the concentration product of carbon and oxygen in the metal (which is a measure of the carbon deoxidation tendency of the metal) with temperature and pressure, for various M-C-O systems. Similarly the relative vapour pressure values of Alsub(2)Osub(g),Alsub(g)andMO(g) (suboxide of the metal) over various M-Al-O systems have been calculated as a function of aluminium and oxygen contents of the metal. From these analyses, it has been shown that a substantial amount of oxygen can be removed from M-Al-O alloys by aluminium deoxidation. The estimated values are compared with the reported values based on experiment. (author)

  19. Thermodynamic screening of metal-substituted MOFs for carbon capture.

    Science.gov (United States)

    Koh, Hyun Seung; Rana, Malay Kumar; Hwang, Jinhyung; Siegel, Donald J

    2013-04-07

    Metal-organic frameworks (MOFs) have emerged as promising materials for carbon capture applications due to their high CO2 capacities and tunable properties. Amongst the many possible MOFs, metal-substituted compounds based on M-DOBDC and M-HKUST-1 have demonstrated amongst the highest CO2 capacities at the low pressures typical of flue gasses. Here we explore the possibility for additional performance tuning of these compounds by computationally screening 36 metal-substituted variants (M = Be, Mg, Ca, Sr, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, W, Sn, and Pb) with respect to their CO2 adsorption enthalpy, ΔH(T=300K). Supercell calculations based on van der Waals density functional theory (vdW-DF) yield enthalpies in good agreement with experimental measurements, out-performing semi-empirical (DFT-D2) and conventional (LDA & GGA) functionals. Our screening identifies 13 compounds having ΔH values within the targeted thermodynamic window -40 ≤ ΔH ≤ -75 kJ mol(-1): 8 are based on M-DODBC (M = Mg, Ca, Sr, Sc, Ti, V, Mo, and W), and 5 on M-HKUST-1 (M = Be, Mg, Ca, Sr and Sc). Variations in the electronic structure and the geometry of the structural building unit are examined and used to rationalize trends in CO2 affinity. In particular, the partial charge on the coordinatively unsaturated metal sites is found to correlate with ΔH, suggesting that this property may be used as a simple performance descriptor. The ability to rapidly distinguish promising MOFs from those that are "thermodynamic dead-ends" will be helpful in guiding synthesis efforts towards promising compounds.

  20. Simulation of Cu-Mg metallic glass: Thermodynamics and structure

    International Nuclear Information System (INIS)

    Bailey, Nicholas P.; Schioetz, Jakob; Jacobsen, Karsten W.

    2004-01-01

    We have obtained effective medium theory interatomic potential parameters suitable for studying Cu-Mg metallic glasses. We present thermodynamic and structural results from simulations of such glasses over a range of compositions. We have produced low-temperature configurations by cooling from the melt at as slow a rate as practical, using constant temperature and pressure molecular dynamics. During the cooling process we have carried out thermodynamic analyses based on the temperature dependence of the enthalpy and its derivative, the specific heat, from which the glass transition temperature may be determined. We have also carried out structural analyses using the radial distribution function (RDF) and common neighbor analysis (CNA). Our analysis suggests that the splitting of the second peak, commonly associated with metallic glasses, in fact, has little to do with the glass transition itself, but is simply a consequence of the narrowing of peaks associated with structural features present in the liquid state. In fact, the splitting temperature for the Cu-Cu RDF is well above T g . The CNA also highlights a strong similarity between the structure of the intermetallic alloys and the amorphous alloys of similar composition. We have also investigated the diffusivity in the supercooled regime. Its temperature dependence indicates fragile-liquid behavior, typical of binary metallic glasses. On the other hand, the relatively low specific-heat jump of around 1.5k B /atom indicates apparent strong-liquid behavior, but this can be explained by the width of the transition due to the high cooling rates

  1. Metal viscoplasticity with two-temperature thermodynamics and two dislocation densities

    Science.gov (United States)

    Roy Chowdhury, Shubhankar; Kar, Gurudas; Roy, Debasish; Reddy, J. N.

    2018-03-01

    Posed within the two-temperature theory of non-equilibrium thermodynamics, we propose a model for thermoviscoplastic deformation in metals. We incorporate the dynamics of dislocation densities-mobile and forest—that play the role of internal state variables in the formulation. The description based on two temperatures appears naturally when one recognizes that the thermodynamic system undergoing viscoplastic deformation is composed of two weakly interacting subsystems, viz. a kinetic-vibrational subsystem of the vibrating atomic lattices and a configurational subsystem of the slower degrees of freedom relating to defect motion, each with its own temperature. Starting with a basic model that involves only homogeneous deformation, a three-dimensional model for inhomogeneous viscoplasticity applicable to finite deformation is charted out in an overstress driven viscoplastic deformation framework. The model shows how the coupled evolutions of mobile and forest dislocation densities, which are critically influenced by the dynamics of configurational temperature, govern the strength and ductility of the metal. Unlike most contemporary models, the current proposal also affords a prediction of certain finer details as observed in the experimental data on stress-strain behaviour of metals and this in turn enhances the understanding of the evolving and interacting dislocation densities.

  2. Electronic and thermodynamic properties of transition metal elements and compounds

    International Nuclear Information System (INIS)

    Haeglund, J.

    1993-01-01

    This thesis focuses on the use of band-structure calculations for studying thermodynamic properties of solids. We discuss 3d-, 4d- and 5d-transition metal carbides and nitrides. Through a detailed comparison between theoretical and experimental results, we draw conclusions on the character of the atomic bonds in these materials. We show how electronic structure calculations can be used to give accurate predictions for bonding energies. Part of the thesis is devoted to the application of the generalized gradient approximation in electronic structure calculations on transition metals. For structures with vibrational disorder, we present a method for calculating averaged phonon frequencies without using empirical information. For magnetic excitations, we show how a combined use of theoretical results and experimental data can yield information on magnetic fluctuations at high temperatures. The main results in the thesis are: Apart for an almost constant shift, theoretically calculated bonding energies for transition metal carbides and nitrides agree with experimental data or with values from analysis of thermochemical information. The electronic spectrum of transition metal carbides and nitrides can be separated into bonding, antibonding and nonbonding electronic states. The lowest enthalpy of formation for substoichiometric vanadium carbide VC 1-X at zero temperature and pressure occurs for a structure containing vacancies (x not equal to 0). The generalized gradient approximation improves theoretical calculated cohesive energies for 3d-transition metals. Magnetic phase transitions are sensitive to the description of exchange-correlation effects in electronic structure calculations. Trends in Debye temperatures can be successfully analysed in electronic structure calculations on disordered lattices. For the elements, there is a clear dependence on the crystal structure (e.g., bcc, fcc or hcp). Chromium has fluctuating local magnetic moments at temperatures well above

  3. On the thermodynamics of phase transitions in metal hydrides

    Science.gov (United States)

    di Vita, Andrea

    2012-02-01

    Metal hydrides are solutions of hydrogen in a metal, where phase transitions may occur depending on temperature, pressure etc. We apply Le Chatelier's principle of thermodynamics to a particular phase transition in TiH x , which can approximately be described as a second-order phase transition. We show that the fluctuations of the order parameter correspond to fluctuations both of the density of H+ ions and of the distance between adjacent H+ ions. Moreover, as the system approaches the transition and the correlation radius increases, we show -with the help of statistical mechanics-that the statistical weight of modes involving a large number of H+ ions (`collective modes') increases sharply, in spite of the fact that the Boltzmann factor of each collective mode is exponentially small. As a result, the interaction of the H+ ions with collective modes makes a tiny suprathermal fraction of the H+ population appear. Our results hold for similar transitions in metal deuterides, too. A violation of an -insofar undisputed-upper bound on hydrogen loading follows.

  4. Thermodynamic properties of some metal oxide-zirconia systems

    Science.gov (United States)

    Jacobson, Nathan S.

    1989-01-01

    Metal oxide-zirconia systems are a potential class of materials for use as structural materials at temperatures above 1900 K. These materials must have no destructive phase changes and low vapor pressures. Both alkaline earth oxide (MgO, CaO, SrO, and BaO)-zirconia and some rare earth oxide (Y2O3, Sc2O3, La2O3, CeO2, Sm2O3, Gd2O3, Yb2O3, Dy2O3, Ho2O3, and Er2O3)-zirconia system are examined. For each system, the phase diagram is discussed and the vapor pressure for each vapor species is calculated via a free energy minimization procedure. The available thermodynamic literature on each system is also surveyed. Some of the systems look promising for high temperature structural materials.

  5. Thermodynamic and structural basis for electrochemical response of Cu–Zr based metallic glass

    International Nuclear Information System (INIS)

    Zhang, Chunzhi; Qiu, Nannan; Kong, Lingliang; Yang, Xiaodan; Li, Huiping

    2015-01-01

    Highlights: • Thermodynamic and structural basis for electrochemical response were proposed. • La improves the corrosion resistance by inhibition of the selective dissolution. • Corrosion of the MG responses well with thermodynamic and structural parameters. - Abstract: Cu–Zr based metallic glasses were prepared by hyperquenching strategy to explore the thermodynamic and structural basis for electrochemical response. The thermodynamic parameters and the local atomic structure were obtained. Corrosion resistance in seawater was investigated via potentiodynamic polarization curve. The results indicate that increasing thermodynamic parameter values improves the corrosion resistance. The topological instability represented by the nearest neighbor atomic distance yields same tendency as the corrosion resistance with La addition

  6. Phase transformations and thermodynamics of aluminum-based metallic glasses

    Science.gov (United States)

    Gao, Changhua (Michael)

    This thesis examines the thermodynamics and associated kinetics and phase transformations of the glass forming Al-Ni-Gd and Al-Fe-Gd systems. In order to fully understand the unique glass forming ability (GFA) of Al-based metallic glasses, the ternary Al-Fe-Gd and Al-Ni-Gd systems in their Al-rich corners were examined experimentally to assist in a thermodynamic assessment. The solid-state phase equilibria are determined using XRD and TEM-EDS techniques. While this work basically confirms the solid-state equilibria in Al-Fe-Gd reported previously, the ternary phase in Al-Ni-Gd system has been identified to be Al15Ni3Gd2 rather than Al16Ni 3Gd reported in the literature. DTA analysis of 24 alloys in the Al-Fe-Gd system and 42 alloys in the Al-Ni-Gd system have yielded critical temperatures pertaining to the solid-liquid transition. Based on these data and information from the literature, a self-consistent thermodynamic database for these systems has been developed using the CALPHAD technique. Parameters describing the Gibbs free energy for various phases of the Al-Gd, Al-Fe-Gd and Al-Ni-Gd systems are manually optimized in this study. Once constructed, the database is used to calculate driving forces for nucleation of crystalline phases which can qualitatively explain the phase formation sequence during crystallization at low temperatures. It was also confirmed that alloy compositions with the lowest Gibbs free energy difference between the equilibrium state and undercooled liquid state exhibit better GFA than other chemistries. Based on 250°C isothermal devitrification phase transformations of 17 Al-Ni-Gd alloys, a phase formation sequence map is constructed. Fcc-Al nanocrystals are formed first in most of the alloys studied, but eutectic crystallization of a metastable phase and fcc-Al is also observed. Addition of Al or Ni promotes fcc-Al phase formation, while increasing Gd suppresses it. The continuous heating DSC scans revealed that crystallization in Al

  7. 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

  8. Universal relation for size dependent thermodynamic properties of metallic nanoparticles.

    Science.gov (United States)

    Xiong, Shiyun; Qi, Weihong; Cheng, Yajuan; Huang, Baiyun; Wang, Mingpu; Li, Yejun

    2011-06-14

    The previous model on surface free energy has been extended to calculate size dependent thermodynamic properties (i.e., melting temperature, melting enthalpy, melting entropy, evaporation temperature, Curie temperature, Debye temperature and specific heat capacity) of nanoparticles. According to the quantitative calculation of size effects on the calculated thermodynamic properties, it is found that most thermodynamic properties of nanoparticles vary linearly with 1/D as a first approximation. In other words, the size dependent thermodynamic properties P(n) have the form of P(n) = P(b)(1 -K/D), in which P(b) is the corresponding bulk value and K is the material constant. This may be regarded as a scaling law for most of the size dependent thermodynamic properties for different materials. The present predictions are consistent literature values. This journal is © the Owner Societies 2011

  9. Thermodynamics analysis of the rare earth metals and their alloys with indium in solid state

    International Nuclear Information System (INIS)

    Vassiliev, V.P.; Benaissa, Ablazeze; Taldrik, A.F.

    2013-01-01

    Graphical abstract: Gibbs energies of formation vs. RE atomic numbers in REIn 3 . Highlights: •Set of experimental values was collected for REIn 3 phases. •Thermodynamic functions of formation were calculated at 298 K and 775 K. •Experimental and calculated values were compared. -- Abstract: Nonlinear correlative analyses between thermodynamic and some physico-chemical properties of rare-earth metals (RE) and their alloys with indium are performed for the isostructural phases RE and REIn 3 . The thermodynamics values (Gibbs energies of formation, enthalpies of formation, and entropies of formation at 298 K and 775 K and standard entropies) of LnIn 3 phases are calculated on the basis of calorimetry and potentiometry results. The proposed correlation between physico-chemical and thermodynamic properties agrees for all the isostructural phases REX (X are others elements of the periodic table). The resulting thermodynamic data are recommended for metallurgical handbook

  10. 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

  11. Sustainable governance of scarce metals: The case of lithium

    Energy Technology Data Exchange (ETDEWEB)

    Prior, Timothy, E-mail: tim.prior@sipo.gess.ethz.ch [Center for Security Studies (CSS), ETH Zürich (Switzerland); Institute for Sustainable Futures, University of Technology, Sydney (Australia); Wäger, Patrick A. [Technology and Society Laboratory, Empa - Swiss Federal Laboratories for Materials Science and Technology, St. Gallen (Switzerland); Stamp, Anna [Technology and Society Laboratory, Empa - Swiss Federal Laboratories for Materials Science and Technology, St. Gallen (Switzerland); Institute for Environmental Decisions, ETH Zürich (Switzerland); Widmer, Rolf [Technology and Society Laboratory, Empa - Swiss Federal Laboratories for Materials Science and Technology, St. Gallen (Switzerland); Giurco, Damien [Institute for Sustainable Futures, University of Technology, Sydney (Australia)

    2013-09-01

    Minerals and metals are finite resources, and recent evidence suggests that for many, primary production is becoming more difficult and more expensive. Yet these resources are fundamentally important for society—they support many critical services like infrastructure, telecommunications and energy generation. A continued reliance on minerals and metals as service providers in modern society requires dedicated and concerted governance in relation to production, use, reuse and recycling. Lithium provides a good example to explore possible sustainable governance strategies. Lithium is a geochemically scarce metal (being found in a wide range of natural systems, but in low concentrations that are difficult to extract), yet recent studies suggest increasing future demand, particularly to supply the lithium in lithium-ion batteries, which are used in a wide variety of modern personal and commercial technologies. This paper explores interventions for sustainable governance and handling of lithium for two different supply and demand contexts: Australia as a net lithium producer and Switzerland as a net lithium consumer. It focuses particularly on possible nation-specific issues for sustainable governance in these two countries' contexts, and links these to the global lithium supply chain and demand scenarios. The article concludes that innovative business models, like ‘servicizing’ the lithium value chain, would hold sustainable governance advantages for both producer and consumer countries. - Highlights: • Lithium is a geochemically scare metal, but demand is forecast to increase in future • We explore sustainable lithium governance implications for Australia and Switzerland • One governance mechanism is the ‘servicization’ of the lithium value chain • We explore one actual, and two hypothetical lithium service business models • ‘Servicizing’ a commodity would require fundamental innovations in minerals policy.

  12. Sustainable governance of scarce metals: The case of lithium

    International Nuclear Information System (INIS)

    Prior, Timothy; Wäger, Patrick A.; Stamp, Anna; Widmer, Rolf; Giurco, Damien

    2013-01-01

    Minerals and metals are finite resources, and recent evidence suggests that for many, primary production is becoming more difficult and more expensive. Yet these resources are fundamentally important for society—they support many critical services like infrastructure, telecommunications and energy generation. A continued reliance on minerals and metals as service providers in modern society requires dedicated and concerted governance in relation to production, use, reuse and recycling. Lithium provides a good example to explore possible sustainable governance strategies. Lithium is a geochemically scarce metal (being found in a wide range of natural systems, but in low concentrations that are difficult to extract), yet recent studies suggest increasing future demand, particularly to supply the lithium in lithium-ion batteries, which are used in a wide variety of modern personal and commercial technologies. This paper explores interventions for sustainable governance and handling of lithium for two different supply and demand contexts: Australia as a net lithium producer and Switzerland as a net lithium consumer. It focuses particularly on possible nation-specific issues for sustainable governance in these two countries' contexts, and links these to the global lithium supply chain and demand scenarios. The article concludes that innovative business models, like ‘servicizing’ the lithium value chain, would hold sustainable governance advantages for both producer and consumer countries. - Highlights: • Lithium is a geochemically scare metal, but demand is forecast to increase in future • We explore sustainable lithium governance implications for Australia and Switzerland • One governance mechanism is the ‘servicization’ of the lithium value chain • We explore one actual, and two hypothetical lithium service business models • ‘Servicizing’ a commodity would require fundamental innovations in minerals policy

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

    International Nuclear Information System (INIS)

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

    1989-12-01

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

  14. Sustainable governance of scarce metals: the case of lithium.

    Science.gov (United States)

    Prior, Timothy; Wäger, Patrick A; Stamp, Anna; Widmer, Rolf; Giurco, Damien

    2013-09-01

    Minerals and metals are finite resources, and recent evidence suggests that for many, primary production is becoming more difficult and more expensive. Yet these resources are fundamentally important for society--they support many critical services like infrastructure, telecommunications and energy generation. A continued reliance on minerals and metals as service providers in modern society requires dedicated and concerted governance in relation to production, use, reuse and recycling. Lithium provides a good example to explore possible sustainable governance strategies. Lithium is a geochemically scarce metal (being found in a wide range of natural systems, but in low concentrations that are difficult to extract), yet recent studies suggest increasing future demand, particularly to supply the lithium in lithium-ion batteries, which are used in a wide variety of modern personal and commercial technologies. This paper explores interventions for sustainable governance and handling of lithium for two different supply and demand contexts: Australia as a net lithium producer and Switzerland as a net lithium consumer. It focuses particularly on possible nation-specific issues for sustainable governance in these two countries' contexts, and links these to the global lithium supply chain and demand scenarios. The article concludes that innovative business models, like 'servicizing' the lithium value chain, would hold sustainable governance advantages for both producer and consumer countries. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Thermodynamics and structure of liquid metals from a consistent optimized random phase approximation

    International Nuclear Information System (INIS)

    Akinlade, O.; Badirkhan, Z.; Pastore, G.

    2000-05-01

    We study thermodynamics and structural properties of several liquid metals to assess the validity of the generalized non-local model potential (GNMP) of Li et. al. [J.Phys. F16,309 (1986)]. By using a new thermodynamically consistent version of the optimized random phase approximation (ORPA), especially adapted to continuous reference potentials, we improve our previous results obtained within the variational approach based on the Gibbs - Bogoliubov inequality. Hinging on the unified and very accurate evaluation of structure factors and thermodynamic quantities provided by the ORPA, we find that the GNMP yields satisfactory results for the alkali metals, however, those for the polyvalent metals point to a substantial inadequacy of the GNMP for high valence systems. (author)

  16. Thermodynamically self-consistent integral equations and the structure of liquid metals

    International Nuclear Information System (INIS)

    Pastore, G.; Kahl, G.

    1987-01-01

    We discuss the application of the new thermodynamically self-consistent integral equations for the determination of the structural properties of liquid metals. We present a detailed comparison of the structure (S(q) and g(r)) for models of liquid alkali metals as obtained from two thermodynamically self-consistent integral equations and some published exact computer simulation results; the range of states extends from the triple point to the expanded metal. The theories which only impose thermodynamic self-consistency without any fitting of external data show an excellent agreement with the simulation results, thus demonstrating that this new type of integral equation is definitely superior to the conventional ones (hypernetted chain, Percus-Yevick, mean spherical approximation, etc). (author)

  17. 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

  18. Solution thermodynamics of rare-earth metal ions - physicochemical study-

    Energy Technology Data Exchange (ETDEWEB)

    Amerkhanova, Sh K; Shlyapov, R M; Uali, A S [Buketov Karaganda state university, University str., 28, Karaganda, 100028 (Kazakhstan)], E-mail: amerkhanova_sh@mail.ru

    2009-02-01

    The results of the studying of interactions in multicomponent systems 'polyvinyl alcohol (PVA) - rare-earth element ion - nitrate of sodium - water' are represented. It is established that for rubidium (I) ions temperature and ionic strength is render destroying action, and for yttrium (III) ions the influence of these factors has return character which is connected with features of an electronic structure of metal ion. It is revealed that a dominating role of non-electrostatic formation composed, hence, the formation of donor-acceptor connection of 'metal - ligand' occurs through atom of oxygen.

  19. The use of molecular dynamics for the thermodynamic properties of simple and transition metals

    International Nuclear Information System (INIS)

    Straub, G.K.

    1987-04-01

    The technique of computer simulation of the molecular dynamics in metallic systems to calculate thermodynamic properties is discussed. The nature of a metal as determined by its electronic structure is used to determine the total adiabatic potential. The effective screened ion-ion interaction can then be used in a molecular dynamics simulation. The method for the construction of a molecular dynamics ensemble, its relation to the canonical ensemble, and the definition of thermodynamic functions from the Helmholtz free energy is given. The method for the analysis of the molecular dynamics results from quasiharmonic lattice dynamics and the decomposition in terms of harmonic and anharmonic contributions is given for solids. For fluid phase metals, procedures for calculating the thermodynamics and determining the constant of entropy are presented. The solid-fluid phase boundary as a function of pressure and temperature is determined using the results of molecular dynamics. Throughout, examples and results for metallic sodium are used. The treatment of the transition metal electronic d-states in terms of an effective pair-wise interaction is also discussed and the phonon dispersion curves of Al, Ni, and Cu are calculated

  20. Governing Influence of Thermodynamic and Chemical Equilibria on the Interfacial Properties in Complex Fluids.

    Science.gov (United States)

    Harikrishnan, A R; Dhar, Purbarun; Gedupudi, Sateesh; Das, Sarit K

    2018-04-12

    We propose a comprehensive analysis and a quasi-analytical mathematical formalism to predict the surface tension and contact angles of complex surfactant-infused nanocolloids. The model rests on the foundations of the interaction potentials for the interfacial adsorption-desorption dynamics in complex multicomponent colloids. Surfactant-infused nanoparticle-laden interface problems are difficult to deal with because of the many-body interactions and interfaces involved at the meso-nanoscales. The model is based on the governing role of thermodynamic and chemical equilibrium parameters in modulating the interfacial energies. The influence of parameters such as the presence of surfactants, nanoparticles, and surfactant-capped nanoparticles on interfacial dynamics is revealed by the analysis. Solely based on the knowledge of interfacial properties of independent surfactant solutions and nanocolloids, the same can be deduced for complex surfactant-based nanocolloids through the proposed approach. The model accurately predicts the equilibrium surface tension and contact angle of complex nanocolloids available in the existing literature and present experimental findings.

  1. Thermodynamic properties of bcc crystals at high temperatures: The transition metals

    International Nuclear Information System (INIS)

    MacDonald, R.A.; Shukla, R.C.

    1985-01-01

    The second-neighbor central-force model of a bcc crystal, previously used in lowest-order anharmonic perturbation theory to calculate the thermodynamic properties of the alkali metals, is here applied to the transition metals V, Nb, Ta, Mo, and W. The limitations of the model are apparent in the thermal-expansion results, which fall away from the experimental trend above about 1800 K. The specific heat similarly fails to exhibit the sharp rise that is observed at higher temperatures. A static treatment of vacancies cannot account for the difference between theory and experiment. The electrons have been taken into account by using a model that specifically includes d-band effects in the electron ground-state energy. The results thus obtained for the bulk moduli are quite satisfactory. In the light of these results, we discuss the prerequisites for a better treatment of metals when the electrons play an important role in determining the thermodynamic properties

  2. 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.

  3. Impact of experimentation in thermodynamic studies of some metallic and oxidic systems

    Directory of Open Access Journals (Sweden)

    Aune R.E.

    2002-01-01

    Full Text Available The importance of experimentation as an ingredient to CALPHAD assessments is brought out in the present paper and is illustrated in the case of a number of metallic and oxidic systems. Two types of experimental techniques have been used in the present laboratory for thermodynamic studies, and the details are presented. The results obtained together with the assessed phase diagram in the case of a few selected systems are presented. It was shown that careful experimentation has brought new features in the case of carbide systems involving Mn, and a new 4-phase equilibrium in the case of Ni-W-O system. New data with regard to the thermodynamic activities of FeO-containing slag systems and sulphide capacities of multicomponent slags, obtained by gas equilibration method, are also presented. A thermodynamic software, THERMOSLAG© based on the experimental data has been found to be extremely useful by the steel industries is also discussed.

  4. Precision measurements of thermodynamic parameters of heavy alkali metals

    Science.gov (United States)

    Blagonravov, L. A.; Modenov, A. A.

    2017-11-01

    On the temperature dependences of a number of one-component liquids, regions of anomalous behavior in the form of kinks and also in the form of limited areas of forced growth have been previously observed (LA Blagonravov, LA Orlov, et al., TVT 2000, vol. 38, No. 4, p.566-572). However, the interpretation of these anomalies is complicated by the small magnitude of the effects themselves (the magnitude of the observed effect was 5%, a random error of 2-3%). An increase in the accuracy of measurements is required for a more confident determination of the detailed shape of the anomalies. In the proposed work, thermodynamic parameters are studied using a technique that uses the elastic-thermal effect. The adiabatic thermal coefficient of pressure (a.t.p.c.) is measured: χ = (1/T)(∂T/∂p)S. An installation in which the pressure change is carried out in a periodic mode is used for measurements. The software allows simultaneous averaging of the values of the amplitude of pressure oscillations and the amplitude of temperature response oscillations with the subsequent determination of their ratio. The facility uses an advanced pressure modulator, which allows creating pressure oscillations of the shape close to sinusoidal (the value of the second harmonic is not more than 10%) and a precision SR-810 nanovoltmeter with a synchronous digital detector. The currently used technique provides an acceptable measurement accuracy (error in the region of 0.5-1%). However, to further increase the accuracy, it was decided to make changes in the measuring path. Namely, by developing and applying a scheme of a precision low-noise preamplifier based on the instrument amplifier INA333, a circuit allowing simultaneous measurement of not only the two above parameters but also the current temperature of the sample (to exclude the effect of temperature drift.) Preliminary results of measurements of the temperature dependence of the a.t.p.c. of liquid cesium in the temperature range up to

  5. The thermodynamics of latent fingerprint corrosion of metal elements and alloys.

    Science.gov (United States)

    Bond, John W

    2008-11-01

    Redox reactions taking place between the surface of a metal and fingerprint residue have been expressed thermodynamically in terms of both the Nernst equation for reduction potential and the complexation constant for the formation of complex metal halide ions in aqueous solution. These expressions are used to explain experimental results for the corrosion of 10 different metal elements by fingerprint residue in air at room temperature. Corrosion of noble metals, such as silver and gold, supports the proposition that the degree of metal corrosion is enhanced by the presence of chloride ions in eccrine sweat. Extending the experiments to include 10 metal alloys enabled the construction of a fingerprint corrosion series for 20 different metals. Fingerprint corrosion on metals alloyed with > approximately 40% copper was found to display third level fingerprint detail. A comparison of both conventional ink on paper and digital (Livescan) fingerprinting techniques with fingerprints deposited on 9 Karat gold alloy has shown that gold alloy depositions are least susceptible to third level detail obliteration by poor fingerprint capturing techniques.

  6. A thermodynamic approach to the quantitative evaluation of the metallic melts glass-forming ability

    International Nuclear Information System (INIS)

    Zajtsev, A.I.

    2004-01-01

    The outlook for development of quantitative criteria of the tendency of metallic melt to render amorphous is shown with taking into account specific features of chemical interaction between components. With the use of statistical physics methods and thermodynamics as well as concepts of association the techniques are devised for quantitative separation of contributions to liquid alloy thermodynamic functions conditioned by various types of chemical interaction between components. The results Knudsen mass-spectroscopic comprehensive thermodynamic study of a wide range of systems with various tendency to vitrification are summarized. It is shown that excessive (configurational) entropy and specific heat of the liquid are key features predetermining thermodynamic and kinetic stimuli of amorphization. Their values are completely determined by a covalent constituent of chemical interaction on entropic term of association reaction. The possibility of construction of quantitative amorphization criteria on the basis of this feature and the outlook for the use of the approach proposed to predict physicochemical and mechanical properties of solid amorphous materials are illustrated [ru

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

    Energy Technology Data Exchange (ETDEWEB)

    1978-02-01

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

  8. Shape-Controlled Synthesis of Colloidal Metal Nanocrystals: Thermodynamic versus Kinetic Products.

    Science.gov (United States)

    Xia, Younan; Xia, Xiaohu; Peng, Hsin-Chieh

    2015-07-01

    This Perspective provides a contemporary understanding of the shape evolution of colloidal metal nanocrystals under thermodynamically and kinetically controlled conditions. It has been extremely challenging to investigate this subject in the setting of one-pot synthesis because both the type and number of seeds involved would be changed whenever the experimental conditions are altered, making it essentially impossible to draw conclusions when comparing the outcomes of two syntheses conducted under different conditions. Because of the uncertainty about seeds, most of the mechanistic insights reported in literature for one-pot syntheses of metal nanocrystals with different shapes are either incomplete or ambiguous, and some of them might be misleading or even wrong. Recently, with the use of well-defined seeds for such syntheses, it became possible to separate growth from nucleation and therefore investigate the explicit role(s) played by a specific thermodynamic or kinetic parameter in directing the evolution of colloidal metal nanocrystals into a specific shape. Starting from single-crystal seeds enclosed by a mix of {100}, {111}, and {110} facets, for example, one can obtain colloidal nanocrystals with diversified shapes by adjusting various thermodynamic or kinetic parameters. The mechanistic insights learnt from these studies can also be extended to account for the products of conventional one-pot syntheses that involve self-nucleation only. The knowledge can be further applied to many other types of seeds with twin defects or stacking faults, making it an exciting time to design and synthesize colloidal metal nanocrystals with the shapes sought for a variety of fundamental studies and technologically important applications.

  9. Dissolved Divalent Metal and pH Effects on Amino Acid Polymerization: A Thermodynamic Evaluation.

    Science.gov (United States)

    Kitadai, Norio

    2017-03-01

    Polymerization of amino acids is a fundamentally important step for the chemical evolution of life. Nevertheless, its response to changing environmental conditions has not yet been well understood because of the lack of reliable quantitative information. For thermodynamics, detailed prediction over diverse combinations of temperature and pH has been made only for a few amino acid-peptide systems. This study used recently reported thermodynamic dataset for the polymerization of the simplest amino acid "glycine (Gly)" to its short peptides (di-glycine and tri-glycine) to examine chemical and structural characteristics of amino acids and peptides that control the temperature and pH dependence of polymerization. Results showed that the dependency is strongly controlled by the intramolecular distance between the amino and carboxyl groups in an amino acid structure, although the side-chain group role is minor. The polymerization behavior of Gly reported earlier in the literature is therefore expected to be a typical feature for those of α-amino acids. Equilibrium calculations were conducted to examine effects of dissolved metals as a function of pH on the monomer-polymer equilibria of Gly. Results showed that metals shift the equilibria toward the monomer side, particularly at neutral and alkaline pH. Metals that form weak interaction with Gly (e.g., Mg 2+ ) have no noticeable influence on the polymerization, although strong interaction engenders significant decrease of the equilibrium concentrations of Gly peptides. Considering chemical and structural characteristics of Gly and Gly peptides that control their interactions with metals, it can be expected that similar responses to the addition of metals are applicable in the polymerization of neutral α-amino acids. Neutral and alkaline aqueous environments with dissolved metals having high affinity with neutral α-amino acids (e.g., Cu 2+ ) are therefore not beneficial places for peptide bond formation on the primitive

  10. Predicting Metal Speciation & Bioavailability via Estimation of Metal-Organic Thermodynamic Properties

    Science.gov (United States)

    Prasad, A.; Howells, A. E.; Shock, E.

    2017-12-01

    The biological fate of any metal depends on its chemical form in the environment. Arsenic for example, is extremely toxic in the form of inorganic As+3 but completely benign in the organic form of arsenobetaine. Thus, given an exhaustive set of reactions and their equilibrium constants (logK), the bioavailability of any metal can be obtained for blood plasma, hydrothermal fluids or any system of interest. While many data exist for metal-inorganic ligands, logK data covering the temperature range of life for metal-organic complexes are sparse. Hence, we decided to estimate metal-organic logK values from correlations with the commonly available values of ligand pKa. Metal ion specific correlations were made with ligands classified according to their electron donor atoms, denticity and other chemical factors. While this approach has been employed before (Carbonaro et al. 2007, GCA 71, 3958-3968), new correlations were developed that provide estimates even when no metal-organic logK is available. In addition, we have used the same methods to make estimates of metal-organic entropy of association (ΔaS), which can provide logK for any temperature of biological relevance. Our current correlations employ logK and ΔaS data from 30 metal ions (like the biologically relevant Fe+3 & Zn+2) and 74 ligands (like formate and ethylenediamine), which can be expanded to estimate the metal-ligand reaction properties for these 30 metal ions with a possibly limitless number of ligands that may belong to our categories of ligands. With the help of such data, copper speciation was obtained for a defined growth medium for methanotrophs employed by Morton et al. (2000, AEM 66, 1730-1733) that agrees with experimental measurements showing that the free metal ion may not be the bioavailable form in all conditions. These results encourage us to keep filling the gaps in metal-organic logK data and continue finding relationships between biological responses (like metal-accumulation ratios

  11. Modelling plastic deformation of metals over a wide range of strain rates using irreversible thermodynamics

    International Nuclear Information System (INIS)

    Huang Mingxin; Rivera-Diaz-del-Castillo, Pedro E J; Zwaag, Sybrand van der; Bouaziz, Olivier

    2009-01-01

    Based on the theory of irreversible thermodynamics, the present work proposes a dislocation-based model to describe the plastic deformation of FCC metals over wide ranges of strain rates. The stress-strain behaviour and the evolution of the average dislocation density are derived. It is found that there is a transitional strain rate (∼ 10 4 s -1 ) over which the phonon drag effects appear, resulting in a significant increase in the flow stress and the average dislocation density. The model is applied to pure Cu deformed at room temperature and at strain rates ranging from 10 -5 to 10 6 s -1 showing good agreement with experimental results.

  12. Thermodynamic evaluation of highly exothermic reactions for the fabrication of ceramic metal composites

    International Nuclear Information System (INIS)

    Rodrigues, J.A.; Pandolfelli, V.C.; Botta Filho, W.J.; Tomasi, R.; Stevens, R.; Brook, R.J.

    1990-01-01

    Highly exothermic reactions allow the synthesis or production of materials. Which present advantages regarding to energy saving, simplicity of process and higher purity of the products. Considering adiabatic conditions these reactions give off a large amount of heat which will raise the temperature of the system, allowing the production of highly refractory materials. This paper presents a thermodynamic forecast of reactants are Nb2O5, Al e Zr. The objective is to produce high toughness alumina matrix composites containing ZrO2 particles and Nb metal. (author)

  13. Interaction of d(10) metal ions with thioether ligands: a thermodynamic and theoretical study.

    Science.gov (United States)

    Melchior, Andrea; Peralta, Elena; Valiente, Manuel; Tavagnacco, Claudio; Endrizzi, Francesco; Tolazzi, Marilena

    2013-05-07

    Thermodynamic parameters of complex formation between d(10) metal ions, such as Zn(2+), Cd(2+), Hg(2+) and Ag(+), and the macrocyclic thioether 1,4,7-trithiacyclononane ([9]AneS3) or the monodentate diethylsulfide (Et(2)S), in acetonitrile (AN) at 298.15 K, were studied by a systematic methodology including potentiometry, calorimetry and polarography. [9]AneS3 is able to form complexes with all the target cations, Et(2)S only reacts with Hg(2+) and Ag(+). Mononuclear ML(j) (j = 1, 2) complexes are formed with all the metal ions investigated, where the affinity order is Hg(2+) > Ag(+) > Cd(2+) ≈ Zn(2+) when L = [9]AneS3 and Hg(2+) > Ag(+) when L = Et(2)S. Enthalpy and entropy values are generally negative, as a consequence of both metal ion interactions with neutral ligands, the reagents' loss of degrees of freedom and the release of solvating molecules. DFT calculations on the complexes formed with [9]AneS3 in vacuum and in AN are also carried out, to correlate experimental and theoretical thermodynamic values and to highlight the interplay between the direct metal-thioether interaction and the solvation effects. Trends obtained for the stability constants and enthalpies of the 1 : 1 and 1 : 2 complexes in solvent well reproduce the experimental ones for all the divalent metal ion complexes with [9]AneS3 and indicate the release of 3 AN molecules in the formation of each consecutive octahedral complex. In addition, calculated and experimental values for Ag(+) complex formation in solution suggest that in AgL(2) species [9]AneS3 ligands are not both tridentate.

  14. Measuring Thermodynamic Properties of Metals and Alloys With Knudsen Effusion Mass Spectrometry

    Science.gov (United States)

    Copland, Evan H.; Jacobson, Nathan S.

    2010-01-01

    This report reviews Knudsen effusion mass spectrometry (KEMS) as it relates to thermodynamic measurements of metals and alloys. First, general aspects are reviewed, with emphasis on the Knudsen-cell vapor source and molecular beam formation, and mass spectrometry issues germane to this type of instrument are discussed briefly. The relationship between the vapor pressure inside the effusion cell and the measured ion intensity is the key to KEMS and is derived in detail. Then common methods used to determine thermodynamic quantities with KEMS are discussed. Enthalpies of vaporization, the fundamental measurement, are determined from the variation of relative partial pressure with temperature using the second-law method or by calculating a free energy of formation and subtracting the entropy contribution using the third-law method. For single-cell KEMS instruments, measurements can be used to determine the partial Gibbs free energy if the sensitivity factor remains constant over multiple experiments. The ion-current ratio method and dimer-monomer method are also viable in some systems. For a multiple-cell KEMS instrument, activities are obtained by direct comparison with a suitable component reference state or a secondary standard. Internal checks for correct instrument operation and general procedural guidelines also are discussed. Finally, general comments are made about future directions in measuring alloy thermodynamics with KEMS.

  15. The thermodynamics of pyrochemical processes for liquid metal reactor fuel cycles

    International Nuclear Information System (INIS)

    Johnson, I.

    1987-01-01

    The thermodynamic basis for pyrochemical processes for the recovery and purification of fuel for the liquid metal reactor fuel cycle is described. These processes involve the transport of the uranium and plutonium from one liquid alloy to another through a molten salt. The processes discussed use liquid alloys of cadmium, zinc, and magnesium and molten chloride salts. The oxidation-reduction steps are done either chemically by the use of an auxiliary redox couple or electrochemically by the use of an external electrical supply. The same basic thermodynamics apply to both the salt transport and the electrotransport processes. Large deviations from ideal solution behavior of the actinides and lanthanides in the liquid alloys have a major influence on the solubilities and the performance of both the salt transport and electrotransport processes. Separation of plutonium and uranium from each other and decontamination from the more noble fission product elements can be achieved using both transport processes. The thermodynamic analysis is used to make process design computations for different process conditions

  16. Character of changes in the thermodynamic properties of alloyed melts of rare-earth metals with low-melting-point p- and d-metals

    International Nuclear Information System (INIS)

    Yamshchikov, L.F.; Zyapaev, A.A.; Raspopin, S.P.

    2003-01-01

    Published data on thermodynamic characteristics of lanthanides in liquid-metal melts of gallium, indium and zinc were systematized. The monotonous change from lanthanum to lutetium was ascertained for activity values and activity coefficients of trivalent lanthanides in the melts, which permits calculating the values for the systems of fusible metals, where no experimental data are available [ru

  17. Investigation of thermodynamic and transport properties of liquid transition metals using Wills-Harrison potentials

    International Nuclear Information System (INIS)

    Khaleque, M.A.; Bhuiyan, G.M.; Rashid, R.I.M.A.

    1998-01-01

    Thermodynamic properties such as entropy, specific heat capacity at constant pressure and isothermal compressibility have been calculated for liquid 3d, 4d and 5d transition metals near melting temperature. The hard sphere diameter for all such systems is estimated from the potential profile generated from the Wills and Harrison's prescription using linearized WCA theory of liquid. Evaluated values of entropy and specific heat capacity are found to be in good agreement with the experimental data. Transport property like shear viscosity for these liquid metals is obtained using the same potential profile. Lack of experimental data at melting temperatures hampers detailed comparison for all such systems. However, for the case of transport property, the results obtained are found to compare qualitatively well with the available experimental data. (author)

  18. Equation of state for thermodynamic properties of pure and mixtures liquid alkali metals

    International Nuclear Information System (INIS)

    Mousazadeh, M.H.; Faramarzi, E.; Maleki, Z.

    2010-01-01

    We developed an equation of state based on statistical-mechanical perturbation theory for pure and mixtures alkali metals. Thermodynamic properties were calculated by the equation of state, based on the perturbed-chain statistical associating fluid theory (PC-SAFT). The model uses two parameters for a monatomic system, segment size, σ, and segment energy, ε. In this work, we calculate the saturation and compressed liquid density, heat capacity at constant pressure and constant volume, isobaric expansion coefficient, for which accurate experimental data exist in the literatures. Results on the density of binary and ternary alkali metal alloys of Cs-K, Na-K, Na-K-Cs, at temperatures from the freezing point up to several hundred degrees above the boiling point are presented. The calculated results are in good agreement with experimental data.

  19. Thermodynamic and kinetic analysis of solid-phase interaction of alkali metal carbonates with arsenic pentoxide

    International Nuclear Information System (INIS)

    Pashinkin, A.S.; Buketov, E.A.; Isabaeva, S.M.; Kasenov, B.K.

    1985-01-01

    The thermodynamic analysis of solid-phase reactions of alkali metal carbonates with arsenic pentoxide showing the possibility of formation of all arsenates at a higher than the room temperature is performed. Energetically most advantageous is formation of meta-arsenates. It is shown that temperature increase favours the reaction process. By Gibbs standard energy decrease the reactions form the Li>Na>K>Rb>Cs series. On the base of calculation data linear dependence of Gibbs standard energy in reactions on the atomic number of alkali metalis established. By the continuous weighing method the kinetics of interaction of alkali metal carbonates with arsenic pentoxide under isothermal conditions in the 450-500 deg C range is studied. Studies is the dependence of apparent energy of interaction of carbonates wih As 2 0 5 an atomic parameters of al

  20. A metallic solution model with adjustable parameter for describing ternary thermodynamic properties from its binary constituents

    International Nuclear Information System (INIS)

    Fang Zheng; Qiu Guanzhou

    2007-01-01

    A metallic solution model with adjustable parameter k has been developed to predict thermodynamic properties of ternary systems from those of its constituent three binaries. In the present model, the excess Gibbs free energy for a ternary mixture is expressed as a weighted probability sum of those of binaries and the k value is determined based on an assumption that the ternary interaction generally strengthens the mixing effects for metallic solutions with weak interaction, making the Gibbs free energy of mixing of the ternary system more negative than that before considering the interaction. This point is never considered in the models currently reported, where the only difference in a geometrical definition of molar values of components is considered that do not involve thermodynamic principles but are completely empirical. The current model describes the results of experiments very well, and by adjusting the k value also agrees with those from models used widely in the literature. Three ternary systems, Mg-Cu-Ni, Zn-In-Cd, and Cd-Bi-Pb are recalculated to demonstrate the method of determining k and the precision of the model. The results of the calculations, especially those in Mg-Cu-Ni system, are better than those predicted by the current models in the literature

  1. Superabundant vacancies in fcc metals: A combination of ab-initio, thermodynamic and kinetics approaches

    Energy Technology Data Exchange (ETDEWEB)

    Nazarov, Roman; Hickel, Tilmann; Neugebauer, Joerg [Max-Planck-Institut fuer Eisenforschung, Duesseldorf (Germany)

    2011-07-01

    A dramatic increase of the vacancy concentration in a H-rich atmosphere, the so called superabundant vacancy formation, has been experimentally observed in several metals and alloys. In order to study this phenomenon we systematically applied density functional theory to a large set of fcc metals. We found that a large amount of H can be trapped by a monovacancy with, e.g., up to 15 H atoms in an Al vacancy, up to 12 H atoms in the case of Pd and more than 17 H atoms for Pb. Based on the defect formation energies from DFT calculations, we have constructed a thermodynamic model that determines the equilibrium concentration of point defects as a function of temperature and H chemical potential. By applying this approach we revealed that the vacancy concentration can indeed strongly increase if H is added. To understand the phenomenon of accelerated self-diffusion in a H-rich atmosphere we coupled the information on the number of vacancies from the thermodynamic treatment with self-diffusion barriers obtained from DFT calculations. Using this approach we found that the self-diffusion coefficient is reduced not only due to the increased vacancy concentration, but also as a result of a H-induced lubricant effect.

  2. Gases and carbon in metals - thermodynamics, kinetics, and properties. Pt. 11

    International Nuclear Information System (INIS)

    Jehn, H.; Speck, H.; Fromm, E.; Hoerz, G.

    1980-01-01

    This issue is part of a series of data on Gases and Carbon in Metals which supplements the data compilation in the book Gase and Kohlenstoff in Metallen (Gases and Carbon in Metals), edited by E.Fromm and E.Gebhardt, Springer-Verlag, Berlin 1976. The present survey includes results from papers published after the copy deadline and recommends critically selected data. Furthermore it comprises a bibliography of relevant literature. For each element the information is given in two parts. In a first section data are listed and in a second section the relevant literature is compiled. For each element, firstly data on binary systems are presented, starting with hydrogen and followed by carbon, nitrogen, oxygen, and rare gases. Within one metal-metalloid system the data are listed under topics such as solubility, solubility limit, dissociation pressure of compounds, vapour pressure of volatile oxides, thermodynamic data, diffusion, transport parameters (effective valence, heat of transport), permeation of gases through metals, gas absorption and gas desorption kinetics, compound formation kinetics, precipitation kinetics, and property changes. (orig./GE)

  3. Thermodynamics of Pore Filling Metal Clusters in Metal Organic Frameworks: Pd in UiO-66

    DEFF Research Database (Denmark)

    Vilhelmsen, Lasse; Sholl, David S.

    2012-01-01

    Metal organic frameworks (MOFs) have experimentally been demonstrated to be capable of supporting isolated transition-metal clusters, but the stability of these clusters with respect to aggregation is unclear. In this letter we use a genetic algorithm together with density functional theory...... calculations to predict the structure of Pd clusters in UiO-66. The cluster sizes examined are far larger than those in any previous modeling studies of metal clusters in MOFs and allow us to test the hypothesis that the physically separated cavities in UiO-66 could stabilize isolated Pd clusters. Our...... calculations show that Pd clusters in UiO-66 are, at best, metastable and will aggregate into connected pore filling structures at equilibrium....

  4. 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

  5. Thermodynamic studies on the interaction between some amino acids with some rare earth metal ions in aqueous solutions

    International Nuclear Information System (INIS)

    Mohamed, AbdAllah A.; Bakr, Moustafa F.; Abd El-Fattah, Khaled A.

    2003-01-01

    The interactions between the amino acids (glycine and L-threonine) with some rare earth metal ions (Pr 3+ , Nd 3+ , Eu 3+ , Gd 3+ , Dy 3+ , Ho 3+ and Yb 3+ ) were studied at a wide range from ionic strengths (0.07-0.32 M KNO 3 ) and temperatures (25-45 deg. C) in aqueous solutions by using Bjerrum potentiometric method. The stoichiometric and thermodynamic stability constants were calculated as well as the standard thermodynamic parameters (ΔG deg., ΔH deg. and ΔS deg. ) for all possible reactions that occur. The degree of formation (n-bar) for all studied systems was determined and discussed. The thermodynamic parameters differences (ΔΔG deg., ΔΔH deg. and ΔΔS deg. ) were calculated and discussed to determine the factors which control these complexation processes from the thermodynamic point of view

  6. Study of Thermodynamics of Liquid Noble-Metals Alloys Through a Pseudopotential Theory

    International Nuclear Information System (INIS)

    Vora, Aditya M.

    2010-01-01

    The Gibbs-Bogoliubov (GB) inequality is applied to investigate the thermodynamic properties of some equiatomic noble metal alloys in liquid phase such as Au-Cu, Ag-Cu, and Ag-Au using well recognized pseudopotential formalism. For description of the structure, well known Percus-Yevick (PY) hard sphere model is used as a reference system. By applying a variation method the best hard core diameters have been found which correspond to minimum free energy. With this procedure the thermodynamic properties such as entropy and heat of mixing have been computed. The influence of local field correction function viz; Hartree (H), Taylor (T), Ichimaru-Utsumi (IU), Farid et al. (F), and Sarkar et al. (S) is also investigated. The computed results of the excess entropy compares favourably in the case of liquid alloys while the agreement with experiment is poor in the case of heats of mixing. This may be due to the sensitivity of the heats of mixing with the potential parameters and the dielectric function. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  7. A thermodynamic perturbation theory for the surface tension and ion density profile of a liquid metal

    International Nuclear Information System (INIS)

    Evans, R.; Kumaravadivel, R.

    1976-01-01

    A simple scheme for determining the ion density profile and the surface tension of a liquid metal is described. Assuming that the interaction between metallic pseudo-ions is of the form introduced by Evans, an approximate expression for the excess free energy of the system is derived using the thermodynamic perturbation theory of Weeks, Chandler and Anderson. This excess free energy is then minimized with respect to a parameter which specifies the ion density profile, and the surface tension is given directly. From a consideration of the dependence of the interionic forces on the electron density it is predicted that the ions should take up a very steep density profile at the liquid metal surface. This behaviour is contrasted with that to be expected for rare-gas fluids in which the interatomic forces are density-independent. The values of the surface tension calculated for liquid Na, K and Al from a simplified version of the theory are in reasonable agreement with experiment. (author)

  8. Electronic and thermodynamic properties of the transition between metallic and nonmetallic states in dense media

    International Nuclear Information System (INIS)

    Fortin, Xavier

    1971-01-01

    The effects of thermal excitation are introduced in the study of a simple electronic structure model for condensed media. The choice of a particle-interaction potential leads to a self-consistent calculation performed on a computer. This calculation gives a metal - nonmetal transition similar to the MOTT transition. We consider the effects of temperature and density variations upon this transition. It is possible to make use of this electronic structure to obtain the thermodynamic properties near the transition: pressure, free energy, sound velocity. The numerical results of this simple model are satisfactory. Particularly, if a dielectric constant is taken into account, the transition temperature and density are of the same order of magnitude as those observed experimentally in semiconductors. (author) [fr

  9. Thermodynamic analysis of trimethylgallium decomposition during GaN metal organic vapor phase epitaxy

    Science.gov (United States)

    Sekiguchi, Kazuki; Shirakawa, Hiroki; Chokawa, Kenta; Araidai, Masaaki; Kangawa, Yoshihiro; Kakimoto, Koichi; Shiraishi, Kenji

    2018-04-01

    We analyzed the decomposition of Ga(CH3)3 (TMG) during the metal organic vapor phase epitaxy (MOVPE) of GaN on the basis of first-principles calculations and thermodynamic analysis. We performed activation energy calculations of TMG decomposition and determined the main reaction processes of TMG during GaN MOVPE. We found that TMG reacts with the H2 carrier gas and that (CH3)2GaH is generated after the desorption of the methyl group. Next, (CH3)2GaH decomposes into (CH3)GaH2 and this decomposes into GaH3. Finally, GaH3 becomes GaH. In the MOVPE growth of GaN, TMG decomposes into GaH by the successive desorption of its methyl groups. The results presented here concur with recent high-resolution mass spectroscopy results.

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

    International Nuclear Information System (INIS)

    Ackermann, R.J.; Chandrasekharaiah, M.S.

    1975-01-01

    The thermodynamic data for the actinide metals and oxides (thorium to curium ) have been assessed, examined for consistency, and compared with the lanthanides. Correlations relating the enthalpies of formation of the solid oxides with the corresponding aquo ions make possible the estimation of the thermodynamic properties of AmO 2 (s) and Am 2 O 3 (s) which are in accordance with vaporization data. The known thermodynamic properties of the substoichiometric dioxides MOsub(2-x)(s) at high temperatures demonstrate the relative stabilities of valence states less than 4+ and lead to the examination of stability requirements for the sesquioxides M 2 O 3 (s) and the monoxides MO(s). Sequential trends in the gaseous metals, monoxides and dioxides are examined, compared, and contrasted with the lanthanides. (author)

  11. Chemical Constraints Governing the Origin of Metabolism: The Thermodynamic Landscape of Carbon Group Transformations

    Science.gov (United States)

    Weber, Arthur L.; Fonda, Mark (Technical Monitor)

    2001-01-01

    The thermodynamics of organic chemistry under mild aqueous conditions was examined in order to begin to understand its influence on the structure and operation of metabolism and its antecedents. Free energies were estimated for four types reactions of biochemical importance carbon-carbon bond cleavage and synthesis, hydrogen transfer between carbon groups, dehydration of alcohol groups, and aldo-keto isomerization. The energies were calculated for mainly aliphatic groups composed of carbon, hydrogen, and oxygen. The energy values showed that (1) when carbon-carbon bond cleavage involves two different types of functional groups, transfer of the shared electron-pair to the more reduced carbon group is energetically favored over transfer to the more oxidized carbon group, and (2) the energy of carbon-carbon bond transformation is strongly dependent on the type of functional group that donates the shared electron-pair during cleavage, and the group that accepts the shared electron-pair during synthesis, and (3) the energetics of C-C bond transformation is determined primarily by the half-reaction energies of the couples: carbonyl/carboxylic acid, carboxylic acid/carbon dioxide, alcohol/carbonyl, and hydrocarbon/alcohol. The energy of hydrogen-transfer between carbon groups was found to depend on the functional group class of both the hydrogen-donor and hydrogen-acceptor. From these and other observations we concluded that the chemistry of the origin of metabolism (and to a lesser degree modem metabolism) is strongly constrained by the (1) limited disproportionation energy of organic substrates that can be dissipated in a few irreversible reactions, (2) the energy-dominance of few half-reaction couples in carbon-carbon bond transformation that establishes whether a chemical reaction is energetically irreversible, reversible or unfeasible, and (3) the dependence of the transformation-energy on the oxidation state of carbon groups (functional group type) which is

  12. Thermodynamic assessment and experimental verification of reactive ion etching of magnetic metal elements

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Taeseung; Chen, Jack Kun-Chieh; Chang, Jane P., E-mail: jpchang@ucla.edu [Chemical and Biomolecular Engineering, UCLA, Los Angeles, California 90095 (United States)

    2014-07-01

    A thermodynamic analysis of etch chemistries for Co, Fe, and Ni using a combination of hydrogen, oxygen, and halogen gases suggested that a single etchant does not work at 300 K; however, a sequential exposure to multiple etchants results in sufficiently high partial pressure of the reaction products for the process to be considered viable. This sequential dose utilized the two reactions, a surface halogenation followed by the secondary etchant exposure. (MX{sub 2} (c) + 3Y →MY(g) + 2XY(g), where M = Co, Fe, Ni; X = F, Cl, Br; Y = O, H) The volatilization reaction induced by sequential plasma exposure changed the equilibrium point, increasing the partial pressure of the etch product. Amongst all combinations, Cl{sub 2} or Br{sub 2} plasmas followed by H{sub 2} plasma were the most effective. From both the gas phase diagnostics and surface composition analysis, H{sub 2} plasma alone could not etch metallic Co, Fe, and Ni films but alternating doses of Cl{sub 2} and H{sub 2} plasmas resulted in more effective removal of chlorinated metals and increased the overall etch rate.

  13. Solvent isotope effects upon the thermodynamics of some transition-metal redox couples in aqueous media

    International Nuclear Information System (INIS)

    Weaver, M.J.; Nettles, S.M.

    1980-01-01

    The effects of substituting D 2 O for H 2 O as solvent upon the formal potentials of a number of transition-metal redox couples containing aquo, ammine, and simple chelating ligands have been investigated with the intention of evaluating the importance of specific solvation factors in the thermodynamics of such couples. The solvent liquid junction formed between H 2 O and D 2 O was shown to have a negligible effect on the measured formal potentials. Substantial solvent isotope effects were observed for a number of these systems, particularly for couples containing aquo ligands. The effects of separately deuterating the ligands and the surrounding solvent were investigated for some ammine couples. Possible origins of the solvent isotope effects are discussed in terms of changes in metal-ligand and ligand-solvent interactions. It is tentatively concluded that the latter influence provides the predominant contribution to the observed effects for aquo couples arising from increases in the extent of hydrogen bonding between the aquo ligands and surrounding solvent when D 2 O replaces H 2 O. The implications of these results in unraveling the solvent isotope effects upon the kinetics of simple redox reactions are also considered

  14. Thermodynamic Features of Benzene-1,2-Diphosphonic Acid Complexes with Several Metal Ions

    Energy Technology Data Exchange (ETDEWEB)

    Syouhei Nishihama; Ryan P. Witty; Leigh R Martin; Kenneth L. Nash

    2013-08-01

    Among his many contributions to the advancement of f-element chemistry and separation science, Professor Gregory R. Choppin’s research group completed numerous investigations featuring the application of distribution techniques to the determination of metal complexation equilibrium quotients. Most of these studies focused on the chemistry of lanthanide and actinide complexes. In keeping with that tradition, this report discusses the complex formation equilibrium constants for complexes of trivalent europium (Eu3+) with benzene-1,2-diphosphonic acid (H4BzDP) determined using solvent extraction distribution experiments in 0.2 M (Na,H)ClO4 media in the temperature range of 5 – 45 degrees C. Protonation constants for HnBzDP4-n and stoichiometry and stability of BzDP4- complexes with Zn2+, Ni2+, and Cu2+ have also been determined using potentiometric titration (at I = 0.1 M) and 31P NMR spectroscopy. Heats of protonation of HnBzDPn-4 species have been determined by titration calorimetry. From the temperature dependence of the complex Eu3+-HnBzDPn-4 equilibrium constant, a composite enthalpy (?H = -15.1 (+/-1.0) kJ mol-1) of complexation has been computed. Comparing these thermodynamic parameters with literature reports on other diphosphonic acids and structurally similar carboxylic acids indicates that exothermic heats of complexation are unique to the Eu-BzDP system. Comparisons with thermodynamic data from the literature indicate that the fixed geometry imposed by the benzene ring enhances complex stability.

  15. A new model for predicting thermodynamic properties of ternary metallic solution from binary components

    International Nuclear Information System (INIS)

    Fang Zheng; Zhang Quanru

    2006-01-01

    A model has been derived to predict thermodynamic properties of ternary metallic systems from those of its three binaries. In the model, the excess Gibbs free energies and the interaction parameter ω 123 for three components of a ternary are expressed as a simple sum of those of the three sub-binaries, and the mole fractions of the components of the ternary are identical with the sub-binaries. This model is greatly simplified compared with the current symmetrical and asymmetrical models. It is able to overcome some shortcomings of the current models, such as the arrangement of the components in the Gibbs triangle, the conversion of mole fractions between ternary and corresponding binaries, and some necessary processes for optimizing the various parameters of these models. Two ternary systems, Mg-Cu-Ni and Cd-Bi-Pb are recalculated to demonstrate the validity and precision of the present model. The calculated results on the Mg-Cu-Ni system are better than those in the literature. New parameters in the Margules equations expressing the excess Gibbs free energies of three binary systems of the Cd-Bi-Pb ternary system are also given

  16. Modeling nanostructural surface modifications in metal cutting by an approach of thermodynamic irreversibility: Derivation and experimental validation

    Science.gov (United States)

    Buchkremer, S.; Klocke, F.

    2017-01-01

    Performance and operational safety of many metal parts in engineering depend on their surface integrity. During metal cutting, large thermomechanical loads and high gradients of the loads concerning time and location act on the surfaces and may yield significant structural material modifications, which alter the surface integrity. In this work, the derivation and validation of a model of nanostructural surface modifications in metal cutting are presented. For the first time in process modeling, initiation and kinetics of these modifications are predicted using a thermodynamic potential, which considers the interdependent developments of plastic work, dissipation, heat conduction and interface energy as well as the associated productions and flows of entropy. The potential is expressed based on the free Helmholtz energy. The irreversible thermodynamic state changes in the workpiece surface are homogenized over the volume in order to bridge the gap between discrete phenomena involved with the initiation and kinetics of dynamic recrystallization and its macroscopic implications for surface integrity. The formulation of the thermodynamic potential is implemented into a finite element model of orthogonal cutting of steel AISI 4140. Close agreement is achieved between predicted nanostructures and those obtained in transmission electron microscopical investigations of specimen produced in cutting experiments.

  17. Thermodynamic analysis on heavy metals partitioning impacted by moisture during the MSW incineration

    International Nuclear Information System (INIS)

    Zhang Yanguo; Li Qinghai; Jia Jinyan; Meng Aihong

    2012-01-01

    Highlights: ► Partitioning of HMs affected by moisture was investigated by thermodynamic analysis. ► Increase in moisture and in temperature was opposite impact on HMs contribution. ► The extent of temperature decreased by increase in moisture determines the impact. - Abstract: A thermodynamic calculation was carried out to predict the behavior and speciation of heavy metals (HMs), Pb, Zn, Cu, and Cd, during municipal solid waste (MSW) incineration with the different moisture levels. The calculation was based on the minimization of the total Gibbs free energy of the multi-components and multi-phases closed system reaching chemical equilibrium. The calculation also indicated the reaction directions and tendencies of HMs components. The impacts of chlorine additives (No PVC, 1%PVC, and 5%PVC) and moisture on the behavior of HMs were investigated at different temperature levels in the system (750 °C, 950 °C, and 1150 °C). Furthermore, because the incineration temperature falls down with the increase in moisture in waste, the co-influence of moisture and temperature in combusting MSW on the HMs was also studied with the given chlorine (as 1%PVC + 0.5%NaCl). The results showed that in the non-chlorine system, the impact of the moisture on Pb, Zn, and Cu was not significant, and the ratio of compound transformation was less than 10%, except the Cd compounds at 950 °C and 1150 °C. In the system with low chlorine (as 1%PVC) at constant temperature, the chlorides of HMs (Cd, Pb, Zn, and Cu) transferred to oxides, and when the content of chlorine rose up (as 5%PVC), the ratio of the chlorides of HMs (Cd, Pb, Zn, and Cu) transferring to oxides fell down noticeably. When the moisture varied together with the temperature, the Zn and Cu compounds transferred from chlorides to oxides with increase in moisture as well as decrease in temperature. At the temperature of 700–1000 °C, the impact of temperature on Pb and Cd was little and the moisture was the main factor

  18. Thermodynamics of solvent interaction with the metal-organic framework MOF-5.

    Science.gov (United States)

    Akimbekov, Zamirbek; Wu, Di; Brozek, Carl K; Dincă, Mircea; Navrotsky, Alexandra

    2016-01-14

    The inclusion of solvent in metal-organic framework (MOF) materials is a highly specific form of guest-host interaction. In this work, the energetics of solvent MOF-5 interactions has been investigated by solution calorimetry in 5 M sodium hydroxide (NaOH) at room temperature. Solution calorimetric measurement of enthalpy of formation (ΔH(f)) of Zn4O(C8H4O4)3·C3H7NO (MOF-5·DMF) and Zn4O(C8H4O4)3·0.60C5H11NO (MOF-5·0.60DEF) from the dense components zinc oxide (ZnO), 1,4-benzenedicarboxylic acid (H2BDC), N,N-dimethylformamide (DMF) and N,N-diethylformamide (DEF) gives values of 16.69 ± 1.21 and 45.90 ± 1.46 kJ (mol Zn4O)(-1), respectively. The enthalpies of interaction (ΔH(int)) for DMF and DEF with MOF-5 are -82.78 ± 4.84 kJ (mol DMF)(-1) and -89.28 ± 3.05 kJ (mol DEF)(-1), respectively. These exothermic interaction energies suggest that, at low guest loading, Lewis base solvents interact more strongly with electron accepting Zn4O clusters in the MOF than at high solvent loading. These data provide a quantitative thermodynamic basis to investigate transmetallation and solvent assisted linker exchange (SALE) methods and to synthesize new MOFs.

  19. Acid leaching of heavy metals from contaminated soil collected from Jeddah, Saudi Arabia: kinetic and thermodynamics studies

    Directory of Open Access Journals (Sweden)

    Shorouq I. Alghanmi

    2015-09-01

    Full Text Available Urban soils polluted with heavy metals are of increasing concern because it is greatly affecting human health and the ecological systems. Hence, it is mandatory to understand the reasons behind this pollution and remediate the contaminated solid. The removal of heavy metals from contaminated soil samples collected from the vicinity of the sewage lake in Jeddah, Saudi Arabia, was explored. The leaching process was studied kinetically and thermodynamically for better understanding of the remediation process. The results showed that the soil samples were slightly basic in nature, and tend to be more neutral away from the main contaminated sewage lake area. The total metal content in the soil samples was measured using the aqua regia extractions by ICP-OES and the results showed that many of the heavy metals present have significant concentrations above the tolerable limits. In general, the metal concentrations at different sites indicated that the heavy metal pollution is mainly due to the sewage discharge to the lake. The results showed excellent correlation between the concentrations of Co, As, and Hg with the distance from the main contaminated area. The leaching of Co, As, and Hg using 1.0 M hydrochloric acid from the soil was studied kinetically at different temperatures and the experimental results were fitted using different kinetics models. The experimental data were best described with two-constant rate and Elovich equation kinetic models. Also, the thermodynamic study showed that the leaching process was spontaneous, endothermic and accompanied with increase in the entropy. In general, the polluted soil could be remediated successfully from the heavy metals using the acid leaching procedure in a short period of time.

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

    International Nuclear Information System (INIS)

    Gurvich, L.V.; Bergman, G.A.; Gorokhov, L.N.; Iorish, V.S.; Leonidov, V.Y.; Yungman, V.S.

    1997-01-01

    The data on thermodynamic and molecular properties of the potassium, rubidium and cesium hydroxides have been collected, critically reviewed, analyzed, and evaluated. Tables of the thermodynamic properties [C p circ , Φ=-(G -H(0)/T, S, H -H(0), Δ f H, Δ f G)] of these hydroxides in the condensed and gaseous states have been calculated using the results of the analysis and some estimated values. The recommendations are compared with earlier evaluations given in the JANAF Thermochemical Tables and Thermodynamic Properties of Individual Substances. The properties considered are: the temperature and enthalpy of phase transitions and fusion, heat capacities, spectroscopic data, structures, bond energies, and enthalpies of formation at 298.15 K. The thermodynamic functions in solid, liquid, and gaseous states are calculated from T=0 to 2000 K for substances in condensed phase and up to 6000 K for gases. copyright 1997 American Institute of Physics and American Chemical Society

  1. Ion association thermodynamics of alkali metal tetraphenylborates in the mixed solvent propylenecarbonate-1,2-dimethoxyethane

    International Nuclear Information System (INIS)

    Fialkov, Yu.Ya.; Gorbachev, V.Yu.

    1997-01-01

    Polythermal dependences of constants of ion association of (Li + -Cs + )BPh 4 salts in mixed solvent differ significantly in permittivity. Thermodynamic characteristics of this process are calculated and their relation with solvation processes is analyzed. (author)

  2. Thermodynamic stability of binary systems involving metal ions and the 4-methoxy benzylidenepyruvate in aqueous solution

    International Nuclear Information System (INIS)

    Redigolo, H.

    1989-01-01

    A review on studies previously carried out in this laboratory involving metal ions and benzylidene-pyruvate, in aqueous solutions, is presented; emphasis is mainly placed on complexes comprising 4-Dimethyl-amino-benzylidene-pyruvate (DMBP, p K a 3.79) and 2-Chloro-4-Dimethyl-amino-benzylidene-pyruvate (2 Cl-DMBP, p k a = 3.08). In an endeavour to extend the previous work, the dissociation constant of 4-methoxy-benzylidene-pyruvic acid (H-4-Me O-BP) was determined spectrophotometrically at 25.0 +- 0.1 0 C and ionic strength 0.500 M, held with sodium perchlorate (p k a = 1.473). The complex formation equilibria in M-4-Me O-BP systems, where M = Cu(II), La(III), Pr(III), Sm(III), Lu(III), Sc (III), In(III), Ga(III) or Th(IV) were investigated, also spectrophotometrically, in the above mentioned experimental conditions. In addition, the system involving Sm(III) was reinvestigated at ionic strengths 0.100 and 2.00 M, the remaining experimental conditions being maintained. The study is mostly concerned with the determination of formation constants of 1:1 complex species (β 1 ) and spectrophotometric parameters associated with these species. The investigation of possible higher binary complexes (ML n , n > 1) was prevented by solubility limitations. For all considered metal ions, log β 1 (DMBP) > log β 1 (4-Me O-BP) indicating that the stability is governed, at least in part, by ligand basicity. (author). 121 refs, 36 figs, 20 tabs

  3. Thermodynamic Considerations of Direct Oxygen Removal from Titanium by Utilizing the Deoxidation Capability of Rare Earth Metals

    Science.gov (United States)

    Okabe, Toru H.; Zheng, Chenyi; Taninouchi, Yu-ki

    2018-06-01

    Oxygen removal from metallic Ti is extremely difficult and, currently, there is no commercial process for effectively deoxidizing Ti or its alloys. The oxygen concentration in Ti scraps is normally higher than that in virgin metals such as in Ti sponges produced by the Kroll process. When scraps are remelted with virgin metals for producing primary ingots of Ti or its alloys, the amount of scrap that can be used is limited owing to the accumulation of oxygen impurities. Future demands of an increase in Ti production and of mitigating environmental impacts require that the amount of scrap recycled as a feed material of Ti ingots should also increase. Therefore, it is important to develop methods for removing oxygen directly from Ti scraps. In this study, we evaluated the deoxidation limit for β-Ti using Y or light rare earth metals (La, Ce, Pr, or Nd) as a deoxidant. Thermodynamic considerations suggest that extra-low-oxygen Ti, with an oxygen concentration of 100 mass ppm or less can be obtained using a molten salt equilibrating with rare earth metals. The results presented herein also indicate that methods based on molten salt electrolysis for producing rare earth metals can be utilized for effectively and directly deoxidizing Ti scraps.

  4. The effect of substrate orientation on the kinetics and thermodynamics of initial oxide-film growth on metals

    Energy Technology Data Exchange (ETDEWEB)

    Reichel, Friederike

    2007-11-19

    This thesis addresses the effect of the parent metal-substrate orientation on the thermodynamics and kinetics of ultra-thin oxide-film growth on bare metals upon their exposure to oxygen gas at low temperatures (up to 650 K). A model description has been developed to predict the thermodynamically stable microstructure of a thin oxide film grown on its bare metal substrate as function of the oxidation conditions and the substrate orientation. For Mg and Ni, the critical oxide-film thickness is less than 1 oxide monolayer and therefore the initial development of an amorphous oxide phase on these metal substrates is unlikely. Finally, for Cu and densely packed Cr and Fe metal surfaces, oxide overgrowth is predicted to proceed by the direct formation and growth of a crystalline oxide phase. Further, polished Al single-crystals with {l_brace}111{r_brace}, {l_brace}100{r_brace} and {l_brace}110{r_brace} surface orientations were introduced in an ultra-high vacuum system for specimen processing and analysis. After surface cleaning and annealing, the bare Al substrates have been oxidized by exposure to pure oxygen gas. During the oxidation, the oxide-film growth kinetics has been established by real-time in-situ spectroscopic ellipsometry. After the oxidation, the oxide-film microstructures were investigated by angle-resolved X-ray photoelectron spectroscopy and low energy electron diffraction. Finally, high-resolution transmission electron microscopic analysis was applied to study the microstructure and morphology of the grown oxide films on an atomic scale. (orig.)

  5. The use of isothermal titration calorimetry to determine the thermodynamics of metal ion binding to low-cost sorbents

    International Nuclear Information System (INIS)

    Karlsen, Vigdis; Heggset, Ellinor Baevre; Sorlie, Morten

    2010-01-01

    The thermodynamics of Al 3+ , Cr 3+ , and Pb 2+ binding to the abundant biopolymer chitin have been determined using isothermal titration calorimetry (ITC) and compared to what is observed for binding to activated carbon. The use of ITC enables the detection of two distinct binding sites on chitin for all three metal ions. For the relative strong binding sites, free energy changes ranges from -37.6 kJ/mol to -41.8 kJ/mol while the same values are from -30.1 kJ/mol to -31.8 kJ/mol for the relative weak binding sites. All binding reactions to chitin are entropically driven. Interactions of the metal ions to activated carbon are best fitted as a single-site binding with relative weak binding with free energy changes from -26.3 kJ/mol to -26.8 kJ/mol.

  6. Thermodynamics of binding interactions between extracellular polymeric substances and heavy metals by isothermal titration microcalorimetry.

    Science.gov (United States)

    Yan, Peng; Xia, Jia-Shuai; Chen, You-Peng; Liu, Zhi-Ping; Guo, Jin-Song; Shen, Yu; Zhang, Cheng-Cheng; Wang, Jing

    2017-05-01

    Extracellular polymeric substances (EPS) play a crucial role in heavy metal bio-adsorption using activated sludge, but the interaction mechanism between heavy metals and EPS remains unclear. Isothermal titration calorimetry was employed to illuminate the mechanism in this study. The results indicate that binding between heavy metals and EPS is spontaneous and driven mainly by enthalpy change. Extracellular proteins in EPS are major participants in the binding process. Environmental conditions have significant impact on the adsorption performance. Divalent and trivalent cations severely impeded the binding of heavy metal ions to EPS. Electrostatic interaction mainly attributed to competition between divalent cations and heavy metal ions; trivalent cations directly competed with heavy metal ions for EPS binding sites. Trivalent cations were more competitive than divalent cations for heavy metal ion binding because they formed complexing bonds. This study facilitates a better understanding about the interaction between heavy metals and EPS in wastewater treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. 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.

  8. Thermodynamic characteristics of sorption of metal-ions by ion exchangers

    OpenAIRE

    ABBASOV ALIADDIN DAYYAN; JAFARLI MAHNUR MOYSUN; MEMMEDOVA FIZZA SADIKH; HEYDEROVA FARAH FARMAN

    2016-01-01

    Conditions of sorption equilibrium of copper, zinc, cadmium and lead-ions by chelatforming resins Diaion CR 11, Dowex M 4195 and Duolite C 467 depending on the degree of neutralization of their ionogenic groups, the acidity of the medium and concentration of solutions are studied; corresponding equations expressing the isotherms of sorption are offered. Kinetics of these processes is studied; on the basis of equilibrium and kinetic parameters are calculated thermodynamic quantities. It is sho...

  9. Kinetic and thermodynamic bases to resolve issues regarding conditioning of uranium metal fuels

    International Nuclear Information System (INIS)

    Johnson, A.B.; Ballinger, R.G.; Simpson, K.A.

    1994-12-01

    Numerous uranium - bearing fuels are corroding in fuel storage pools in several countries. At facilities where reprocessing is no longer available, dry storage is being evaluated to preclude aqueous corrosion that is ongoing. It is essential that thermodynamic and kinetic factors are accounted for in transitions of corroding uranium-bearing fuels to dry storage. This paper addresses a process that has been proposed to move Hanford N-Reactor fuel from wet storage to dry storage

  10. 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

  11. Thermodynamics of the Volatilization of Actinind metals in the High-Temperature Treatment of Radioactive Wastes

    International Nuclear Information System (INIS)

    Adamson, Martyn G.; Olander, Donald R.

    1999-01-01

    We are performing a detailed study of the volatilization behavior of U, Pu and possibly Am and Np under conditions relevant to the thermal treatment (destruction) of actinide containing organic-based mixed and radioactive wastes. The primary scientific goal of the work is to develop a basic thermochemical understanding of actinide volatilization and partitioning/speciation behavior in the thermal processes that are central to DOE/EM's mixed waste treatment program. This subject addresses at least two key technical needs/problem areas recently identified by DOE/EM's Office of Science and Technology: emission-free destruction of organic wastes, and interactions between actinides and organic residues in materials stabilization. A sound basis for designing safe and effective treatment systems, and the ability to allay public concerns about radioactive fugitive emissions, will be the principal benefits of the project. The proposed work is a combination of experimental studies and thermodynamic modeling. Vapor pressure measurements will be made to determine U, Pu and possibly Am volatile species and the extent of their volatilization when UO2/U3O8, PuO2 and AmO2 solids are heated to temperatures of 500 to1200 C under pyrolyzing (reducing) conditions or under oxidizing conditions in the presence of chlorine. Work on uranium volatilization under reducing conditions is being performed in a laboratory at UC Berkeley in a collaboration with Professor D.R. Olander. In parallel with the experimental effort, a complete thermodynamic database for expected actinide gaseous species will be developed from literature data, from the proposed measurements, and from data predictions using bond energy correlation and statistical thermodynamics estimation methods

  12. Potentiometric and Thermodynamic Studies of Some Schiff-Base Derivatives of 4-Aminoantipyrine and Their Metal Complexes

    Directory of Open Access Journals (Sweden)

    A. A. El-Bindary

    2013-01-01

    Full Text Available The proton-ligand dissociation constant of 4-(4-amino-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazol-3-ylideneamino-phenol ( and 4-(4-amino-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazol-3-ylideneamino-benzoic acid ( and metal-ligand stability constants of their complexes with metal ions (Mn2+, Co2+, Ni2+, and Cu2+ have been determined potentiometrically in 0.1 mol·dm−3 KCl and 10% (by volume ethanol-water mixture and at 298, 308, and 318 K. The stability constants of the formed complexes increase in the order Mn2+, Co2+, Ni2+, and Cu2+. The effect of temperature was studied, and the corresponding thermodynamic parameters (, , and were derived and discussed. The dissociation process is nonspontaneous, endothermic, and entropically unfavourable. The formation of the metal complexes has been found to be spontaneous, endothermic, and entropically favourable.

  13. Theoretical studies on the thermodynamic properties and detonation properties of cyclotrimethylene trinitramine (RDX with aluminum and boron metals.

    Directory of Open Access Journals (Sweden)

    Nilgün Şen

    2016-10-01

    Full Text Available The B3LYP/6-311++G(2df,2p density functional theory (DFT method was used to investigate molecular geometry and thermodynamic properties of RDX and RDX derivatives containing Al and B metals. The detonation velocity (D and detonation pressure (P, estimated by using Kamlet–Jacobs and in literature equations, respectively. Total energies (Et, frontier orbital energy (EHOMO, ELOMO, energy gap (ΔELUMO–HOMO and theoretical molecular density (ρ were calculated with Spartan 14 software package program. It was shown that the presence of aluminum and boron atoms affects the good thermal stabilities. The results show that the composite RDX-Al, RDX-B derivatives have higher detonation performance and higher density than RDX. RDX-Al derivatives appeared to be superior to RDX-B mixtures in terms of these parameters. These results provide information on the moleculer design of new energetic materials.

  14. Rational extended thermodynamics

    CERN Document Server

    Müller, Ingo

    1998-01-01

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

  15. Spectral descriptors for bulk metallic glasses based on the thermodynamics of competing crystalline phases

    OpenAIRE

    Perim, Eric; Lee, Dongwoo; Liu, Yanhui; Toher, Cormac; Gong, Pan; Li, Yanglin; Simmons, W. Neal; Levy, Ohad; Vlassak, Joost J.; Schroers, Jan; Curtarolo, Stefano

    2016-01-01

    Metallic glasses have attracted considerable interest in recent years due to their unique combination of superb properties and processability. Predicting bulk metallic glass formers from known parameters remains a challenge and the search for new systems is still performed by trial and error. It has been speculated that some sort of "confusion" during crystallization of the crystalline phases competing with glass formation could play a key role. Here, we propose a heuristic descriptor quantif...

  16. Gases and carbon in metals (thermodynamics, kinetics, and properties). Pt. 10

    International Nuclear Information System (INIS)

    Jehn, H.; Speck, H.; Fromm, E.; Hoerz, G.

    1980-01-01

    This issue is part of a series of data on Gases and Carbon in Metals which supplements the data compilation in the book Gase und Kohlenstoff in Metallen (Gases and Carbon in Metals), edited by E. Fromm and E. Gebhardt, Springer-Verlag, Berlin 1976. The present survey covers chromium and tungsten, includes results from papers published after the copy deadline and recommends critically selected data. Furthermore it comprises a bibliography of relevant literature. (GE) [de

  17. Regularities of changes of metal melting entropy

    International Nuclear Information System (INIS)

    Kats, S.A.; Chekhovskoj, V.Ya.

    1980-01-01

    Most trustworthy data on temperatures, heats and entropies of fusion of metals have been used as a basis to throw light on the laws governing variations of the entropy of metals fusion. The elaborated procedure is used to predict the entropies of the metals fusion whose thermodynamic properties under high temperatures have not yet been investigated

  18. 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.

  19. When is thermodynamics relevant to ion-induced atomic rearrangements in metals

    International Nuclear Information System (INIS)

    Johnson, W.L.; Cheng, Y.T.; Van Rossum, M.; Nicolet, M.A.

    1984-08-01

    The problem of ion-induced mixing of metal bilayers is examined in the limit of heavy metals (Z > 20) and heavy energetic ions (E > 100 keV) and in the absence of delayed effects such as radiation enhanced thermal diffusion. Thermochemical effects are shown to play an important role in biasing the random walk process of mixing. A universal mixing equation is derived which predicts the evolution of the concentration profile as a function of ion dose. Finally, a model is presented which allows one to predict what metallurgical phases are formed during the mixing process. Criteria for amorphous phase formation are particularly emphasized

  20. Ab initio study on half-metallic, electronic and thermodynamic attributes of LaFeO3

    Science.gov (United States)

    Tariq, Saad; Saad, Saher; Jamil, M. Imran; Sohail Gilani, S. M.; Mahmood Ramay, Shahid; Mahmood, Asif

    2018-03-01

    By using the density functional theory (DFT) the systematic study of the structural, electronic and thermodynamic properties of lanthanum ferrite (LaFeO3) has been conducted. The elastic stability criterion and structural tolerance factor reveal that LaFeO3 exists in the cubic phase and is found to be stable under the ambient conditions. In electronic properties, the optical spectrum of the compound has been found to fall in the range of 488 to 688nm which has been calculated from the electronic band gap values by using the PBE-GGA and mBJ-GGA techniques. The light between 488 to 688nm would cause the valence electrons to jump in the conduction band showing the photoconductivity. The pronounced half-metallic character has been discussed by using the projected electronic density of states. The ferromagnetic response has been observed which may be attributed to the Fe-O bonding situation. The compound exhibits ductile, indirect band gap and half-metallic traits in the bulk phase. We expect the compound to be felicitous for the novel spintronic applications.

  1. Metal-hydrogen systems with an exceptionally large and tunable thermodynamic destabilization

    NARCIS (Netherlands)

    Ngene, Peter; Longo, Alessandro; Mooij, L.P.A.; Bras, Wim; Dam, B.

    2017-01-01

    Hydrogen is a key element in the energy transition. Hydrogen-metal systems have been studied for various energy-related applications, e.g., for their use in reversible hydrogen storage, catalysis, hydrogen sensing, and rechargeable batteries. These applications depend strongly on the

  2. Thermodynamic driving force effects in the oxygen reduction catalyzed by a metal-free porphyrin

    Czech Academy of Sciences Publication Activity Database

    Trojánek, Antonín; Langmaier, Jan; Samec, Zdeněk

    2012-01-01

    Roč. 82, SI (2012), s. 457-462 ISSN 0013-4686 R&D Projects: GA ČR GAP208/11/0697 Institutional research plan: CEZ:AV0Z40400503 Keywords : oxygen reduction * metal-free porphyrin * electrocatalysis Subject RIV: CG - Electrochemistry Impact factor: 3.777, year: 2012

  3. A Systematic Transport and Thermodynamic Study of Heavy Transition Metal Oxides with Hexagonal Structure

    Science.gov (United States)

    Butrouna, Kamal

    There is no apparent, dominant interaction in heavy transition metal oxides (TMO), especially in 5d-TMO, where all relevant interactions are of comparable energy scales, and therefore strongly compete. In particular, the spin-orbit interaction (SOI) strongly competes with the electron-lattice and on-site Coulomb interaction (U). Therefore, any tool that allows one to tune the relative strengths of SOI and U is expected to offer an opportunity for the discovery and study of novel materials. BaIrO3 is a magnetic insulator driven by SOI, whereas the isostructural BaRuO3 is a paramagnetic metal. The contrasting ground states have been shown to result from the critical role of SOI in the iridate. This dissertation thoroughly examines a wide array of newly observed novel phenomena induced by adjusting the relative strengths of SOI and U via a systematic chemical substitution of the Ru4+(4d 4) ions for Ir4+(5d5) ions in BaIrO3, i.e., in high quality single crystals of BaIr1--x RuxO3(0.0 ≤ x ≤ 1.0). Our investigation of structural, magnetic, transport and thermal properties reveals that Ru substitution directly rebalances the competing energies so profoundly that it generates a rich phase diagram for BaIr 1--xRuxO 3 featuring two major effects: (1) Light Ru doping (0 ≤ x ≤ 0.15) prompts a simultaneous and precipitous drop in both the magnetic ordering temperature TC and the electrical resistivity, which exhibits metal-insulator transition at around TC. (2) Heavier Ru doping (0.41 ≤ x ≤ 0.82) induces a robust metallic and spin frustration state. For comparison and contrast, we also substituted Rh4+(4d 5) ions for Ir4+(5d5) ions in BaIrO3, i.e. in BaIr1--xRhxO 3(0.0 ≤ x ≤ 0.1), where Rh only reduces the SOI, but without altering the band filling. Hence, this system remains tuned at the Mott instability and is very susceptible to disorder scattering which gives rise to Anderson localization. KEYWORDS: spin-orbit interaction, heavy transition metal oxides

  4. Thermodynamic characteristics of viscous flow activation in aqueous solutions of alkali metal iodides

    International Nuclear Information System (INIS)

    Renskij, I.A.; Rudnitskaya, A.A.; Fialkov, Yu.A.

    2003-01-01

    The Gibbs activation energy of the viscous flow of the alkali metal iodides aqueous solutions MI (M = Li, Na, K, Cs) and from its temperature dependence - the enthalpy and entropy of this process are calculated by the Eyring modified equation. The kinetic compensation effects, related to the viscous flow of the unbound water and to the ion-hydrate complexes are established. The relative contribution of the enthalpy and entropy constituents for these solution components is analyzed [ru

  5. Henry's Law vaporization studies and thermodynamics of einsteinium-253 metal dissolved in ytterbium

    International Nuclear Information System (INIS)

    Kleinschmidt, P.D.; Ward, J.W.; Matlack, G.M.; Haire, R.G.

    1984-01-01

    The cohesive energy of metallic einsteinium determines whether einsteinium is a trivalent or divalent metal. The enthalpy of sublimation, a measure of the cohesive energy, is calculated from the partial pressures of einsteinium over an alloy. The partial pressure of 253 Es has been measured over the range 470--870 K, using combined target and mass spectrometric Knudsen effusion techniques. An alloy was prepared with einsteinium dissolved in a ytterbium solvent to produce a very dilute solution. Partial pressure measurements on the alloy were amenable to the experimental technique and a data analysis using a Henry's law treatment of the data. Vapor pressure data are combined with an estimated crystal entropy S 0 298 and ΔC 0 /sub p/ for ytterbium, to produce enthalpy, entropy, and free energy functions from 298 to 1300 K. The vapor pressure of einsteinium in a dilute einsteinium--ytterbium alloy is described by the equation log P(atm) = -(6815 +- 216)/T+2.576 +- 0.337, from which we calculate for the enthalpy of sublimation of pure einsteinium ΔH 0 298 (second law) = 31.76 kcal/mol. The value of the enthalpy of sublimation is consistent with the conclusion that Es is a divalent metal

  6. An efficient laser vaporization source for chemically modified metal clusters characterized by thermodynamics and kinetics

    Science.gov (United States)

    Masubuchi, Tsugunosuke; Eckhard, Jan F.; Lange, Kathrin; Visser, Bradley; Tschurl, Martin; Heiz, Ulrich

    2018-02-01

    A laser vaporization cluster source that has a room for cluster aggregation and a reactor volume, each equipped with a pulsed valve, is presented for the efficient gas-phase production of chemically modified metal clusters. The performance of the cluster source is evaluated through the production of Ta and Ta oxide cluster cations, TaxOy+ (y ≥ 0). It is demonstrated that the cluster source produces TaxOy+ over a wide mass range, the metal-to-oxygen ratio of which can easily be controlled by changing the pulse duration that influences the amount of reactant O2 introduced into the cluster source. Reaction kinetic modeling shows that the generation of the oxides takes place under thermalized conditions at less than 300 K, whereas metal cluster cores are presumably created with excess heat. These characteristics are also advantageous to yield "reaction intermediates" of interest via reactions between clusters and reactive molecules in the cluster source, which may subsequently be mass selected for their reactivity measurements.

  7. Chitosan metal-crosslinked beads applied for n-alkylmonoamines removal from aqueous solutions – a thermodynamic study

    International Nuclear Information System (INIS)

    Oliveira, Margarete; Simoni, Jose A.; Airoldi, Claudio

    2014-01-01

    Highlights: • Chitosan beads were successfully synthesized with divalent cations. • Well-formed bead structures containing cations act as acceptor electron sites. • n-Alkylmonoamine/bead interactions are favorably sorbed at the solid/liquid interface. • The thermodynamic data were favorably obtained from calorimetric titrations. • Crosslinked metal–chitosan beads can remove amine-like substances from an ecosystem. - Abstract: Chitosan has ability in coordinating divalent cations when immersed in crosslinked beads, after dripping: (i) chitosan gel into a copper solution, (ii) nickel chitosan gel into sodium hydroxide and (iii) chitosan/cobalt gel into sodium tripolyphosphate. The amounts of (1.82; 1.27 and 0.44) mmol · g −1 for copper, nickel and cobalt cations in these well-formed structures were determined, to give nitrogen/metal ratios of 3.52; 2.09 and 8.51, indicating the least effectiveness for cobalt in the coordination. Copper cation is well-adjusted in the coordination model through free amino and hydroxyl electron pairs, while amino and acetamino groups for nickel and cobalt were used. The chitosan–hydrogen bond breaking in bead formation caused decreases in crystallinity to yield amorphous structures for cobalt and nickel. The water mass fraction released during heating depends on the hydration of the cations, with the highest value of 0.20 for cobalt. The quantitative aspects of the interaction among cations on beads and basic n-alkylmonoamines determined via sorption batch methodology adjusted to the Langmuir isothermal model, with maximum sorption quantities to saturate nickel of (2.50; 2.38; 2.03; 1.79) mmol · g −1 and copper of (2.59; 2.29; 2.28; 1.92) mmol · g −1 for ethyl- propyl-, butyl- and pentylamines, respectively. The interaction energies quantitatively determined from isothermal titration calorimetry (ITC) at the solid/liquid interface resulted in exothermic enthalpic values. These negative enthalpy values combined to

  8. A numerical simulation of thermodynamic processes for cryogenic metal forming of aluminum sheets and comparison with experimental results

    International Nuclear Information System (INIS)

    Reichl, Ch.; Schneider, R.; Hohenauer, W.; Grabner, F.; Grant, R.J.

    2017-01-01

    Highlights: • Thermodynamic processes for cryogenic sheet metal forming tools were examined. • Static and transient temperature field simulations are evaluated on a Nakajima tool. • Differently arranged cooling loops lead to homogeneous temperature distribution. • Scaling of the geometry leads to significantly increased heat transfer times. • The temperature management of complex forming tools can be developed numerically. - Abstract: Forming at cryogenic temperatures provides a significant improvement in formability of aluminum sheets. This offers the potential for light, complex and highly integrated one-piece components to be produced out of aluminum alloys at sub-zero temperatures. This would allow weight reduction, environmental conservation and cost reduction of a car body to give one example in the automotive industry. For temperature supported processes special forming tools and cooling strategies are required to be able to reach and maintain process stability. Time dependent numerical simulations of the thermodynamic processes of cryogenic sheet metal forming covering all aspects of heat transfer through conduction, convection and radiation play a vital role in the design and development of future tools and are presented for several geometries. Cooling (and heating) strategies (including selection of the number of cooling loops and their relative positioning) in a Nakajima testing tool were evaluated using computational fluid dynamics. These simulations were performed with static and transient solvers to demonstrate the extraction of tool surface temperature distributions on different forming tool geometries. Comparisons of predicted temperature characteristics of an aluminum sheet and experimentally determined temperature distributions were made. The temperature distribution of the surface of an aluminum sheet could be predicted with high accuracy. Further, the influence of the tool size on the parameters temperature transfer times and

  9. Exploring the kinetic and thermodynamic aspects of four-electron electrochemical reactions: electrocatalysis of oxygen evolution by metal oxides and biological systems.

    Science.gov (United States)

    Wang, Vincent C-C

    2016-08-10

    Finding fundamental and general mechanisms for electrochemical reactions, such as the oxygen evolution reaction (OER) from water and reduction of CO2, plays vital roles in developing the desired electrocatalysts for facilitating solar fuel production. Recently, density functional theory (DFT) calculations have shown that there is a universal scaling relation of adsorption energy between key intermediate species, HO(ad) and HOO(ad), on the surface of metal oxides as OER electrocatalysts. In this paper, a kinetic and thermodynamic model for the four-electron electrochemical reaction based on previous OER mechanisms proposed by DFT calculations is developed to further investigate the electrocatalytic properties over a wide range of metal oxides and photosystem II. The OER activity of metal oxides (i.e. electrocatalytic current) calculated from the DFT-calculated equilibrium potentials with kinetic properties, such as the rate constants for interfacial electron transfer and catalytic turnover, can lead to a volcano-shaped trend that agrees with the results observed in experiments. In addition, the kinetic aspects of the impact on the electrocatalysts are evaluated. Finally, comparing the results of metal oxides and photosystem II, and fitting experimental voltammograms give further insights into kinetic and thermodynamic roles. Here, the general guidelines for designing OER electrocatalysts with unified kinetic and thermodynamic properties are presented.

  10. Chemical constraints governing the origin of metabolism: the thermodynamic landscape of carbon group transformations under mild aqueous conditions

    Science.gov (United States)

    Weber, Arthur L.

    2002-01-01

    The thermodynamics of organic chemistry under mild aqueous conditions was examined in order to begin to understand its influence on the structure and operation of metabolism and its antecedents. Free energies (deltaG) were estimated for four types of reactions of biochemical importance carbon-carbon bond cleavage and synthesis, hydrogen transfer between carbon groups, dehydration of alcohol groups, and aldo-keto isomerization. The energies were calculated for mainly aliphatic groups composed of carbon, hydrogen, and oxygen. The energy values showed (1) that generally when carbon-carbon bond cleavage involves groups from different functional group classes (i.e., carboxylic acids, carbonyl groups, alcohols, and hydrocarbons), the transfer of the shared electron-pair to the more reduced carbon group is energetically favored over transfer to the more oxidized carbon group, and (2) that the energy of carbon-carbon bond transformation is primarily determined by the functional group class of the group that changes oxidation state in the reaction (i.e., the functional group class of the group that donates the shared electron-pair during cleavage, or that accepts the incipient shared electron-pair during synthesis). In contrast, the energy of hydrogen transfer between carbon groups is determined by the functional group class of both the hydrogen-donor group and the hydrogen-acceptor group. From these and other observations we concluded that the chemistry involved in the origin of metabolism (and to a lesser degree modern metabolism) was strongly constrained by (1) the limited redox-based transformation energy of organic substrates that is readily dissipated in a few energetically favorable irreversible reactions; (2) the energy dominance of a few transformation half-reactions that determines whether carbon-carbon bond transformation (cleavage or synthesis) is energetically favorable (deltaG +3.5 kcal/mol); and (3) the dependence of carbon group transformation energy on the

  11. Applications in environmental bioinorganic: Nutritional and ultrastructural evaluation and calculus of thermodynamic and structural properties of metal-oxalate complexes.

    Science.gov (United States)

    Tolentino, Terezinha Alves; Bertoli, Alexandre Carvalho; dos Santos Pires, Maíra; Carvalho, Ruy; Labory, Claudia Regina Gontijo; Nunes, Janaira Santana; Bastos, Ana Rosa Ribeiro; de Freitas, Matheus Puggina

    2015-01-01

    Lead (Pb) is known by its toxicity both for animals and plants. In order to evaluate its toxicity, plants of Brachiaria brizantha were cultivated on nutritive solution of Hoagland during 90 days and submitted to different concentrations of Pb. The content of macro and micronutrients was evaluated and there was a reduction on root content of Ca, besides the lowest dosages of Pb had induced an increase of N, S, Mn, Cu, Zn and Fe. The cell ultrastructure of leaves and roots were analyzed by transmission electronic microscopy (TEM). Among the main alterations occurred there were invaginations on cell walls, the presence of crystals on the root cells, accumulation of material on the interior of cells and vacuolar compartmentalization. On the leaves the degradation of chloroplasts was observed, as well as the increase of vacuoles. Structures for the formation of oxalate crystals were proposed through molecular modeling and thermodynamic stability. Calculi suggest the formation of highly stable metal-oxalate complexes. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Influence of compositions on thermal stability and thermodynamic parameter in Ca-Mg-Cu bulk metallic glasses

    Science.gov (United States)

    Deshmukh, A. A.; Khond, A. A.; Palikundwar, U. A.

    2018-05-01

    In the present manuscript, influence of compositions on thermal stability (ΔTx) and thermodynamic parameter PHSS of Ca-Mg-Cu bulk metallic glasses (BMGs) is evaluated. The statistical approach of regression analysis is adopted to investigate the compositional variation with ΔTx and PHSS. It is found that calcium (Ca) and copper (Cu) content has goodlinear relationship with ΔTx and PHSS. It is observed that with increase in Ca content, ΔTx and PHSS decreases. On the other hand, increase in Cu content, both ΔTx and PHSS increases. Correlation fit of magnesium (Mg) content with both ΔTx and PHSS is very poor. A graph is also plotted to understand the relationship between ΔTx and PHSS. Result of the relationship between ΔTx and PHSS reveals that the alloy composition having more negative value of PHSS will have more stability. Therefore, compositions with more negative value of PHSS will lead to ease of BMGs formation in Ca-Mg-Cu alloy system and hence more stable it will be. It is expected that these results will be supportive in identifying the compositions having these elements for making BMGs.

  13. Sorption studies of heavy metal ions by salicylic acid–formaldehyde–catechol terpolymeric resin: Isotherm, kinetic and thermodynamics

    Directory of Open Access Journals (Sweden)

    Riddhish R. Bhatt

    2015-05-01

    Full Text Available Terpolymeric resin has been synthesized by condensing salicylic acid with catechol employing formaldehyde as a cross linking agent at 80 ± 5 °C using DMF as a solvent. The resin was characterized by elemental analysis, FTIR, XRD and thermal analysis (TGA, DTA and DTG. The morphology of the resin was studied by optical photographs and scanning electron micrographs (SEM at different magnifications. The physico-chemical properties have been studied. The uptake behavior of various metal ions viz. Ni(II, Cu(II, Zn(II, Cd(II and Pb(II towards synthesized resin has been studied depending on contact time, pH and temperature. The selectivity order found is: Cu(II > Zn(II > Pb(II > Ni(II > Cd(II. The sorption data obtained at optimized conditions were analyzed by six two parameter isotherm models like Langmuir, Freundlich, Temkin, Dubinin–Radushkevich (D–R, Halsey and Harkins–Jura. The Langmuir, Freundlich and Dubinin–Radushkevich (D–R isotherms were found better to describe the sorption data with high correlation for the adsorption with a low SSE value for all the metals under study. The adsorption capacities of the SFC resin for removal of Ni(II, Cu(II, Zn(II, Cd(II and Pb(II were determined with the Langmuir equation and found to be 0.815, 1.104, 1.215, 0.498, and 0.931 mmol/g respectively. The adsorption process follows first order kinetics and specific rate constant Kr was obtained by the application of Lagergren equation. Thermodynamic parameters viz. ΔGads, ΔSads and ΔHads have also been calculated for the metal-resin systems. The external diffusion rate constant (Ks and intra-particle diffusion rate constant (Kid were calculated by Spahn–Schlunder and Weber–Morris models respectively. Desorption studies were done using various desorbing agents viz. de-ionized water, boiled water, various concentrations of HCl, ammonia, thiourea, citric acid and tartaric acid.

  14. Thermodynamic properties of heavy ion heated refractory metals; Thermodynamische Eigenschaften von schwerionengeheizten hochschmelzenden Metallen

    Energy Technology Data Exchange (ETDEWEB)

    Hug, Alexander

    2011-05-04

    Knowledge of basic physical properties of matter in high-energy-density (HED) states such as the equation-of-state (EOS) is of fundamental importance for various branches of basic and applied physics. However, such matter under extreme conditions of temperature and pressure - also called ''warm dense matter'' (WDM) - can only be generated in dynamic experiments employing the most powerful drivers. At the high temperature experimental area HHT of the GSI Helmholtzzentrum fuer Schwerionenforschung (Darmstadt, Germany), intense beams of energetic heavy ions are used for this purpose. The aim of this work is to study thermophysical properties of refractory metals in hot solid and liquid states by precise temperature measurements. In order to identify the melting plateau and to limit the maximum target temperature to the region of interest, relatively long (one microsecond) bunches of uranium and xenon ions have been used to heat initially solid samples. The intense ion beams were focused on a millimetre spot at the target in order to achieve uniform conditions. The temperature on the target surface was determined by analysing thermal radiation emitted from a 0.03 mm{sup 2} area at five different wavelengths. In order to obtain the physical temperature, one has to measure not only the thermal radiation but also the emissivity, ε(T,λ) of the target surface which is not known ab initio. For this purpose, a set-up for direct target reflection measurement was designed and embedded into the fast multichannel pyrometer system. The reflection signal provides the necessary information about modifications of the target surface properties during the interaction with the ion beam. Beside the pyrometric and reflection measurement set-ups, various hardware and software components of the data acquisition system for the heavy-ion beam driven experiments were substantially enhanced. The emissivity was also obtained by identifying the melting plateau and using the

  15. Thermodynamic modeling of volatile hazardous metal behavior in the Vortec Vitrification System

    International Nuclear Information System (INIS)

    Nowok, J.W.; Hurley, J.P.

    2000-01-01

    The thermochemical equilibrium calculations indicate that at the temperature of a propane--air flame, some volatilization of uranium, plutonium, technetium, and cesium will occur. The expected concentrations of plutonium, technetium, and cesium in the flame will be very low because of the small maximum concentration of these elements in the projected feed materials for the first 30-day test. The quantities volatilized can generally be decreased by operating the flame in a fuel-rich mode, although this will lead to greater carbon monoxide production, which may be more objectionable. The concentrations of chlorine and fluorine, at least at the maximum levels in the projected Vortec feed, are not projected to greatly influence the vaporization rates. Therefore, blending to reduce the concentrations of those elements would most likely not be effective in reducing metal vaporization. Most of the elements vaporized condense by the time the gas cools to 2000 F. These elements would condense either on surfaces near the front of the heat recuperator or on entrained particulates or homogeneously as relatively pure submicron particles. Cesium would be expected to condense at the lower temperatures near the rear of the recuperator, although the expected maximum concentration in the Vortec feed material is extremely low so it should be greatly diluted by other particulates. The elements that condense on other entrained particles will form enriched surface coatings. Particles larger than 10microm or so will be collected in the scrubber. Smaller particles, especially the submicron particles formed from homogeneous nucleation, should be largely collected in the HEPA filter. Deposits formed in the heat recuperator can normally be handled via sootblowing. To reduce handling problems, we suggest that the recuperator be oriented vertically so that the deposits blown off of the heat exchanger fall directly into the molten glass. The large size of the deposits should help to reduce the

  16. 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.

  17. The thermodynamic study of alkali metal clusters, and gaseous molecules in the lithium hydride, oxide and cyanide systems

    International Nuclear Information System (INIS)

    Wu, C.H.

    1983-11-01

    Thermodynamic properties have been evaluated by the third law or second law method using the equilibrium constant measured by mass spectrometry of the species in an effurate from a Knudsen cell. (GG) [de

  18. Dehydrogenation Kinetics and Modeling Studies of MgH2 Enhanced by Transition Metal Oxide Catalysts Using Constant Pressure Thermodynamic Driving Forces

    Directory of Open Access Journals (Sweden)

    Saidi Temitope Sabitu

    2012-06-01

    Full Text Available The influence of transition metal oxide catalysts (ZrO2, CeO2, Fe3O4 and Nb2O5 on the hydrogen desorption kinetics of MgH2 was investigated using constant pressure thermodynamic driving forces in which the ratio of the equilibrium plateau pressure (pm to the opposing plateau (pop was the same in all the reactions studied. The results showed Nb2O5 to be vastly superior to other catalysts for improving the thermodynamics and kinetics of MgH2. The modeling studies showed reaction at the phase boundary to be likely process controlling the reaction rates of all the systems studied.

  19. Design of a new integrated chitosan-PAMAM dendrimer biosorbent for heavy metals removing and study of its adsorption kinetics and thermodynamics.

    Science.gov (United States)

    Zarghami, Zabihullah; Akbari, Ahmad; Latifi, Ali Mohammad; Amani, Mohammad Ali

    2016-04-01

    In this research, different generations of PAMAM-grafted chitosan as integrated biosorbents were successfully synthesized via step by step divergent growth approach of dendrimer. The synthesized products were utilized as adsorbents for heavy metals (Pb(2+) in this study) removing from aqueous solution and their reactive Pb(2+) removal potential was evaluated. The results showed that as-synthesized products with higher generations of dendrimer, have more adsorption capacity compared to products with lower generations of dendrimer and sole chitosan. Adsorption capacity of as-prepared product with generation 3 of dendrimer is 18times more than sole chitosan. Thermodynamic and kinetic studies were performed for understanding equilibrium data of the uptake capacity and kinetic rate uptake, respectively. Thermodynamic and kinetic studies showed that Langmuir isotherm model and pseudo second order kinetic model are more compatible for describing equilibrium data of the uptake capacity and kinetic rate of the Pb(2+) uptake, respectively. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. Statistical thermodynamics of alloys

    CERN Document Server

    Gokcen, N A

    1986-01-01

    This book is intended for scientists, researchers, and graduate students interested in solutions in general, and solutions of metals in particular. Readers are assumed to have a good background in thermodynamics, presented in such books as those cited at the end of Chapter 1, "Thermo­ dynamic Background." The contents of the book are limited to the solutions of metals + metals, and metals + metalloids, but the results are also appli­ cable to numerous other types of solutions encountered by metallurgists, materials scientists, geologists, ceramists, and chemists. Attempts have been made to cover each topic in depth with numerical examples whenever necessary. Chapter 2 presents phase equilibria and phase diagrams as related to the thermodynamics of solutions. The emphasis is on the binary diagrams since the ternary diagrams can be understood in terms of the binary diagrams coupled with the phase rule, and the Gibbs energies of mixing. The cal­ culation of thermodynamic properties from the phase diagrams is ...

  1. 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

  2. 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.

  3. Application of the electromotive force method with fluoride-xon electrolyte for establishing of thermodynamic properties of oxyfluorides of yttrium and rare-earth metals

    International Nuclear Information System (INIS)

    Levitskij, V.A.; Balak, G.M.

    1983-01-01

    Cells of the type (-) O 2 , Pt β v , CaF 2 β v β v CaF 2 β v CaF 2 β v β v Pt, O 2 (+) have been used for the first time to study high-temperature thermodynamic properties of Y and Nb oxyfluorides of the composition. Using the method of e. m. f., X-ray phase and chemical analyses it has been established that Y 2 O 3 and Nd 2 O 3 in the range 960-1465 K coexist with ROF oxyfluorides which are similar in composition to stoichiometric ones. On the basis of dependences E=f(T) of the cells studied ΔG deg=f(T), ΔHsub( anti T) deg and ΔSsub(anti T) deg of the YOF and NdOF formation from simple substances and R 2 O 3 and RF 3 are determined. High stability and reproducibility of potentials of the cells with oxyfluoride electrodes as well as coincidence of thermodynamic results obtained on the basis of data for independent cells testifies to the prospects of application of the above cells for thermodynamical studies of rare earth and transition metals

  4. Study on the thermodynamics of the gadolinium-hydrogen binary system (H/Gd = 0.0–2.0) and implications to metallic gadolinium purification

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Kai; Li, Guoling [Beijing National Laboratory of Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China); Department of Materials Physics and Chemistry, University of Science and Technology Beijing, NO. 30, Xueyuan Road, Beijing 100083 (China); Li, Jigang [Beijing National Laboratory of Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China); Liu, Yang [Department of Food Science, College of Arts and Science, Beijing Union University, Beijing, 100101 (China); Tian, Wenhuai, E-mail: wenhuaitian@ustb.edu.cn [Department of Materials Physics and Chemistry, University of Science and Technology Beijing, NO. 30, Xueyuan Road, Beijing 100083 (China); Zheng, Jie [Beijing National Laboratory of Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China); Li, Xingguo, E-mail: xgli@pku.edu.cn [Beijing National Laboratory of Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China)

    2016-07-15

    The thermodynamics of the gadolinium-hydrogen (Gd–H) binary system (H/Gd = 0.0–2.0) between 650 and 900 °C is studied by pressure composition isotherm measurement. Significant H dissolution in Gd is observed, up to H/Gd = 0.34 at 650 °C and 0.55 at 900 °C. The metal-rich phase boundary of nonstoichiometric gadolinium dihydride was found to occur with nominal composition of GdH{sub 1.80} at 650 °C and GdH{sub 1.53} at 900 °C. The results are in fairly good agreement with previous experimental work but with improved accuracy. The binary phase diagram is obtained using the CALPHAD method. The thermodynamic study here assists the understanding on the efficient deoxygenation effect by the H in Gd for Gd purification. - Highlights: • PCI measurements with high accuracy has been carried out. • A first assessment of Gd–H system has been carried out by the CALPHAD method. • A set of self-consistent thermodynamic parameters was derived for this system.

  5. 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

  6. Kinetic and thermodynamic studies on the adsorption of heavy metals from aqueous solution by melanin nanopigment obtained from marine source: Pseudomonas stutzeri.

    Science.gov (United States)

    Manirethan, Vishnu; Raval, Keyur; Rajan, Reju; Thaira, Harsha; Balakrishnan, Raj Mohan

    2018-05-15

    The difficulty in removal of heavy metals at concentrations below 10 mg/L has led to the exploration of efficient adsorbents for removal of heavy metals. The adsorption capacity of biosynthesized melanin for Mercury (Hg(II)), Chromium (Cr(VI)), Lead (Pb(II)) and Copper (Cu(II)) was investigated at different operating conditions like pH, time, initial concentration and temperature. The heavy metals adsorption process was well illustrated by the Lagergren's pseudo-second-order kinetic model and the equilibrium data fitted excellently to Langmuir isotherm. Maximum adsorption capacity obtained from Langmuir isotherm for Hg(II) was 82.4 mg/g, Cr(VI) was 126.9 mg/g, Pb(II) was 147.5 mg/g and Cu(II) was 167.8 mg/g. The thermodynamic parameters revealed that the adsorption of heavy metals on melanin is favorable, spontaneous and endothermic in nature. Binding of heavy metals on melanin surface was proved by Fourier Transform Infrared Spectroscopy (FT-IR) and X-ray Photoelectron Spectroscopy (XPS). Contemplating the results, biosynthesized melanin can be a potential adsorbent for efficient removal of Hg(II), Cr(VI), Pb(II) and Cu(II) ions from aqueous solution. Copyright © 2018 Elsevier Ltd. All rights reserved.

  7. Identifying environmental and geochemical variables governing metal concentrations in a stream draining headwaters in NW Spain

    International Nuclear Information System (INIS)

    Soto-Varela, F.; Rodríguez-Blanco, M.L.; Taboada-Castro, M.M.; Taboada-Castro, M.T.

    2014-01-01

    Highlights: • All metals occur in association with suspended sediment. • DOC and SS appeared to influence the partitioning of metals. • The SS was a good predictor of particulate metal levels. • The most important variable to explain storm-event K D for Al and Fe is DOC. • Enrichment factor values suggest a natural origin for the particulate metals. - Abstract: Headwater stream, draining from a rural catchment in NW Spain, was sampled during baseflow and storm-event conditions to investigate the temporal variability in dissolved and particulate Al, Fe, Mn, Cu and Zn concentrations and the role of discharge (Q), pH, dissolved organic carbon (DOC) and suspended sediment (SS) in the transport of dissolved and particulate metals. Under baseflow and storm-event conditions, concentrations of the five metals were highly variable. The results of this study reveal that all metal concentrations are correlated with SS. DOC and SS appeared to influence both the metal concentrations and the partitioning of metals between dissolved and particulate. The SS was a good predictor of particulate metal levels. Distribution coefficients (K D ) were similar between metals (4.72–6.55) and did not change significantly as a function of discharge regime. Stepwise multiple linear regression analysis reveals that the most important variable to explain storm-event K D for Al and Fe is DOC. The positive relationships found between metals, in each fraction, indicate that these elements mainly come from the same source. Metal concentrations in the stream were relatively low

  8. Structural, electronic, magnetic, half-metallic, mechanical, and thermodynamic properties of the quaternary Heusler compound FeCrRuSi: A first-principles study.

    Science.gov (United States)

    Wang, Xiaotian; Khachai, Houari; Khenata, Rabah; Yuan, Hongkuan; Wang, Liying; Wang, Wenhong; Bouhemadou, Abdelmadjid; Hao, Liyu; Dai, Xuefang; Guo, Ruikang; Liu, Guodong; Cheng, Zhenxiang

    2017-11-23

    In this paper, we have investigated the structural, electronic, magnetic, half-metallic, mechanical, and thermodynamic properties of the equiatomic quaternary Heusler (EQH) compound FeCrRuSi using the density functional theory (DFT) and the quasi-harmonic Debye model. Our results reveal that FeCrRuSi is a half-metallic material (HMM) with a total magnetic moment of 2.0 μ B in agreement with the well-known Slater-Pauling rule M t  = Z t  - 24. Furthermore, the origin of the half-metallic band gap in FeCrRuSi is well studied through a schematic diagram of the possible d-d hybridization between Fe, Cr and Ru elements. The half-metallic behavior of FeCrRuSi can be maintained in a relatively wide range of variations of the lattice constant (5.5-5.8 Å) under uniform strain and the c/a ratio (0.96-1.05) under tetragonal distortion. The calculated phonon dispersion, cohesive and formation energies, and mechanical properties reveal that FeCrRuSi is stable with an EQH structure. Importantly, the compound of interest has been prepared and is found to exist in an EQH type structure with the presence of some B2 disorder. Moreover, the thermodynamic properties, such as the thermal expansion coefficient α, the heat capacity C V , the Grüneisen constant γ, and the Debye temperature Θ D are calculated.

  9. Thermodynamics of nuclear materials

    International Nuclear Information System (INIS)

    1979-01-01

    Full text: The science of chemical thermodynamics has substantially contributed to the understanding of the many problems encountered in nuclear and reactor technology. These problems include reaction of materials with their surroundings and chemical and physical changes of fuels. Modern reactor technology, by its very nature, has offered new fields of investigations for the scientists and engineers concerned with the design of nuclear fuel elements. Moreover, thermodynamics has been vital in predicting the behaviour of new materials for fission as well as fusion reactors. In this regard, the Symposium was organized to provide a mechanism for review and discussion of recent thermodynamic investigations of nuclear materials. The Symposium was held in the Juelich Nuclear Research Centre, at the invitation of the Government of the Federal Republic of Germany. The International Atomic Energy Agency has given much attention to the thermodynamics of nuclear materials, as is evidenced by its sponsorship of four international symposia in 1962, 1965, 1967, and 1974. The first three meetings were primarily concerned with the fundamental thermodynamics of nuclear materials; as with the 1974 meeting, this last Symposium was primarily aimed at the thermodynamic behaviour of nuclear materials in actual practice, i.e., applied thermodynamics. Many advances have been made since the 1974 meeting, both in fundamental and applied thermodynamics of nuclear materials, and this meeting provided opportunities for an exchange of new information on this topic. The Symposium dealt in part with the thermodynamic analysis of nuclear materials under conditions of high temperatures and a severe radiation environment. Several sessions were devoted to the thermodynamic studies of nuclear fuels and fission and fusion reactor materials under adverse conditions. These papers and ensuing discussions provided a better understanding of the chemical behaviour of fuels and materials under these

  10. Surface thermodynamics

    International Nuclear Information System (INIS)

    Garcia-Moliner, F.

    1975-01-01

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

  11. 48 CFR 252.208-7000 - Intent to furnish precious metals as Government-furnished material.

    Science.gov (United States)

    2010-10-01

    ...-furnished silver is mandatory when the quantity required is one hundred troy ounces or more. The precious... quantity in whole troy ounces of precious metals required in the performance of this contract (including...

  12. TOXIC METALS IN THE ENVIRONMENT: THERMODYNAMIC CONSIDERATIONS FOR POSSIBLE IMMOBILIZATION STRATEGIES FOR PB, CD, AS, AND HG

    Science.gov (United States)

    The contamination of soils by toxic metals is a widespread, serious problem that demands immediate action either by removal or immobilization, which is defined as a process which puts the metal into a chemical form, probably as a mineral, which will be inert and highly insoluble ...

  13. Development of the high-temperature, solid-state, electromotive force technique to study the thermodynamics of Lewis-acid-base transition metal alloys

    International Nuclear Information System (INIS)

    Bullard, G.L.

    1978-05-01

    The basic principles of the Engel-Brewer theory of metals are summarized and illustrated. Definitions of words used to describe its fundamentals are clarified. The theory predicts the extreme stability of the Lewis-acid-base alloys. The thermodynamics of such alloys may be obtained through the use of oxide-electrolyte, electrochemical cells. Experimental techniques associated with the use of these cells are explained in detail. Much attention is given to the preparation and processing of the materials required. A selective review of the cell literature demonstrates frequent difficulty in obtaining accurate thermodynamic data. In an attempt to correct this situation, as well as to correct problems discovered in this work, the physical processes which create the cell emf are clearly identified. The fundamental understanding afforded by the resulting cell model implies the procedures used to both discover and eliminate errors. Those due to concentration overpotentials, reactive impurities in the gas phase, and interfacial reactions are carefully analyzed. The procedures used to test for and attain equilibrium in an alloy-oxide, powder compact are supported through identification of the transport processes that mediate equilibration

  14. Development of the high-temperature, solid-state, electromotive force technique to study the thermodynamics of Lewis-acid-base transition metal alloys

    Energy Technology Data Exchange (ETDEWEB)

    Bullard, G.L.

    1978-05-01

    The basic principles of the Engel-Brewer theory of metals are summarized and illustrated. Definitions of words used to describe its fundamentals are clarified. The theory predicts the extreme stability of the Lewis-acid-base alloys. The thermodynamics of such alloys may be obtained through the use of oxide-electrolyte, electrochemical cells. Experimental techniques associated with the use of these cells are explained in detail. Much attention is given to the preparation and processing of the materials required. A selective review of the cell literature demonstrates frequent difficulty in obtaining accurate thermodynamic data. In an attempt to correct this situation, as well as to correct problems discovered in this work, the physical processes which create the cell emf are clearly identified. The fundamental understanding afforded by the resulting cell model implies the procedures used to both discover and eliminate errors. Those due to concentration overpotentials, reactive impurities in the gas phase, and interfacial reactions are carefully analyzed. The procedures used to test for and attain equilibrium in an alloy-oxide, powder compact are supported through identification of the transport processes that mediate equilibration.

  15. Thermodynamic and structural properties of ball-milled mixtures composed of nano-structural graphite and alkali(-earth) metal hydride

    International Nuclear Information System (INIS)

    Miyaoka, Hiroki; Ichikawa, Takayuki; Fujii, Hironobu

    2007-01-01

    Hydrogen desorption properties of mechanically milled materials composed of nano-structural hydrogenated-graphite (C nano H x ) and alkali(-earth) metal hydride (MH; M = Na, Mg and Ca) were investigated from the thermodynamic and structural points of view. The hydrogen desorption temperature for all the C nano H x and MH composites was obviously lower than that of the corresponding each hydride. In addition, the desorption of hydrocarbons from C nano H x was significantly suppressed by making composite of C nano H x with MH, even though C nano H x itself thermally desorbs a considerably large amount of hydrocarbons. These results indicate that an interaction exists between C nano H x and MH, and hydrogen in both the phases is destabilized by a close contact between polar C-H groups in C nano H x and the MH solid phase. Moreover, a new type of chemical bonding between the nano-structural carbon (C nano ) and the Li, Ca, or Mg metal atoms may be formed after hydrogen desorption. Thus, the above metal-C-H system would be recognized as a new family of H-storage materials

  16. Kinetics versus thermodynamics of the metal incorporation in molecular beam epitaxy of (InxGa1−x2O3

    Directory of Open Access Journals (Sweden)

    Patrick Vogt

    2016-08-01

    Full Text Available We present a detailed study of the reaction kinetics and thermodynamics of the plasma-assisted oxide molecular beam epitaxy of the ternary compound (InxGa1−x2O3 for 0 ≤ x ≤ 1. We measured the growth rate of the alloy in situ by laser reflectrometry as a function of growth temperature TG for different metal-to-oxygen flux ratios rMe, and nominal In concentrations xnom in the metal flux. We determined ex situ the In and Ga concentrations in the grown film by energy dispersive X-ray spectroscopy. The measured In concentration x shows a strong dependence on the growth parameters TG, rMe, and xnom whereas growth on different co-loaded substrates shows that in the macroscopic regime of ∼μm3 x does neither depend on the detailed layer crystallinity nor on crystal orientation. The data unveil that, in presence of In, Ga incorporation is kinetically limited by Ga2O desorption the same way as during Ga2O 3 growth. In contrast, In incorporation during ternary growth is thermodynamically suppressed by the presence of Ga due to stronger Ga–O bonds. Our experiments revealed that Ga adatoms decompose/etch the In–O bonds whereas In adatoms do not decompose/etch the Ga–O bonds. This result is supported by our thermochemical calculations. In addition we found that a low TG and/or excessively low rMe kinetically enables In incorporation into (InxGa1−x2O3. This study may help growing high-quality ternary compounds (InxGa1−x2O3 allowing band gap engineering over the range of 2.7–4.7 eV.

  17. Thermodynamics of Small Alkali Metal Halide Cluster Ions: Comparison of Classical Molecular Simulations with Experiment and Quantum Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Vlcek, Lukas [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Uhlik, Filip [Charles Univ., Prague (Czech Republic); Moucka, Filip [Purkinje Univ. (Czech Republic); Nezbeda, Ivo [Purkinje Univ. (Czech Republic); Academy of Sciences of the Czech Republic (ASCR), Prague (Czech Republic); Chialvo, Ariel A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2015-12-16

    We evaluate the ability of selected classical molecular models to describe the thermodynamic and structural aspects of gas-phase hydration of alkali halide ions and the formation of small water clusters. To understand the effect of many-body interactions (polarization) and charge penetration effects on the accuracy of a force field, we perform Monte Carlo simulations with three rigid water models using different functional forms to account for these effects: (i) point charge non-polarizable SPC/E, (ii) Drude point charge polarizable SWM4- DP, and (iii) Drude Gaussian charge polarizable BK3. Model predictions are compared with experimental Gibbs free energies and enthalpies of ion hydration, and with microscopic structural properties obtained from quantum DFT calculations. We find that all three models provide comparable predictions for pure water clusters and cation hydration, but differ significantly in their description of anion hydration. None of the investigated classical force fields can consistently and quantitatively reproduce the experimental gas phase hydration thermodynamics. The outcome of this study highlights the relation between the functional form that describes the effective intermolecular interactions and the accuracy of the resulting ion hydration properties.

  18. Extended thermodynamics

    CERN Document Server

    Müller, Ingo

    1993-01-01

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

  19. Thermodynamics: The Unique Universal Science

    Directory of Open Access Journals (Sweden)

    Wassim M. Haddad

    2017-11-01

    Full Text Available Thermodynamics is a physical branch of science that governs the thermal behavior of dynamical systems from those as simple as refrigerators to those as complex as our expanding universe. The laws of thermodynamics involving conservation of energy and nonconservation of entropy are, without a doubt, two of the most useful and general laws in all sciences. The first law of thermodynamics, according to which energy cannot be created or destroyed, merely transformed from one form to another, and the second law of thermodynamics, according to which the usable energy in an adiabatically isolated dynamical system is always diminishing in spite of the fact that energy is conserved, have had an impact far beyond science and engineering. In this paper, we trace the history of thermodynamics from its classical to its postmodern forms, and present a tutorial and didactic exposition of thermodynamics as it pertains to some of the deepest secrets of the universe.

  20. Thermodynamic Constraints in Using AuM (M = Fe, Co, Ni, and Mo) Alloys as N₂ Dissociation Catalysts: Functionalizing a Plasmon-Active Metal.

    Science.gov (United States)

    Martirez, John Mark P; Carter, Emily A

    2016-02-23

    The Haber-Bosch process for NH3 synthesis is arguably one of the greatest inventions of the 20th century, with a massive footprint in agriculture and, historically, warfare. Current catalysts for this reaction use Fe for N2 activation, conducted at high temperatures and pressures to improve conversion rate and efficiency. A recent finding shows that plasmonic metal nanoparticles can either generate highly reactive electrons and holes or induce resonant surface excitations through plasmonic decay, which catalyze dissociation and redox reactions under mild conditions. It is therefore appealing to consider AuM (M = Fe, Co, Ni, and Mo) alloys to combine the strongly plasmonic nature of Au and the catalytic nature of M metals toward N2 dissociation, which together might facilitate ammonia production. To this end, through density functional theory, we (i) explore the feasibility of forming these surface alloys, (ii) find a pathway that may stabilize/deactivate surface M substituents during fabrication, and (iii) define a complementary route to reactivate them under operational conditions. Finally, we evaluate their reactivity toward N2, as well as their ability to support a pathway for N2 dissociation with a low thermodynamic barrier. We find that AuFe possesses similar appealing qualities, including relative stability with respect to phase separation, reversibility of Fe oxidation and reduction, and reactivity toward N2. While AuMo achieves the best affinity toward N2, its strong propensity toward oxidation could greatly limit its use.

  1. A thermodynamic model for predicting surface melting and overheating of different crystal planes in BCC, FCC and HCP pure metallic thin films

    International Nuclear Information System (INIS)

    Jahangir, Vafa; Riahifar, Reza; Sahba Yaghmaee, Maziar

    2016-01-01

    In order to predict as well as study the surface melting phenomena in contradiction to surface overheating, a generalized thermodynamics model including the surface free energy of solid and the melt state along with the interfacial energy of solid–liquid (melt on substrate) has been introduced. In addition, the effect of different crystal structures of surfaces in fcc, bcc and hcp metals was included in surface energies as well as in the atomistic model. These considerations lead us to predict surface melting and overheating as two contradictory melting phenomena. The results of the calculation are demonstrated on the example of Pb and Al thin films in three groups of (100), (110) and (111) surface planes. Our conclusions show good agreement with experimental results and other theoretical investigations. Moreover, a computational algorithm has been developed which enables users to investigate the surface melt or overheating of single component metallic thin film with variable crystal structures and different crystalline planes. This model and developed software can be used for studying all related surface phenomena. - Highlights: • Investigating the surface melting and overheating phenomena • Effect of crystal orientations, surface energies, geometry and different atomic surface layers • Developing a computational algorithm and its related code (free-software SMSO-Ver1) • Thickness and orientation of surface plane dominate the surface melting or overheating. • Total excess surface energy as a function of thickness and temperature explains melting.

  2. A thermodynamic model for predicting surface melting and overheating of different crystal planes in BCC, FCC and HCP pure metallic thin films

    Energy Technology Data Exchange (ETDEWEB)

    Jahangir, Vafa, E-mail: vafa.jahangir@yahoo.com; Riahifar, Reza, E-mail: reza_rfr@yahoo.com; Sahba Yaghmaee, Maziar, E-mail: fkmsahba@uni-miskolc.hu

    2016-03-31

    In order to predict as well as study the surface melting phenomena in contradiction to surface overheating, a generalized thermodynamics model including the surface free energy of solid and the melt state along with the interfacial energy of solid–liquid (melt on substrate) has been introduced. In addition, the effect of different crystal structures of surfaces in fcc, bcc and hcp metals was included in surface energies as well as in the atomistic model. These considerations lead us to predict surface melting and overheating as two contradictory melting phenomena. The results of the calculation are demonstrated on the example of Pb and Al thin films in three groups of (100), (110) and (111) surface planes. Our conclusions show good agreement with experimental results and other theoretical investigations. Moreover, a computational algorithm has been developed which enables users to investigate the surface melt or overheating of single component metallic thin film with variable crystal structures and different crystalline planes. This model and developed software can be used for studying all related surface phenomena. - Highlights: • Investigating the surface melting and overheating phenomena • Effect of crystal orientations, surface energies, geometry and different atomic surface layers • Developing a computational algorithm and its related code (free-software SMSO-Ver1) • Thickness and orientation of surface plane dominate the surface melting or overheating. • Total excess surface energy as a function of thickness and temperature explains melting.

  3. ARTICLES: Physical laws governing the interaction of pulse-periodic CO2 laser radiation with metals

    Science.gov (United States)

    Vedenov, A. A.; Gladush, G. G.; Drobyazko, S. V.; Pavlovich, Yu V.; Senatorov, Yu M.

    1985-01-01

    It is shown theoretically and experimentally that the efficiency of welding metals with a pulse-periodic CO2 laser beam of low duty ratio, at low velocities, can exceed that of welding with cw lasers and with electron beams. For the first time an investigation was made of the influence of the laser radiation parameters (energy and frequency) and of the welding velocity on the characteristics of the weld and on the shape of the weldpool. The influence of the laser radiation polarization on the efficiency of deep penetration was analyzed.

  4. Statistical thermodynamics of alloys

    International Nuclear Information System (INIS)

    Gokcen, N.A.

    1986-01-01

    This book presents information on the following topics: consequences of laws of thermodynamics; Helmholtz and Gibbs energies; analytical forms of excess partial molar properties; single-component and multicomponent equilibria; phase rules and diagrams; lever rule; fermions, bosons, and Boltzons; approximate equations; enthalpy and heat capacity; Pd-H system; hydrogen-metal systems; limitations of Wagner model; energy of electrons and hols; dopants in semiconductors; derived thermodynamic properties; simple equivalent circuit; calculation procedure; multicompoent diagrams re; Engel-Brewer theories; p-n junctions; and solar cells

  5. General thermodynamics

    CERN Document Server

    Olander, Donald

    2007-01-01

    The book’s methodology is unified, concise, and multidisciplinary, allowing students to understand how the principles of thermodynamics apply to all technical fields that touch upon this most fundamental of scientific theories. It also offers a rigorous approach to the quantitative aspects of thermodynamics, accompanied by clear explanations to help students transition smoothly from the physical concepts to their mathematical representations

  6. Thermodynamics of the conversion of calcium and magnesium fluorides to the parent metal oxides and hydrogen fluoride

    International Nuclear Information System (INIS)

    West, M.H.; Axler, K.M.

    1997-02-01

    The authors have used thermodynamic modeling to examine the reaction of calcium fluoride (CaF 2 ) and magnesium fluoride (MgF 2 ) with water (H 2 O) at elevated temperatures. The calculated, equilibrium composition corresponds to the global free-energy minimum for the system. Optimum, predicted reaction temperatures and reactant mole ratios are reported for the recovery of hydrogen fluoride (HF), a valuable industrial feedstock. Complete conversion of MgF 2 is found at 1,000 C and a ratio of 40 moles of H 2 O per 1 mole of MgF 2 . For CaF 2 , temperatures as high as 1,400 C are required for complete conversion at a corresponding mole ratio of 40 moles of H 2 O per 1 mole of CaF 2 . The authors discuss the presence of minor chemical constituents as well as the stability of various potential container materials for the pyrohydrolysis reactions at elevated temperatures. CaF 2 and MgF 2 slags are available as wastes at former uranium production facilities within the Department of Energy Complex and other facilities regulated by the Nuclear Regulatory Commission. Recovery of HF from these wastes is an example of environmental remediation at such facilities

  7. Metal Chelation as a Powerful Strategy to Probe Cellular Circuitry Governing Fungal Drug Resistance and Morphogenesis.

    Directory of Open Access Journals (Sweden)

    Elizabeth J Polvi

    2016-10-01

    metal chelation modulates morphogenetic circuitry and echinocandin resistance, and illuminate a novel facet to metal homeostasis at the host-pathogen interface, with broad therapeutic potential.

  8. Thermodynamics of Crystalline States

    CERN Document Server

    Fujimoto, Minoru

    2010-01-01

    Thermodynamics is a well-established discipline of physics for properties of matter in thermal equilibrium surroundings. Applying to crystals, however, the laws encounter undefined properties of crystal lattices, which therefore need to be determined for a clear and well-defined description of crystalline states. Thermodynamics of Crystalline States explores the roles played by order variables and dynamic lattices in crystals in a wholly new way. This book is divided into three parts. The book begins by clarifying basic concepts for stable crystals. Next, binary phase transitions are discussed to study collective motion of order variables, as described mostly as classical phenomena. In the third part, the multi-electron system is discussed theoretically, as a quantum-mechanical example, for the superconducting state in metallic crystals. Throughout the book, the role played by the lattice is emphasized and examined in-depth. Thermodynamics of Crystalline States is an introductory treatise and textbook on meso...

  9. Re-evaluation of the thermodynamic activity quantities in aqueous alkali metal nitrate solutions at T = 298.15 K

    Energy Technology Data Exchange (ETDEWEB)

    Partanen, Jaakko I., E-mail: jpartane@lut.f [Laboratory of Physical Chemistry, Department of Chemical Technology, Lappeenranta University of Technology, P.O. Box 20, FIN-53851 Lappeenranta (Finland)

    2010-12-15

    The Hueckel equation used in this study to correlate the experimental activities of dilute alkali metal nitrate solutions up to a molality of about 1.5 mol . kg{sup -1} contains two parameters being dependent on the electrolyte: B [that is related closely to the ion-size parameter (a*) in the Debye-Hueckel equation] and b{sub 1} (this parameter is the coefficient of the linear term with respect to the molality and this coefficient is related to hydration numbers of the ions of the electrolyte). In more concentrated solutions up to a molality of 7 mol . kg{sup -1}, an extended Hueckel equation was used, and it contains additionally a quadratic term with respect to the molality and the coefficient of this term is parameter b{sub 2}. All parameter values for the Hueckel equations of LiNO{sub 3}, NaNO{sub 3}, and KNO{sub 3} were determined from the isopiestic data measured by Robinson for solutions of these salts against KCl solutions [J. Am. Chem. Soc. 57 (1935) 1165]. In these estimations, the Hueckel parameters determined recently for KCl solutions [J. Chem. Eng. Data 54 (2009) 208] were used. The Hueckel parameters for RbNO{sub 3} and CsNO{sub 3} were determined from the reported osmotic coefficients of Robinson [J. Am. Chem. Soc. 59 (1937) 84]. The resulting parameter values were tested with the vapour pressure and isopiestic data existing in the literature for alkali metal nitrate solutions. These data support well the recommended Hueckel parameters up to a molality of 7.0 mol . kg{sup -1} for LiNO{sub 3} and NaNO{sub 3}, up to 4.5 mol . kg{sup -1} for RbNO{sub 3}, up to 3.5 mol . kg{sup -1} for KNO{sub 3}, and up to 1.4 mol . kg{sup -1} for CsNO{sub 3} solutions. Reliable activity and osmotic coefficients of alkali metal nitrate solutions can, therefore, be calculated by using the new Hueckel equations, and they have been tabulated at rounded molalities. The activity and osmotic coefficients obtained from these equations were compared to the values suggested by

  10. 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...

  11. 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

  12. “Covalent Hydration” Reactions in Model Monomeric Ru 2,2'-Bipyridine Complexes: Thermodynamic Favorability as a Function of Metal Oxidation and Overall Spin States

    Energy Technology Data Exchange (ETDEWEB)

    Ozkanlar, Abdullah; Cape, Jonathan L.; Hurst, James K.; Clark, Aurora E.

    2011-09-05

    Density functional theory (DFT) has been used to investigate the plausibility of water addition to the simple mononuclear ruthenium complexes, [(NH{sub 3}){sub 3}(bpy)Ru=O]{sup 2+}/{sup 3+} and [(NH{sub 3}){sub 3}(bpy)RuOH]{sup 3+}, in which the OH fragment adds to the 2,2{prime}-bipyridine (bpy) ligand. Activation of bpy toward water addition has frequently been postulated within the literature, although there exists little definitive experimental evidence for this type of 'covalent hydration'. In this study, we examine the energetic dependence of the reaction upon metal oxidation state, overall spin state of the complex, as well as selectivity for various positions on the bipyridine ring. The thermodynamic favorability is found to be highly dependent upon all three parameters, with free energies of reaction that span favorable and unfavorable regimes. Aqueous addition to [(NH{sub 3}){sub 3}(bpy)Ru=O]{sup 3+} was found to be highly favorable for the S = 1/2 state, while reduction of the formal oxidation state on the metal center makes the reaction highly unfavorable. Examination of both facial and meridional isomers reveals that when bipyridine occupies the position trans to the ruthenyl oxo atom, reactivity toward OH addition decreases and the site preferences are altered. The electronic structure and spectroscopic signatures (EPR parameters and simulated spectra) have been determined to aid in recognition of 'covalent hydration' in experimental systems. EPR parameters are found to uniquely characterize the position of the OH addition to the bpy as well as the overall spin state of the system.

  13. Structural and thermodynamic aspects of the dissociation of cyclopentadienyl rings from homoleptic cyclopentadienyl early transition metal, cerium, and thorium derivatives

    International Nuclear Information System (INIS)

    Peng Bin; Cheng Feng; Li Qianshu; Xie Yaoming; King, R. Bruce; Schaefer, Henry F.

    2011-01-01

    Graphical abstract: Density functional theory indicates that for Cp 4 M the S 4 structures are saddle points and the minima have C 1 symmetry with all η 5 -Cp rings for M = Ce and Th, three η 5 -Cp rings and one η 5 -Cp ring for M = Zr, and two η 5 -Cp rings and two η 5 -Cp rings for M = Ti and Hf. The dissociation energies for Cp 4 M → Cp 3 M + Cp · increase in the sequence Ti 3h structures with all η 5 -Cp rings are genuine minima for most of the Cp 3 M compounds except for Cp 3 Ti, which has a Cs symmetry minimum with two η 5 -Cp rings and one η 2 -Cp ring. The dissociation energies for Cp 3 M → Cp 2 M + Cp · increase in the sequence V 4 M the S 4 structures are saddle points. → The minima for Cp 4 M have all η 5 -Cp rings for M = Ce and Th, three η 5 -Cp rings and one η 1 -Cp ring for M = Zr, and two η 5 -Cp rings and two η 5 -Cp rings for M = Ti and Hf. → The dissociation energies for Cp 4 M → Cp 3 M + Cp · increase in the sequence Ti 3h structures with all η 5 -Cp rings are genuine minima for all of the Cp 3 M compounds except for Cp 3 Ti. → The dissociation energies for Cp 3 M → Cp 2 M + Cp · increase in the sequence V 4 M (M = Ti, Zr, Ce, Hf, Th), Cp 3 M (M = Sc, Y, most lanthanides, Ti, Zr, Hf, Th), and Cp 2 M (M = Ti, V). Density functional theory shows that the Cp 4 M structures with unusual S 4 symmetry are saddle points for the d-block metals Ti, Zr, Hf but genuine minima for the f-block metals Ce and Th. The true equilibrium Cp 4 M geometries have C 1 symmetry with two η 5 -Cp rings and two η 1 -Cp rings for M = Ti and Hf but three η 5 -Cp rings and one η 1 -Cp ring for M = Zr. The dissociation energies for Cp 4 M → Cp 3 M + Cp · are substantial and in the order Ti 3h structures with all η 5 -Cp rings are genuine minima for most of the Cp 3 M compounds except for Cp 3 Ti, which has a C s symmetry minimum with two η 5 -Cp rings and one η 2 -Cp ring, and Cp 3 V, which has two η 5 -Cp rings and one η 1 -Cp ring

  14. Novel elastic, lattice dynamics and thermodynamic properties of metallic single-layer transition metal phosphides: 2H-M 2P (Mo2P, W2P, Nb2P and Ta2P)

    Science.gov (United States)

    Yin, Jiuren; Wu, Bozhao; Wang, Yanggang; Li, Zhimi; Yao, Yuanpeng; Jiang, Yong; Ding, Yanhuai; Xu, Fu; Zhang, Ping

    2018-04-01

    Recently, there has been a surge of interest in the research of two-dimensional (2D) phosphides due to their unique physical properties and wide applications. Transition metal phosphides 2H-M 2Ps (Mo2P, W2P, Nb2P and Ta2P) show considerable catalytic activity and energy storage potential. However, the electronic structure and mechanical properties of 2D 2H-M 2Ps are still unrevealed. Here, first-principles calculations are employed to investigate the lattice dynamics, elasticity and thermodynamic properties of 2H-M 2Ps. Results show that M 2Ps with lower stiffness exhibit remarkable lateral deformation under unidirectional loads. Due to the largest average Grüneisen parameter, single-layer Nb2P has the strongest anharmonic vibrations, resulting in the highest thermal expansion coefficient. The lattice thermal conductivities of Ta2P, W2P and Nb2P contradict classical theory, which would predict a smaller thermal conductivity due to the much heavier atom mass. Moreover, the calculations also demonstrate that the thermal conductivity of Ta2P is the highest as well as the lowest thermal expansion, owing to its weak anharmonic phonon scattering and the lowest average Grüneisen parameter. The insight provided by this study may be useful for future experimental and theoretical studies concerning 2D transition metal phosphide materials.

  15. Kinetics and thermodynamics of ceramic/metal interface reactions related to high T(sub c) superconducting applications

    Science.gov (United States)

    Notis, Michael R.; Oh, Min-Seok

    1990-01-01

    Superconducting ceramic materials, no matter what their form, size or shape, must eventually make contact with non-superconducting materials in order to accomplish current transfer to other parts of a real operating system, or for testing and measurement of properties. Thus, whether the configuration is a clad wire, a bulk superconducting disc, tape, or a thick or thin superconducting film on a substrate, the physical and mechanical behavior of interface (interconnections, joints, etc.) between superconductors and normal conductor materials of all kinds is of extreme importance to the technological development of these systems. Fabrication heat treatments associated with the particular joining process allow possible reactions between the superconducting ceramic and the contact to occur, and consequently influence properties at the interface region. The nature of these reactions is therefore of great broad interest, as these may be a primary determinant for the real capability of these materials. Research related both to fabrication of composite sheathed wire products, and the joining contacts for physical property measurements, as well as, a review of other related literature in the field are described. Comparison are made between 1-2-3, Bi-, and Tl-based ceramic superconductors joined to a variety of metals including Cu, Ni, Fe, Cr, Ag, Ag-Pd, Au, In, and Ga. The morphology of reaction products and the nature of interface degradation as a function of time will be highlighted.

  16. Quantum molecular dynamics: Numerical methods and physical study of the structure, thermodynamics, stability and fragmentation of sodium metallic clusters

    International Nuclear Information System (INIS)

    Blaise, Philippe

    1998-01-01

    The aim of this thesis is to study metallic sodium clusters by numerical simulation. We have developed two ab initio molecular dynamics programs within the formalism of density functional theory. The first is based on the semi-classical extended Thomas-Fermi approach. We use a real-space grid and a Car-Parrinello-like scheme. The computational cost is O(N), and we have built a pseudopotential that speeds up the calculations. By neglecting quantum shell effects, we are able to study a very large set of clusters. We show that sodium cluster energies fit well a liquid drop formula, by adjusting a few parameters. We have investigated breathing modes, surface oscillations and the net charge density. We have shown that the surface energy varies strongly with temperature, and that clusters have a lower melting point than bulk material. We have calculated fission barriers by a constraint method. The second program is based on the quantum Kohn-Sham approach. We use a real-space grid, and combine a generalized Broyden scheme for assuring self-consistency with an iterative Davidson-Lanczos algorithm for solving the Eigen-problem. The cost of the method is much higher. First of all, we have calculated some stable structures for small clusters and their energetics. We obtained very good agreement with previous works. Then, we have investigated highly charged cluster dynamics. We have identified a chaotic fission process. For high fissility systems, we observe a multi-fragmentation dynamics and we find preferential emission of monomers on a characteristic time scale less than a pico-second. This has been simulated for the first time, with the help of our adaptive grid method which follows each fragment as they move apart during the fragmentation. (author)

  17. Quantum Thermodynamics at Strong Coupling: Operator Thermodynamic Functions and Relations

    Directory of Open Access Journals (Sweden)

    Jen-Tsung Hsiang

    2018-05-01

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

  18. 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

  19. 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...

  20. Statistical thermodynamics

    CERN Document Server

    Schrödinger, Erwin

    1952-01-01

    Nobel Laureate's brilliant attempt to develop a simple, unified standard method of dealing with all cases of statistical thermodynamics - classical, quantum, Bose-Einstein, Fermi-Dirac, and more.The work also includes discussions of Nernst theorem, Planck's oscillator, fluctuations, the n-particle problem, problem of radiation, much more.

  1. A commentary on thermodynamics

    CERN Document Server

    Day, William Alan

    1988-01-01

    The aim of this book is to comment on, and clarify, the mathematical aspects of the theory of thermodynamics. The standard presentations of the subject are often beset by a number of obscurities associated with the words "state", "reversible", "irreversible", and "quasi-static". This book is written in the belief that such obscurities are best removed not by the formal axiomatization of thermodynamics, but by setting the theory in the wider context of a genuine field theory which incorporates the effects of heat conduction and intertia, and proving appropriate results about the governing differential equations of this field theory. Even in the simplest one-dimensional case it is a nontrivial task to carry through the details of this program, and many challenging problems remain open.

  2. Statistical mechanics and the foundations of thermodynamics

    International Nuclear Information System (INIS)

    Loef, A.M.

    1979-01-01

    An introduction to classical statistical mechanics and its relation to thermodynamics is presented. Emphasis is put on getting a detailed and logical presentation of the foundations of thermodynamics based on the maximum entropy principles which govern the values taken by macroscopic variables according to the laws of large numbers

  3. Thermodynamics of Crystalline States

    CERN Document Server

    Fujimoto, Minoru

    2013-01-01

    Thermodynamics is a well-established discipline of physics for properties of matter in thermal equilibrium with the surroundings. Applying to crystals, however, the laws encounter undefined properties of crystal lattice, which therefore need to be determined for a clear and well-defined description of crystalline states. Thermodynamics of Crystalline States explores the roles played by order variables and dynamic lattices in crystals in a wholly new way. The book begins by clarifying basic concepts for stable crystals. Next, binary phase transitions are discussed to study collective motion of order variables, as described mostly as classical phenomena. New to this edition is the examination of magnetic crystals, where magnetic symmetry is essential for magnetic phase transitions. The multi-electron system is also discussed  theoretically, as a quantum-mechanical example, for superconductivity in metallic crystals. Throughout the book, the role played by the lattice is emphasized and studied in-depth. Thermod...

  4. Microsoft excel spreadsheets for calculation of P-V-T relations and thermodynamic properties from equations of state of MgO, diamond and nine metals as pressure markers in high-pressure and high-temperature experiments

    Science.gov (United States)

    Sokolova, Tatiana S.; Dorogokupets, Peter I.; Dymshits, Anna M.; Danilov, Boris S.; Litasov, Konstantin D.

    2016-09-01

    We present Microsoft Excel spreadsheets for calculation of thermodynamic functions and P-V-T properties of MgO, diamond and 9 metals, Al, Cu, Ag, Au, Pt, Nb, Ta, Mo, and W, depending on temperature and volume or temperature and pressure. The spreadsheets include the most common pressure markers used in in situ experiments with diamond anvil cell and multianvil techniques. The calculations are based on the equation of state formalism via the Helmholtz free energy. The program was developed using Visual Basic for Applications in Microsoft Excel and is a time-efficient tool to evaluate volume, pressure and other thermodynamic functions using T-P and T-V data only as input parameters. This application is aimed to solve practical issues of high pressure experiments in geosciences and mineral physics.

  5. Solvation thermodynamics

    CERN Document Server

    Ben-Naim, Arieh

    1987-01-01

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

  6. Assessment of the governance system for the management of the East Sea-Jung dumping site, Korea through analysis of heavy metal concentrations in bottom sediments

    Science.gov (United States)

    Song, Ki-Hoon; Choi, Ki-Young; Kim, Chang-Joon; Kim, Young-Il; Chung, Chang-Soo

    2015-12-01

    As with many countries, the Korea government has made a variety of efforts to meet the precautionary principle under the London Convention and Protocol acceded in 1994 and 2009. However, new strategies for the suitable marine dumping of waste materials have since been developed. In this study, the distribution and contamination of heavy metals including Al, Fe, Mn, Li, Co, Cr, Ni, Cu, Zn, As, Cd, Pb and Hg in bottom sediments were analyzed and compared to various criteria in order to evaluate the effectiveness of the management of the East Sea-Jung (ES-Jung) dumping site by the Korea government. The results indicate that the average metal concentrations were significantly lower than Effects Range Low (ERL) values, and generally similar to or lower than the Threshold Effect Levels (TEL) from the Sediment Quality Guidelinces (SQGs). According to analyses of various metal contamination indexes (Enrichment Factor: EF, Pollution Load Index: PLI and the Index of Geoaccumulation: Igeo), most areas were found to be uncontaminated by heavy metals with the exception of several moderately contaminated stations (ESJ 33, 54, 64 and ESJR 20). Heavy metal concentrations in areas grouped as G1, G2, DMDA, N-Ref and S-Ref which showed similar characteristics between 2007-2013 and 2014, were compared. Unexpectedly, most concentrations in the northern reference area (N-Ref) were much higher than those in the actual dumping areas (G1 and G2), may be due to the influences from nearby cities to the west of the ES-Jung site, rather than from the dumping site itself. Additionally, heavy metal concentrations in the dredged material dumping area (DMDA) were found to be low although they have slightly increased over time and those in the southern reference area (S-Ref) were found to have gradually decreased with year. The concentrations of most metals in the East Sea-Jung dumping site were similar to or less than those in the Earth's crust and approximately the same as those in continental

  7. Universalities of thermodynamic signatures in topological phases

    NARCIS (Netherlands)

    Kempkes, S. N.; Quelle, A.; de Morais Smith, C.

    2016-01-01

    Topological insulators (superconductors) are materials that host symmetry-protected metallic edge states in an insulating (superconducting) bulk. Although they are well understood, a thermodynamic description of these materials remained elusive, firstly because the edges yield a non-extensive

  8. Engineering metal (hydr)oxide sorbents for removal of arsenate and similar weak-acid oxyanion contaminants: A critical review with emphasis on factors governing sorption processes.

    Science.gov (United States)

    Hristovski, Kiril D; Markovski, Jasmina

    2017-11-15

    To create an integrative foundation for engineering of the next generation inexpensive sorbent systems, this critical review addresses the existing knowledge gap in factor/performance relationships between weak-acid oxyanion contaminants and metal (hydr)oxide sorbents. In-depth understanding of fundamental thermodynamics and kinetics mechanisms, material fabrication, and analytical and characterization techniques, is necessary to engineer sorbent that exhibit high capacity, selectivity, stability, durability and mass transport of contaminants under a wide range of operating and water matrix conditions requirements. From the perspective of thermodynamics and kinetics, this critical review examines the factors affecting sorbent performances and analyzes the existing research to elucidate future directions aimed at developing novel sorbents for removal of weak-acid oxyanion contaminants from water. Only sorbents that allow construction of simple and inexpensive water treatment systems adapted to overcome fiscal and technological barriers burdening small communities could pave the road for providing inexpensive potable water to millions of people. Novel sorbents, which exhibit (1) poor performances in realistic operating and water matrix conditions and/or (2) do not comply with the purely driven economics factors of production scalability or cost expectations, are predestined to never be commercialized. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Thermodynamics of Crystals

    Science.gov (United States)

    Navrotsky, Alexandra

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

  10. The discovery of thermodynamics

    Science.gov (United States)

    Weinberger, Peter

    2013-07-01

    Based on the idea that a scientific journal is also an "agora" (Greek: market place) for the exchange of ideas and scientific concepts, the history of thermodynamics between 1800 and 1910 as documented in the Philosophical Magazine Archives is uncovered. Famous scientists such as Joule, Thomson (Lord Kelvin), Clausius, Maxwell or Boltzmann shared this forum. Not always in the most friendly manner. It is interesting to find out, how difficult it was to describe in a scientific (mathematical) language a phenomenon like "heat", to see, how long it took to arrive at one of the fundamental principles in physics: entropy. Scientific progress started from the simple rule of Boyle and Mariotte dating from the late eighteenth century and arrived in the twentieth century with the concept of probabilities. Thermodynamics was the driving intellectual force behind the industrial revolution, behind the enormous social changes caused by this revolution. The history of thermodynamics is a fascinating story, which also gives insights into the mechanism that seem to govern science.

  11. Thermodynamic laws apply to brain function.

    Science.gov (United States)

    Salerian, Alen J

    2010-02-01

    Thermodynamic laws and complex system dynamics govern brain function. Thus, any change in brain homeostasis by an alteration in brain temperature, neurotransmission or content may cause region-specific brain dysfunction. This is the premise for the Salerian Theory of Brain built upon a new paradigm for neuropsychiatric disorders: the governing influence of neuroanatomy, neurophysiology, thermodynamic laws. The principles of region-specific brain function thermodynamics are reviewed. The clinical and supporting evidence including the paradoxical effects of various agents that alter brain homeostasis is demonstrated.

  12. 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

  13. Microbial diversity arising from thermodynamic constraints

    Science.gov (United States)

    Großkopf, Tobias; Soyer, Orkun S

    2016-01-01

    The microbial world displays an immense taxonomic diversity. This diversity is manifested also in a multitude of metabolic pathways that can utilise different substrates and produce different products. Here, we propose that these observations directly link to thermodynamic constraints that inherently arise from the metabolic basis of microbial growth. We show that thermodynamic constraints can enable coexistence of microbes that utilise the same substrate but produce different end products. We find that this thermodynamics-driven emergence of diversity is most relevant for metabolic conversions with low free energy as seen for example under anaerobic conditions, where population dynamics is governed by thermodynamic effects rather than kinetic factors such as substrate uptake rates. These findings provide a general understanding of the microbial diversity based on the first principles of thermodynamics. As such they provide a thermodynamics-based framework for explaining the observed microbial diversity in different natural and synthetic environments. PMID:27035705

  14. Microbial diversity arising from thermodynamic constraints.

    Science.gov (United States)

    Großkopf, Tobias; Soyer, Orkun S

    2016-11-01

    The microbial world displays an immense taxonomic diversity. This diversity is manifested also in a multitude of metabolic pathways that can utilise different substrates and produce different products. Here, we propose that these observations directly link to thermodynamic constraints that inherently arise from the metabolic basis of microbial growth. We show that thermodynamic constraints can enable coexistence of microbes that utilise the same substrate but produce different end products. We find that this thermodynamics-driven emergence of diversity is most relevant for metabolic conversions with low free energy as seen for example under anaerobic conditions, where population dynamics is governed by thermodynamic effects rather than kinetic factors such as substrate uptake rates. These findings provide a general understanding of the microbial diversity based on the first principles of thermodynamics. As such they provide a thermodynamics-based framework for explaining the observed microbial diversity in different natural and synthetic environments.

  15. Thermodynamics of nuclear power systems

    International Nuclear Information System (INIS)

    Anno, J.

    1983-01-01

    The conversion of nuclear energy to useful work follows essentially the same course as the conversion of thermal energy from fossil fuel to work. The thermal energy released in the reactor core is first transferred to the primary coolant which then generally transfers its heat to a secondary fluid. The secondary fluid serves as the working fluid in a heat engine. In this chapter the authors briefly examine the thermodynamic principles governing the operation of such engines, the major thermodynamic cycles used, and their application to nuclear power plants

  16. Thermodynamics of nuclear power systems

    International Nuclear Information System (INIS)

    Anno, J.

    1977-01-01

    The conversion of nuclear energy to useful work follows essentially the same course as the conversion of thermal energy from fossil fuel to work. The thermal energy released in the reactor core is first transferred to the primary coolant which then generally transfers its heat to a secondary fluid. The secondary fluid serves as the working fluid in a heat engine. The author briefly examines the thermodynamic principles governing the operation of such engines, the major thermodynamic cycles used, and their application to nuclear power plants. (Auth.)

  17. 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...

  18. 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...

  19. Statistical thermodynamics of clustered populations.

    Science.gov (United States)

    Matsoukas, Themis

    2014-08-01

    We present a thermodynamic theory for a generic population of M individuals distributed into N groups (clusters). We construct the ensemble of all distributions with fixed M and N, introduce a selection functional that embodies the physics that governs the population, and obtain the distribution that emerges in the scaling limit as the most probable among all distributions consistent with the given physics. We develop the thermodynamics of the ensemble and establish a rigorous mapping to regular thermodynamics. We treat the emergence of a so-called giant component as a formal phase transition and show that the criteria for its emergence are entirely analogous to the equilibrium conditions in molecular systems. We demonstrate the theory by an analytic model and confirm the predictions by Monte Carlo simulation.

  20. Coherence and measurement in quantum thermodynamics.

    Science.gov (United States)

    Kammerlander, P; Anders, J

    2016-02-26

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

  1. 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

  2. Coupled Geochemical and Hydrological Processes Governing the Fate and Transport of Radionuclides and Toxic Metals Beneath the Hanford Tank Farms

    International Nuclear Information System (INIS)

    Scott Fendorf; Phil Jardine

    2006-01-01

    The goal of this research was to provide an improved understanding and predictive capability of coupled hydrological and geochemical mechanisms that are responsible for the accelerated migration and immobilization of radionuclides and toxic metals in the vadose zone beneath the Hanford Tank Farms

  3. 'Good Governance' dan 'Governability'

    Directory of Open Access Journals (Sweden)

    - Pratikno

    2005-03-01

    Full Text Available The article endeavors to trace the outset of governance concept, its dominant meanings and discourse, and its implication towards governability. The central role of government in the governing processes has predominantly been adopted. The concept of governance was emerged precisely in the context of the failure of government as key player in regulation, economic redistribution and political participation. Governance is therefore aimed to emphasize pattern of governing which are based both on democratic mechanism and sound development management. However, practices of such good governance concept –which are mainly adopted and promoted by donor states and agencies– tend to degrade state and/or government authority and legitimacy. Traditional function of the state as sole facilitator of equal societal, political and legal membership among citizens has been diminished. The logic of fair competition has been substituted almost completely by the logic of free competition in nearly all sectors of public life. The concept and practices of good governance have resulted in decayed state authority and failed state which in turn created a condition for "ungovernability". By promoting democratic and humane governance, the article accordingly encourages discourse to reinstall and bring the idea of accountable state back in.

  4. Physical energy cost serves as the 'invisible hand' governing economic valuation. Direct evidence from biogeochemical data and the U.S. metal market

    International Nuclear Information System (INIS)

    Liu, Zhicen; Koerwer, Joel; Nemoto, Jiro; Imura, Hidefumi

    2008-01-01

    Energy supply is mandatory for the production of economic value. Nevertheless, tradition dictates that an enigmatic 'invisible hand' governs economic valuation. Physical scientists have long proposed alternative but testable energy cost theories of economic valuation, and have shown the gross correlation between energy consumption and economic output at the national level through input-output energy analysis. However, due to the difficulty of precise energy analysis and highly complicated real markets, no decisive evidence directly linking energy costs to the selling prices of individual commodities has yet been found. Over the past century, the US metal market has accumulated a huge body of price data, which for the first time ever provides us the opportunity to quantitatively examine the direct energy-value correlation. Here, by analyzing the market price data of 65 purified chemical elements (mainly metals) relative to the total energy consumption for refining them from naturally occurring geochemical conditions, we found a clear correlation between the energy cost and their market prices. The underlying physics we proposed has compatibility with conventional economic concepts such as the ratio between supply and demand or scarcity's role in economic valuation. It demonstrates how energy cost serves as the 'invisible hand' governing economic valuation. Thorough understanding of this energy connection between the human economic and the Earth's biogeochemical metabolism is essential for improving the overall energy efficiency and furthermore the sustainability of the human society. (author)

  5. Chemical thermodynamics of uranium

    International Nuclear Information System (INIS)

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

    1992-01-01

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

  6. 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…

  7. Thermodynamic and structural properties of the specific binding between Ag⁺ ion and C:C mismatched base pair in duplex DNA to form C-Ag-C metal-mediated base pair.

    Science.gov (United States)

    Torigoe, Hidetaka; Okamoto, Itaru; Dairaku, Takenori; Tanaka, Yoshiyuki; Ono, Akira; Kozasa, Tetsuo

    2012-11-01

    Metal ion-nucleic acid interactions have attracted considerable interest for their involvement in structure formation and catalytic activity of nucleic acids. Although interactions between metal ion and mismatched base pair duplex are important to understand mechanism of gene mutations related to heavy metal ions, they have not been well-characterized. We recently found that the Ag(+) ion stabilized a C:C mismatched base pair duplex DNA. A C-Ag-C metal-mediated base pair was supposed to be formed by the binding between the Ag(+) ion and the C:C mismatched base pair to stabilize the duplex. Here, we examined specificity, thermodynamics and structure of possible C-Ag-C metal-mediated base pair. UV melting indicated that only the duplex with the C:C mismatched base pair, and not of the duplexes with the perfectly matched and other mismatched base pairs, was specifically stabilized on adding the Ag(+) ion. Isothermal titration calorimetry demonstrated that the Ag(+) ion specifically bound with the C:C base pair at 1:1 molar ratio with a binding constant of 10(6) M(-1), which was significantly larger than those for nonspecific metal ion-DNA interactions. Electrospray ionization mass spectrometry also supported the specific 1:1 binding between the Ag(+) ion and the C:C base pair. Circular dichroism spectroscopy and NMR revealed that the Ag(+) ion may bind with the N3 positions of the C:C base pair without distorting the higher-order structure of the duplex. We conclude that the specific formation of C-Ag-C base pair with large binding affinity would provide a binding mode of metal ion-DNA interactions, similar to that of the previously reported T-Hg-T base pair. The C-Ag-C base pair may be useful not only for understanding of molecular mechanism of gene mutations related to heavy metal ions but also for wide variety of potential applications of metal-mediated base pairs in various fields, such as material, life and environmental sciences. Copyright © 2012 Elsevier

  8. Ternary alloy systems. Phase diagrams, crystallographic and thermodynamic data critically evaluated by MSIT registered. Subvol. C. Non-ferrous metal systems. Pt. 4: Selected nuclear materials and engineering systems

    International Nuclear Information System (INIS)

    Effenberg, Guenter; Ilyenko, Svitlana; Aldinger, Fritz; Bochvar, Nataliya; Cacciamani, Gabriele

    2007-01-01

    The present volume in the New Series of Landolt-Boernstein provides critically evaluated data on phase diagrams, crystallographic and thermodynamic data of ternary alloy systems. Reliable phase diagrams provide materials scientists and engineers with basic information important for fundamental research, development and optimization of materials. The often conflicting literature data have been critically evaluated by Materials Science International Team, MSIT registered , a team working together since many years, and with expertise in a broad range of methods, materials and applications. All evaluation reports published here have undergone a thorough review process in which the reviewers had access to all the original data. The data for each ternary system are provided in a standard format which includes text, tables and diagrams. The topics presented are literature data, binary systems, solid phases, pseudobinary systems, invariant equilibria, liquidus, solidus, and solvus surfaces, isothermal sections, temperature-composition sections, thermodynamics, materials properties and applications, and miscellanea. Finally, a detailed bibliography of all cited references is provided. In the present volume IV/11C selected non-ferrous-metal systems are considered, especially selected nuclear materials and engineering systems in this Part 4. (orig.)

  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. Thermodynamic tables to accompany Modern engineering thermodynamics

    CERN Document Server

    Balmer, Robert T

    2011-01-01

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

  11. Classical and statistical thermodynamics

    CERN Document Server

    Rizk, Hanna A

    2016-01-01

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

  12. The thermodynamic approach of the pilot-scale purification of refractory metals; Application de la thermodynamique a la mise au point des methodes de purification industrielle des metaux et semi-metaux refractaires

    Energy Technology Data Exchange (ETDEWEB)

    Accary, A [Commissariat a l' Energie Atomique, Dir. des Piles Atomiques, Saclay (France). Centre d' Etudes Nucleaires

    1967-06-15

    The author shows how the thermodynamic can be applied to the prediction of the evolution of impurities from a metal or an alloy being melted and cast at the pilot-scale using electron bombardment and continuous casting in a water cooled copper. He studies this possibility on two examples: - the melting vanadium, - the melting of the uranium monocarbide. He shows using only the constants available in the literature and a few special runs in the pilot-equipment itself it is possible to determine: - the possibility of elimination of anyone impurity by keeping the material in the melting state under vacuum as well as the limit of purification which is achievable under given technological conditions, - the proportion of an impure metal which should be vaporized in order to bring the level of a given impurity down to a predetermined level and the necessary duration of heating. (author) [French] L'auteur montre comment la thermodynamique peut etre appliquee a la prevision de l'evolution d'un metal ou d'un alliage fondu a l'echelle pilote par bombardement d'electrons et coule en continu dans un creuset de cuivre refroidi. Il etudie cette possibilite sur deux cas particuliers: - la fusion de vanadium, - la fusion du monocarbure d'uranium. Il montre que, grace aux constantes disponibles dans la litterature et a des essais simples faits a l'aide de l'appareillage pilote lui-meme, on peut determiner: - la possibilite d'eliminer une impurete par maintien a l'etat fondu ainsi que la limite de purification dans des conditions technologiques donnees, - la proportion d'un metal brut qu'il faut evaporer pour amener sa teneur en une impurete a un niveau donne ainsi que la duree de chauffage necessaire, - la nature des additions propres a favoriser le depart d'une impurete et l'efficacite comparee des additions possibles. (auteur)

  13. Sequestering Potential of Peach Nut Shells as an Efficient Sorbent for Sequestering Some Toxic Metal Ions from Aqueous Waste: A Kinetic and Thermodynamic Study

    Directory of Open Access Journals (Sweden)

    Muhammad Ashraf Shaheen

    2016-06-01

    Full Text Available The peach nut shells potential as a low cost biosorbent for separation of certain metal ions from aqueous media was investigated. The effects of different parameters such as pH, shaking speed, initial metal ions concentration and their contact time with adsorbent on sorption efficiency of biosorbent was investigated to optimize the parameters for maximum sorption. The FT–IR spectroscopy and TGA were used to characterize the biosorbent. A significant increase in sorption was noted with rise in pH of metal ions solution and maximum sorption was observed at pH 6. The isothermal data was fitted to Langmuir, Dubinin–Radushkevich (D–R, Freundlich isotherms and equilibrium process was best fitted to Langmuir isotherm. The removal efficiency of chemically activated samples was found to be ~35 to 45% greater than raw sample. The results showed that peach nut shell was an effective biosorbent for the remediation of the contaminated water with lead (II, Nickle (II and Chromium (III ions. Being low cost material, PNS has a potential to be exploited in waste water treatment technologies. This study shows that activated PNS exhibited appreciable sorption for Pb, Cr and Ni metals ions (97%, 95% and 94% respectively from aqueous solution even at very low concentration of sorbent. The chemical and thermal activation of peach nut shells enhances the removal efficiency for all the metal ions and from the reported data; it was found that the adsorption ability of Pb ions was greater than nickel and chromium.

  14. Reassessing SERS enhancement factors: using thermodynamics to drive substrate design.

    Science.gov (United States)

    Guicheteau, J A; Tripathi, A; Emmons, E D; Christesen, S D; Fountain, Augustus W

    2017-12-04

    Over the past 40 years fundamental and application research into Surface-Enhanced Raman Scattering (SERS) has been explored by academia, industry, and government laboratories. To date however, SERS has achieved little commercial success as an analytical technique. Researchers are tackling a variety of paths to help break through the commercial barrier by addressing the reproducibility in both the SERS substrates and SERS signals as well as continuing to explore the underlying mechanisms. To this end, investigators use a variety of methodologies, typically studying strongly binding analytes such as aromatic thiols and azarenes, and report SERS enhancement factor calculations. However a drawback of the traditional SERS enhancement factor calculation is that it does not yield enough information to understand substrate reproducibility, application potential with another analyte, or the driving factors behind the molecule-metal interaction. Our work at the US Army Edgewood Chemical Biological Center has focused on these questions and we have shown that thermodynamic principles play a key role in the SERS response and are an essential factor in future designs of substrates and applications. This work will discuss the advantages and disadvantages of various experimental techniques used to report SERS enhancement with planar SERS substrates and present our alternative SERS enhancement value. We will report on three types of analysis scenarios that all yield different information concerning the effectiveness of the SERS substrate, practical application of the substrate, and finally the thermodynamic properties of the substrate. We believe that through this work a greater understanding for designing substrates will be achieved, one that is based on both thermodynamic and plasmonic properties as opposed to just plasmonic properties. This new understanding and potential change in substrate design will enable more applications for SERS based methodologies including targeting

  15. Thermodiffusion in Multicomponent Mixtures Thermodynamic, Algebraic, and Neuro-Computing Models

    CERN Document Server

    Srinivasan, Seshasai

    2013-01-01

    Thermodiffusion in Multicomponent Mixtures presents the computational approaches that are employed in the study of thermodiffusion in various types of mixtures, namely, hydrocarbons, polymers, water-alcohol, molten metals, and so forth. We present a detailed formalism of these methods that are based on non-equilibrium thermodynamics or algebraic correlations or principles of the artificial neural network. The book will serve as single complete reference to understand the theoretical derivations of thermodiffusion models and its application to different types of multi-component mixtures. An exhaustive discussion of these is used to give a complete perspective of the principles and the key factors that govern the thermodiffusion process.

  16. Thermodynamics in Einstein's thought

    International Nuclear Information System (INIS)

    Klein, M.J.

    1983-01-01

    The role of the thermodynamical approach in the Einstein's scientific work is analyzed. The Einstein's development of a notion about statistical fluctuations of thermodynamical systems that leads him to discovery of corpuscular-wave dualism is retraced

  17. Metals

    Science.gov (United States)

    Kirkemo, Harold; Goudarzi, Gus H.

    1978-01-01

    There has been a general lag in minerals-exploration activity in the past few years. Government concern is reviewed in this article, along with significant developments that included the discovery of additional bauxite, copper, and molybdenum deposits and the reopening of different mining operations. (MA)

  18. Heat and thermodynamics

    CERN Document Server

    Saxena, A K

    2014-01-01

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

  19. 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

  20. Intriguing structures and magic sizes of heavy noble metal nanoclusters around size 55 governed by relativistic effect and covalent bonding

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, X. J.; Xue, X. L.; Jia, Yu [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001 (China); Guo, Z. X. [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001 (China); Department of Chemistry and London Centre for Nanotechnology, University College London, London WC1H (United Kingdom); Li, S. F., E-mail: sflizzu@zzu.edu.cn [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001 (China); ICQD, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026 (China); Zhang, Zhenyu, E-mail: zhangzy@ustc.edu.cn [ICQD, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026 (China); Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Gao, Y. F., E-mail: ygao7@utk.edu [Department of Materials Science and Engineering, University of Tennessee, Knoxville, Tennessee 37996 (United States); Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States)

    2015-11-07

    Nanoclusters usually display exotic physical and chemical properties due to their intriguing geometric structures in contrast to their bulk counterparts. By means of first-principles calculations within density functional theory, we find that heavy noble metal Pt{sub N} nanoclusters around the size N = 55 begin to prefer an open configuration, rather than previously reported close-packed icosahedron or core-shell structures. Particularly, for Pt{sub N}, the widely supposed icosahedronal magic cluster is changed to a three-atomic-layered structure with D{sub 6h} symmetry, which can be well addressed by our recently established generalized Wulff construction principle (GWCP). However, the magic number of Pt{sub N} clusters around 55 is shifted to a new odd number of 57. The high symmetric three-layered Pt{sub 57} motif is mainly stabilized by the enhanced covalent bonding contributed by both spin-orbital coupling effect and the open d orbital (5d{sup 9}6s{sup 1}) of Pt, which result in a delicate balance between the enhanced Pt–Pt covalent bonding of the interlayers and negligible d dangling bonds on the cluster edges. These findings about Pt{sub N} clusters are also applicable to Ir{sub N} clusters, but qualitatively different from their earlier neighboring element Os and their later neighboring element Au. The magic numbers for Os and Au are even, being 56 and 58, respectively. The findings of the new odd magic number 57 are the important supplementary of the recently established GWCP.

  1. Systemic analysis of thermodynamic properties of lanthanide halides

    International Nuclear Information System (INIS)

    Mirsaidov, U.; Badalov, A.; Marufi, V.K.

    1992-01-01

    System analysis of thermodynamic characteristics of lanthanide halides was carried out. A method making allowances for the influence of spin and orbital moments of momentum of the main states of lanthanide trivalent ions in their natural series was employed. Unknown in literature thermodynamic values were calculated and corrected for certain compounds. The character of lanthanide halide thermodynamic parameter change depending on ordinal number of the metals was ascertained. Pronouncement of tetrad-effect in series of compounds considered was pointed out

  2. Mathematical modelling of municipal solid waste incineration and thermodynamic study of the behaviour of heavy metals; Modelisation de l'incineration sur grille d'ordures menageres et approche thermodynamique du comportement des metaux lourds

    Energy Technology Data Exchange (ETDEWEB)

    Menard, Y

    2003-07-15

    The present dissertation describes experimental and theoretical investigations undertaken for the mathematical modelling of municipal solid waste (MSW) incineration in a grate furnace and the thermodynamic study of the speciation of heavy metals (HM), originally contained into MSW, during combustion. Thermogravimetric and gaseous analysis (mass spectrometry and gas chromatography) experiments were performed on MSW samples to get pyrolysis kinetics and to quantify the gaseous species that evolve during the primary reactions of devolatilization. Other experiments were carried out in a fixed bed pilot-scale reactor: the combustion of two types of solids (wood chips and MSW) was studied, and the influence of operating conditions (flow rate, staging and temperature of the primary air) as well as fuel characteristics (moisture content, inert material fraction, lower calorific value) was investigated. A mathematical model was developed for simulating the combustion of a solid fuel, either in a fixed bed reactor or on the grate of an incineration plant. It has been validated by comparison of the calculated results and the experiments carried out on the pilot. Thanks to this model, we have been able to localize the different processes taking place in the fuel bed and to evaluate the influence of the operating conditions on the combustion efficiency. Numerical simulations of the gas flow and combustion in the post-combustion chamber and the heater of an incineration plant were performed using the CFD code FLUENT. The local thermal conditions as well as local gaseous species concentrations obtained from these simulations were eventually used to carry out thermodynamic calculations of the speciation of HM during incineration. (author)

  3. Mathematical modelling of municipal solid waste incineration and thermodynamic study of the behaviour of heavy metals; Modelisation de l'incineration sur grille d'ordures menageres et approche thermodynamique du comportement des metaux lourds

    Energy Technology Data Exchange (ETDEWEB)

    Menard, Y.

    2003-07-15

    The present dissertation describes experimental and theoretical investigations undertaken for the mathematical modelling of municipal solid waste (MSW) incineration in a grate furnace and the thermodynamic study of the speciation of heavy metals (HM), originally contained into MSW, during combustion. Thermogravimetric and gaseous analysis (mass spectrometry and gas chromatography) experiments were performed on MSW samples to get pyrolysis kinetics and to quantify the gaseous species that evolve during the primary reactions of devolatilization. Other experiments were carried out in a fixed bed pilot-scale reactor: the combustion of two types of solids (wood chips and MSW) was studied, and the influence of operating conditions (flow rate, staging and temperature of the primary air) as well as fuel characteristics (moisture content, inert material fraction, lower calorific value) was investigated. A mathematical model was developed for simulating the combustion of a solid fuel, either in a fixed bed reactor or on the grate of an incineration plant. It has been validated by comparison of the calculated results and the experiments carried out on the pilot. Thanks to this model, we have been able to localize the different processes taking place in the fuel bed and to evaluate the influence of the operating conditions on the combustion efficiency. Numerical simulations of the gas flow and combustion in the post-combustion chamber and the heater of an incineration plant were performed using the CFD code FLUENT. The local thermal conditions as well as local gaseous species concentrations obtained from these simulations were eventually used to carry out thermodynamic calculations of the speciation of HM during incineration. (author)

  4. The Efficient Removal of Heavy Metal Ions from Industry Effluents Using Waste Biomass as Low-Cost Adsorbent: Thermodynamic and Kinetic Models

    Science.gov (United States)

    Indhumathi, Ponnuswamy; Sathiyaraj, Subbaiyan; Koelmel, Jeremy P.; Shoba, Srinivasan U.; Jayabalakrishnan, Chinnasamy; Saravanabhavan, Munusamy

    2018-05-01

    The ability of green micro algae Chlorella vulgaris for biosorption of Cu(II) ions from an aqueous solution was studied. The biosorption process was affected by the solution pH, contact time, temperature and initial Cu(II) concentration. Experimental data were analyzed in terms of pseudo-first order, pseudo-second order and intra particle diffusion models. Results showed that the sorption process of Cu(II) ions followed pseudo-second order kinetics. The sorption data of Cu(II) ions are fitted to Langmuir, Freundlich, and Redlich-Peterson isotherms, and the Temkin isotherm. The thermodynamic study shows the Cu(II) biosorption was exothermic in nature. The Cu(II) ions were recovered effectively from Chlorella vulgaris biomass using 0.1 M H2SO4 with up to 90.3% recovery, allowing for recycling of the Cu. Green algae from freshwater bodies showed significant potential for Cu(II) removal and recovery from industrial wastewater.

  5. Catalytic Proton Coupled Electron Transfer from Metal Hydrides to Titanocene Amides, Hydrazides and Imides: Determination of Thermodynamic Parameters Relevant to Nitrogen Fixation.

    Science.gov (United States)

    Pappas, Iraklis; Chirik, Paul J

    2016-10-03

    The hydrogenolysis of titanium-nitrogen bonds in a series of bis(cyclopentadienyl) titanium amides, hydrazides and imides by proton coupled electron transfer (PCET) is described. Twelve different N-H bond dissociation free energies (BDFEs) among the various nitrogen-containing ligands were measured or calculated, and effects of metal oxidation state and N-ligand substituent were determined. Two metal hydride complexes, (η 5 -C 5 Me 5 )(py-Ph)Rh-H (py-Ph = 2-pyridylphenyl, [Rh]-H) and (η 5 -C 5 R 5 )(CO) 3 Cr-H ([Cr] R -H, R= H, Me) were evaluated for formal H atom transfer reactivity and were selected due to their relatively weak M-H bond strengths yet ability to activate and cleave molecular hydrogen. Despite comparable M-H BDFEs, disparate reactivity between the two compounds was observed and was traced to the vastly different acidities of the M-H bonds and overall redox potentials of the molecules. With [Rh]-H, catalytic syntheses of ammonia, silylamine and N,N-dimethylhydrazine have been accomplished from the corresponding titanium(IV) complex using H 2 as the stoichiometric H atom source. The data presented in this study provides the thermochemical foundation for the synthesis of NH 3 by proton coupled electron transfer at a well-defined transition metal center.

  6. Introduction to applied thermodynamics

    CERN Document Server

    Helsdon, R M; Walker, G E

    1965-01-01

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

  7. Twenty lectures on thermodynamics

    CERN Document Server

    Buchdahl, H A

    2013-01-01

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

  8. Structure and thermodynamics of molten salts

    International Nuclear Information System (INIS)

    Papatheodorou, G.N.

    1983-01-01

    This chapter investigates single-component molten salts and multicomponent salt mixtures. Molten salts provide an important testing ground for theories of liquids, solutions, and plasmas. Topics considered include molten salts as liquids (the pair potential, the radial distribution function, methods of characterization), single salts (structure, thermodynamic correlations), and salt mixtures (the thermodynamics of mixing; spectroscopy and structure). Neutron and X-ray scattering techniques are used to determine the structure of molten metal halide salts. The corresponding-states theory is used to obtain thermodynamic correlations on single salts. Structural information on salt mixtures is obtained by using vibrational (Raman) and electronic absorption spectroscopy. Charge-symmetrical systems and charge-unsymmetrical systems are used to examine the thermodynamics of salt mixtures

  9. Thermodynamic and relative approach to compute glass-forming ...

    Indian Academy of Sciences (India)

    models) characteristic: the isobaric heat capacity (Cp) of oxides, and execute a mathematical treatment of oxides thermodynamic data. We note this coefficient as thermodynamical relative glass-forming ability (ThRGFA) and for- mulate a model to compute it. Computed values of 2nd, 3rd, 4th and 5th period metal oxides ...

  10. Pressure-induced structural transition and thermodynamic properties of RhN2 and the effect of metallic bonding on its hardness

    International Nuclear Information System (INIS)

    Liu Jun; Kuang Xiao-Yu; Wang Zhen-Hua; Huang Xiao-Fen

    2012-01-01

    The elastic constant, structural phase transition, and effect of metallic bonding on the hardness of RhN 2 under high pressure are investigated through the first-principles calculation by means of the pseudopotential plane-wave method. Three structures are chosen to investigate for RhN 2 , namely, simple hexagonal P6/mmm (denoted as SH), orthorhombic Pnnm (marcasite), and simple tetragonal P4/mbm (denoted as ST). Our calculations show that the SH phase is energetically more stable than the other two phases at zero pressure. On the basis of the third-order Birch—Murnaghan equation of states, we find that the phase transition pressures from an SH to a marcasite structure and from a marcasite to an ST structure are 1.09 GPa and 354.57 GPa, respectively. Elastic constants, formation enthalpies, shear modulus, Young's modulus, and Debye temperature of RhN 2 are derived. The calculated values are, generally speaking, in good agreement with the previous theoretical results. Meanwhile, it is found that the pressure has an important influence on physical properties. Moreover, the effect of metallic bonding on the hardness of RhN 2 is investigated. This is a quantitative investigation on the structural properties of RhN 2 , and it still awaits experimental confirmation. (condensed matter: structural, mechanical, and thermal properties)

  11. Thermodynamic basis for cluster kinetics

    DEFF Research Database (Denmark)

    Hu, Lina; Bian, Xiufang; Qin, Xubo

    2006-01-01

    Due to the inaccessibility of the supercooled region of marginal metallic glasses (MMGs) within the experimental time window, we study the cluster kinetics above the liquidus temperature, Tl, to acquire information on the fragility of the MMG systems. Thermodynamic basis for the stability...... of locally ordered structure in the MMG liquids is discussed in terms of the two-order-parameter model. It is found that the Arrhenius activation energy of clusters, h, is proportional to the chemical mixing enthalpy of alloys, Hchem. Fragility of the MMG forming liquids can be described by the ratio...

  12. Thermodynamic aspects of heavy metal volatility during utilisation of the energetic and material fraction of waste materials; Schwermetallfluechtigkeit bei der energetischen und stofflichen Verwertung von Abfaellen aus der Sicht der Thermodynamik

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, B; Starke, A [TU Bergakademie Freiberg (Germany). Inst. IEC

    1998-09-01

    Co-combustion plants, in which fuel is partly substituted by waste materials, are subject to the 17th BImSchV (Nuisance Control Ordinance) provided that the thermal fraction of 25% is not exceeded. Emission limits are calculated proportionately on the basis of limiting values for emissions from coal power stations (13th BImSchV) and waste incinerators (17th BImSchV). Compared to coal, waste has higher concentrations of heavy metals and halogens, which results in enhanced emissions of heavy metal compounds and chlorides with the flue gas and gasification gas. Plant operators intending to opt for co-combustion must check if the existing flue gas purification system is efficient enough to meet the specifications of the 17th BImSchV. In general, thermodynamic modelling is the most common method of evaluation and optimisation for high-temperature processes of this kind. (orig./SR) [Deutsch] Da bei der Mitverbrennung ein Teil des Brennstoffes durch den Reststoff substituiert wird, unterliegen diese Anlagen der Anteilsregelung nach 17. BImSchV, sofern ein thermischer Anteil von 25% nicht ueberschritten wird. Emissionsgrenzwerte werden anteilig aus den z.B. fuer Kohlekraftwerke gueltigen Grenzwerten nach TA Luft oder 13. BImSchV und denen fuer Abfaelle u.ae. nach 17 BImSchV ermittelt. Der hier betrachtete Reststoff Muell beinhaltet im Vergleich zur Kohle hohe Konzentrationen an Schwermetallen und Halogenen. Dies laesst eine erhoehte Emission von Schwermetallverbindungen und Chloriden mit dem Rauchgas bzw. Vergasungsgas erwarten. Es muss in jedem Fall ueberprueft werden, ob die vorhandene Rauchgasreinigung ausreicht, wenn bei der Mitverbrennung/-vergasung die Emissionsgrenzwerte der 17. BImSchV zur Anwendung kommen. Als Bewertungs- und Optimierungsmethode fuer derartige Hochtemperaturprozesse setzt sich die thermodynamische Modellierung zunehmend durch. (orig./SR)

  13. 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

  14. 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.

  15. Nonequilibrium thermodynamics and information theory: basic concepts and relaxing dynamics

    International Nuclear Information System (INIS)

    Altaner, Bernhard

    2017-01-01

    Thermodynamics is based on the notions of energy and entropy. While energy is the elementary quantity governing physical dynamics, entropy is the fundamental concept in information theory. In this work, starting from first principles, we give a detailed didactic account on the relations between energy and entropy and thus physics and information theory. We show that thermodynamic process inequalities, like the second law, are equivalent to the requirement that an effective description for physical dynamics is strongly relaxing. From the perspective of information theory, strongly relaxing dynamics govern the irreversible convergence of a statistical ensemble towards the maximally non-commital probability distribution that is compatible with thermodynamic equilibrium parameters. In particular, Markov processes that converge to a thermodynamic equilibrium state are strongly relaxing. Our framework generalizes previous results to arbitrary open and driven systems, yielding novel thermodynamic bounds for idealized and real processes. (paper)

  16. Thermodynamics of Bioreactions.

    Science.gov (United States)

    Held, Christoph; Sadowski, Gabriele

    2016-06-07

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

  17. Thermodynamically efficient solar concentrators

    Science.gov (United States)

    Winston, Roland

    2012-10-01

    Non-imaging Optics is the theory of thermodynamically efficient optics and as such depends more on thermodynamics than on optics. Hence in this paper a condition for the "best" design is proposed based on purely thermodynamic arguments, which we believe has profound consequences for design of thermal and even photovoltaic systems. This new way of looking at the problem of efficient concentration depends on probabilities, the ingredients of entropy and information theory while "optics" in the conventional sense recedes into the background.

  18. Black Holes and Thermodynamics

    OpenAIRE

    Wald, Robert M.

    1997-01-01

    We review the remarkable relationship between the laws of black hole mechanics and the ordinary laws of thermodynamics. It is emphasized that - in analogy with the laws of thermodynamics - the validity the laws of black hole mechanics does not appear to depend upon the details of the underlying dynamical theory (i.e., upon the particular field equations of general relativity). It also is emphasized that a number of unresolved issues arise in ``ordinary thermodynamics'' in the context of gener...

  19. Methods of thermodynamics

    CERN Document Server

    Reiss, Howard

    1997-01-01

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

  20. Thermodynamics of nuclear materials

    International Nuclear Information System (INIS)

    Rand, M.H.

    1975-01-01

    A report is presented of the Fourth International Symposium on Thermodynamics of Nuclear Materials held in Vienna, 21-25 October 1974. The technological theme of the Symposium was the application of thermodynamics to the understanding of the chemistry of irradiated nuclear fuels and to safety assessments for hypothetical accident conditions in reactors. The first four sessions were devoted to these topics and they were followed by four more sessions on the more basic thermodynamics, phase diagrams and the thermodynamic properties of a wide range of nuclear materials. Sixty-seven papers were presented

  1. Chemo-thermal Treatment of Tribulus tresstris to Enhance Its Sequestering Potential for Adsorption of Some Heavy Metals from Aqueous Media: Kinetic and Thermodynamic Study

    International Nuclear Information System (INIS)

    Shaheen, M.A.; Bibi, N.; Mehmood, T.; Karim, A.; Iqbal, M.

    2016-01-01

    The plant based renewable biosorbents have extensively been investigated for removing water pollutants. The present study describes the sequestering of metal ions by exploiting a low cost biomaterial derived from Tribulus tresstris as sorbent. The batch equilibrium studies have been carried out both with raw and chemically/thermally treated biomaterial as a function of pH, contact time, shaking speed and shaking time to decide the effectiveness of biosorbent. The sorbent was activated chemically by utilizing 0.1M HCl and 0.1M K/sub 2/CO/sub 3/. A close muffle furnace was used for thermal treatment of the sorbent. The adsorption capacity was enhanced to 25 percent by thermal treatment and 54 percent by chemical treatment because of increase in pore volume and surface area. The greatest sorption was found for particle size of 200 micro m with a 0.5 g dosage at pH 6 for 20 min at shaking speed 100 rpm. The FT-IR and SEM study was performed to discover the adsorption capacity of various functional groups and their binding mechanism. The adsorption data demonstrates that Langmuir, Freundlich and Dubinin-Radushkevich isotherm models were very much fitted to describe the adsorption behavior. (author)

  2. Kinetics, morphology and thermodynamics of the solid-liquid transition of non-metals. Progress report, March 1, 1979-February 28, 1980

    International Nuclear Information System (INIS)

    Sekerka, R.F.

    1979-08-01

    Some previous work on Internal Centrifugal Zone Growth was documented. New calculations have been made to show that for large rf skin depths, the temperature of the sample depends in a systematic way on only three dimensionless parameters; these characterize the rf power level, the surface heat transfer coefficient, and the ambient temperature. Critical values are given for the ambient temperature below which curves of sample temperature versus RF power level are S-shaped. Based on this improvement in understanding, our previous numerical results, valid for arbitrary skin depths, are being prepared for publication. Work continues toward the measurement of the solid-liquid surface tensions of non-metallic materials via the grain-boundary groove technique. Degassed samples of GeO 2 have been obtained, but the necessary temperature caused damage to the quartz tube in our present apparatus, necessitating a new design. While the new apparatus is under construction, sodium sulfate will be used as a prototype material to enable work on the optical system. Use of an astronomical telescope in conjunction with the optical viewpoint leads to poor image quality so we are considering the substitution of a microscope with a large working distance. Previous difficulties with numerical calculation of the temperature profiles in the system have been alleviated by using finer grid sizes for the finite difference scheme. Further effort has been expended to form the basis of new work on the application of Onsager's theory of reciprocity to transport phenomena in solids

  3. Adsorption and preconcentration of divalent metal ions in fossil fuels and biofuels: gasoline, diesel, biodiesel, diesel-like and ethanol by using chitosan microspheres and thermodynamic approach.

    Science.gov (United States)

    Prado, Alexandre G S; Pescara, Igor C; Evangelista, Sheila M; Holanda, Matheus S; Andrade, Romulo D; Suarez, Paulo A Z; Zara, Luiz F

    2011-05-15

    Biodiesel and diesel-like have been obtained from soybean oil by transesterification and thermal cracking process, respectively. These biofuels were characterized as according to ANP standards by using specific ASTM methods. Ethanol, gasoline, and diesel were purchased from a gas station. Deacetylation degree of chitosan was determined by three distinct methods (conductimetry, FTIR and NMR), and the average degree was 78.95%. The chitosan microspheres were prepared from chitosan by split-coating and these spheres were crosslinked using glutaraldehyde. The surface area of microspheres was determined by BET method, and the surface area of crosslinked microspheres was 9.2m(2)g(-1). The adsorption isotherms of cooper, nickel and zinc on microspheres of chitosan were determined in petroleum derivatives (gasoline and diesel oil), as well as in biofuels (alcohol, biodiesel and diesel-like). The adsorption order in all fuels was: Cu>Ni>Zn. The elution tests presented the following preconcentration degrees: >4.5 to ethanol, >4.4 to gasoline, >4.0 to diesel, >3.8 to biodiesel and >3.6 to diesel-like. The application of chitosan microspheres in the metal ions preconcentration showed the potential of this biopolymer to enrich fuel sample in order to be analyzed by flame atomic absorption spectrometry. Copyright © 2011 Elsevier B.V. All rights reserved.

  4. Ablation by ultrashort laser pulses: Atomistic and thermodynamic analysis of the processes at the ablation threshold

    International Nuclear Information System (INIS)

    Upadhyay, Arun K.; Inogamov, Nail A.; Rethfeld, Baerbel; Urbassek, Herbert M.

    2008-01-01

    Ultrafast laser irradiation of solids may ablate material off the surface. We study this process for thin films using molecular-dynamics simulation and thermodynamic analysis. Both metals and Lennard-Jones (LJ) materials are studied. We find that despite the large difference in thermodynamical properties between these two classes of materials--e.g., for aluminum versus LJ the ratio T c /T tr of critical to triple-point temperature differs by more than a factor of 4--the values of the ablation threshold energy E abl normalized to the cohesion energy, ε abl =E abl /E coh , are surprisingly universal: all are near 0.3 with ±30% scattering. The difference in the ratio T c /T tr means that for metals the melting threshold ε m is low, ε m abl , while for LJ it is high, ε m >ε abl . This thermodynamical consideration gives a simple explanation for the difference between metals and LJ. It explains why despite the universality in ε abl , metals thermomechanically ablate always from the liquid state. This is opposite to LJ materials, which (near threshold) ablate from the solid state. Furthermore, we find that immediately below the ablation threshold, the formation of large voids (cavitation) in the irradiated material leads to a strong temporary expansion on a very slow time scale. This feature is easily distinguished from the acoustic oscillations governing the material response at smaller intensities, on the one hand, and the ablation occurring at larger intensities, on the other hand. This finding allows us to explain the puzzle of huge surface excursions found in experiments at near-threshold laser irradiation

  5. 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.

  6. Thermodynamics and heat power

    CERN Document Server

    Granet, Irving

    2014-01-01

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

  7. The thermodynamic solar energy

    International Nuclear Information System (INIS)

    Rivoire, B.

    2002-04-01

    The thermodynamic solar energy is the technic in the whole aiming to transform the solar radiation energy in high temperature heat and then in mechanical energy by a thermodynamic cycle. These technic are most often at an experimental scale. This paper describes and analyzes the research programs developed in the advanced countries, since 1980. (A.L.B.)

  8. Quasiparticles and thermodynamical consistency

    International Nuclear Information System (INIS)

    Shanenko, A.A.; Biro, T.S.; Toneev, V.D.

    2003-01-01

    A brief and simple introduction into the problem of the thermodynamical consistency is given. The thermodynamical consistency relations, which should be taken into account under constructing a quasiparticle model, are found in a general manner from the finite-temperature extension of the Hellmann-Feynman theorem. Restrictions following from these relations are illustrated by simple physical examples. (author)

  9. 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

  10. Applied chemical engineering thermodynamics

    CERN Document Server

    Tassios, Dimitrios P

    1993-01-01

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

  11. Thermodynamics an engineering approach

    CERN Document Server

    Cengel, Yunus A

    2014-01-01

    Thermodynamics, An Engineering Approach, eighth edition, covers the basic principles of thermodynamics while presenting a wealth of real-world engineering examples so students get a feel for how thermodynamics is applied in engineering practice. This text helps students develop an intuitive understanding by emphasizing the physics and physical arguments. Cengel and Boles explore the various facets of thermodynamics through careful explanations of concepts and use of numerous practical examples and figures, having students develop necessary skills to bridge the gap between knowledge and the confidence to properly apply their knowledge. McGraw-Hill is proud to offer Connect with the eighth edition of Cengel/Boles, Thermodynamics, An Engineering Approach. This innovative and powerful new system helps your students learn more efficiently and gives you the ability to assign homework problems simply and easily. Problems are graded automatically, and the results are recorded immediately. Track individual stude...

  12. In vitro thermodynamic dissection of human copper transfer from chaperone to target protein.

    Science.gov (United States)

    Niemiec, Moritz S; Weise, Christoph F; Wittung-Stafshede, Pernilla

    2012-01-01

    Transient protein-protein and protein-ligand interactions are fundamental components of biological activity. To understand biological activity, not only the structures of the involved proteins are important but also the energetics of the individual steps of a reaction. Here we use in vitro biophysical methods to deduce thermodynamic parameters of copper (Cu) transfer from the human copper chaperone Atox1 to the fourth metal-binding domain of the Wilson disease protein (WD4). Atox1 and WD4 have the same fold (ferredoxin-like fold) and Cu-binding site (two surface exposed cysteine residues) and thus it is not clear what drives metal transfer from one protein to the other. Cu transfer is a two-step reaction involving a metal-dependent ternary complex in which the metal is coordinated by cysteines from both proteins (i.e., Atox1-Cu-WD4). We employ size exclusion chromatography to estimate individual equilibrium constants for the two steps. This information together with calorimetric titration data are used to reveal enthalpic and entropic contributions of each step in the transfer process. Upon combining the equilibrium constants for both steps, a metal exchange factor (from Atox1 to WD4) of 10 is calculated, governed by a negative net enthalpy change of ∼10 kJ/mol. Thus, small variations in interaction energies, not always obvious upon comparing protein structures alone, may fuel vectorial metal transfer.

  13. Thermodynamic estimation: Ionic materials

    International Nuclear Information System (INIS)

    Glasser, Leslie

    2013-01-01

    Thermodynamics establishes equilibrium relations among thermodynamic parameters (“properties”) and delineates the effects of variation of the thermodynamic functions (typically temperature and pressure) on those parameters. However, classical thermodynamics does not provide values for the necessary thermodynamic properties, which must be established by extra-thermodynamic means such as experiment, theoretical calculation, or empirical estimation. While many values may be found in the numerous collected tables in the literature, these are necessarily incomplete because either the experimental measurements have not been made or the materials may be hypothetical. The current paper presents a number of simple and relible estimation methods for thermodynamic properties, principally for ionic materials. The results may also be used as a check for obvious errors in published values. The estimation methods described are typically based on addition of properties of individual ions, or sums of properties of neutral ion groups (such as “double” salts, in the Simple Salt Approximation), or based upon correlations such as with formula unit volumes (Volume-Based Thermodynamics). - Graphical abstract: Thermodynamic properties of ionic materials may be readily estimated by summation of the properties of individual ions, by summation of the properties of ‘double salts’, and by correlation with formula volume. Such estimates may fill gaps in the literature, and may also be used as checks of published values. This simplicity arises from exploitation of the fact that repulsive energy terms are of short range and very similar across materials, while coulombic interactions provide a very large component of the attractive energy in ionic systems. Display Omitted - Highlights: • Estimation methods for thermodynamic properties of ionic materials are introduced. • Methods are based on summation of single ions, multiple salts, and correlations. • Heat capacity, entropy

  14. Interactive governance

    DEFF Research Database (Denmark)

    Sørensen, Eva; Torfing, Jacob; Peters, B. Guy

    Governance has become one of the most commonly used concepts in contemporary political science. It is, however, often used to mean a variety of different things. This book helps to clarify this conceptual muddle by concentrating on one variety of governance-interactive governance. The authors argue...... that although the state may remain important for many aspects of governing, interactions between state and society represent an important, and perhaps increasingly important, dimension of governance. These interactions may be with social actors such as networks, with market actors or with other governments......, but all these forms represent means of governing involving mixtures of state action with the actions of other entities.This book explores thoroughly this meaning of governance, and links it to broader questions of governance. In the process of explicating this dimension of governance the authors also...

  15. Thermodynamics and economics

    International Nuclear Information System (INIS)

    Mansson, B.A.

    1990-01-01

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

  16. 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

  17. Thermodynamics I essentials

    CERN Document Server

    REA, The Editors of

    2012-01-01

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

  18. 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

  19. Thermodynamics of quantum strings

    CERN Document Server

    Morgan, M J

    1994-01-01

    A statistical mechanical analysis of an ideal gas of non-relativistic quantum strings is presented, in which the thermodynamic properties of the string gas are calculated from a canonical partition function. This toy model enables students to gain insight into the thermodynamics of a simple 'quantum field' theory, and provides a useful pedagogical introduction to the more complicated relativistic string theories. A review is also given of the thermodynamics of the open bosonic string gas and the type I (open) superstring gas. (author)

  20. Modern engineering thermodynamics

    CERN Document Server

    Balmer, Robert T

    2010-01-01

    Designed for use in a standard two-semester engineering thermodynamics course sequence. The first half of the text contains material suitable for a basic Thermodynamics course taken by engineers from all majors. The second half of the text is suitable for an Applied Thermodynamics course in mechanical engineering programs. The text has numerous features that are unique among engineering textbooks, including historical vignettes, critical thinking boxes, and case studies. All are designed to bring real engineering applications into a subject that can be somewhat abstract and mathematica

  1. The second laws of quantum thermodynamics.

    Science.gov (United States)

    Brandão, Fernando; Horodecki, Michał; Ng, Nelly; Oppenheim, Jonathan; Wehner, Stephanie

    2015-03-17

    The second law of thermodynamics places constraints on state transformations. It applies to systems composed of many particles, however, we are seeing that one can formulate laws of thermodynamics when only a small number of particles are interacting with a heat bath. Is there a second law of thermodynamics in this regime? Here, we find that for processes which are approximately cyclic, the second law for microscopic systems takes on a different form compared to the macroscopic scale, imposing not just one constraint on state transformations, but an entire family of constraints. We find a family of free energies which generalize the traditional one, and show that they can never increase. The ordinary second law relates to one of these, with the remainder imposing additional constraints on thermodynamic transitions. We find three regimes which determine which family of second laws govern state transitions, depending on how cyclic the process is. In one regime one can cause an apparent violation of the usual second law, through a process of embezzling work from a large system which remains arbitrarily close to its original state. These second laws are relevant for small systems, and also apply to individual macroscopic systems interacting via long-range interactions. By making precise the definition of thermal operations, the laws of thermodynamics are unified in this framework, with the first law defining the class of operations, the zeroth law emerging as an equivalence relation between thermal states, and the remaining laws being monotonicity of our generalized free energies.

  2. Thermodynamics of quasi-topological cosmology

    International Nuclear Information System (INIS)

    Dehghani, M.H.; Sheykhi, A.; Dehghani, R.

    2013-01-01

    In this Letter, we study thermodynamical properties of the apparent horizon in a universe governed by quasi-topological gravity. Our aim is twofold. First, by using the variational method we derive the general form of Friedmann equation in quasi-topological gravity. Then, by applying the first law of thermodynamics on the apparent horizon, after using the entropy expression associated with the black hole horizon in quasi-topological gravity, and replacing the horizon radius, r + , with the apparent horizon radius, r -tilde A , we derive the corresponding Friedmann equation in quasi-topological gravity. We find that these two different approaches yield the same result which shows the profound connection between the first law of thermodynamics and the gravitational field equations of quasi-topological gravity. We also study the validity of the generalized second law of thermodynamics in quasi-topological cosmology. We find that, with the assumption of the local equilibrium hypothesis, the generalized second law of thermodynamics is fulfilled for the universe enveloped by the apparent horizon for the late time cosmology

  3. Interactive Governance

    DEFF Research Database (Denmark)

    Bang, Henrik

    2016-01-01

    Governance analysis has exploded in recent years, and it has become nearly impossible to tell what difference the concept and practice of governance makes from those of government and state. In addition governance analysis has been placed more and more in the shadow of the new institutionalisms and...... and growth. However, interactive governance is not a property or effect of institutions; nor does it apply solely to those individuals who seek success above everything else. It is connective more than individualistic or collectivistic in nature; and it manifests a governability capacity which...

  4. Theoretical physics 5 thermodynamics

    CERN Document Server

    Nolting, Wolfgang

    2017-01-01

    This concise textbook offers a clear and comprehensive introduction to thermodynamics, one of the core components of undergraduate physics courses. It follows on naturally from the previous volumes in this series, defining macroscopic variables, such as internal energy, entropy and pressure,together with thermodynamic principles. The first part of the book introduces the laws of thermodynamics and thermodynamic potentials. More complex themes are covered in the second part of the book, which describes phases and phase transitions in depth. Ideally suited to undergraduate students with some grounding in classical mechanics, the book is enhanced throughout with learning features such as boxed inserts and chapter summaries, with key mathematical derivations highlighted to aid understanding. The text is supported by numerous worked examples and end of chapter problem sets. About the Theoretical Physics series Translated from the renowned and highly successful German editions, the eight volumes of this series cove...

  5. 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.

  6. Elements of statistical thermodynamics

    CERN Document Server

    Nash, Leonard K

    2006-01-01

    Encompassing essentially all aspects of statistical mechanics that appear in undergraduate texts, this concise, elementary treatment shows how an atomic-molecular perspective yields new insights into macroscopic thermodynamics. 1974 edition.

  7. Electrochemical thermodynamic measurement system

    Science.gov (United States)

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

    2009-09-29

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

  8. Workshop on Teaching Thermodynamics

    CERN Document Server

    1985-01-01

    It seemed appropriate to arrange a meeting of teachers of thermodynamics in the United Kingdom, a meeting held in the pleasant surroundings of Emmanuel College, Cambridge, in Sept~mber, 1984. This volume records the ideas put forward by authors, the discussion generated and an account of the action that discussion has initiated. Emphasis was placed on the Teaching of Thermodynamics to degree-level students in their first and second years. The meeting, a workshop for practitioners in which all were expected to take part, was remarkably well supported. This was notable in the representation of essentially every UK university and polytechnic engaged in teaching engineering thermodynamics and has led to a stimulating spread of ideas. By intention, the emphasis for attendance was put on teachers of engineering concerned with thermodynamics, both mechanical and chemical engineering disciplines. Attendance from others was encouraged but limited as follows: non-engineering acad­ emics, 10%, industrialists, 10%. The ...

  9. Black-hole thermodynamics

    International Nuclear Information System (INIS)

    Bekenstein, J.D.

    1980-01-01

    Including black holes in the scheme of thermodynamics has disclosed a deep-seated connection between gravitation, heat and the quantum that may lead us to a synthesis of the corresponding branches of physics

  10. Polyelectrolytes thermodynamics and rheology

    CERN Document Server

    P M, Visakh; Picó, Guillermo Alfredo

    2014-01-01

    This book discusses current development of theoretical models and experimental findings on the thermodynamics of polyelectrolytes. Particular emphasis is placed on the rheological description of polyelectrolyte solutions and hydrogels.

  11. A New Perspective on Thermodynamics

    CERN Document Server

    Lavenda, Bernard H

    2010-01-01

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

  12. Thermodynamics of dinonylnaphthalene sulfonic acid (HD)

    International Nuclear Information System (INIS)

    Raieh, M.A.; Aly, H.F.

    1980-01-01

    The effect of temperature on the extraction of the trivalent actinides Am 3+ , Cm 3+ and Cf 3+ with the liquid cation exchanger dinonylnaphtalenesulphonic acid (HD) in toluene is studied. The different thermodynamic functions of this system are determined from the experimental results. It is found that the free energy variation for the extraction of these metal ions by HD is mainly determined by the entropic terms arising from the hydration-dehydration process of the exchanged ions. (author)

  13. Electronic Government

    DEFF Research Database (Denmark)

    Wimmer, Maria A.; Traunmüller, Roland; Grönlund, Åke

    This book constitutes the refereed proceedings of the 4th International Conference on Electronic Government, EGOV 2005, held in Copenhagen, Denmark, in August 2005. The 30 revised papers presented were carefully reviewed and selected from numerous submissions, and assess the state-of-the-art in e-government/e-governance...

  14. Leadership, Governance

    Science.gov (United States)

    : Environmental Documents, Reports LANL Home Calendar Search Contacts About » Leadership, Governance Leadership national security and energy challenges. Leadership, Governance Ethics, Accountability Los Alamos National . Director's Office terry wallace in leadership, governance Director Terry C. Wallace, Jr. Terry C. Wallace, Jr

  15. Stakeholder Governance

    DEFF Research Database (Denmark)

    Flak, Leif Skiftenes; Rose, Jeremy

    2005-01-01

    to e-Government. Originally a management theory, stakeholder theory advocates addressing the concerns of all stakeholders in a firm, as opposed to concentration on the interests of senior managers and stockholders. Apart from the original profit focus, there is no serious conceptual mismatch between...... of governance. Finally, the paper makes recommendations for future work in adapting ST to the e-government context....

  16. Thermodynamic stability of binary systems involving metal ions and the 4-methoxy benzylidenepyruvate in aqueous solution; Estabilidade termodinamica de sistemas binarios envolvendo ions metalicos e o 4-metoxibenzalpiruvato, em solucao aquosa

    Energy Technology Data Exchange (ETDEWEB)

    Redigolo, H.

    1989-12-31

    A review on studies previously carried out in this laboratory involving metal ions and benzylidene-pyruvate, in aqueous solutions, is presented; emphasis is mainly placed on complexes comprising 4-Dimethyl-amino-benzylidene-pyruvate (DMBP, p{sup K}{sub a} 3.79) and 2-Chloro-4-Dimethyl-amino-benzylidene-pyruvate (2 Cl-DMBP, p{sup k}{sub a} = 3.08). In an endeavour to extend the previous work, the dissociation constant of 4-methoxy-benzylidene-pyruvic acid (H-4-Me O-BP) was determined spectrophotometrically at 25.0 +- 0.1{sup 0} C and ionic strength 0.500 M, held with sodium perchlorate (p{sup k}{sub a} = 1.473). The complex formation equilibria in M-4-Me O-BP systems, where M = Cu(II), La(III), Pr(III), Sm(III), Lu(III), Sc (III), In(III), Ga(III) or Th(IV) were investigated, also spectrophotometrically, in the above mentioned experimental conditions. In addition, the system involving Sm(III) was reinvestigated at ionic strengths 0.100 and 2.00 M, the remaining experimental conditions being maintained. The study is mostly concerned with the determination of formation constants of 1:1 complex species ({beta}{sub 1}) and spectrophotometric parameters associated with these species. The investigation of possible higher binary complexes (ML{sub n}, n > 1) was prevented by solubility limitations. For all considered metal ions, log {beta}{sub 1} (DMBP) > log {beta}{sub 1} (4-Me O-BP) indicating that the stability is governed, at least in part, by ligand basicity. (author). 121 refs, 36 figs, 20 tabs.

  17. Gravity as a thermodynamic phenomenon

    OpenAIRE

    Moustos, Dimitris

    2017-01-01

    The analogy between the laws of black hole mechanics and the laws of thermodynamics led Bekenstein and Hawking to argue that black holes should be considered as real thermodynamic systems that are characterised by entropy and temperature. Black hole thermodynamics indicates a deeper connection between thermodynamics and gravity. We review and examine in detail the arguments that suggest an interpretation of gravity itself as a thermodynamic theory.

  18. Program governance

    CERN Document Server

    Khan, Muhammad Ehsan

    2014-01-01

    FOUNDATION OF GOVERNANCEGovernanceDefining GovernanceGovernance at Multiple LevelsSummaryReferencesTransaction Cost EconomicsTransactions-Core Elements and Attributes     Behavioral Assumptions     Governance Structure AttributesHazards of Concern     Incomplete Contracting     Bilateral Dependency and Fundamental Transformation     Adaptation or MaladaptationLinking Governance, Governance Structures, and ContractsThe Impact of Asset Specificity and Behavioral Assumptions on ContractsAp

  19. Plural Governance

    DEFF Research Database (Denmark)

    Mols, Niels Peter; Menard, Claude

    2014-01-01

    Plural governance is a form of governance where a firm both makes and buys similar goods or services. Despite a widespread use of plural governance there are no transaction cost models of how plural governance affects performance. This paper reviews the literature about plural forms and proposes...... a model relating transaction cost and resource-based variables to the cost of the plural form. The model is then used to analyze when the plural form is efficient compared to alternative governance structures. We also use the model to discuss the strength of three plural form synergies....

  20. High-level waste disposal, ethics and thermodynamics

    Science.gov (United States)

    Schwartz, Michael O.

    2008-06-01

    Moral philosophy applied to nuclear waste disposal can be linked to paradigmatic science. Simple thermodynamic principles tell us something about rightness or wrongness of our action. Ethical judgement can be orientated towards the chemical compatibility between waste container and geological repository. A container-repository system as close as possible to thermodynamic equilibrium is ethically acceptable. It aims at unlimited stability, similar to the stability of natural metal deposits within the Earth’s crust. The practicability of the guideline can be demonstrated.

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

    International Nuclear Information System (INIS)

    Soldatova, Je.D.; Snegyir'ov, M.G.

    2001-01-01

    The thermodynamical method for studing a critical state is illustrated by the example of critical behavior of metallic cerium in the frameworks of the improved Rainford-Edwards model. Thermodynamical stability of the model is investigated, and behavior of the whole complex of thermodynamical characteristics of the system is analyzed. It is concluded that the model has the first type of critical behaviour

  2. The thermodynamic basis of entransy and entransy dissipation

    International Nuclear Information System (INIS)

    Xu, Mingtian

    2011-01-01

    In the present work, the entransy and entransy dissipation are defined from the thermodynamic point of view. It is shown that the entransy is a state variable and can be employed to describe the second law of thermodynamics. For heat conduction, a principle of minimum entransy dissipation is established based on the second law of thermodynamics in terms of entransy dissipation, which leads to the governing equation of the steady Fourier heat conduction without heat source. Furthermore, we derive the expressions of the entransy dissipation in duct flows and heat exchangers from the second law of thermodynamics, which paves the way for applications of the entransy dissipation theory in heat exchanger design. -- Highlights: → The concepts of entransy and entransy dissipation are defined from the thermodynamic point of view. → We find that the entransy is a new thermodynamic property. → The second law of thermodynamics can be described by the entransy and entransy dissipation. → The expressions of entransy dissipation in duct flows and heat exchangers are derived from the second law of thermodynamics.

  3. Thermodynamics of nuclear materials

    International Nuclear Information System (INIS)

    1962-01-01

    The first session of the symposium discussed in general the thermodynamic properties of actinides, including thorium, uranium and Plutonium which provide reactor fuel. The second session was devoted to applications of thermodynamic theory to the study of nuclear materials, while the experimental techniques for the determination of thermodynamic data were examined at the next session. The thermodynamic properties of alloys were considered at a separate session, and another session was concerned with solids other than alloys. Vaporization processes, which are of special interest in the development of high-temperature reactors, were discussed at a separate session. The discussions on the methods of developing the data and ascertaining their accuracy were especially useful in highlighting the importance of determining whether any given data are reliable before they can be put to practical application. Many alloys and refractory materials (i. e. materials which evaporate only at very high temperatures) are of great importance in nuclear technology, and some of these substances are extremely complex in their chemical composition. For example, until recently the phase composition of the oxides of thorium, uranium and plutonium had been only very imperfectly understood, and the same was true of the carbides of these elements. Recent developments in experimental techniques have made it possible to investigate the phase composition of these complex materials as well as the chemical species of these materials in the gaseous phase. Recent developments in measuring techniques, such as fluorine bomb calorimetry and Knudsen effusion technique, have greatly increased the accuracy of thermodynamic data

  4. Theoretical microcontact spectra of metal electron-phonon coupling

    International Nuclear Information System (INIS)

    Kulagina, T.N.; Zhernov, A.P.

    1987-01-01

    Theoretical and experimental microcontact spectra of simple and certain transition metals are discussed. The Eliashberg thermodynamic functions for the metals are considered, as well as correlations between spectra peculiarities and parameters of metals and microbridge models

  5. Thermodynamics of complexity

    DEFF Research Database (Denmark)

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

    1998-01-01

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

  6. 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...

  7. Thermodynamic potential in quantum electrodynamics

    International Nuclear Information System (INIS)

    Morley, P.D.

    1978-01-01

    The thermodynamic potential, Ω, in quantum electrodynamics (QED) is derived using the path-integral formalism. Renormalization of Ω is shown by proving the following theorem: Ω/sub B/(e/sub B/,m/sub B/,T,μ) - Ω/sub B/(e/sub B/,m/sub B/,T = 0,μ = 0) = Ω/sub R/(e/sub R/,m/sub R/,T,μ,S), where B and R refer to bare and renormalized quantities, respectively, and S is the Euclidean subtraction momentum squared. This theorem is proved explicitly to e/sub R/ 4 order and could be analogously extended to any higher order. Renormalization-group equations are derived for Ω/sub R/, and it is shown that perturbation theory in a medium is governed by effective coupling constants which are functions of the density. The behavior of the theory at high densities is governed by the Euclidean ultraviolet behavior of the theory in the vacuum

  8. Concise chemical thermodynamics

    CERN Document Server

    Peters, APH

    2010-01-01

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

  9. Thermodynamics II essentials

    CERN Document Server

    REA, The Editors of

    2013-01-01

    REA's Essentials provide quick and easy access to critical information in a variety of different fields, ranging from the most basic to the most advanced. As its name implies, these concise, comprehensive study guides summarize the essentials of the field covered. Essentials are helpful when preparing for exams, doing homework and will remain a lasting reference source for students, teachers, and professionals. Thermodynamics II includes review of thermodynamic relations, power and refrigeration cycles, mixtures and solutions, chemical reactions, chemical equilibrium, and flow through nozzl

  10. Thermodynamics for engineers

    CERN Document Server

    Wong, Kaufui Vincent

    2011-01-01

    Praise for the First Edition from Students: "It is a great thermodynamics text…I loved it!-Mathew Walters "The book is comprehensive and easy to understand. I love the real world examples and problems, they make you feel like you are learning something very practical."-Craig Paxton"I would recommend the book to friends."-Faure J. Malo-Molina"The clear diction, as well as informative illustrations and diagrams, help convey the material clearly to the reader."-Paul C. Start"An inspiring and effective tool for any aspiring scientist or engineer. Definitely the best book on Classical Thermodynamics out."-Seth Marini.

  11. Mechanics, Waves and Thermodynamics

    Science.gov (United States)

    Ranjan Jain, Sudhir

    2016-05-01

    Figures; Preface; Acknowledgement; 1. Energy, mass, momentum; 2. Kinematics, Newton's laws of motion; 3. Circular motion; 4. The principle of least action; 5. Work and energy; 6. Mechanics of a system of particles; 7. Friction; 8. Impulse and collisions; 9. Central forces; 10. Dimensional analysis; 11. Oscillations; 12. Waves; 13. Sound of music; 14. Fluid mechanics; 15. Water waves; 16. The kinetic theory of gases; 17. Concepts and laws of thermodynamics; 18. Some applications of thermodynamics; 19. Basic ideas of statistical mechanics; Bibliography; Index.

  12. Experimental thermodynamics experimental thermodynamics of non-reacting fluids

    CERN Document Server

    Neindre, B Le

    2013-01-01

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

  13. Black Hole Thermodynamics in an Undergraduate Thermodynamics Course.

    Science.gov (United States)

    Parker, Barry R.; McLeod, Robert J.

    1980-01-01

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

  14. Correct thermodynamic forces in Tsallis thermodynamics: connection with Hill nanothermodynamics

    International Nuclear Information System (INIS)

    Garcia-Morales, Vladimir; Cervera, Javier; Pellicer, Julio

    2005-01-01

    The equivalence between Tsallis thermodynamics and Hill's nanothermodynamics is established. The correct thermodynamic forces in Tsallis thermodynamics are pointed out. Through this connection we also find a general expression for the entropic index q which we illustrate with two physical examples, allowing in both cases to relate q to the underlying dynamics of the Hamiltonian systems

  15. Regulatory Governance

    DEFF Research Database (Denmark)

    Kjær, Poul F.; Vetterlein, Antje

    2018-01-01

    Regulatory governance frameworks have become essential building blocks of world society. From supply chains to the regimes surrounding international organizations, extensive governance frameworks have emerged which structure and channel a variety of social exchanges, including economic, political...... by the International Transitional Administrations (ITAs) in Kosovo and Iraq as well as global supply chains and their impact on the garment industry in Bangladesh....

  16. Experimentalist governance

    NARCIS (Netherlands)

    Sabel, C.F.; Zeitlin, J.; Levi-Faur, D.

    2012-01-01

    A secular rise in volatility and uncertainty is overwhelming the capacities of conventional hierarchical governance and ‘command-and-control’ regulation in many settings. One significant response is the emergence of a novel, ‘experimentalist’ form of governance that establishes deliberately

  17. Remaking Governance.

    Science.gov (United States)

    Carver, John

    2000-01-01

    The Policy Governance model's philosophical foundations lie in Rousseau's social contract, Greenleaf's servant-leadership, and modern management theory. Policy Governance stresses primacy of the owner-representative role; full-board authority; superintendents as chief executive officers; authoritative prescription of "ends," bounded…

  18. Fluctuating Thermodynamics for Biological Processes

    Science.gov (United States)

    Ham, Sihyun

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

  19. A Hamiltonian approach to Thermodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Baldiotti, M.C., E-mail: baldiotti@uel.br [Departamento de Física, Universidade Estadual de Londrina, 86051-990, Londrina-PR (Brazil); Fresneda, R., E-mail: rodrigo.fresneda@ufabc.edu.br [Universidade Federal do ABC, Av. dos Estados 5001, 09210-580, Santo André-SP (Brazil); Molina, C., E-mail: cmolina@usp.br [Escola de Artes, Ciências e Humanidades, Universidade de São Paulo, Av. Arlindo Bettio 1000, CEP 03828-000, São Paulo-SP (Brazil)

    2016-10-15

    In the present work we develop a strictly Hamiltonian approach to Thermodynamics. A thermodynamic description based on symplectic geometry is introduced, where all thermodynamic processes can be described within the framework of Analytic Mechanics. Our proposal is constructed on top of a usual symplectic manifold, where phase space is even dimensional and one has well-defined Poisson brackets. The main idea is the introduction of an extended phase space where thermodynamic equations of state are realized as constraints. We are then able to apply the canonical transformation toolkit to thermodynamic problems. Throughout this development, Dirac’s theory of constrained systems is extensively used. To illustrate the formalism, we consider paradigmatic examples, namely, the ideal, van der Waals and Clausius gases. - Highlights: • A strictly Hamiltonian approach to Thermodynamics is proposed. • Dirac’s theory of constrained systems is extensively used. • Thermodynamic equations of state are realized as constraints. • Thermodynamic potentials are related by canonical transformations.

  20. A Hamiltonian approach to Thermodynamics

    International Nuclear Information System (INIS)

    Baldiotti, M.C.; Fresneda, R.; Molina, C.

    2016-01-01

    In the present work we develop a strictly Hamiltonian approach to Thermodynamics. A thermodynamic description based on symplectic geometry is introduced, where all thermodynamic processes can be described within the framework of Analytic Mechanics. Our proposal is constructed on top of a usual symplectic manifold, where phase space is even dimensional and one has well-defined Poisson brackets. The main idea is the introduction of an extended phase space where thermodynamic equations of state are realized as constraints. We are then able to apply the canonical transformation toolkit to thermodynamic problems. Throughout this development, Dirac’s theory of constrained systems is extensively used. To illustrate the formalism, we consider paradigmatic examples, namely, the ideal, van der Waals and Clausius gases. - Highlights: • A strictly Hamiltonian approach to Thermodynamics is proposed. • Dirac’s theory of constrained systems is extensively used. • Thermodynamic equations of state are realized as constraints. • Thermodynamic potentials are related by canonical transformations.

  1. New perspectives in thermodynamics

    International Nuclear Information System (INIS)

    Serrin, J.

    1986-01-01

    The last decade has seen a unity of method and approach in the foundations of thermodynamics and continuum mechanics, in which rigorous laws of thermodynamics have been combined with invariance notions of mechanics to produce new and deep understanding. Real progress has been made in finding a set of appropriate concepts for classical thermodynamics, by which energy conservation and the Clausius inequality can be given well-defined meanings for arbitrary processes and which allow an approach to the entropy concept which is free of traditional ambiguities. There has been, moreover, a careful scrutiny of long established but nevertheless not sharply defined concepts such as the Maxwell equal-area rule, the famous Gibbs phase rule, and the equivalence of work and heat. The thirteen papers in this volume accordingly gather together for the first time the many ideas and concepts which have raised classical thermodynamics from a heuristic and intuitive science to the level of precision presently demanded of other branches of mathematical physics

  2. Thermodynamics and statistical mechanics

    CERN Document Server

    Landsberg, Peter T

    1990-01-01

    Exceptionally articulate treatment combines precise mathematical style with strong physical intuition. Wide range of applications includes negative temperatures, negative heat capacities, special and general relativistic effects, black hole thermodynamics, gravitational collapse, more. Over 100 problems with worked solutions. Advanced undergraduate, graduate level. Table of applications. Useful formulas and other data.

  3. Thermodynamic stabilization of colloids

    NARCIS (Netherlands)

    Stol, R.J.; Bruyn, P.L. de

    An analysis is given of the conditions necessary for obtaining a thermodynamically stable dispersion (TSD) of solid particles in a continuous aqueous solution phase. The role of the adsorption of potential-determining ions at the planar interface in lowering the interfacial free energy (γ) to

  4. Chemical thermodynamics. An introduction

    Energy Technology Data Exchange (ETDEWEB)

    Keszei, Ernoe [Budapest Univ. (Hungary). Dept. of Physical Chemistry

    2012-07-01

    Eminently suitable as a required textbook comprising complete material for or an undergraduate chemistry major course in chemical thermodynamics. Clearly explains details of formal derivations that students can easily follow and so master applied mathematical operations. Offers problems and solutions at the end of each chapter for self-test and self- or group study. This course-derived undergraduate textbook provides a concise explanation of the key concepts and calculations of chemical thermodynamics. Instead of the usual 'classical' introduction, this text adopts a straightforward postulatory approach that introduces thermodynamic potentials such as entropy and energy more directly and transparently. Structured around several features to assist students' understanding, Chemical Thermodynamics: - Develops applications and methods for the ready treatment of equilibria on a sound quantitative basis. - Requires minimal background in calculus to understand the text and presents formal derivations to the student in a detailed but understandable way. - Offers end-of-chapter problems (and answers) for self-testing and review and reinforcement, of use for self- or group study. This book is suitable as essential reading for courses in a bachelor and master chemistry program and is also valuable as a reference or textbook for students of physics, biochemistry and materials science.

  5. Thermodynamics applied. Where? Why?

    NARCIS (Netherlands)

    Hirs, Gerard

    2003-01-01

    In recent years, thermodynamics has been applied in a number of new fields leading to a greater societal impact. This paper gives a survey of these new fields and the reasons why these applications are important. In addition, it is shown that the number of fields could be even greater in the future

  6. Thermodynamics, applied. : Where? why?

    NARCIS (Netherlands)

    Hirs, Gerard

    1999-01-01

    In recent years thermodynamics has been applied in a number of new fields leading to a greater societal impact. The paper gives a survey of these new fields and the reasons why these applications are important. In addition it is shown that the number of fields could be even greater in the future and

  7. Nonequilibrium thermodynamics of nucleation

    NARCIS (Netherlands)

    Schweizer, M.; Sagis, L.M.C.

    2014-01-01

    We present a novel approach to nucleation processes based on the GENERIC framework (general equation for the nonequilibrium reversible-irreversible coupling). Solely based on the GENERIC structure of time-evolution equations and thermodynamic consistency arguments of exchange processes between a

  8. On Teaching Thermodynamics

    Science.gov (United States)

    Debbasch, F.

    2011-01-01

    The logical structure of classical thermodynamics is presented in a modern, geometrical manner. The first and second law receive clear, operatively oriented statements and the Gibbs free energy extremum principle is fully discussed. Applications relevant to chemistry, such as phase transitions, dilute solutions theory and, in particular, the law…

  9. Black hole thermodynamical entropy

    International Nuclear Information System (INIS)

    Tsallis, Constantino; Cirto, Leonardo J.L.

    2013-01-01

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

  10. Thermodynamics Far from the Thermodynamic Limit.

    Science.gov (United States)

    de Miguel, Rodrigo; Rubí, J Miguel

    2017-11-16

    Understanding how small systems exchange energy with a heat bath is important to describe how their unique properties can be affected by the environment. In this contribution, we apply Landsberg's theory of temperature-dependent energy levels to describe the progressive thermalization of small systems as their spectrum is perturbed by a heat bath. We propose a mechanism whereby the small system undergoes a discrete series of excitations and isentropic spectrum adjustments leading to a final state of thermal equilibrium. This produces standard thermodynamic results without invoking system size. The thermal relaxation of a single harmonic oscillator is analyzed as a model example of a system with a quantized spectrum than can be embedded in a thermal environment. A description of how the thermal environment affects the spectrum of a small system can be the first step in using environmental factors, such as temperature, as parameters in the design and operation of nanosystem properties.

  11. Thermodynamic analysis of dust sulphation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Yang Yongxiang; Jokilaakso, A.

    1997-12-31

    Sulphation reactions of metal oxides with SO{sub 2} and O. or SO{sub 3} play significant roles in sulphation roasting of sulphide and oxide minerals as well as in desulphurisation process of combustion gases. In metallurgical waste-heat boilers for sulphide smelting, the sulphation of the oxidic flue dust in the atmosphere containing sulphur oxides is an unavoidable process, and the sulphation reactions have to be guided in a controlled way in the proper parts of the gas handling equipment. In this report, some thermodynamic analyses were conducted for the oxide sulphation reactions in relation to sulphide smelting processes. The phase stability of Me-S-O systems especially for oxides - sulphates equilibrium was studied under different thermodynamic conditions of gas compositions and temperatures. The sulphate stability was analysed for an example of gas compositions in the copper flash smelter of Outokumpu Harjavalta Metals Oy, in relation to temperature. In the report, most of the information was from literature. Moreover, a number of thermodynamic computations were carried out with the HSC program, and the constructed phase stability diagrams were compared with those from the literature whenever possible. The maximum temperatures for stable sulphates under normal operating conditions of the waste-heat boilers in sulphide smelting processes were obtained. This report will serve as the basis for the kinetic studies of the sulphation reactions and the sulphation reaction modelling in pyrometallurgical processes. (orig.) SULA 2 Programme. 36 refs.

  12. 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.

  13. 1/ f noise from the laws of thermodynamics for finite-size fluctuations.

    Science.gov (United States)

    Chamberlin, Ralph V; Nasir, Derek M

    2014-07-01

    Computer simulations of the Ising model exhibit white noise if thermal fluctuations are governed by Boltzmann's factor alone; whereas we find that the same model exhibits 1/f noise if Boltzmann's factor is extended to include local alignment entropy to all orders. We show that this nonlinear correction maintains maximum entropy during equilibrium fluctuations. Indeed, as with the usual way to resolve Gibbs' paradox that avoids entropy reduction during reversible processes, the correction yields the statistics of indistinguishable particles. The correction also ensures conservation of energy if an instantaneous contribution from local entropy is included. Thus, a common mechanism for 1/f noise comes from assuming that finite-size fluctuations strictly obey the laws of thermodynamics, even in small parts of a large system. Empirical evidence for the model comes from its ability to match the measured temperature dependence of the spectral-density exponents in several metals and to show non-Gaussian fluctuations characteristic of nanoscale systems.

  14. 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

  15. Renewing governance.

    Science.gov (United States)

    Loos, Gregory P

    2003-01-01

    Globalization's profound influence on social and political institutions need not be negative. Critics of globalization have often referred to the "Impossible Trinity" because decision-making must 1. respect national sovereignty, 2. develop and implement firm regulation, and 3. allow capital markets to be as free as possible. To many, such goals are mutually exclusive because history conditions us to view policy-making and governance in traditional molds. Thus, transnational governance merely appears impossible because current forms of governance were not designed to provide it. The world needs new tools for governing, and its citizens must seize the opportunity to help develop them. The rise of a global society requires a greater level of generality and inclusion than is found in most policy bodies today. Politicians need to re-examine key assumptions about government. States must develop ways to discharge their regulatory responsibilities across borders and collaborate with neighboring jurisdictions, multilateral bodies, and business. Concepts such as multilateralism and tripartism show great promise. Governments must engage civil society in the spirit of shared responsibility and democratic decision-making. Such changes will result in a renewal of the state's purpose and better use of international resources and expertise in governance.

  16. Organizational governance

    DEFF Research Database (Denmark)

    Foss, Nicolai Juul; Klein, Peter G.

    This chapter reviews and discusses rational-choice approaches to organizational governance. These approaches are found primarily in organizational economics (virtually no rational-choice organizational sociology exists), particularly in transaction cost economics, principal-agent theory...

  17. Waste governance

    CSIR Research Space (South Africa)

    Oelofse, Suzanna HH

    2018-06-01

    Full Text Available of governance in Africa. The next section focuses on regulation, and the status of the regulatory frameworks in different African countries. Shortcomings in the regulatory framework are highlighted through examples in various countries. Specific policy...

  18. Heavy metals binding properties of esterified lemon

    Energy Technology Data Exchange (ETDEWEB)

    Arslanoglu, Hasan; Altundogan, Hamdi Soner [Department of Chemical Engineering, Firat University, 23279 Elazig (Turkey); Tumen, Fikret, E-mail: ftumen@firat.edu.tr [Department of Chemical Engineering, Firat University, 23279 Elazig (Turkey)

    2009-05-30

    Sorption of Cd{sup 2+}, Cr{sup 3+}, Cu{sup 2+}, Ni{sup 2+}, Pb{sup 2+} and Zn{sup 2+} onto a carboxyl groups-rich material prepared from lemon was investigated in batch systems. The results revealed that the sorption is highly pH dependent. Sorption kinetic data indicated that the equilibrium was achieved in the range of 30-240 min for different metal ions and sorption kinetics followed the pseudo-second-order model for all metals studied. Relative sorption rate of various metal cations was found to be in the general order of Ni{sup 2+} > Cd{sup 2+} > Cu{sup 2+} > Pb{sup 2+} > Zn{sup 2+} > Cr{sup 3+}. The binding characteristics of the sorbent for heavy metal ions were analyzed under various conditions and isotherm data was accurately fitted to the Langmuir equation. The metal binding capacity order calculated from Langmuir isotherm was Pb{sup 2+} > Cu{sup 2+} > Ni{sup 2+} > Cd{sup 2+} > Zn{sup 2+} > Cr{sup 3+}. The mean free energy of metal sorption process calculated from Dubinin-Radushkevich parameter and the Polanyi potential was found to be in the range of 8-11 kJ mol{sup -1} for the metals studied showing that the main mechanism governing the sorption process seems to be ion exchange. The basic thermodynamic parameters of metals ion sorption process were calculated by using the Langmuir constants obtained from equilibration study. The {Delta}G{sup o} and {Delta}H{sup o} values for metals ion sorption on the lemon sorbent showed the process to be spontaneous and exothermic in nature. Relatively low {Delta}H{sup o} values revealed that physical adsorption significantly contributed to the mechanism.

  19. Corporate Governance

    Directory of Open Access Journals (Sweden)

    Dragoș-Mihail Daghie

    2011-05-01

    Full Text Available The purpose of this study is to analyze and understand the recently introduced form of managementof a company limited by shares. The Law no. 441/2006, which fundamentally amended Company Law,created this form of controlling the company, the corporate governance, but the legislation does not explicitlydefine what it wants to achieve through this instrument. This topic is recent in research as the theme ofgerman-roman commercial law systems (in French corporate governance system was introduced in 1966 andin Romania in 2006 but in terms of Anglo-Saxon law, the topic has been addressed years since 1776 (AdamSmith: The Wealth of Nations The concept of corporate governance would like, as a result, to establish somerules that companies must comply in order to achieve effective governance, transparent and beneficial forboth shareholders and for the minority. Corporate governance is a key element with an aim at improvingefficiency and economic growth in full accordance with the increase of investors’ confidence. Corporategovernance assumes a series of relationship between the company management, leadership, shareholders andthe other people concerned. Also corporate governance provides for that structure by means of which thecompany’s targets are set out and the means to achieve them and also the manner how to monitor such.

  20. 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

  1. Modeling and experimental verification of the thermodynamic properties of hydrogen storage materials

    NARCIS (Netherlands)

    Ledovskikh, A.V.; Danilov, D.L.; Vliex, M.F.H.; Notten, P.H.L.

    2016-01-01

    A new mathematical model has been developed describing the thermodynamics of the hydrogen absorption and desorption process in Metal Hydrides via the gas phase. This model is based on first principles chemical and statistical thermodynamics and takes into account structural changes occurring inside

  2. 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.

  3. Fragile Thermodynamic Order

    International Nuclear Information System (INIS)

    Bernhoeft, N.; Lander, G.H.; Colineau, E.

    2003-01-01

    An asymmetric shift in the position of the magnetic Bragg peak with respect to the fiducial lattice has been observed by resonant X-ray scattering in a diverse series of antiferromagnetic compounds. This apparent violation of Bragg's law is interpreted in terms of a dynamically phased order parameter. We demonstrate the use of this effect as a novel probe of fragile or dynamic thermodynamic order in strongly correlated electronic systems. In particular, fresh light is shed on the paradoxical situation encountered in URu 2 Si 2 where the measured entropy gain on passing through T Neel is incompatible with the ground state moment estimated by neutron diffraction. The intrinsic space-time averaging of the probe used to characterise the thermodynamic macroscopic state may play a crucial and previously neglected role. In turn, this suggests the further use of resonant X-ray scattering in investigations of systems dominated by quantum fluctuations. (author)

  4. Mechanics and thermodynamics

    CERN Document Server

    Demtröder, Wolfgang

    2017-01-01

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

  5. Thermodynamical quantum information sharing

    International Nuclear Information System (INIS)

    Wiesniak, M.; Vedral, V.; Brukner, C.

    2005-01-01

    Full text: Thermodynamical properties fully originate from classical physics and can be easily measured for macroscopic systems. On the other hand, entanglement is a widely spoken feature of quantum physics, which allows to perform certain task with efficiency unavailable with any classical resource. Therefore an interesting question is whether we can witness entanglement in a state of a macroscopic sample. We show, that some macroscopic properties, in particular magnetic susceptibility, can serve as an entanglement witnesses. We also study a mutual relation between magnetic susceptibility and magnetisation. Such a complementarity exhibits quantum information sharing between these two thermodynamical quantities. Magnetization expresses properties of individual spins, while susceptibility might reveal non-classical correlations as a witness. Therefore, a rapid change of one of these two quantities may mean a phase transition also in terms of entanglement. The complementarity relation is demonstrated by an analytical solution of an exemplary model. (author)

  6. Nonequilibrium thermodynamic fluctuations and phase transition in black holes

    International Nuclear Information System (INIS)

    Su, R.; Cai, R.; Yu, P.K.N.

    1994-01-01

    Landau nonequilibrium fluctuation and phase transition theory is applied to the discussion of the phase transition of black holes. Some second moments of relevant thermodynamical quantities for Kerr-Newman black holes are estimated. A theorem governing the divergence of some second moments and the occurrence of the phase transition in black holes is given

  7. Thermodynamics of clan production

    International Nuclear Information System (INIS)

    Giovannini, Alberto; Lupia, Sergio; Ugoccioni, Roberto

    2002-01-01

    Scenarios for particle production in the GeV and TeV regions are reviewed. The expected increase with the c.m. energy of the average number of clans for the soft component and the decrease for the semihard one indicate possible classical and quantum behavior of gluons, respectively. Clan thermodynamics, discussed in the paper, appears as the natural framework to deal with such phenomena

  8. Work reservoirs in thermodynamics

    International Nuclear Information System (INIS)

    Anacleto, Joaquim

    2010-01-01

    We stress the usefulness of the work reservoir in the formalism of thermodynamics, in particular in the context of the first law. To elucidate its usefulness, the formalism is then applied to the Joule expansion and other peculiar and instructive experimental situations, clarifying the concepts of configuration and dissipative work. The ideas and discussions presented in this study are primarily intended for undergraduate students, but they might also be useful to graduate students, researchers and teachers.

  9. Work reservoirs in thermodynamics

    Science.gov (United States)

    Anacleto, Joaquim

    2010-05-01

    We stress the usefulness of the work reservoir in the formalism of thermodynamics, in particular in the context of the first law. To elucidate its usefulness, the formalism is then applied to the Joule expansion and other peculiar and instructive experimental situations, clarifying the concepts of configuration and dissipative work. The ideas and discussions presented in this study are primarily intended for undergraduate students, but they might also be useful to graduate students, researchers and teachers.

  10. Thermodynamics of chaos

    International Nuclear Information System (INIS)

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

    1996-07-01

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

  11. Advanced thermodynamic (exergetic) analysis

    International Nuclear Information System (INIS)

    Tsatsaronis, G; Morosuk, T

    2012-01-01

    Exergy analysis is a powerful tool for developing, evaluating and improving an energy conversion system. However, the lack of a formal procedure in using the results obtained by an exergy analysis is one of the reasons for exergy analysis not being very popular among energy practitioners. Such a formal procedure cannot be developed as long as the interactions among components of the overall system are not being taken properly into account. Splitting the exergy destruction into unavoidable and avoidable parts in a component provides a realistic measure of the potential for improving the thermodynamic efficiency of this component. Alternatively splitting the exergy destruction into endogenous and exogenous parts provides information on the interactions among system components. Distinctions between avoidable and unavoidable exergy destruction on one side and endogenous and exogenous exergy destruction on the other side allow the engineer to focus on the thermodynamic inefficiencies that can be avoided and to consider the interactions among system components. The avoidable endogenous and the avoidable exogenous exergy destruction provide the best guidance for improving the thermodynamic performance of energy conversion systems.

  12. INTERACTION OF LASER RADIATION WITH MATTER. LASER PLASMA: Spectroscopic investigation of thermodynamic parameters of a plasma plume formed by the action of cw CO2 laser radiation on a metal substrate

    Science.gov (United States)

    Vasil'chenko, Zh V.; Azharonok, V. V.; Filatova, I. I.; Shimanovich, V. D.; Golubev, V. S.; Zabelin, A. M.

    1996-09-01

    Emission spectroscopy methods were used in an investigation of thermodynamic parameters of a surface plasma formed by the action of cw CO2 laser radiation of (2-5)×106 W cm-2 intensity on stainless steel in a protective He or Ar atmosphere. The spatiotemporal structure and pulsation characteristics of the plasma plume were used to determine the fields of the plasma electron density and temperature.

  13. Thermodynamic Bethe ansatz with Haldane statistics

    International Nuclear Information System (INIS)

    Bytsko, A.G.; Fring, A.

    1998-01-01

    We derive the thermodynamic Bethe ansatz equation for the situation in which the statistical interaction of a multi-particle system is governed by Haldane statistics. We formulate a macroscopical equivalence principle for such systems. Particular CDD ambiguities play a distinguished role in compensating the ambiguity in the exclusion statistics. We derive Y-systems related to generalized statistics. We discuss several fermionic, bosonic and anyonic versions of affine Toda field theories and Calogero-Sutherland type models in the context of generalized statistics. (orig.)

  14. Irreversible thermodynamics of overdriven shocks in solids

    International Nuclear Information System (INIS)

    Wallace, D.C.

    1981-01-01

    An isotropic solid capable of transporting heat and of undergoing dissipative plastic flow, is treated. The shock is assumed to be a steady wave, and any phase changes or macroscopic inhomogeneities which might be induced by the shock are neglected. Under these conditions it is established that for an overdriven shock, no solution is possible without heat transport, and when the heat transport is governed by the steady conduction equation, no solution is possible without plastic dissipation as well. Upper and lower bounds are established for the thermodynamic variables, namely the shear stress, temperature, entropy, plastic strain, and heat flux, as functions of compression through the shock

  15. Thermodynamics of complexation of lanthanides and some of transition metal ions by 5,5-dimethyl-cyclohexane-2-(2-hydroxyphenyl)-hydrazono-1,3-dione (DCPHD) and its derivatives

    International Nuclear Information System (INIS)

    Ramadan, A.A.T.; Abdel-Moez, M.S.; El-Shetary, B.A.; Seleim, H.S.

    1993-01-01

    Equilibrium between DCPHD, DC-4-Cl-PHD, and DC-4-Me-PHD and protons, transition, and lanthanide ions have been investigated at 30 o C by means of potentiometric titration in 75%(v/v) methanol-water mixture containing 0.10M KNO 3 as a constant ionic medium. Thermodynamic parameters(ΔG,ΔH and ΔS) referring to the formation of species HL - ,L -- ,ML +n-2 and ML 2 +n-4 (L -- denotes the ligand anion) have been determined in solutions. The solvent effects on the thermodynamic parameters of the complex formation are discussed in terms of differences in the donor ability of methanol and water solvents. The plots of thermodynamic parameters versus ionic potential (Z 2 /r) of the lanthanide elements is not linear as expected from ionic theory. The obtained curve can be resolved in an initial group (the lighter lanthanides), an intermediate group (Sm-Dy), and a final group (the heavier ones, Tb-Lu). This behavior was explained in terms of differences in the dehydration of lighter lanthanide(III) from that of heavier ones

  16. Influence of adsorption thermodynamics on guest diffusivities in nanoporous crystalline materials

    NARCIS (Netherlands)

    Krishna, R.; van Baten, J.M.

    2013-01-01

    Published experimental data, underpinned by molecular simulations, are used to highlight the strong influence of adsorption thermodynamics on diffusivities of guest molecules inside ordered nanoporous crystalline materials such as zeolites, metal-organic frameworks (MOFs), and zeolitic imidazolate

  17. Tax Governance

    DEFF Research Database (Denmark)

    Boll, Karen; Brehm Johansen, Mette

    to wider international trends within tax administration, especially concerning the development of risk assessments and internal control in the corporations and a greater focus on monitoring of these elements by the tax authorities. Overall, the working paper concludes that Tax Governance as a model......This working paper presents an analysis of the experiences of Cooperative Compliance in Denmark. Cooperative Compliance denotes a specific kind of collaborative program for the regulation of large corporate taxpayers by the tax authorities. Cooperative Compliance programs have been implemented...... in several countries worldwide. In Denmark the program is called Tax Governance. Tax Governance has been studied using qualitative method and the analyses of the working paper build on an extensive base of in-depth interviews – primarily with tax directors from corporations participating in the program...

  18. Phenomenological understanding of dewetting and embedding of noble metal nanoparticles in thin films induced by ion irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Prakash, Jai, E-mail: jai.gupta1983@gmail.com [Department of Chemistry, MMH College (Ch. Charan Singh University Meerut), Ghaiziabad 201001 (India); Chemical Physics of Materials, Université Libre de Bruxelles, Campus de la Plaine, CP 243, B-1050 Bruxelles (Belgium); Tripathi, A. [Inter University Accelerator Centre, Aruna Asif Ali Marg, New Delhi 110067 (India); Gautam, Sanjeev; Chae, K.H.; Song, Jonghan [Advanced Analysis Center, Korea Institute of Science and Technology, Seoul 136–791 (Korea, Republic of); Rigato, V. [INFN Laboratori Nazionali di Legnaro, Via Romea. 4, 35020 Legnaro, Padova (Italy); Tripathi, Jalaj [Department of Chemistry, MMH College (Ch. Charan Singh University Meerut), Ghaiziabad 201001 (India); Asokan, K. [Inter University Accelerator Centre, Aruna Asif Ali Marg, New Delhi 110067 (India)

    2014-10-15

    The present experimental work provides the phenomenological approach to understand the dewetting in thin noble metal films with subsequent formation of nanoparticles (NPs) and embedding of NPs induced by ion irradiation. Au/polyethyleneterepthlate (PET) bilayers were irradiated with 150 keV Ar ions at varying fluences and were studied using scanning electron microscopy (SEM) and cross-sectional transmission electron microscopy (X-TEM). Thin Au film begins to dewet from the substrate after irradiation and subsequent irradiation results in spherical nanoparticles on the surface that at a fluence of 5 × 10{sup 16} ions/cm{sup 2} become embedded into the substrate. In addition to dewetting in thin films, synthesis and embedding of metal NPs by ion irradiation, the present article explores fundamental thermodynamic principles that govern these events systematically under the effect of irradiation. The results are explained on the basis of ion induced sputtering, thermal spike inducing local melting and of thermodynamic driving forces by minimization of the system free energy where contributions of surface and interfacial energies are considered with subsequent ion induced viscous flow in substrate. - Highlights: • Phenomenological interpretation of dewetting and embedding of metal NPs in thin film. • Exploring fundamental thermodynamic principles under influence of ion irradiation. • Ion induced surface/interface microstructural changes using SEM/X-TEM. • Ion induced sputtering, thermal spike induced local melting. • Thermodynamic driving forces relate to surface and interfacial energies.

  19. Mobilizing Government

    DEFF Research Database (Denmark)

    Wang, Cancan; Medaglia, Rony; Jensen, Tina Blegind

    2016-01-01

    The nature of inter-organizational collaboration between government and other stakeholders is rapidly changing with the introduction of open social media (OSM) platforms. Characterized by a high degree of informality as well as a blurred personal/professional nature, OSM can potentially introduce...... changes and tensions in the well-established routines of the public sector. This paper aims at shedding light on such changes, presenting findings from a study on the use of an OSM platform, WeChat, in an interorganizational collaboration project between government, university, and industry stakeholders...

  20. Hamiltonian and Thermodynamic Modeling of Quantum Turbulence

    Science.gov (United States)

    Grmela, Miroslav

    2010-10-01

    The state variables in the novel model introduced in this paper are the fields playing this role in the classical Landau-Tisza model and additional fields of mass, entropy (or temperature), superfluid velocity, and gradient of the superfluid velocity, all depending on the position vector and another tree dimensional vector labeling the scale, describing the small-scale structure developed in 4He superfluid experiencing turbulent motion. The fluxes of mass, momentum, energy, and entropy in the position space as well as the fluxes of energy and entropy in scales, appear in the time evolution equations as explicit functions of the state variables and of their conjugates. The fundamental thermodynamic relation relating the fields to their conjugates is left in this paper undetermined. The GENERIC structure of the equations serves two purposes: (i) it guarantees that solutions to the governing equations, independently of the choice of the fundamental thermodynamic relation, agree with the observed compatibility with thermodynamics, and (ii) it is used as a guide in the construction of the novel model.

  1. Non-uniform Solute Segregation at Semi-Coherent Metal/Oxide Interfaces

    Science.gov (United States)

    Choudhury, Samrat; Aguiar, Jeffery A.; Fluss, Michael J.; Hsiung, Luke L.; Misra, Amit; Uberuaga, Blas P.

    2015-08-01

    The properties and performance of metal/oxide nanocomposites are governed by the structure and chemistry of the metal/oxide interfaces. Here we report an integrated theoretical and experimental study examining the role of interfacial structure, particularly misfit dislocations, on solute segregation at a metal/oxide interface. We find that the local oxygen environment, which varies significantly between the misfit dislocations and the coherent terraces, dictates the segregation tendency of solutes to the interface. Depending on the nature of the solute and local oxygen content, segregation to misfit dislocations can change from attraction to repulsion, revealing the complex interplay between chemistry and structure at metal/oxide interfaces. These findings indicate that the solute chemistry at misfit dislocations is controlled by the dislocation density and oxygen content. Fundamental thermodynamic concepts - the Hume-Rothery rules and the Ellingham diagram - qualitatively predict the segregation behavior of solutes to such interfaces, providing design rules for novel interfacial chemistries.

  2. Nonequilibrium thermodynamics and information theory: basic concepts and relaxing dynamics

    Science.gov (United States)

    Altaner, Bernhard

    2017-11-01

    Thermodynamics is based on the notions of energy and entropy. While energy is the elementary quantity governing physical dynamics, entropy is the fundamental concept in information theory. In this work, starting from first principles, we give a detailed didactic account on the relations between energy and entropy and thus physics and information theory. We show that thermodynamic process inequalities, like the second law, are equivalent to the requirement that an effective description for physical dynamics is strongly relaxing. From the perspective of information theory, strongly relaxing dynamics govern the irreversible convergence of a statistical ensemble towards the maximally non-commital probability distribution that is compatible with thermodynamic equilibrium parameters. In particular, Markov processes that converge to a thermodynamic equilibrium state are strongly relaxing. Our framework generalizes previous results to arbitrary open and driven systems, yielding novel thermodynamic bounds for idealized and real processes. , which features invited work from the best early-career researchers working within the scope of J. Phys. A. This project is part of the Journal of Physics series’ 50th anniversary celebrations in 2017. Bernhard Altaner was selected by the Editorial Board of J. Phys. A as an Emerging Talent.

  3. Bank Governance

    OpenAIRE

    Laura Ard; Alexander Berg

    2010-01-01

    Principles of good governance have been a major component of international financial standards and are seen as essential to the stability and integrity of financial systems. Over the past 10 years much energy and attention have gone to improving the ability of company boards, managers, and owners to prudently navigate rapidly changing and volatile market conditions. So, how to explain the ...

  4. Government Organizations

    DEFF Research Database (Denmark)

    Krause Hansen, Hans; Salskov-Iversen, Dorte

    2017-01-01

    , with clearly defined boundaries between the public and private; and in terms of polycentrism, where power and authority are seen as dispersed among state and nonstate organizations, including business and civil society organizations. Globalization and new media technologies imply changes in the relationship...... democracy and the public sphere; and discourse approaches to studying the intersections of government, organizational change, and information and communication technology....

  5. Corporate Governance

    International Development Research Centre (IDRC) Digital Library (Canada)

    Andy Knight; David Malone; Faith Mitchell. Finance and Audit Committee. Members: Denis Desautels (Chairman); Ahmed Galal;. Frieda Granot; Elizabeth Parr-Johnston; Andrés Rozental;. Gordon Shirley. Governance Committee. Members: The Honourable Barbara McDougall (Chairman);. Claude-Yves Charron; Denis ...

  6. Thermodynamics of adaptive molecular resolution.

    Science.gov (United States)

    Delgado-Buscalioni, R

    2016-11-13

    A relatively general thermodynamic formalism for adaptive molecular resolution (AMR) is presented. The description is based on the approximation of local thermodynamic equilibrium and considers the alchemic parameter λ as the conjugate variable of the potential energy difference between the atomistic and coarse-grained model Φ=U (1) -U (0) The thermodynamic formalism recovers the relations obtained from statistical mechanics of H-AdResS (Español et al, J. Chem. Phys. 142, 064115, 2015 (doi:10.1063/1.4907006)) and provides relations between the free energy compensation and thermodynamic potentials. Inspired by this thermodynamic analogy, several generalizations of AMR are proposed, such as the exploration of new Maxwell relations and how to treat λ and Φ as 'real' thermodynamic variablesThis article is part of the themed issue 'Multiscale modelling at the physics-chemistry-biology interface'. © 2016 The Author(s).

  7. RNA Thermodynamic Structural Entropy.

    Science.gov (United States)

    Garcia-Martin, Juan Antonio; Clote, Peter

    2015-01-01

    Conformational entropy for atomic-level, three dimensional biomolecules is known experimentally to play an important role in protein-ligand discrimination, yet reliable computation of entropy remains a difficult problem. Here we describe the first two accurate and efficient algorithms to compute the conformational entropy for RNA secondary structures, with respect to the Turner energy model, where free energy parameters are determined from UV absorption experiments. An algorithm to compute the derivational entropy for RNA secondary structures had previously been introduced, using stochastic context free grammars (SCFGs). However, the numerical value of derivational entropy depends heavily on the chosen context free grammar and on the training set used to estimate rule probabilities. Using data from the Rfam database, we determine that both of our thermodynamic methods, which agree in numerical value, are substantially faster than the SCFG method. Thermodynamic structural entropy is much smaller than derivational entropy, and the correlation between length-normalized thermodynamic entropy and derivational entropy is moderately weak to poor. In applications, we plot the structural entropy as a function of temperature for known thermoswitches, such as the repression of heat shock gene expression (ROSE) element, we determine that the correlation between hammerhead ribozyme cleavage activity and total free energy is improved by including an additional free energy term arising from conformational entropy, and we plot the structural entropy of windows of the HIV-1 genome. Our software RNAentropy can compute structural entropy for any user-specified temperature, and supports both the Turner'99 and Turner'04 energy parameters. It follows that RNAentropy is state-of-the-art software to compute RNA secondary structure conformational entropy. Source code is available at https://github.com/clotelab/RNAentropy/; a full web server is available at http

  8. RNA Thermodynamic Structural Entropy.

    Directory of Open Access Journals (Sweden)

    Juan Antonio Garcia-Martin

    Full Text Available Conformational entropy for atomic-level, three dimensional biomolecules is known experimentally to play an important role in protein-ligand discrimination, yet reliable computation of entropy remains a difficult problem. Here we describe the first two accurate and efficient algorithms to compute the conformational entropy for RNA secondary structures, with respect to the Turner energy model, where free energy parameters are determined from UV absorption experiments. An algorithm to compute the derivational entropy for RNA secondary structures had previously been introduced, using stochastic context free grammars (SCFGs. However, the numerical value of derivational entropy depends heavily on the chosen context free grammar and on the training set used to estimate rule probabilities. Using data from the Rfam database, we determine that both of our thermodynamic methods, which agree in numerical value, are substantially faster than the SCFG method. Thermodynamic structural entropy is much smaller than derivational entropy, and the correlation between length-normalized thermodynamic entropy and derivational entropy is moderately weak to poor. In applications, we plot the structural entropy as a function of temperature for known thermoswitches, such as the repression of heat shock gene expression (ROSE element, we determine that the correlation between hammerhead ribozyme cleavage activity and total free energy is improved by including an additional free energy term arising from conformational entropy, and we plot the structural entropy of windows of the HIV-1 genome. Our software RNAentropy can compute structural entropy for any user-specified temperature, and supports both the Turner'99 and Turner'04 energy parameters. It follows that RNAentropy is state-of-the-art software to compute RNA secondary structure conformational entropy. Source code is available at https://github.com/clotelab/RNAentropy/; a full web server is available at http

  9. Thermodynamics of phase transitions

    International Nuclear Information System (INIS)

    Cofta, H.

    1972-01-01

    The phenomenology of the phase transitions has been considered. The definitions of thermodynamic functions and parameters, as well as those of the phase transitions, are given and some of the relations between those quantities are discussed. The phase transitions classification proposed by Ehrenfest has been described. The most important features of phase transitions are discussed using the selected physical examples including the critical behaviour of ferromagnetic materials at the Curie temperature and antiferromagnetic materials at the Neel temperature. Some aspects of the Ehrenfest's equations, that have been derived, for the interfacial lines and surfaces are considered as well as the role the notion of interfaces. (S.B.)

  10. Thermodynamics of quark gas

    Energy Technology Data Exchange (ETDEWEB)

    Biswas, S. N.

    1980-07-01

    The application of quantum statistical mechanics to a system of particles consisting of quarks is considered. Realistic theoretical investigations have been underway to understand highly dense objects such as white dwarfs and neutron stars. The various possibilities in the case of very high densities such as 10/sup 15/ or 10/sup 16/ g/cm/sup 3/ are enumerated. The thermodynamics of a phase transition from neutron matter phase to quark matter phase is analysed. Preliminary results based on quantum chromodynamics and other phenomenological models are reported.

  11. Time and Thermodynamics

    CERN Document Server

    Kirkland, Kyle

    2007-01-01

    Temperature is vital to the health and welfare of all living beings, and Earth's temperature varies considerably from place to place. Early humans could only live in warm areas such as the tropics. Although modern humans have the technology to keep their houses and offices warm even in cold environments, the growth and development of civilization has created unintentional effects. Cities are warmer than their surrounding regions, and on a global scale, Earth is experiencing rising temperatures. Thus, the science of thermodynamics offers an important tool to study these effects. "Time and

  12. Interfacial solvation thermodynamics

    International Nuclear Information System (INIS)

    Ben-Amotz, Dor

    2016-01-01

    Previous studies have reached conflicting conclusions regarding the interplay of cavity formation, polarizability, desolvation, and surface capillary waves in driving the interfacial adsorptions of ions and molecules at air–water interfaces. Here we revisit these questions by combining exact potential distribution results with linear response theory and other physically motivated approximations. The results highlight both exact and approximate compensation relations pertaining to direct (solute–solvent) and indirect (solvent–solvent) contributions to adsorption thermodynamics, of relevance to solvation at air–water interfaces, as well as a broader class of processes linked to the mean force potential between ions, molecules, nanoparticles, proteins, and biological assemblies. (paper)

  13. Principles of thermodynamics

    CERN Document Server

    Kaufman, Myron

    2002-01-01

    Ideal for one- or two-semester courses that assume elementary knowledge of calculus, This text presents the fundamental concepts of thermodynamics and applies these to problems dealing with properties of materials, phase transformations, chemical reactions, solutions and surfaces. The author utilizes principles of statistical mechanics to illustrate key concepts from a microscopic perspective, as well as develop equations of kinetic theory. The book provides end-of-chapter question and problem sets, some using Mathcad™ and Mathematica™; a useful glossary containing important symbols, definitions, and units; and appendices covering multivariable calculus and valuable numerical methods.

  14. Gravitation, Thermodynamics, and Quantum Theory

    OpenAIRE

    Wald, Robert M.

    1999-01-01

    During the past 30 years, research in general relativity has brought to light strong hints of a very deep and fundamental relationship between gravitation, thermodynamics, and quantum theory. The most striking indication of such a relationship comes from black hole thermodynamics, where it appears that certain laws of black hole mechanics are, in fact, simply the ordinary laws of thermodynamics applied to a system containing a black hole. This article will review the present status of black h...

  15. On thermodynamic and microscopic reversibility

    International Nuclear Information System (INIS)

    Crooks, Gavin E

    2011-01-01

    The word 'reversible' has two (apparently) distinct applications in statistical thermodynamics. A thermodynamically reversible process indicates an experimental protocol for which the entropy change is zero, whereas the principle of microscopic reversibility asserts that the probability of any trajectory of a system through phase space equals that of the time reversed trajectory. However, these two terms are actually synonymous: a thermodynamically reversible process is microscopically reversible, and vice versa

  16. Experimental approaches to membrane thermodynamics

    DEFF Research Database (Denmark)

    Westh, Peter

    2009-01-01

    Thermodynamics describes a system on the macroscopic scale, yet it is becoming an important tool for the elucidation of many specific molecular aspects of membrane properties. In this note we discuss this application of thermodynamics, and give a number of examples on how thermodynamic measurements...... have contributed to the understanding of specific membrane phenomena. We mainly focus on non-specific interactions of bilayers and small molecules (water and solutes) in the surrounding solvent, and the changes in membrane properties they bring about. Differences between thermodynamic...

  17. Molecular thermodynamics of nonideal fluids

    CERN Document Server

    Lee, Lloyd L

    2013-01-01

    Molecular Thermodynamics of Nonideal Fluids serves as an introductory presentation for engineers to the concepts and principles behind and the advances in molecular thermodynamics of nonideal fluids. The book covers related topics such as the laws of thermodynamics; entropy; its ensembles; the different properties of the ideal gas; and the structure of liquids. Also covered in the book are topics such as integral equation theories; theories for polar fluids; solution thermodynamics; and molecular dynamics. The text is recommended for engineers who would like to be familiarized with the concept

  18. Thermodynamics of Accelerating Black Holes.

    Science.gov (United States)

    Appels, Michael; Gregory, Ruth; Kubizňák, David

    2016-09-23

    We address a long-standing problem of describing the thermodynamics of an accelerating black hole. We derive a standard first law of black hole thermodynamics, with the usual identification of entropy proportional to the area of the event horizon-even though the event horizon contains a conical singularity. This result not only extends the applicability of black hole thermodynamics to realms previously not anticipated, it also opens a possibility for studying novel properties of an important class of exact radiative solutions of Einstein equations describing accelerated objects. We discuss the thermodynamic volume, stability, and phase structure of these black holes.

  19. Light element thermodynamics related to actinide separations

    International Nuclear Information System (INIS)

    Johnson, I.; Johnson, C.E.

    1997-01-01

    The accumulation of waste from the last five decades of nuclear reactor development has resulted in large quantities of materials of very diverse chemical composition. An electrometallurgical (EM) method is being developed to separate the components of the waste into several unique streams suitable for permanent disposal and an actinide stream suitable for retrievable storage. The principal types of nuclear wastes are spent oxide or metallic fuel. Since the EM module requires a metallic feed, and oxygen interferes with its operation, the oxide fuel has to be reduced prior to EM treatment. Further, the wastes contain, in addition to oxygen, other light elements (first- and second-row elements) that may also interfere with the operation of the EM module. The extent that these light elements interfere with the operation of the EM module has been determined by chemical thermodynamic calculations. (orig.)

  20. Physics of amorphous metals

    CERN Document Server

    Kovalenko, Nikolai P; Krey, Uwe

    2008-01-01

    The discovery of bulk metallic glasses has led to a large increase in the industrial importance of amorphous metals, and this is expected to continue. This book is the first to describe the theoretical physics of amorphous metals, including the important theoretical development of the last 20 years.The renowned authors stress the universal aspects in their description of the phonon or magnon low-energy excitations in the amorphous metals, e.g. concerning the remarkable consequences of the properties of these excitations for the thermodynamics at low and intermediate temperatures. Tunneling

  1. Thermodynamics of geothermal fluids

    Energy Technology Data Exchange (ETDEWEB)

    Rogers, P.S.Z.

    1981-03-01

    A model to predict the thermodynamic properties of geothermal brines, based on a minimum amount of experimental data on a few key systems, is tested. Volumetric properties of aqueous sodium chloride, taken from the literature, are represented by a parametric equation over the range 0 to 300{sup 0}C and 1 bar to 1 kbar. Density measurements at 20 bar needed to complete the volumetric description also are presented. The pressure dependence of activity and thermal properties, derived from the volumetric equation, can be used to complete an equation of state for sodium chloride solutions. A flow calorimeter, used to obtain heat capacity data at high temperatures and pressures, is described. Heat capacity measurements, from 30 to 200{sup 0}C and 1 bar to 200 bar, are used to derive values for the activity coefficient and other thermodynamic properties of sodium sulfate solutions as a function of temperature. Literature data on the solubility of gypsum in mixed electrolyte solutions have been used to evaluate model parameters for calculating gypsum solubility in seawater and natural brines. Predictions of strontium and barium sulfate solubility in seawater also are given.

  2. Thermodynamics of Error Correction

    Directory of Open Access Journals (Sweden)

    Pablo Sartori

    2015-12-01

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

  3. Chemical thermodynamic representation of

    International Nuclear Information System (INIS)

    Lindemer, T.B.; Besmann, T.M.

    1984-01-01

    The entire data base for the dependence of the nonstoichiometry, x, on temperature and chemical potential of oxygen (oxygen potential) was retrieved from the literature and represented. This data base was interpreted by least-squares analysis using equations derived from the classical thermodynamic theory for the solid solution of a solute in a solvent. For hyperstoichiometric oxide at oxygen potentials more positive than -266700 + 16.5T kJ/mol, the data were best represented by a [UO 2 ]-[U 3 O 7 ] solution. For O/U ratios above 2 and oxygen potentials below this boundary, a [UO 2 ]-[U 2 O 4 . 5 ] solution represented the data. The data were represented by a [UO 2 ]-[U 1 / 3 ] solution. The resulting equations represent the experimental ln(PO 2 ) - ln(x) behavior and can be used in thermodynamic calculations to predict phase boundary compositions consistent with the literature. Collectively, the present analysis permits a mathematical representation of the behavior of the total data base

  4. Light cone thermodynamics

    Science.gov (United States)

    De Lorenzo, Tommaso; Perez, Alejandro

    2018-02-01

    We show that null surfaces defined by the outgoing and infalling wave fronts emanating from and arriving at a sphere in Minkowski spacetime have thermodynamical properties that are in strict formal correspondence with those of black hole horizons in curved spacetimes. Such null surfaces, made of pieces of light cones, are bifurcate conformal Killing horizons for suitable conformally stationary observers. They can be extremal and nonextremal depending on the radius of the shining sphere. Such conformal Killing horizons have a constant light cone (conformal) temperature, given by the standard expression in terms of the generalization of surface gravity for conformal Killing horizons. Exchanges of conformally invariant energy across the horizon are described by a first law where entropy changes are given by 1 /(4 ℓp2) of the changes of a geometric quantity with the meaning of horizon area in a suitable conformal frame. These conformal horizons satisfy the zeroth to the third laws of thermodynamics in an appropriate way. In the extremal case they become light cones associated with a single event; these have vanishing temperature as well as vanishing entropy.

  5. FORMATION CONSTANTS AND THERMODYNAMIC ...

    African Journals Online (AJOL)

    KEY WORDS: Metal complexes, Schiff base ligand, Formation constant, DFT calculation ... best values for the formation constants of the proposed equilibrium model by .... to its positive charge distribution and the ligand deformation geometry.

  6. 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

  7. Thermodynamic Properties and Thermodynamic Geometries of Black p-Branes

    International Nuclear Information System (INIS)

    Yi-Huan Wei; Xiao Cui; Jia-Xin Zhao

    2016-01-01

    The heat capacity and the electric capacitance of the black p-branes (BPB) are generally defined, then they are calculated for some special processes. It is found that the Ruppeiner thermodynamic geometry of BPB is flat. Finally, we give some discussions for the flatness of the Ruppeiner thermodynamic geometry of BPB and some black holes. (paper)

  8. Plural Governance

    DEFF Research Database (Denmark)

    Mols, Niels Peter; Hansen, Jesper Rosenberg; Villadsen, Anders Ryom

    We suggest that both making and buying the same product or service has several effects on market performance. A model is developed and tested by use of 170 answers gathered from the Danish municipalities. The results support the hypotheses that both making and buying: (1) moderates the negative r...... on how the plurality is measured. The results indicate that internal production may facilitate effective governance of the relationships with suppliers. Implications for research on firm boundaries and for practice are also discussed....

  9. IT Governance

    OpenAIRE

    Šimková, Hana

    2008-01-01

    IT governance (control of information technology) is a frequently discussed topic today which represents current needs to take control of IT, judge impacts of all resolutions and lead up investments running to the information technology. It is very important for both small and large organizations to have IT which encourages business strategy and helps to meet objectives of a company. The theoretical part of this paper is focused on characterization of the main areas, benefits, rules and vario...

  10. Thermodynamic stability studies of Ce-Sb compounds with Fe

    Science.gov (United States)

    Xie, Yi; Zhang, Jinsuo; Benson, Michael T.; Mariani, Robert D.

    2018-02-01

    Lanthanide fission products can migrate to the fuel periphery and react with cladding, causing fuel-cladding chemical interaction (FCCI). Adding a fuel additive dopant, such as Sb, can bind lanthanide, such as Ce, into metallic compounds and thus prevent migration. The present study focuses on the thermodynamic stability of Ce-Sb compounds when in contact with the major cladding constituent Fe by conducting diffusion couple tests. Ce-Sb compounds have shown high thermodynamic stability as they did not react with Fe. When Fe-Sb compounds contacted with Ce, Sb was separated out of Fe-Sb compounds and formed the more stable Ce-Sb compounds.

  11. Thermodynamics of the Earth

    International Nuclear Information System (INIS)

    Stacey, Frank D

    2010-01-01

    Applications of elementary thermodynamic principles to the dynamics of the Earth lead to robust, quantitative conclusions about the tectonic effects that arise from convection. The grand pattern of motion conveys deep heat to the surface, generating mechanical energy with a thermodynamic efficiency corresponding to that of a Carnot engine operating over the adiabatic temperature gradient between the heat source and sink. Referred to the total heat flux derived from the Earth's silicate mantle, the efficiency is 24% and the power generated, 7.7 x 10 12 W, causes all the material deformation apparent as plate tectonics and the consequent geological processes. About 3.5% of this is released in seismic zones but little more than 0.2% as seismic waves. Even major earthquakes are only localized hiccups in this motion. Complications that arise from mineral phase transitions can be used to illuminate details of the motion. There are two superimposed patterns of convection, plate subduction and deep mantle plumes, driven by sources of buoyancy, negative and positive respectively, at the top and bottom of the mantle. The patterns of motion are controlled by the viscosity contrasts (>10 4 : 1) at these boundaries and are self-selected as the least dissipative mechanisms of heat transfer for convection in a body with very strong viscosity variation. Both are subjects of the thermodynamic efficiency argument. Convection also drives the motion in the fluid outer core that generates the geomagnetic field, although in that case there is an important energy contribution by compositional separation, as light solute is rejected by the solidifying inner core and mixed into the outer core, a process referred to as compositional convection. Uncertainty persists over the core energy balance because thermal conduction is a drain on core energy that has been a subject of diverse estimates, with attendant debate over the need for radiogenic heat in the core. The geophysical approach to

  12. 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

  13. Thermodynamics of negative absolute pressures

    International Nuclear Information System (INIS)

    Lukacs, B.; Martinas, K.

    1984-03-01

    The authors show that the possibility of negative absolute pressure can be incorporated into the axiomatic thermodynamics, analogously to the negative absolute temperature. There are examples for such systems (GUT, QCD) processing negative absolute pressure in such domains where it can be expected from thermodynamical considerations. (author)

  14. Thermodynamic study of selected monoterpenes

    Czech Academy of Sciences Publication Activity Database

    Štejfa, V.; Fulem, Michal; Růžička, K.; Červinka, C.; Rocha, M.A.A.; Santos, L.M.N.B.F.; Schröder, B.

    2013-01-01

    Roč. 60, MAY (2013), 117-125 ISSN 0021-9614 Institutional support: RVO:68378271 Keywords : monoterpenes * pinene * vapor pressure * heat capacity * vaporization and sublimation enthalpy * ideal - gas thermodynamic Subject RIV: BJ - Thermodynamics Impact factor: 2.423, year: 2013

  15. Thermodynamic optimization of power plants

    NARCIS (Netherlands)

    Haseli, Y.

    2011-01-01

    Thermodynamic Optimization of Power Plants aims to establish and illustrate comparative multi-criteria optimization of various models and configurations of power plants. It intends to show what optimization objectives one may define on the basis of the thermodynamic laws, and how they can be applied

  16. Ch. 33 Modeling: Computational Thermodynamics

    International Nuclear Information System (INIS)

    Besmann, Theodore M.

    2012-01-01

    This chapter considers methods and techniques for computational modeling for nuclear materials with a focus on fuels. The basic concepts for chemical thermodynamics are described and various current models for complex crystalline and liquid phases are illustrated. Also included are descriptions of available databases for use in chemical thermodynamic studies and commercial codes for performing complex equilibrium calculations.

  17. Thermodynamics of urban population flows.

    Science.gov (United States)

    Hernando, A; Plastino, A

    2012-12-01

    Orderliness, reflected via mathematical laws, is encountered in different frameworks involving social groups. Here we show that a thermodynamics can be constructed that macroscopically describes urban population flows. Microscopic dynamic equations and simulations with random walkers underlie the macroscopic approach. Our results might be regarded, via suitable analogies, as a step towards building an explicit social thermodynamics.

  18. Thermodynamics from Car to Kitchen

    Science.gov (United States)

    Auty, Geoff

    2014-01-01

    The historical background to the laws of thermodynamics is explained using examples we can all observe in the world around us, focusing on motorised transport, refrigeration and solar heating. This is not to be considered as an academic article. The purpose is to improve understanding of thermodynamics rather than impart new knowledge, and for…

  19. Applied thermodynamics: A new frontier for biotechnology

    DEFF Research Database (Denmark)

    Mollerup, Jørgen

    2006-01-01

    The scientific career of one of the most outstanding scientists in molecular thermodynamics, Professor John M. Prausnitz at Berkeley, reflects the change in the agenda of molecular thermodynamics, from hydrocarbon chemistry to biotechnology. To make thermodynamics a frontier for biotechnology...

  20. Thermodynamics in Loop Quantum Cosmology

    International Nuclear Information System (INIS)

    Li, L.F.; Zhu, J.Y.

    2009-01-01

    Loop quantum cosmology (LQC) is very powerful to deal with the behavior of early universe. Moreover, the effective loop quantum cosmology gives a successful description of the universe in the semiclassical region. We consider the apparent horizon of the Friedmann-Robertson-Walker universe as a thermodynamical system and investigate the thermodynamics of LQC in the semiclassical region. The effective density and effective pressure in the modified Friedmann equation from LQC not only determine the evolution of the universe in LQC scenario but also are actually found to be the thermodynamic quantities. This result comes from the energy definition in cosmology (the Misner-Sharp gravitational energy) and is consistent with thermodynamic laws. We prove that within the framework of loop quantum cosmology, the elementary equation of equilibrium thermodynamics is still valid.

  1. Thermodynamic properties of cryogenic fluids

    CERN Document Server

    Leachman, Jacob; Lemmon, Eric; Penoncello, Steven

    2017-01-01

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

  2. Structural thermodynamics of alloys

    CERN Document Server

    Manenc, Jack

    1973-01-01

    Technical progress has for a very long time been directly dependent on progress in metallurgy, which is itself connected with improvements in the technology of alloys. Metals are most frequently used in the form of alloys for several reasons: the quantity of pure metal in its native state in the earth's crust is very limited; pure metals must be extracted from ores which are themselves impure. Finally, the methods of treatment used lead more easily to alloys than to pure metals. The most typical case is that of iron, where a pure ore may be found, but which is the starting point for cast iron or steel, alloys of iron and carbon. In addition, the properties of alloys are in general superior to those of pure metals and modem metallurgy consists of controlling these properties so as to make them conform to the requirements of the design office. Whilst the engineer was formerly compelled to adapt his designs and constructions to the materials available, such as wood, stone, bronze, iron, cast iron and ordinary st...

  3. Applied statistical thermodynamics

    CERN Document Server

    Lucas, Klaus

    1991-01-01

    The book guides the reader from the foundations of statisti- cal thermodynamics including the theory of intermolecular forces to modern computer-aided applications in chemical en- gineering and physical chemistry. The approach is new. The foundations of quantum and statistical mechanics are presen- ted in a simple way and their applications to the prediction of fluid phase behavior of real systems are demonstrated. A particular effort is made to introduce the reader to expli- cit formulations of intermolecular interaction models and to show how these models influence the properties of fluid sy- stems. The established methods of statistical mechanics - computer simulation, perturbation theory, and numerical in- tegration - are discussed in a style appropriate for newcom- ers and are extensively applied. Numerous worked examples illustrate how practical calculations should be carried out.

  4. Thermodynamic properties of vanadium

    International Nuclear Information System (INIS)

    Desai, P.D.

    1986-01-01

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

  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. Thermodynamics of Fluid Polyamorphism

    Directory of Open Access Journals (Sweden)

    Mikhail A. Anisimov

    2018-01-01

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

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

    International Nuclear Information System (INIS)

    Elsner, Albrecht

    2012-01-01

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

  8. On the kinetic and thermodynamic fragility of the Pt{sub 60}Cu{sub 16}Co{sub 2}P{sub 22} and Pt{sub 57.3}Cu{sub 14.6}Ni{sub 5.3}P{sub 22.8} bulk metallic glasses

    Energy Technology Data Exchange (ETDEWEB)

    Gallino, Isabella, E-mail: i.gallino@mx.uni-saarland.de [Saarland University, Department of Materials Science and Engineering, Campus C6.3, 66123 Saarbruecken (Germany); Gross, Oliver [Saarland University, Department of Materials Science and Engineering, Campus C6.3, 66123 Saarbruecken (Germany); Dalla Fontana, Giulia [Department of Chemistry IFM and NIS, University of Torino, V. Giuria 7, 10125 Torino (Italy); Evenson, Zach; Busch, Ralf [Saarland University, Department of Materials Science and Engineering, Campus C6.3, 66123 Saarbruecken (Germany)

    2014-12-05

    Highlights: • The studied Pt–Cu–(Ni,Co)–P glasses are more fragile than Zr-based alloys. • They show large increases in the C{sub p} at T{sub g} and small barriers for cooperative rearrangements of atoms. • They have fragility parameters among the lowest reported for BMG systems (D{sup *} = 10–12). • They crystallize into a state that melts with distinctly high entropy of fusion. • The microscopic origin of their fragility seems different than that for Zr- and Pd-based BMGs. - Abstract: The investigations in this study focus on bulk metallic glass (BMG) alloy families based on noble metals like Pt, which are more kinetically fragile than Zr-based BMG systems. Thermophysical properties have been investigated by calorimetry and thermal mechanical analyses for the determination of the specific heat capacity and viscosity, respectively. For the Pt{sub 60}Cu{sub 16}Co{sub 2}P{sub 22} and Pt{sub 57.3}Cu{sub 14.6}Ni{sub 5.3}P{sub 22.8} BMG compositions consistent Vogel–Fulcher–Tammann (VFT) fits of the viscosity measurements are established, and the temperature dependence of the configurational entropy is calculated from thermodynamic data. Fits to the Adam–Gibbs equation are performed using this configurational entropy change. Their fragile nature is compared to that of Zr-based alloys in terms of structural considerations.

  9. Governing Engineering

    DEFF Research Database (Denmark)

    Buch, Anders

    2012-01-01

    Most people agree that our world face daunting problems and, correctly or not, technological solutions are seen as an integral part of an overall solution. But what exactly are the problems and how does the engineering ‘mind set’ frame these problems? This chapter sets out to unravel dominant...... perspectives in challenge per-ception in engineering in the US and Denmark. Challenge perception and response strategies are closely linked through discursive practices. Challenge perceptions within the engineering community and the surrounding society are thus critical for the shaping of engineering education...... and the engineering profession. Through an analysis of influential reports and position papers on engineering and engineering education the chapter sets out to identify how engineering is problematized and eventually governed. Drawing on insights from governmentality studies the chapter strives to elicit the bodies...

  10. Governing Engineering

    DEFF Research Database (Denmark)

    Buch, Anders

    2011-01-01

    Abstract: Most people agree that our world faces daunting problems and, correctly or not, technological solutions are seen as an integral part of an overall solution. But what exactly are the problems and how does the engineering ‘mind set’ frame these problems? This chapter sets out to unravel...... dominant perspectives in challenge perception in engineering in the US and Denmark. Challenge perception and response strategies are closely linked through discursive practices. Challenge perceptions within the engineering community and the surrounding society are thus critical for the shaping...... of engineering education and the engineering profession. Through an analysis of influential reports and position papers on engineering and engineering education the chapter sets out to identify how engineering is problematized and eventually governed. Drawing on insights from governmentality studies the chapter...

  11. Statistical Thermodynamics of Disperse Systems

    DEFF Research Database (Denmark)

    Shapiro, Alexander

    1996-01-01

    Principles of statistical physics are applied for the description of thermodynamic equilibrium in disperse systems. The cells of disperse systems are shown to possess a number of non-standard thermodynamic parameters. A random distribution of these parameters in the system is determined....... On the basis of this distribution, it is established that the disperse system has an additional degree of freedom called the macro-entropy. A large set of bounded ideal disperse systems allows exact evaluation of thermodynamic characteristics. The theory developed is applied to the description of equilibrium...

  12. Thermodynamic light on black holes

    International Nuclear Information System (INIS)

    Davies, P.

    1977-01-01

    The existence of black holes and their relevance to our understanding of the nature of space and time are considered, with especial reference to the application of thermodynamic arguments which can reveal their energy-transfer processes in a new light. The application of thermodynamics to strongly gravitating systems promises some fascinating new insights into the nature of gravity. Situations can occur during gravitational collapse in which existing physics breaks down. Under these circumstances, the application of universal thermodynamical principles might be our only guide. (U.K.)

  13. Thermodynamic metrics and optimal paths.

    Science.gov (United States)

    Sivak, David A; Crooks, Gavin E

    2012-05-11

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

  14. Some aspects of plasma thermodynamics

    International Nuclear Information System (INIS)

    Gorgoraki, V.I.

    1986-01-01

    The objective reasons which have inhibited the development of a plasma-thermodynamics theory are discussed and the authors formulate the fundamental principles which can be the basis of a common plasma-thermodynamics theory. Two kinds of thermodynamic equilibrium plasmas are discussed, an isothermal plasma and a nonisothermal plasma. An isothermal plasma is a high-temperature plasma; the Saha-Eggert equation describes its behavior. A nonisothermal plasma is a low-temperature plasma, and the reactions taking place therein are purely plasma-chemical. The ionization equilibrium and the composition of such a plasma can be found with the aid of the equations presented in this paper

  15. Practical chemical thermodynamics for geoscientists

    CERN Document Server

    Fegley, Bruce, Jr

    2012-01-01

    Practical Chemical Thermodynamics for Geoscientists covers classical chemical thermodynamics and focuses on applications to practical problems in the geosciences, environmental sciences, and planetary sciences. This book will provide a strong theoretical foundation for students, while also proving beneficial for earth and planetary scientists seeking a review of thermodynamic principles and their application to a specific problem. Strong theoretical foundation and emphasis on applications Numerous worked examples in each chapter Brief historical summaries and biographies of key thermodynamicists-including their fundamental research and discoveries Extensive references to relevant literature.

  16. Thermodynamic analysis of biochemical systems

    International Nuclear Information System (INIS)

    Yuan, Y.; Fan, L.T.; Shieh, J.H.

    1989-01-01

    Introduction of the concepts of the availability (or exergy), datum level materials, and the dead state has been regarded as some of the most significant recent developments in classical thermodynamics. Not only the available energy balance but also the material and energy balances of a biological system may be established in reference to the datum level materials in the dead state or environment. In this paper these concepts are illustrated with two examples of fermentation and are shown to be useful in identifying sources of thermodynamic inefficiency, thereby leading naturally to the rational definition of thermodynamic efficiency of a biochemical process

  17. Electrochemical dissolution of surface alloys in acids: Thermodynamic trends from first-principles calculations

    DEFF Research Database (Denmark)

    Greeley, Jeffrey Philip; Nørskov, Jens Kehlet

    2007-01-01

    A simple procedure is introduced to use periodic Density Functional Theory calculations to estimate trends in the thermodynamics of surface alloy dissolution in acidic media. With this approach, the dissolution potentials for solute metal atoms embedded in the surface layer of various host metals...

  18. Thermodynamic Calculation of the Distribution Coefficient Between the Liquid and Solid Phases of an Element in Dilute Solution in a Metal: Application to the Purification of Beryllium; Calcul Thermodynamique du Coefficient de Distribution Entre Phases Liquide et Solide d'un Element en Presence d'Autres Constituants en Solution Diluee dans un Metal: Application a la Purification du Beryllium

    Energy Technology Data Exchange (ETDEWEB)

    Desre, P. [Ecole Nationale Superieure d' Electrochimie et d' Electrometallurgie (France); Schaub, B. [Centre d' Etudes Nucleaires de Grenoble (France); Bonnier, I. E. [Ecole Nationale Superieure d' Electrochimie et d' Electrometallurgie, Grenoble (France)

    1966-01-15

    The authors calculate the distribution coefficient {Gamma}{sub i} between the liquid and solid phases of an element i in the presence of other elements j in a solvent M ({Gamma}{sub i} = x'{sub i}/x{sub i}, where x'{sub i} and x{sub i} are the atomic fractions of i in the solid and liquid phases respectively) from the thermodynamic properties of binary systems of the type (i, M), (j, M) and (i, j). They show that the interaction of all the elements present may, under certain conditions, strongly affect the value of the coefficient {Gamma}{sub i}. This effect is pronounced if the following condition is fulfilled: {gamma}{sup {infinity}}{sub i(M)}, {gamma}{sup {infinity}}{sub j(M)} > {gamma}{sup {infinity}}{sub ij} where {gamma}{sup {infinity}}{sub i(M)}, {gamma}{sup {infinity}}{sub j(M)} and {gamma}{sup {infinity}}{sub ij} are limiting activity coefficients of the constituents i and j in the (i, M) (j, M) and (i, j) liquid state systems. It is a simple matter to deduce from this condition an application to the purification of metals by the zone-melting method; the condition enables one to choose an element j which is added deliberately to a metal in order to facilitate the elimination-of an element i (subsequent elimination of the element j being also, of course, a simple matter). For example, the authors were able to confirm that the addition of aluminium to beryllium enables one to improve the elimination of iron during the purification of the beryllium by the zone-melting technique, the aluminium acting as a carrier. (author) [French] Les auteurs calculent le coefficient de distribution Greek-Capital-Letter-Gamma {sub i} entre phases liquide et solide d'un element i en presence d'autres elements j dans un solvant M ( Greek-Capital-Letter-Gamma {sub i} = x'{sub i}/x{sub i}, x'{sub i} et x{sub i} representant respectivement les fractions atomiques de i dans les phases solide et liquide), a partir des proprietes thermodynamiques des systemes binaires de type: (i, M

  19. Thermodynamical string fragmentation

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, Nadine [Theoretical Particle Physics, Department of Astronomy and Theoretical Physics, Lund University,Sölvegatan 14A, Lund, SE-223 62 (Sweden); School of Physics and Astronomy, Monash University,Wellington Road, Clayton, VIC-3800 (Australia); Sjöstrand, Torbjörn [Theoretical Particle Physics, Department of Astronomy and Theoretical Physics, Lund University,Sölvegatan 14A, Lund, SE-223 62 (Sweden)

    2017-01-31

    The observation of heavy-ion-like behaviour in pp collisions at the LHC suggests that more physics mechanisms are at play than traditionally assumed. The introduction e.g. of quark-gluon plasma or colour rope formation can describe several of the observations, but as of yet there is no established paradigm. In this article we study a few possible modifications to the Pythia event generator, which describes a wealth of data but fails for a number of recent observations. Firstly, we present a new model for generating the transverse momentum of hadrons during the string fragmentation process, inspired by thermodynamics, where heavier hadrons naturally are suppressed in rate but obtain a higher average transverse momentum. Secondly, close-packing of strings is taken into account by making the temperature or string tension environment-dependent. Thirdly, a simple model for hadron rescattering is added. The effect of these modifications is studied, individually and taken together, and compared with data mainly from the LHC. While some improvements can be noted, it turns out to be nontrivial to obtain effects as big as required, and further work is called for.

  20. Modelling grain growth in the framework of Rational Extended Thermodynamics

    International Nuclear Information System (INIS)

    Kertsch, Lukas; Helm, Dirk

    2016-01-01

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

  1. Modelling grain growth in the framework of Rational Extended Thermodynamics

    Science.gov (United States)

    Kertsch, Lukas; Helm, Dirk

    2016-05-01

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

  2. 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...

  3. Shock Thermodynamic Applied Research Facility

    Data.gov (United States)

    Federal Laboratory Consortium — The Shock Thermodynamic Applied Research Facility (STAR) facility, within Sandia’s Solid Dynamic Physics Department, is one of a few institutions in the world with a...

  4. Thermodynamic analysis of PBMR plant

    International Nuclear Information System (INIS)

    Sen, S.; Kadiroglu, O.K.

    2002-01-01

    The thermodynamic analysis of a PBMR is presented for various pressures and temperatures values. The design parameters of the components of the power plant are calculated and an optimum cycle for the maximum thermal efficiency is sought for. (author)

  5. Thermodynamic efficiency of solar concentrators.

    Science.gov (United States)

    Shatz, Narkis; Bortz, John; Winston, Roland

    2010-04-26

    The optical thermodynamic efficiency is a comprehensive metric that takes into account all loss mechanisms associated with transferring flux from the source to the target phase space, which may include losses due to inadequate design, non-ideal materials, fabrication errors, and less than maximal concentration. We discuss consequences of Fermat's principle of geometrical optics and review étendue dilution and optical loss mechanisms associated with nonimaging concentrators. We develop an expression for the optical thermodynamic efficiency which combines the first and second laws of thermodynamics. As such, this metric is a gold standard for evaluating the performance of nonimaging concentrators. We provide examples illustrating the use of this new metric for concentrating photovoltaic systems for solar power applications, and in particular show how skewness mismatch limits the attainable optical thermodynamic efficiency.

  6. Thermodynamic origin of nonimaging optics

    Science.gov (United States)

    Jiang, Lun; Winston, Roland

    2016-10-01

    Nonimaging optics is the theory of thermodynamically efficient optics and as such depends more on thermodynamics than on optics. Hence, in this paper, a condition for the "best" design is proposed based on purely thermodynamic arguments, which we believe has profound consequences for the designs of thermal and even photovoltaic systems. This way of looking at the problem of efficient concentration depends on probabilities, the ingredients of entropy and information theory, while "optics" in the conventional sense recedes into the background. Much of the paper is pedagogical and retrospective. Some of the development of flowline designs will be introduced at the end and the connection between the thermodynamics and flowline design will be graphically presented. We will conclude with some speculative directions of where the ideas might lead.

  7. First principles thermodynamics of alloys

    International Nuclear Information System (INIS)

    Ducastelle, F.

    1993-01-01

    We present a brief report on the methods of solid state physics (electronic structure, statistical thermodynamics) that allow us to discuss the phase stability of alloys and to determine their phase diagrams. (orig.)

  8. Thermodynamic approach to biomass gasification

    International Nuclear Information System (INIS)

    Boissonnet, G.; Seiler, J.M.

    2003-01-01

    The document presents an approach of biomass transformation in presence of steam, hydrogen or oxygen. Calculation results based on thermodynamic equilibrium are discussed. The objective of gasification techniques is to increase the gas content in CO and H 2 . The maximum content in these gases is obtained when thermodynamic equilibrium is approached. Any optimisation action of a process. will, thus, tend to approach thermodynamic equilibrium conditions. On the other hand, such calculations can be used to determine the conditions which lead to an increase in the production of CO and H 2 . An objective is also to determine transformation enthalpies that are an important input for process calculations. Various existing processes are assessed, and associated thermodynamic limitations are evidenced. (author)

  9. Thermodynamic theory of transport in magnetized plasmas

    International Nuclear Information System (INIS)

    Misguich, J.H.

    1990-10-01

    Transport laws relating thermodynamic flows to forces by means of transport coefficients in a magnetized plasma are derived here from basic plasmadynamics and nonequilibrium thermodynamics. Macroscopic balance equations are derived in the first part, taking into account the energy of relative diffusion between species in an exact way. The resulting plasmadynamical equations appear to be more general than the usual ones. In the second part, the particular features of a two-temperature diffusing plasma are taken into account in deriving the balance equation for the entropy density, the differences with thermodynamics of neutral fluid mixtures or metals are explained. The general expressions obtained for the entropy production rate are used in part III to derive transport laws. Onsager symmetry relations are applied to interrelate crossed transport coefficients. Basic transport coefficients are the electrical conductivity, the thermo-electric coefficient, along with the thermal conductivities and the viscosities for each species. The slight difference between thermo-electric effect and thermo-diffusion is explained. An important resistive thermo-electric effect appears which describes crossed transport coefficients between thermal and electric flows. Because of the anisotropy introduced by the magnetic field, the transport coefficients are tensors, with non diagonal elements associated with the Hall, Nernst and Ettinghausen effects in the plasma. The field geometry and applications to several particular cases are treated explicitly in part IV, namely the neo-classical transport laws. The Ettinghausen effect appears to play an important role in the transport laws for radial electron heat flow and particle flow in confined plasmas. Practical prescriptions are given to apply the Onsager symmetry relations in a correct way

  10. 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.

  11. 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.

  12. Dynamics and Thermodynamics of Molecular Machines

    DEFF Research Database (Denmark)

    Golubeva, Natalia

    2014-01-01

    to their microscopic size, molecular motors are governed by principles fundamentally different from those describing the operation of man-made motors such as car engines. In this dissertation the dynamic and thermodynamic properties of molecular machines are studied using the tools of nonequilibrium statistical......Molecular machines, or molecular motors, are small biophysical devices that perform a variety of essential metabolic processes such as DNA replication, protein synthesis and intracellular transport. Typically, these machines operate by converting chemical energy into motion and mechanical work. Due...... mechanics. The first part focuses on noninteracting molecular machines described by a paradigmatic continuum model with the aim of comparing and contrasting such a description to the one offered by the widely used discrete models. Many molecular motors, for example, kinesin involved in cellular cargo...

  13. Thermodynamics of firms' growth

    Science.gov (United States)

    Zambrano, Eduardo; Hernando, Alberto; Hernando, Ricardo; Plastino, Angelo

    2015-01-01

    The distribution of firms' growth and firms' sizes is a topic under intense scrutiny. In this paper, we show that a thermodynamic model based on the maximum entropy principle, with dynamical prior information, can be constructed that adequately describes the dynamics and distribution of firms' growth. Our theoretical framework is tested against a comprehensive database of Spanish firms, which covers, to a very large extent, Spain's economic activity, with a total of 1 155 142 firms evolving along a full decade. We show that the empirical exponent of Pareto's law, a rule often observed in the rank distribution of large-size firms, is explained by the capacity of economic system for creating/destroying firms, and that can be used to measure the health of a capitalist-based economy. Indeed, our model predicts that when the exponent is larger than 1, creation of firms is favoured; when it is smaller than 1, destruction of firms is favoured instead; and when it equals 1 (matching Zipf's law), the system is in a full macroeconomic equilibrium, entailing ‘free’ creation and/or destruction of firms. For medium and smaller firm sizes, the dynamical regime changes, the whole distribution can no longer be fitted to a single simple analytical form and numerical prediction is required. Our model constitutes the basis for a full predictive framework regarding the economic evolution of an ensemble of firms. Such a structure can be potentially used to develop simulations and test hypothetical scenarios, such as economic crisis or the response to specific policy measures. PMID:26510828

  14. The thermodynamics and kinetics of interstitial solid solutions

    International Nuclear Information System (INIS)

    Silva, J.R.G. da.

    1976-04-01

    Studies of hydrogen metal systems where the hidrogen is disolved in a solid solution are presented. Particular items of interest are: the thermodynamics of the hydrogen-iron system; the solubility of hidrogen in super pure iron single crytals; the thermodinamic functions of hydrogen in solid solutions of Nb, Ta and V; and the solubility of hydrogen in α-manganese. The diffusion of carbon and nitrogen in BCC iron is also studied

  15. Critical evaluation and thermodynamic optimization of the U-Pb and U-Sb binary systems

    International Nuclear Information System (INIS)

    Wang, Jian; Jin, Liling; Chen, Chuchu; Rao, Weifeng; Wang, Cuiping; Liu, Xingjun

    2016-01-01

    A complete literature review, critical evaluation and thermodynamic optimization of the phase diagrams and thermodynamic properties of U-Pb and U-Sb binary systems are presented. The CALculation of PHAse Diagrams (CALPHAD) method was used for the thermodynamic optimization, the results of which can reproduce all available reliable experimental phase equilibria and thermodynamic data. The modified quasi-chemical model in the pair approximation (MQMPA) was used for modeling the liquid solution. The Gibbs energies of all terminal solid solutions and intermetallic compounds were described by the compound energy formalism (CEF) model. All reliable experimental data of the U-Pb and U-Sb systems have been reproduced. A self-consistent thermodynamic database has been constructed for these binary systems; this database can be used in liquid-metal fuel reactor (LMFR) research.

  16. Computational thermodynamics in electric current metallurgy

    DEFF Research Database (Denmark)

    Bhowmik, Arghya; Qin, R.S.

    2015-01-01

    . The method has been validated against the analytical solution of current distribution and experimental observation of microstructure evolution. It provides a basis for the design, prediction and implementation of the electric current metallurgy. The applicability of the theory is discussed in the derivations.......A priori derivation for the extra free energy caused by the passing electric current in metal is presented. The analytical expression and its discrete format in support of the numerical calculation of thermodynamics in electric current metallurgy have been developed. This enables the calculation...... of electric current distribution, current induced temperature distribution and free energy sequence of various phase transitions in multiphase materials. The work is particularly suitable for the study of magnetic materials that contain various magnetic phases. The latter has not been considered in literature...

  17. 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.

  18. Nickel Solubility and Precipitation in Soils: A Thermodynamic Study

    International Nuclear Information System (INIS)

    Peltier, E.; Allada, R.; Navrotsky, A.; Sparks, D.

    2006-01-01

    The formation of mixed-metal-Al layered double hydroxide (LDH) phases similar to hydrotalcite has been identified as a significant mechanism for immobilization of trace metals in some environmental systems. These precipitate phases become increasingly stable as they age, and their formation may therefore be an important pathway for sequestration of toxic metals in contaminated soils. However, the lack of thermodynamic data for LDH phases makes it difficult to model their behavior in natural systems. In this work, enthalpies of formation for Ni LDH phases with nitrate and sulfate interlayers were determined and compared to recently published data on carbonate interlayer LDHs. Differences in the identity of the anion interlayer resulted in substantial changes in the enthalpies of formation of the LDH phases, in the order of increasing enthalpy carbonatethermodynamic properties of the LDH phases. Modeling results based on these thermodynamic data indicated that the formation of LDH phases on soil mineral substrates decreased Ni solubility compared to Ni(OH)2 over pH 5-9 when soluble Al is present in the soil substrate. Over time, both of these precipitate phases will transform to more stable Ni phyllosilicates

  19. Design of thermodynamic experiments and analyses of thermodynamic relationships

    International Nuclear Information System (INIS)

    Oezer Arnas, A.

    2009-01-01

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

  20. An Integrated approach (thermodynamic, structural, and computational) to the study of complexation of alkali-metal cations by a lower-rim calix[4]arene amide derivative in acetonitrile.

    Science.gov (United States)

    Horvat, Gordan; Stilinović, Vladimir; Hrenar, Tomica; Kaitner, Branko; Frkanec, Leo; Tomišić, Vladislav

    2012-06-04

    The calix[4]arene secondary-amide derivative L was synthesized, and its complexation with alkali-metal cations in acetonitrile (MeCN) was studied by means of spectrophotometric, NMR, conductometric, and microcalorimetric titrations at 25 °C. The stability constants of the 1:1 (metal/ligand) complexes determined by different methods were in excellent agreement. For the complexation of M(+) (M = Li, Na, K) with L, both enthalpic and entropic contributions were favorable, with their values and mutual relations being quite strongly dependent on the cation. The enthalpic and overall stability was the largest in the case of the sodium complex. Molecular and crystal structures of free L, its methanol and MeCN solvates, the sodium complex, and its MeCN solvate were determined by single-crystal X-ray diffraction. The inclusion of a MeCN molecule in the calixarene hydrophobic cavity was observed both in solution and in the solid state. This specific interaction was found to be stronger in the case of metal complexes compared to the free ligand because of the better preorganization of the hydrophobic cone to accept the solvent molecule. Density functional theory calculations showed that the flattened cone conformation (C(2) point group) of L was generally more favorable than the square cone conformation (C(4) point group). In the complex with Na(+), L was in square cone conformation, whereas in its adduct with MeCN, the conformation was slightly distorted from the full symmetry. These conformations were in agreement with those observed in the solid state. The classical molecular dynamics simulations indicated that the MeCN molecule enters the L hydrophobic cavity of both the free ligand and its alkali-metal complexes. The inclusion of MeCN in the cone of free L was accompanied by the conformational change from C(2) to C(4) symmetry. As in solution studies, in the case of ML(+) complexes, an allosteric effect was observed: the ligand was already in the appropriate square cone

  1. Engineering governance: introducing a governance meta framework.

    OpenAIRE

    Brand, N.; Beens, B.; Vuuregge, E.; Batenburg, R.

    2011-01-01

    There is a need for a framework that depicts strategic choices within an organisation with regard to potential governance structures. The governance meta framework provides the necessary structure in the current developments of governance. Performance as well as conformance are embedded in this framework and provide the balance for all governance domains. (aut.ref.)

  2. Corrosion in waste-fired boilers: A thermodynamic study

    DEFF Research Database (Denmark)

    Becidan, Michael; Sørum, Lars; Frandsen, Flemming

    2009-01-01

    A twofold study using thermodynamic equilibrium calculations was carried out to study corrosion in MSW incinerators. Corrosion was associated with the amount of alkalis and trace metals gaseous chlorides. Firstly, a two-level factorial experimental design combined with a data analysis were used...... to determine the main and interaction effects for various alkalis and trace metals gaseous chlorides responses. The factors studied were Na, K, S and Cl concentrations. The results provided a picture of the controlling parameters and insight about the processes taking place. Secondly, the efficiency of two...

  3. Thermodynamic properties of binary melts of manganese(II) bromide with lithium, cesium, and francium bromides

    International Nuclear Information System (INIS)

    Kritskaya, E.B.; Burylev, B.P.; Mojsov, L.P.; Kritskij, V.E.

    2005-01-01

    Relaying on the experimentally ascertained linear dependence of the Gibbs excessive mole energies on alkali metal ordinal number in the systems MnBr 2 -MBr (M=Na, K, Rb), thermodynamic properties of the melts in binary systems MBr 2 -M'Br (M'=Li, Cs, Fr) were prepared. Concentration dependences of the Gibbs energies, and thermodynamic activities of compounds in the above systems at 1125 K were calculated [ru

  4. Charged hard spheres in a uniform neutralizing background: The role of thermodynamics selfconsistence

    International Nuclear Information System (INIS)

    Badirkhan, Z.; Pastore, G.; Tosi, M.P.

    1991-06-01

    Calculations of the thermodynamic properties and pair distribution function of a one-component classical fluid of charged hard spheres in a uniform neutralizing background are reported and compared with Monte Carlo results of Hansen and Weis. Thermodynamic selfconsistence between the virial pressure and the fluctuations formula for the isothermal compressibility is enforced in the calculations by various alternative approaches. The role of thermodynamic selfconsistence is crucial to obtain a satisfactory quantitative description of this model fluid, in view of its applications in the theory of liquid metals and of dispersions of charged colloidal particles. (author). 23 refs, 4 figs, 3 tabs

  5. Chemical Thermodynamics Vol. 12 - Chemical Thermodynamics of tin

    International Nuclear Information System (INIS)

    Gamsjaeger, Heinz; GAJDA, Tamas; Sangster, James; Saxena, Surendra K.; Voigt, Wolfgang; Perrone, Jane

    2012-01-01

    This is the 12th volume of a series of expert reviews of the chemical thermodynamics of key chemical elements in nuclear technology and waste management. This volume is devoted to the inorganic species and compounds of tin. The tables contained in Chapters III and IV list the currently selected thermodynamic values within the NEA TDB Project. The database system developed at the NEA Data Bank, see Section II.6, assures consistency among all the selected and auxiliary data sets. The recommended thermodynamic data are the result of a critical assessment of published information. The values in the auxiliary data set, see Tables IV-1 and IV-2, have been adopted from CODATA key values or have been critically reviewed in this or earlier volumes of the series

  6. Membrane extraction with thermodynamically unstable diphosphonic acid derivatives

    Science.gov (United States)

    Horwitz, E.P.; Gatrone, R.C.; Nash, K.L.

    1997-10-14

    Thermodynamically-unstable complexing agents which are diphosphonic acids and diphosphonic acid derivatives (or sulphur containing analogs), like carboxyhydroxymethanediphosphonic acid and vinylidene-1,1-diphosphonic acid, are capable of complexing with metal ions, and especially metal ions in the II, III, IV, V and VI oxidation states, to form stable, water-soluble metal ion complexes in moderately alkaline to highly-acidic media. However, the complexing agents can be decomposed, under mild conditions, into non-organic compounds which, for many purposes are environmentally-nondamaging compounds thereby degrading the complex and releasing the metal ion for disposal or recovery. Uses for such complexing agents as well as methods for their manufacture are also described. 1 fig.

  7. Thermodynamic Database for Zirconium Alloys

    International Nuclear Information System (INIS)

    Jerlerud Perez, Rosa

    2003-05-01

    For many decades zirconium alloys have been commonly used in the nuclear power industry as fuel cladding material. Besides their good corrosion resistance and acceptable mechanical properties the main reason of using these alloys is the low neutron absorption. Zirconium alloys are exposed to a very severe environment during the nuclear fission process and there is a demand for better design of this material. To meet this requirement a thermodynamic database is developed to support material designers. In this thesis some aspects about the development of a thermodynamic database for zirconium alloys are presented. A thermodynamic database represents an important facility in applying thermodynamic equilibrium calculations for a given material providing: 1) relevant information about the thermodynamic properties of the alloys e.g. enthalpies, activities, heat capacity, and 2) significant information for the manufacturing process e.g. heat treatment temperature. The basic information in the database is first the unary data, i.e. pure elements; those are taken from the compilation of the Scientific Group Thermodata Europe (SGTE) and then the binary and ternary systems. All phases present in those binary and ternary systems are described by means of the Gibbs energy dependence on composition and temperature. Many of those binary systems have been taken from published or unpublished works and others have been assessed in the present work. All the calculations have been made using Thermo C alc software and the representation of the Gibbs energy obtained by applying Calphad technique

  8. Thermodynamics and kinetics insight into reaction mechanism of Cu{sub 2}ZnSnSe{sub 4} nanoink based on binary metal-amine complexes in polyetheramine-synthesized process

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Chi-Jie [Institute of Microelectronics and Department of Electrical Engineering, National Cheng Kung University, Tainan 701, Taiwan, ROC (China); Shei, Shih-Chang, E-mail: scshei@mail.nutn.edu.tw [Department of Electrical Engineering, National University of Tainan, 700, Taiwan, ROC (China); Chang, Shoou-Jinn [Institute of Microelectronics and Department of Electrical Engineering, National Cheng Kung University, Tainan 701, Taiwan, ROC (China)

    2016-08-15

    This paper reports on the reaction mechanism of Cu{sub 2}ZnSnSe{sub 4} (CZTSe) nanoink via a solvent-thermal reflux method using copper (Cu), zinc (Zn), tin (Sn), and selenium (Se) powders as precursors and polyetheramine as a reaction solvent. The formation of CZTSe nanoparticles in polyetheramine began with the formation of binary phase CuSe and CuSe{sub 2} due to the strong catalysis provided by polyetheramine. Finally, ternary crystals of Cu{sub 2}SnSe{sub 3} transformed into well-dispersed nanocrystals of Cu{sub 2}ZnSnSe{sub 4}. The size of the crystals was shown to decrease with reaction time due to the emulsification effect of the polyetheramine epoxy group. The PH value-reaction time curves for single Cu, Zn elements and CZTSe from all participants elements reacted together have a relationship just reversed each other and both multistage feature were observed, which indicates that the CZTSe reaction was dominated by copper and zinc elements. The PH-temperature mechanism demonstrates that the reaction was controlled by the formation of metal-amine complexes, especially, after heating the PH-time variation manner is the same for pure element and all four elements reacted together. To the best of our knowledge, this is the first study on the mechanism underlying CZTSe formation based on the reactivity and stability of reaction species. - Highlights: • Reaction mechanism of Cu{sub 2}ZnSnSe{sub 4} (CZTSe) nanoink via a solvent-thermal reflux method using polyetheramine was developed. • PH effect on thermal dynamics and characteristics of reagents and solvents in the CZTSe nanoink has been realized. • PH-temperature mechanism demonstrates that the reaction controlled by the formation of metal-amine complexes.

  9. The Thermodynamic Machinery of Life

    CERN Document Server

    Kurzynski, Michal

    2006-01-01

    Living organisms are open thermodynamic systems whose functional structure has developed and been kinetically frozen during the historical process of biological evolution. A thermodynamics of both nonequilibrium and complex systems is needed for their description. In this book, the foundations of such a thermodynamics are presented. Biological processes at the cellular level are considered as coupled chemical reactions and transport processes across internal and the cytoplasmic membrane. All these processes are catalyzed by specific enzymes hence the kinetics of enzymatic catalysis and its control are described here in detail. The coupling of several processes through a common enzyme is considered in the context of free energy or signal transduction. Special attention is paid to evidence for a rich stochastic internal dynamics of native proteins and its possible role in the control of enzyme activity and in the action of biological molecular machines.

  10. Complexation thermodynamics of modified cyclodextrins

    DEFF Research Database (Denmark)

    Schönbeck, Jens Christian Sidney; Westh, Peter; Holm, Rene

    2014-01-01

    Inclusion complexes between two bile salts and a range of differently methylated β-cyclodextrins were studied in an attempt to rationalize the complexation thermodynamics of modified cyclodextrins. Calorimetric titrations at a range of temperatures provided precise values of the enthalpies (ΔH......°), entropies (ΔS°), and heat capacities (ΔCp) of complexation, while molecular dynamics simulations assisted the interpretation of the obtained thermodynamic parameters. As previously observed for several types of modified cyclodextrins, the substituents at the rims of the cyclodextrin induced large changes......° and then a strong decrease when the degree of substitution exceeded some threshold. Exactly the same trend was observed for ΔCp. The dehydration of nonpolar surface, as quantified by the simulations, can to a large extent explain the variation in the thermodynamic parameters. The methyl substituents form additional...

  11. Thermodynamics a complete undergraduate course

    CERN Document Server

    Steane, Andrew M

    2016-01-01

    This is an undergraduate textbook in thermodynamics—the science of heat, work, temperature, and entropy. The text presents thermodynamics in and of itself, as an elegant and powerful set of ideas and methods. These methods open the way to understanding a very wide range of phenomena in physics, chemistry, engineering, and biology. Starting out from an introduction of concepts at first year undergraduate level, the roles of temperature, internal energy, and entropy are explained via the laws of thermodynamics. The text employs a combination of examples, exercises, and careful discussion, with a view to conveying the feel of the subject as well as avoiding common misunderstandings. The Feynman–Smuluchowski ratchet, Szilard’s engine, and Maxwell’s daemon are used to elucidate entropy and the second law. Free energy and thermodynamic potentials are discussed at length, with applications to solids as well as fluids and flow processes. Thermal radiation is discussed, and the main ideas significant to global...

  12. 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...

  13. Development of Thermodynamic Conceptual Evaluation

    Science.gov (United States)

    Talaeb, P.; Wattanakasiwich, P.

    2010-07-01

    This research aims to develop a test for assessing student understanding of fundamental principles in thermodynamics. Misconceptions found from previous physics education research were used to develop the test. Its topics include heat and temperature, the zeroth and the first law of thermodynamics, and the thermodynamics processes. The content validity was analyzed by three physics experts. Then the test was administered to freshmen, sophomores and juniors majored in physics in order to determine item difficulties and item discrimination of the test. A few items were eliminated from the test. Finally, the test will be administered to students taking Physics I course in order to evaluate the effectiveness of Interactive Lecture Demonstrations that will be used for the first time at Chiang Mai University.

  14. Thermodynamics and kinetics of molecular motors.

    Science.gov (United States)

    Astumian, R Dean

    2010-06-02

    Molecular motors are first and foremost molecules, governed by the laws of chemistry rather than of mechanics. The dynamical behavior of motors based on chemical principles can be described as a random walk on a network of states. A key insight is that any molecular motor in solution explores all possible motions and configurations at thermodynamic equilibrium. By using input energy and chemical design to prevent motion that is not wanted, what is left behind is the motion that is desired. This review is focused on two-headed motors such as kinesin and Myosin V that move on a polymeric track. By use of microscopic reversibility, it is shown that the ratio between the number of forward steps and the number of backward steps in any sufficiently long time period does not directly depend on the mechanical properties of the linker between the two heads. Instead, this ratio is governed by the relative chemical specificity of the heads in the front-versus-rear position for the fuel, adenosine triphosphate and its products, adenosine diphosphate and inorganic phosphate. These insights have been key factors in the design of biologically inspired synthetic molecular walkers constructed out of DNA or out of small organic molecules. Copyright (c) 2010 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  15. Placement by thermodynamic simulated annealing

    International Nuclear Information System (INIS)

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

    2003-01-01

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

  16. Thermodynamics of Dipolar Chain Systems

    DEFF Research Database (Denmark)

    R. Armstrong, J.; Zinner, Nikolaj Thomas; V. Fedorov, D.

    2012-01-01

    The thermodynamics of a quantum system of layers containing perpendicularly oriented dipolar molecules is studied within an oscillator approximation for both bosonic and fermionic species. The system is assumed to be built from chains with one molecule in each layer. We consider the effects...... numerically. Our findings indicate that thermodynamic observables, such as the heat capacity, can be used to probe the signatures of the intralayer interaction between chains. This should be relevant for near future experiments on polar molecules with strong dipole moments....

  17. Applied Thermodynamics: Grain Boundary Segregation

    Directory of Open Access Journals (Sweden)

    Pavel Lejček

    2014-03-01

    Full Text Available Chemical composition of interfaces—free surfaces and grain boundaries—is generally described by the Langmuir–McLean segregation isotherm controlled by Gibbs energy of segregation. Various components of the Gibbs energy of segregation, the standard and the excess ones as well as other thermodynamic state functions—enthalpy, entropy and volume—of interfacial segregation are derived and their physical meaning is elucidated. The importance of the thermodynamic state functions of grain boundary segregation, their dependence on volume solid solubility, mutual solute–solute interaction and pressure effect in ferrous alloys is demonstrated.

  18. Thermodynamics of de Sitter universes

    International Nuclear Information System (INIS)

    Huang Chaoguang; Liu Liao; Wang Bobo

    2002-01-01

    It is shown that the first law of thermodynamics can be applied to the de Sitter universe to relate its vacuum energy, pressure, entropy of horizon, chemical potential, etc., when the cosmological constant changes due to the fluctuation of the vacuum or other reasons. The second law should be reformulated in the form that the spontaneous decay of the vacuum never makes the entropy of the de Sitter universe decrease. The third law of thermodynamics, applying to the de Sitter universe, implies that the cosmological constant cannot reach zero by finite physical processes. The relation to the holographic principle is also briefly discussed

  19. Nuclear thermodynamics below particle threshold

    International Nuclear Information System (INIS)

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

    2005-01-01

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

  20. Peaceful nuclear explosions and thermodynamics

    International Nuclear Information System (INIS)

    Prieto, F.E.

    1975-01-01

    Some theoretical advances in the thermodynamics of very high pressures are reviewed. A universal (system-independent) formulation of the thermodynamics is sketched, and some of the equations more frequently used are written in system-independent form. Among these equations are: Hugoniot pressure and temperature as functions of volume; the Mie-Gruneisen equation; and an explicit form for the equation of state. It is also shown that this formalism can be used to interpret and predict results from peaceful nuclear explosions. (author)

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

    Directory of Open Access Journals (Sweden)

    Álvaro M. Alhambra

    2016-10-01

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

  2. Thermodynamics of Minerals Stable Near the Earth's Surface

    International Nuclear Information System (INIS)

    Navrotsky, Alexandra

    2003-01-01

    OAK B262 Research and Education Activities We are working on developing calorimetric techniques for sulfide minerals. We have completed calorimetric studies of (Na, K, H3O) jarosites, of Na and K jarosite -alunite solid solutions, and of Cr6+ - containing jarosites. We are now working on phases containing As and Pb. These studies are important to issues of heavy metal pollution in the environment. A number of postdocs, graduate students, and undergrads have participated in the research. We have active collaboration with Dirk Baron, faculty at California State University, Bakersfield. In a collaboration with Peter Burns, Notre Dame University, we are working on thermochemistry of U6+ minerals. Navrotsky has participated in a number of national workshops that are helping to define the interfaces between nanotechnology and earth/environmental science. Major Findings Our first finding on uranyl minerals shows that studtite, a phase containing structural peroxide ion, is thermodynamically unstable in the absence of a source of aqueous peroxide ion but is thermodynamically stable in contact with a solution containing peroxide concentrations expected for the radiolysis of water in contact with spent nuclear fuel. This work is in press in Science. We have a consistent thermodynamic data set for the (Na, K, H3O) (Al, Fe) jarosite, alunite minerals and for Cr6+ substituting for S6+ in jarosite. The latter phases represent one of the few solid sinks for trapping toxic Cr6+ in groundwater. Contributions within Discipline Better understanding of thermodynamic driving for and constraints on geochemical and environmental processes

  3. Economics of Metal Markets

    OpenAIRE

    Tilton, J.E.

    1984-01-01

    Simple economic principles can provide useful insights into the behavior of metal markets. In applying these principles, however, the analyst must take into account technology, market structure, government policies, and other institutional factors influencing the nature of metal supply and demand. Knowledge of both economics and the metal markets is essential. One without the other is likely to lead to sterile or even misleading results. In support of the above conclusion, this study exa...

  4. Review of the synthesis of layered double hydroxides: a thermodynamic approach

    Directory of Open Access Journals (Sweden)

    Bravo-Suárez Juan J.

    2004-01-01

    Full Text Available The synthesis of layered double hydroxides (LDHs by hydrothermal-LDH reconstruction and coprecipitation methods is reviewed using a thermodynamic approach. A mixture model was used for the estimation of the thermodynamics of formation of LDHs. The synthesis and solubility of LDHs are discussed in terms of standard molar Gibbs free energy change of reaction. Data for numerous divalent and trivalent metals as well as for some monovalent and tetravalent metals that may be part of the LDH structure have been compiled. Good agreement is found between theoretical and experimental data. Diagrams and tables for the prediction of possible new LDH materials are provided.

  5. Government and governance strategies in medical tourism

    NARCIS (Netherlands)

    Ormond, M.E.; Mainil, T.

    2015-01-01

    This chapter provides an overview of current government and governance strategies relative to medical tourism development and management around the world. Most studies on medical tourism have privileged national governments as key actors in medical tourism regulation and, in some cases, even

  6. Engineering governance: introducing a governance meta framework.

    NARCIS (Netherlands)

    Brand, N.; Beens, B.; Vuuregge, E.; Batenburg, R.

    2011-01-01

    There is a need for a framework that depicts strategic choices within an organisation with regard to potential governance structures. The governance meta framework provides the necessary structure in the current developments of governance. Performance as well as conformance are embedded in this

  7. Biosorptive uptake of Fe2+, Cu2+ and As5+ by activated biochar derived from Colocasia esculenta: Isotherm, kinetics, thermodynamics, and cost

    Directory of Open Access Journals (Sweden)

    Soumya Banerjee

    2016-09-01

    Full Text Available The adsorptive capability of superheated steam activated biochar (SSAB produced from Colocasia esculenta was investigated for removal of Cu2+, Fe2+ and As5+ from simulated coal mine wastewater. SSAB was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy and Brunauer–Emmett–Teller analyser. Adsorption isotherm indicated monolayer adsorption which fitted best in Langmuir isotherm model. Thermodynamic study suggested the removal process to be exothermic, feasible and spontaneous in nature. Adsorption of Fe2+, Cu2+ and As5+ on to SSAB was found to be governed by pseudo-second order kinetic model. Efficacy of SSAB in terms of metal desorption, regeneration and reusability for multiple cycles was studied. Regeneration of metal desorbed SSAB with 1 N sodium hydroxide maintained its effectiveness towards multiple metal adsorption cycles. Cost estimation of SSAB production substantiated its cost effectiveness as compared to commercially available activated carbon. Hence, SSAB could be a promising adsorbent for metal ions removal from aqueous solution.

  8. Multi-pressure boiler thermodynamics analysis code

    International Nuclear Information System (INIS)

    Lorenzoni, G.

    1992-01-01

    A new method and the relative FORTRAN program for the thermodynamics design analysis of a multipressure boiler are reported. This method permits the thermodynamics design optimization with regard to total exergy production and a preliminary costs

  9. THERMODYNAMIC STUDIES ON THE CHARGE-TRANSFER ...

    African Journals Online (AJOL)

    ... technique was employed to investigate thermodynamic parameters associated with the interaction ... KEY WORDS: Amitriptyline , chloranilic acid, thermodynamic parameters. Global Jnl Pure & Applied Sciences Vol.10(1) 2004: 147-153 ...

  10. On thermodynamic limits of entropy densities

    NARCIS (Netherlands)

    Moriya, H; Van Enter, A

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

  11. Quantum and thermodynamic aspects of Black Holes

    International Nuclear Information System (INIS)

    Sande e Lemos, J.P. de; Videira, A.L.L.

    1983-01-01

    The main results originating from the attempts of trying to incorporate quantum and thermodynamic properties and concepts to the gravitational system black hole, essentially the Hawking effect and the four laws of thermodynamics are reviewed. (Author) [pt

  12. 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.

  13. Thermodynamic efficiency of nonimaging concentrators

    Science.gov (United States)

    Shatz, Narkis; Bortz, John; Winston, Roland

    2009-08-01

    The purpose of a nonimaging concentrator is to transfer maximal flux from the phase space of a source to that of a target. A concentrator's performance can be expressed relative to a thermodynamic reference. We discuss consequences of Fermat's principle of geometrical optics. We review étendue dilution and optical loss mechanisms associated with nonimaging concentrators, especially for the photovoltaic (PV) role. We introduce the concept of optical thermodynamic efficiency which is a performance metric combining the first and second laws of thermodynamics. The optical thermodynamic efficiency is a comprehensive metric that takes into account all loss mechanisms associated with transferring flux from the source to the target phase space, which may include losses due to inadequate design, non-ideal materials, fabrication errors, and less than maximal concentration. As such, this metric is a gold standard for evaluating the performance of nonimaging concentrators. Examples are provided to illustrate the use of this new metric. In particular we discuss concentrating PV systems for solar power applications.

  14. Thermodynamics of asymptotically safe theories

    DEFF Research Database (Denmark)

    Rischke, Dirk H.; Sannino, Francesco

    2015-01-01

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

  15. Thermodynamics of freezing and melting

    DEFF Research Database (Denmark)

    Pedersen, Ulf Rørbæk; Costigliola, Lorenzo; Bailey, Nicholas

    2016-01-01

    phases at a single thermodynamic state point provide the basis for calculating the pressure, density and entropy of fusion as functions of temperature along the melting line, as well as the variation along this line of the reduced crystalline vibrational mean-square displacement (the Lindemann ratio...

  16. Thermodynamical aspects of pulse tubes

    NARCIS (Netherlands)

    Waele, de A.T.A.M.; Steijaert, P.P.; Gijzen, J.

    1997-01-01

    The cooling power of cryocoolers is determined by the work done by the compressor and the entropy produced by the irreversible processes in the various components of the system. In this paper we discuss the thermodynamics of pulse tubes, but many of the relationships are equally valid for other

  17. Thermodynamics of Oligonucleotide Duplex Melting

    Science.gov (United States)

    Schreiber-Gosche, Sherrie; Edwards, Robert A.

    2009-01-01

    Melting temperatures of oligonucleotides are useful for a number of molecular biology applications, such as the polymerase chain reaction (PCR). Although melting temperatures are often calculated with simplistic empirical equations, application of thermodynamics provides more accurate melting temperatures and an opportunity for students to apply…

  18. Thermodynamic theory of black holes

    Energy Technology Data Exchange (ETDEWEB)

    Davies, P C.W. [King' s Coll., London (UK). Dept. of Mathematics

    1977-04-21

    The thermodynamic theory underlying black hole processes is developed in detail and applied to model systems. It is found that Kerr-Newman black holes undergo a phase transition at a = 0.68M or Q = 0.86M, where the heat capacity has an infinite discontinuity. Above the transition values the specific heat is positive, permitting isothermal equilibrium with a surrounding heat bath. Simple processes and stability criteria for various black hole situations are investigated. The limits for entropically favoured black hole formation are found. The Nernst conditions for the third law of thermodynamics are not satisfied fully for black holes. There is no obvious thermodynamic reason why a black hole may not be cooled down below absolute zero and converted into a naked singularity. Quantum energy-momentum tensor calculations for uncharged black holes are extended to the Reissner-Nordstrom case, and found to be fully consistent with the thermodynamic picture for Q < M. For Q < M the model predicts that 'naked' collapse also produces radiation, with such intensity that the collapsing matter is entirely evaporated away before a naked singularity can form.

  19. One Antimatter— Two Possible Thermodynamics

    Directory of Open Access Journals (Sweden)

    Alexander Y. Klimenko

    2014-02-01

    Full Text Available Conventional thermodynamics, which is formulated for our world populated by radiation and matter, can be extended to describe physical properties of antimatter in two mutually exclusive ways: CP-invariant or CPT-invariant. Here we refer to invariance of physical laws under charge (C, parity (P and time reversal (T transformations. While in quantum field theory CPT invariance is a theorem confirmed by experiments, the symmetry principles applied to macroscopic phenomena or to the whole of the Universe represent only hypotheses. Since both versions of thermodynamics are different only in their treatment of antimatter, but are the same in describing our world dominated by matter, making a clear experimentally justified choice between CP invariance and CPT invariance in context of thermodynamics is not possible at present. This work investigates the comparative properties of the CP- and CPT-invariant extensions of thermodynamics (focusing on the latter, which is less conventional than the former and examines conditions under which these extensions can be experimentally tested.

  20. Simulating metabolism with statistical thermodynamics.

    Science.gov (United States)

    Cannon, William R

    2014-01-01

    New methods are needed for large scale modeling of metabolism that predict metabolite levels and characterize the thermodynamics of individual reactions and pathways. Current approaches use either kinetic simulations, which are difficult to extend to large networks of reactions because of the need for rate constants, or flux-based methods, which have a large number of feasible solutions because they are unconstrained by the law of mass action. This report presents an alternative modeling approach based on statistical thermodynamics. The principles of this approach are demonstrated using a simple set of coupled reactions, and then the system is characterized with respect to the changes in energy, entropy, free energy, and entropy production. Finally, the physical and biochemical insights that this approach can provide for metabolism are demonstrated by application to the tricarboxylic acid (TCA) cycle of Escherichia coli. The reaction and pathway thermodynamics are evaluated and predictions are made regarding changes in concentration of TCA cycle intermediates due to 10- and 100-fold changes in the ratio of NAD+:NADH concentrations. Finally, the assumptions and caveats regarding the use of statistical thermodynamics to model non-equilibrium reactions are discussed.

  1. THERMODYNAMICS USED IN ENVIRONMENTAL ENGINEERING

    Science.gov (United States)

    Thermodynamics is a science in which energy transformations are studied as well as their relationships to the changes in the chemical properties of a system. It is the fundamental basis of many engineering fields. The profession of environmental engineering is no exception. In pa...

  2. Thermodynamics on the Molality Scale

    Science.gov (United States)

    Canagaratna, Sebastian G.; Maheswaran, M.

    2013-01-01

    For physical measurements, the compositions of solutions, especially electrolyte solutions, are expressed in terms of molality rather than mole fractions. The development of the necessary thermodynamic equations directly in terms of molality is not common in textbooks, and the treatment in the literature is not very systematic. We develop a…

  3. A Simple Statistical Thermodynamics Experiment

    Science.gov (United States)

    LoPresto, Michael C.

    2010-01-01

    Comparing the predicted and actual rolls of combinations of both two and three dice can help to introduce many of the basic concepts of statistical thermodynamics, including multiplicity, probability, microstates, and macrostates, and demonstrate that entropy is indeed a measure of randomness, that disordered states (those of higher entropy) are…

  4. Possible extended forms of thermodynamic entropy

    International Nuclear Information System (INIS)

    Sasa, Shin-ichi

    2014-01-01

    Thermodynamic entropy is determined by a heat measurement through the Clausius equality. The entropy then formalizes a fundamental limitation of operations by the second law of thermodynamics. The entropy is also expressed as the Shannon entropy of the microscopic degrees of freedom. Whenever an extension of thermodynamic entropy is attempted, we must pay special attention to how its three different aspects just mentioned are altered. In this paper, we discuss possible extensions of the thermodynamic entropy. (paper)

  5. 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

  6. 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.

  7. Thermodynamics of statistical inference by cells.

    Science.gov (United States)

    Lang, Alex H; Fisher, Charles K; Mora, Thierry; Mehta, Pankaj

    2014-10-03

    The deep connection between thermodynamics, computation, and information is now well established both theoretically and experimentally. Here, we extend these ideas to show that thermodynamics also places fundamental constraints on statistical estimation and learning. To do so, we investigate the constraints placed by (nonequilibrium) thermodynamics on the ability of biochemical signaling networks to estimate the concentration of an external signal. We show that accuracy is limited by energy consumption, suggesting that there are fundamental thermodynamic constraints on statistical inference.

  8. 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....

  9. Casimir effect and thermodynamics of horizon instabilities

    International Nuclear Information System (INIS)

    Hartnoll, Sean A.

    2004-01-01

    We propose a dual thermodynamic description of a classical instability of generalized black hole spacetimes. From a thermodynamic perspective, the instability is due to negative compressibility in regions where the Casimir pressure is large. The argument indicates how the correspondence between thermodynamic and classical instability for horizons may be extended to cases without translational invariance

  10. Federalism and multilevel governance

    NARCIS (Netherlands)

    van der Wusten, H.; Agnew, J.; Mamadouh, V.; Secor, A.J.; Sharp, J.

    2015-01-01

    Federalism and multilevel governance both emphasize polycentricity in governing arrangements. With their different intellectual pedigrees, these concepts are discussed in two separate sections. Fragments are now increasingly mixed up in hybrid forms of governance that also encompass originally

  11. Developing digital forensic governance

    CSIR Research Space (South Africa)

    Grobler, M

    2010-03-01

    Full Text Available This paper presents a Digital Forensic (DF) governance framework and its mapping on the SANS ISO/IEC 38500:2009 Corporate governance of information technology structure. DF governance assists organisations in guiding the management team...

  12. Voluntary Environmental Governance Arrangements

    NARCIS (Netherlands)

    van der Heijden, J.

    2012-01-01

    Voluntary environmental governance arrangements have focal attention in studies on environmental policy, regulation and governance. The four major debates in the contemporary literature on voluntary environmental governance arrangements are studied. The literature falls short of sufficiently

  13. Small metal particles and the ideal Fermi gas

    International Nuclear Information System (INIS)

    Barma, Mustanpir

    1991-01-01

    Kubo's theoretical model of a small metal particle consists of a number of noninteraction electrons (an ideal Fermi gas) confined to a finite volume. By 'small' it meant that the size of the particle is intermediate between that of a few atoms cluster and the bulk solid, the radius of the particle being 5 to 50 Angstroms. The model is discussed and size dependence of various energy scales is studied. For a fermi gas confined in a sphere or a cube, two size-dependent energy scales are important. The inner scale δ is the mean spacing between successive energy levels. It governs the very low temperature behaviour. The outer scale Δ is associated with the shell structure when δ ≤T<Δ, thermodynamic properties show an oscillatory fluctuations around a smooth background as the size or energy is varied. (M.G.B.) 23 refs

  14. Chemical thermodynamics of iron - Part 1 - Chemical thermodynamics volume 13a

    International Nuclear Information System (INIS)

    Lemire, Robert J.; Berner, Urs; Musikas, Claude; Palmer, Donald A.; Taylor, Peter; Tochiyama, Osamu; Perrone, Jane

    2013-01-01

    Volume 13a of the 'Chemical Thermodynamics' (TDB) series, is the first of two volumes describing the selection of chemical thermodynamic data for species of iron. Because of the voluminous information in the literature, it has been more efficient to prepare the review in two (unequal) parts. This larger first part contains assessments of data for the metal, simple ions, aqueous hydroxido, chlorido, sulfido, sulfato and carbonato complexes, and for solid oxides and hydroxides, halides, sulfates, carbonates and simple silicates. The second part will provide assessments of data for other aqueous halido species, sulfide solids, and solid and solution species with nitrate, phosphate and arsenate, as well as some aspects of solid solutions in iron-oxide and iron-sulfide systems. The database system developed at the OECD/NEA Data Bank ensures consistency not only within the recommended data sets of iron, but also among all the data sets published in the series. This volume will be of particular interest to scientists carrying out performance assessments of deep geological disposal sites for radioactive waste

  15. E-Government Dimension

    OpenAIRE

    Rosiyadi, Didi; Suryana, Nana; Cahyana, Ade; Nuryani, Nuryani

    2007-01-01

    Makalah ini mengemukakan E-Government Dimension yang merupakan salah satu hasil TahapanPengumpulan Data, dimana tahapan ini adalah bagian dari penelitian kompetitif di Lembaga Ilmu PengetahuanIndonesia 2007 yang sekarang sedang dilakukan. Data E-Government Dimension ini didapatkan dari berbagaisumber yang meliputi E-Government beberapa Negara di dunia, E-Government yang dibangun oleh beberapapenyedia aplikasi E-Government. E-Government Dimension terdiri dari tiga dimensi yaitu DemocraticDimen...

  16. High-temperature experimental and thermodynamic modelling research on the pyrometallurgical processing of copper

    Science.gov (United States)

    Hidayat, Taufiq; Shishin, Denis; Decterov, Sergei A.; Hayes, Peter C.; Jak, Evgueni

    2017-01-01

    Uncertainty in the metal price and competition between producers mean that the daily operation of a smelter needs to target high recovery of valuable elements at low operating cost. Options for the improvement of the plant operation can be examined and decision making can be informed based on accurate information from laboratory experimentation coupled with predictions using advanced thermodynamic models. Integrated high-temperature experimental and thermodynamic modelling research on phase equilibria and thermodynamics of copper-containing systems have been undertaken at the Pyrometallurgy Innovation Centre (PYROSEARCH). The experimental phase equilibria studies involve high-temperature equilibration, rapid quenching and direct measurement of phase compositions using electron probe X-ray microanalysis (EPMA). The thermodynamic modelling deals with the development of accurate thermodynamic database built through critical evaluation of experimental data, selection of solution models, and optimization of models parameters. The database covers the Al-Ca-Cu-Fe-Mg-O-S-Si chemical system. The gas, slag, matte, liquid and solid metal phases, spinel solid solution as well as numerous solid oxide and sulphide phases are included. The database works within the FactSage software environment. Examples of phase equilibria data and thermodynamic models of selected systems, as well as possible implementation of the research outcomes to selected copper making processes are presented.

  17. Thermodynamic data development using the solubility method (Joint research)

    International Nuclear Information System (INIS)

    Rai, Dhanpat; Yui, Mikazu

    2013-05-01

    The solubility method is one of the most powerful tools to obtain reliable thermodynamic data for 1) solubility products of discrete solids and double salts, 2) complexation constants for various ligands, 3) development of data in a wide range of pH values, 4) evaluation of data for metals that form very insoluble solids (e.g. tetravalent actinides), 5) determining solubility-controlling solids in different types of wastes and 6) elevated temperatures for redox sensitive systems. This document is focused on describing various aspects of obtaining thermodynamic data using the solubility method. This manuscript deals with various aspects of conducting solubility studies, including selecting the study topic, modeling to define important variables, selecting the range of variables and experimental parameters, anticipating results, general equipment requirements, conducting experiments, and interpreting experimental data. (author)

  18. Operational methods of thermodynamics. Volume 1 - Temperature measurement

    Science.gov (United States)

    Eder, F. X.

    The principles of thermometry are examined, taking into account the concept of temperature, the Kelvin scale, the statistical theory of heat, negative absolute temperatures, the thermodynamic temperature scale, the thermodynamic temperature scale below 1 K, noise thermometry, temperature scales based on black-body radiation, acoustical thermometry, and the International Practical Temperature Scale 1968. Aspects of practical temperature measurement are discussed, giving attention to thermometers based on the expansion of a gas or a liquid, instruments utilizing the relative thermal expansion of two different metals, devices measuring the vapor pressure of a liquid, thermocouples, resistance thermometers, radiation pyrometers of various types, instruments utilizing the temperature dependence of a number of material characteristics, devices for temperature control, thermometer calibration, and aspects of thermometer installation and inertia. A description is presented of the approaches employed for the measurement of low temperatures.

  19. Thermodynamics and statistical mechanics. [thermodynamic properties of gases

    Science.gov (United States)

    1976-01-01

    The basic thermodynamic properties of gases are reviewed and the relations between them are derived from the first and second laws. The elements of statistical mechanics are then formulated and the partition function is derived. The classical form of the partition function is used to obtain the Maxwell-Boltzmann distribution of kinetic energies in the gas phase and the equipartition of energy theorem is given in its most general form. The thermodynamic properties are all derived as functions of the partition function. Quantum statistics are reviewed briefly and the differences between the Boltzmann distribution function for classical particles and the Fermi-Dirac and Bose-Einstein distributions for quantum particles are discussed.

  20. Liquid state properties of certain noble and transition metals

    International Nuclear Information System (INIS)

    Bhuiyan, G.M.; Rahman, A.; Khaleque, M.A.; Rashid, R.I.M.A.; Mujibur Rahman, S.M.

    1998-07-01

    Certain structural, thermodynamic and atomic transport properties of a number of liquid noble and transition metals are reported. The underlying theory combines together a simple form of the N-body potential and the thermodynamically self-consistent variational modified hypernetted chain (VMHNC) theory of liquid. The static structure factors calculated by using the VMHNC resemble the hard sphere (HS) values. Consequently the HS model is used to calculate the thermodynamic properties viz. specific heat, entropy, isothermal compressibility and atomic transport properties. (author)

  1. The thermodynamic-buffer enzymes.

    Science.gov (United States)

    Stucki, J W

    1980-08-01

    Oxidative phosphorylation operates at optimal efficiency if and only if the condition of conductance matching L33/L11 = square root 1-q2 is fulfilled. In this relation L11 is the phenomenological conductance of phosphorylation, L33 the phenomenological conductance of the load, i.e. the irreversible ATP-utilizing processes in the cell, and q the degree of coupling of oxidative phosphorylation driven by respiration. Since during short time intervals L11 and q are constant whereas L33 fluctuates in the cell, oxidative phosphorylation would only rarely operate at optimal efficiency due to violation of conductance matching. This paper demonstrates that the reversible ATP-utilizing reaction catalyzed by adenylate kinase can effectively compensate deviations from conductance matching in the presence of a fluctuating L33 and hence allows oxidative phosphorylation to operate at optimal efficiency in the cell. Since the adenylate kinase reaction was found to buffer a thermodynamic potential, i.e. the phosphate potential, this finding was generalized to the concept of thermodynamic buffering. The thermodynamic buffering ability of the adenylate kinase reaction was demonstrated by experiments with incubated rat-liver mitochondria. Considerations of changes introduced in the entropy production by the adenylate kinase reaction allowed to establish the theoretical framework for thermodynamic buffering. The ability of thermodynamic buffering to compensate deviations from conductance matching in the presence of fluctuating loads was demonstrated by computer simulations. The possibility of other reversible ATP-utilizing reactions, like the ones catalyzed by creatine kinase and arginine kinase, to contribute to thermodynamic buffering is discussed. Finally, the comparison of the theoretically calculated steady-stae cytosolic adenine nucleotide concentrations with experimental data from perfused livers demonstrated that in livers from fed rats conductance matching is fulfilled on a

  2. 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

  3. Thermodynamic assessment of the palladium-tellurium (Pd-Te) system

    International Nuclear Information System (INIS)

    Gosse, S.; Gueneau, C.

    2011-01-01

    Among the fission products formed in nuclear fuels, the platinum-group metal palladium and the chalcogen element tellurium exhibit strong interaction. It is therefore of interest to be able to predict the chemical equilibria involving the Pd and Te fission products. A thermodynamic assessment is carried out using the Calphad (Calculation of Phase Diagram) method to investigate the behaviour of Pd-Te alloy system in nuclear fuels under irradiation and under waste disposal conditions. The Pd-Te binary description was optimized using experimental data found in literature including thermodynamic properties and phase diagram data. To validate the calculated phase diagram and thermodynamic properties, the results are compared with data from the literature. Both calculated and experimental phase diagrams and thermodynamic properties are in good agreement in the whole Pd-Te composition range. (authors)

  4. The thermodynamical foundation of electronic conduction in solids

    Science.gov (United States)

    Bringuier, E.

    2018-03-01

    In elementary textbooks, the microscopic justification of Ohm’s local law in a solid medium starts with Drude’s classical model of electron transport and next discusses the quantum-dynamical and statistical amendments. In this paper, emphasis is laid instead upon the thermodynamical background motivated by the Joule-Lenz heating effect accompanying conduction and the fact that the conduction electrons are thermalized at the lattice temperature. Both metals and n-type semiconductors are considered; but conduction under a magnetic field is not. Proficiency in second-year thermodynamics and vector analysis is required from an undergraduate university student in physics so that the content of the paper can be taught to third-year students. The necessary elements of quantum mechanics are posited in this paper without detailed justification. We start with the equilibrium-thermodynamic notion of the chemical potential of the electron gas, the value of which distinguishes metals from semiconductors. Then we turn to the usage of the electrochemical potential in the description of near-equilibrium electron transport. The response of charge carriers to the electrochemical gradient involves the mobility, which is the reciprocal of the coefficient of the effective friction force opposing the carrier drift. Drude’s calculation of mobility is restated with the dynamical requirements of quantum physics. Where the carrier density is inhomogeneous, there appears diffusion, the coefficient of which is thermodynamically related to the mobility. Next, it is remarked that the release of heat was ignored in Drude’s original model. In this paper, the flow of Joule heat is handled thermodynamically within an energy balance where the voltage generator, the conduction electrons and the host lattice are involved in an explicit way. The notion of dissipation is introduced as the rate of entropy creation in a steady state. The body of the paper is restricted to the case of one

  5. The OpenCalphad thermodynamic software interface

    Science.gov (United States)

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

    2017-01-01

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

  6. Thermodynamic Model of Spatial Memory

    Science.gov (United States)

    Kaufman, Miron; Allen, P.

    1998-03-01

    We develop and test a thermodynamic model of spatial memory. Our model is an application of statistical thermodynamics to cognitive science. It is related to applications of the statistical mechanics framework in parallel distributed processes research. Our macroscopic model allows us to evaluate an entropy associated with spatial memory tasks. We find that older adults exhibit higher levels of entropy than younger adults. Thurstone's Law of Categorical Judgment, according to which the discriminal processes along the psychological continuum produced by presentations of a single stimulus are normally distributed, is explained by using a Hooke spring model of spatial memory. We have also analyzed a nonlinear modification of the ideal spring model of spatial memory. This work is supported by NIH/NIA grant AG09282-06.

  7. The 4th Thermodynamic Principle?

    International Nuclear Information System (INIS)

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

    2007-01-01

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

  8. Thermodynamic Geometry and Hawking Radiation

    CERN Document Server

    Bellucci, S

    2010-01-01

    This work explores the role of thermodynamic fluctuations in the two parameter Hawking radiating black hole configurations. The system is characterized by an ensemble of arbitrary mass and radiation frequency of the black holes. In the due course of the Hawking radiations, we find that the intrinsic geometric description exhibits an intriguing set of exact pair correction functions and global correlation lengths. We investigate the nature of the constant amplitude radiation and find that it's not stable under fluctuations of the mass and frequency. Subsequently, the consideration of the York model decreasing amplitude radiation demonstrates that thermodynamic fluctuations are globally stable in the small frequency region. In connection with quantum gravity refinements, we take an account of the logarithmic correction into the constant amplitude and York amplitude over the Hawking radiation. In both considerations, we notice that the nature of the possible parametric fluctuations may precisely be ascertained w...

  9. Statistical thermodynamics of nonequilibrium processes

    CERN Document Server

    Keizer, Joel

    1987-01-01

    The structure of the theory ofthermodynamics has changed enormously since its inception in the middle of the nineteenth century. Shortly after Thomson and Clausius enunciated their versions of the Second Law, Clausius, Maxwell, and Boltzmann began actively pursuing the molecular basis of thermo­ dynamics, work that culminated in the Boltzmann equation and the theory of transport processes in dilute gases. Much later, Onsager undertook the elucidation of the symmetry oftransport coefficients and, thereby, established himself as the father of the theory of nonequilibrium thermodynamics. Com­ bining the statistical ideas of Gibbs and Langevin with the phenomenological transport equations, Onsager and others went on to develop a consistent statistical theory of irreversible processes. The power of that theory is in its ability to relate measurable quantities, such as transport coefficients and thermodynamic derivatives, to the results of experimental measurements. As powerful as that theory is, it is linear and...

  10. Thermodynamical properties of dark energy

    International Nuclear Information System (INIS)

    Gong Yungui; Wang Bin; Wang Anzhong

    2007-01-01

    We have investigated the thermodynamical properties of dark energy. Assuming that the dark energy temperature T∼a -n and considering that the volume of the Universe enveloped by the apparent horizon relates to the temperature, we have derived the dark energy entropy. For dark energy with constant equation of state w>-1 and the generalized Chaplygin gas, the derived entropy can be positive and satisfy the entropy bound. The total entropy, including those of dark energy, the thermal radiation, and the apparent horizon, satisfies the generalized second law of thermodynamics. However, for the phantom with constant equation of state, the positivity of entropy, the entropy bound, and the generalized second law cannot be satisfied simultaneously

  11. Modern Thermodynamics with Statistical Mechanics

    CERN Document Server

    Helrich, Carl S

    2009-01-01

    With the aim of presenting thermodynamics in as simple and as unified a form as possible, this textbook starts with an introduction to the first and second laws and then promptly addresses the complete set of the potentials in a subsequent chapter and as a central theme throughout. Before discussing modern laboratory measurements, the book shows that the fundamental quantities sought in the laboratory are those which are required for determining the potentials. Since the subjects of thermodynamics and statistical mechanics are a seamless whole, statistical mechanics is treated as integral part of the text. Other key topics such as irreversibility, the ideas of Ilya Prigogine, chemical reaction rates, equilibrium of heterogeneous systems, and transition-state theory serve to round out this modern treatment. An additional chapter covers quantum statistical mechanics due to active current research in Bose-Einstein condensation. End-of-chapter exercises, chapter summaries, and an appendix reviewing fundamental pr...

  12. Thermodynamics of Dipolar Chain Systems

    International Nuclear Information System (INIS)

    Armstrong, J.R.; Zinner, N.T.; Fedorov, D.V.; Jensen, A.S.

    2013-01-01

    The thermodynamics of a quantum system of layers containing perpendicularly oriented dipolar molecules is studied within an oscillator approximation for both bosonic and fermionic species. The system is assumed to be built from chains with one molecule in each layer. We consider the effects of the intralayer repulsion and quantum statistical requirements in systems with more than one chain. Specifically, we consider the case of two chains and solve the problem analytically within the harmonic Hamiltonian approach which is accurate for large dipole moments. The case of three chains is calculated numerically. Our findings indicate that thermodynamic observables, such as the heat capacity, can be used to probe the signatures of the intralayer interaction between chains. This should be relevant for near future experiments on polar molecules with strong dipole moments. (author)

  13. Association theories for complex thermodynamics

    DEFF Research Database (Denmark)

    Kontogeorgis, Georgios; Rafiqul Gani

    2013-01-01

    of this review is two-fold: first to illustrate some of the significant capabilities of these association theories and why indeed they have already been extensively used and are expected to find even more applications in the future. The second and most important aspect of this review is to outline many...... applications. While specialized models can handle different cases, even complex ones, with the advent of powerful theories and computers there is the hope that a single or a few models could be suitable for a general modeling of complex thermodynamics. After more than 100 years with active use of thermodynamic...... models, we have now come to the understanding that simple one-fluid theories like the cubic equations of state or the various forms of local composition models will never be able to model a wide range of complex systems with sufficient accuracy. While various modern approaches have appeared, one very...

  14. Model approach for simulating the thermodynamic behavior of the MFTF cryogenic cooling systems - a status report

    International Nuclear Information System (INIS)

    Sutton, S.B.; Stein, W.; Reitter, T.A.; Hindmarsh, A.C.

    1983-01-01

    A numerical model for calculating the thermodynamic behavior of the MFTF-B cryogenic cooling system is described. Nine component types are discussed with governing equations given. The algorithm for solving the coupled set of algebraic and ordinary differential equations is described. The model and its application to the MFTF-B cryogenic cooling system has not been possible due to lack of funding

  15. Chiral thermodynamics of nuclear matter

    Energy Technology Data Exchange (ETDEWEB)

    Fiorilla, Salvatore

    2012-10-23

    The equation of state of nuclear matter is calculated at finite temperature in the framework of in-medium chiral perturbation theory up to three-loop order. The dependence of its thermodynamic properties on the isospin-asymmetry is investigated. The chiral quark condensate is evaluated for symmetric nuclear matter. Its behaviour as a function of density and temperature sets important nuclear physics constraints for the QCD phase diagram.

  16. Thermodynamic properties of sea air

    Directory of Open Access Journals (Sweden)

    R. Feistel

    2010-02-01

    Full Text Available Very accurate thermodynamic potential functions are available for fluid water, ice, seawater and humid air covering wide ranges of temperature and pressure conditions. They permit the consistent computation of all equilibrium properties as, for example, required for coupled atmosphere-ocean models or the analysis of observational or experimental data. With the exception of humid air, these potential functions are already formulated as international standards released by the International Association for the Properties of Water and Steam (IAPWS, and have been adopted in 2009 for oceanography by IOC/UNESCO.

    In this paper, we derive a collection of formulas for important quantities expressed in terms of the thermodynamic potentials, valid for typical phase transitions and composite systems of humid air and water/ice/seawater. Particular attention is given to equilibria between seawater and humid air, referred to as "sea air" here. In a related initiative, these formulas will soon be implemented in a source-code library for easy practical use. The library is primarily aimed at oceanographic applications but will be relevant to air-sea interaction and meteorology as well.

    The formulas provided are valid for any consistent set of suitable thermodynamic potential functions. Here we adopt potential functions from previous publications in which they are constructed from theoretical laws and empirical data; they are briefly summarized in the appendix. The formulas make use of the full accuracy of these thermodynamic potentials, without additional approximations or empirical coefficients. They are expressed in the temperature scale ITS-90 and the 2008 Reference-Composition Salinity Scale.

  17. Improved Estimates of Thermodynamic Parameters

    Science.gov (United States)

    Lawson, D. D.

    1982-01-01

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

  18. Statistics and thermodynamics of fracture

    Science.gov (United States)

    Chudnovsky, A.

    1984-01-01

    A probabilistic model of the fracture processes unifying the phenomenological study of long term strength of materials, fracture mechanics and statistical approaches to fracture is briefly outlined. The general framework of irreversible thermodynamics is employed to model the deterministic side of the failure phenomenon. The stochastic calculus is used to account for thg failure mechanisms controlled by chance; particularly, the random roughness of fracture surfaces.

  19. Thermodynamic data for uranium fluorides

    International Nuclear Information System (INIS)

    Leitnaker, J.M.

    1983-03-01

    Self-consistent thermodynamic data have been tabulated for uranium fluorides between UF 4 and UF 6 , including UF 4 (solid and gas), U 4 F 17 (solid), U 2 F 9 (solid), UF 5 (solid and gas), U 2 F 10 (gas), and UF 6 (solid, liquid, and gas). Included are thermal function - the heat capacity, enthalpy, and free energy function, heats of formation, and vaporization behavior

  20. THERMODYNAMIC MODEL OF GAS HYDRATES

    OpenAIRE

    Недоступ, В. И.; Недоступ, О. В.

    2015-01-01

    The interest to gas hydrates grows last years. Therefore working out of reliable settlement-theoretical methods of definition of their properties is necessary. The thermodynamic model of gas hydrates in which the central place occupies a behaviour of guest molecule in cell is described. The equations of interaction of molecule hydrate formative gas with cell are received, and also an enthalpy and energy of output of molecule from a cell are determined. The equation for calculation of thermody...

  1. Chiral thermodynamics of nuclear matter

    International Nuclear Information System (INIS)

    Fiorilla, Salvatore

    2012-01-01

    The equation of state of nuclear matter is calculated at finite temperature in the framework of in-medium chiral perturbation theory up to three-loop order. The dependence of its thermodynamic properties on the isospin-asymmetry is investigated. The chiral quark condensate is evaluated for symmetric nuclear matter. Its behaviour as a function of density and temperature sets important nuclear physics constraints for the QCD phase diagram.

  2. 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.

  3. PRACTICE OF GOOD GOVERNANCE AND CORPORATE GOVERNANCE

    Directory of Open Access Journals (Sweden)

    Bălăceanu Cristina

    2010-12-01

    Full Text Available Corporate governance reforms are occurring in countries around the globe and potentially impacting the population of the entire planet. In developing countries, such reforms occur in a larger context that is primarily defined by previous attempts at promoting “development” and recent processes of economic globalization. In this context, corporate governance reforms (in combination with the liberalising reforms associated with economic globalization, in effect represent a new development strategy for third world countries. The most basic questions that arise with respect to this situation are what the prospects for this new development model are and whether alternatives should be considered. Keywords: governance, corporate governance, economic globalization, development.

  4. Public management and governance

    National Research Council Canada - National Science Library

    Bovaird, A. G; Löffler, Elke

    2009-01-01

    ... how the process of governing needs to be fundamentally altered if a government is to retain public trust and make better use of society's resources. Key themes covered include: ■ ■ ■ ■ the challenges and pressures which governments experience in an international context; the changing functions of modern government in the global economy; the 'mixed ec...

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

    Energy Technology Data Exchange (ETDEWEB)

    Leigh R. Martin; Peter R. Zalupski

    2010-09-01

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

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

    International Nuclear Information System (INIS)

    Martin, Leigh R.; Zalupski, Peter R.

    2010-01-01

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

  7. Thermodynamic analysis of salt corrosion of titanium alloys

    International Nuclear Information System (INIS)

    Travkin, V.V.; Pshirkov, V.F.; Kolachev, B.A.

    1979-01-01

    About 200 possible chemical reactions of metals, salts and oxides (in a solid state) with water (in a vapour state), and with gases (O 2 , Cl 2 , HCl) were studied by the thermodynamic analysis to elucidate a chemical nature of processes taking place at salt corrosion of titanium alloys (VT22, VT6 and VT16). Temperature dependences of isobaric-isothermic potential were considered to reveal a possibility of spontaneous course and direction of reactions as well as to obtain a comparative estimate of the probability of their pro-cedure. Thermodynamically possible schemes of the chemism of titanium alloy salt corrosion are proposed. Complex che-mical reactions take place in the presence of salt, moisture and oxygen of air on the surface of the alloys. The reactions proceed with the formation of titanium and alloying component chlorides, free chlorine and hydrogen. The free chlorine or HCl are released during pyrohydrolysis and oxidation of chlo-rides. The former ones interact with the alloy with the formation of salts, and hydrogen may be absorbed by the metal and cause embrittlement. Chlorides on the metal surface accelerate the chlorination process. NaCl acts as a cata-lyst. The determination of salt corrosion products has confirmed the process mechanism proposed

  8. 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

  9. Data governance implementation concept

    OpenAIRE

    Ullrichová, Jana

    2016-01-01

    This master´s thesis discusses concept of implementation for data governance. The theoretical part of this thesis is about data governance. It explains why data are important for company, describes definitoons of data governance, its history, its components, its principles and processes and fitting in company. Theoretical part is amended with examples of data governance failures and banking specifics. The main goal of this thesis is to create a concept for implementing data governance and its...

  10. PAD: a one-dimensional, coupled neutronic-thermodynamic-hydrodynamic computer code

    International Nuclear Information System (INIS)

    Peterson, D.M.; Stratton, W.R.; McLaughlin, T.P.

    1976-12-01

    Theoretical and numerical foundations, utilization guide, sample problems, and program listing and glossary are given for the PAD computer code which describes dynamic systems with interactive neutronics, thermodynamics, and hydrodynamics in one-dimensional spherical, cylindrical, and planar geometries. The code has been applied to prompt critical excursions in various fissioning systems (solution, metal, LMFBR, etc.) as well as to nonfissioning systems

  11. Thermodynamically consistent data-driven computational mechanics

    Science.gov (United States)

    González, David; Chinesta, Francisco; Cueto, Elías

    2018-05-01

    In the paradigm of data-intensive science, automated, unsupervised discovering of governing equations for a given physical phenomenon has attracted a lot of attention in several branches of applied sciences. In this work, we propose a method able to avoid the identification of the constitutive equations of complex systems and rather work in a purely numerical manner by employing experimental data. In sharp contrast to most existing techniques, this method does not rely on the assumption on any particular form for the model (other than some fundamental restrictions placed by classical physics such as the second law of thermodynamics, for instance) nor forces the algorithm to find among a predefined set of operators those whose predictions fit best to the available data. Instead, the method is able to identify both the Hamiltonian (conservative) and dissipative parts of the dynamics while satisfying fundamental laws such as energy conservation or positive production of entropy, for instance. The proposed method is tested against some examples of discrete as well as continuum mechanics, whose accurate results demonstrate the validity of the proposed approach.

  12. Singular limits in thermodynamics of viscous fluids

    CERN Document Server

    Feireisl, Eduard

    2017-01-01

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

  13. Transitions governance: Towards a new governance paradigm

    NARCIS (Netherlands)

    N. Frantzeskaki (Niki); D.A. Loorbach (Derk)

    2009-01-01

    textabstractThis paper presents a framework for governance in the context of large scale and long term societal change (transitions). We argue that existing theories of governance offer interesting descriptive insights for such a framework, but do not present innovative prescriptive ideas

  14. Leisure, Government and Governance: A Swedish Perspective

    Science.gov (United States)

    Lindstrom, Lisbeth

    2011-01-01

    The leisure sector has witnessed a tremendous expansion since 1960. The purpose of this article is to analyse the decisions and goals of Swedish government policy during the period 1962 to 2005. The empirical analysis covers government Propositions and governmental investigations. The fields covered are sports, culture, exercise, tourism and…

  15. Thermodynamic Studies for Drug Design and Screening

    Science.gov (United States)

    Garbett, Nichola C.; Chaires, Jonathan B.

    2012-01-01

    Introduction A key part of drug design and development is the optimization of molecular interactions between an engineered drug candidate and its binding target. Thermodynamic characterization provides information about the balance of energetic forces driving binding interactions and is essential for understanding and optimizing molecular interactions. Areas covered This review discusses the information that can be obtained from thermodynamic measurements and how this can be applied to the drug development process. Current approaches for the measurement and optimization of thermodynamic parameters are presented, specifically higher throughput and calorimetric methods. Relevant literature for this review was identified in part by bibliographic searches for the period 2004 – 2011 using the Science Citation Index and PUBMED and the keywords listed below. Expert opinion The most effective drug design and development platform comes from an integrated process utilizing all available information from structural, thermodynamic and biological studies. Continuing evolution in our understanding of the energetic basis of molecular interactions and advances in thermodynamic methods for widespread application are essential to realize the goal of thermodynamically-driven drug design. Comprehensive thermodynamic evaluation is vital early in the drug development process to speed drug development towards an optimal energetic interaction profile while retaining good pharmacological properties. Practical thermodynamic approaches, such as enthalpic optimization, thermodynamic optimization plots and the enthalpic efficiency index, have now matured to provide proven utility in design process. Improved throughput in calorimetric methods remains essential for even greater integration of thermodynamics into drug design. PMID:22458502

  16. Thermodynamic studies for drug design and screening.

    Science.gov (United States)

    Garbett, Nichola C; Chaires, Jonathan B

    2012-04-01

    A key part of drug design and development is the optimization of molecular interactions between an engineered drug candidate and its binding target. Thermodynamic characterization provides information about the balance of energetic forces driving binding interactions and is essential for understanding and optimizing molecular interactions. This review discusses the information that can be obtained from thermodynamic measurements and how this can be applied to the drug development process. Current approaches for the measurement and optimization of thermodynamic parameters are presented, specifically higher throughput and calorimetric methods. Relevant literature for this review was identified in part by bibliographic searches for the period 2004 - 2011 using the Science Citation Index and PUBMED and the keywords listed below. The most effective drug design and development platform comes from an integrated process utilizing all available information from structural, thermodynamic and biological studies. Continuing evolution in our understanding of the energetic basis of molecular interactions and advances in thermodynamic methods for widespread application are essential to realize the goal of thermodynamically driven drug design. Comprehensive thermodynamic evaluation is vital early in the drug development process to speed drug development toward an optimal energetic interaction profile while retaining good pharmacological properties. Practical thermodynamic approaches, such as enthalpic optimization, thermodynamic optimization plots and the enthalpic efficiency index, have now matured to provide proven utility in the design process. Improved throughput in calorimetric methods remains essential for even greater integration of thermodynamics into drug design. © 2012 Informa UK, Ltd.

  17. Free energy of formation of Mo2C and the thermodynamic properties of carbon in solid molybdenum

    Science.gov (United States)

    Seigle, L. L.; Chang, C. L.; Sharma, T. P.

    1979-01-01

    As part of a study of the thermodynamical properties of interstitial elements in refractory metals, the free energy of formation of Mo2C is determined, and the thermodynamical properties of C in solution in solid Mo evaluated. The activity of C in the two-phase region Mo + Mo2C is obtained from the C content of iron rods equilibrated with metal + carbide powder mixtures. The free energy of formation of alpha-Mo2C is determined from the activity data. The thermodynamic properties of C in the terminal solid solution are calculated from available data on the solid solubility of C in Mo. Lattice distortion due to misfit of the C atoms in the interstitial sites appears to play a significant role in determining the thermodynamic properties of C in solid Mo.

  18. Thermodynamic modeling of the stacking fault energy of austenitic steels

    International Nuclear Information System (INIS)

    Curtze, S.; Kuokkala, V.-T.; Oikari, A.; Talonen, J.; Haenninen, H.

    2011-01-01

    The stacking fault energies (SFE) of 10 austenitic steels were determined in the temperature range 50 ≤ T ≤ 600 K by thermodynamic modeling of the Fe-Cr-Ni-Mn-Al-Si-Cu-C-N system using a modified Olson and Cohen modeling approach (Olson GB, Cohen M. Metall Trans 1976;7A:1897 ). The applied model accounts for each element's contribution to the Gibbs energy, the first-order excess free energies, magnetic contributions and the effect of interstitial nitrogen. Experimental SFE values from X-ray diffraction measurements were used for comparison. The effect of SFE on deformation mechanisms was also studied by electron backscatter diffraction.

  19. Chemical and Thermodynamic Properties at High Temperatures: A Symposium

    Science.gov (United States)

    Walker, Raymond F.

    1961-01-01

    This book contains the program and all available abstracts of the 90' invited and contributed papers to be presented at the TUPAC Symposium on Chemical and Thermodynamic Properties at High Temperatures. The Symposium will be held in conjunction with the XVIIIth IUPAC Congress, Montreal, August 6 - 12, 1961. It has been organized, by the Subcommissions on Condensed States and on Gaseous States of the Commission on High Temperatures and Refractories and by the Subcommission on Experimental Thermodynamics of the Commission on Chemical Thermodynamics, acting in conjunction with the Organizing Committee of the IUPAC Congress. All inquiries concerning participation In the Symposium should be directed to: Secretary, XVIIIth International Congress of Pure and Applied Chemistry, National Research Council, Ottawa, 'Canada. Owing to the limited time and facilities available for the preparation and printing of the book, it has not been possible to refer the proofs of the abstracts to the authors for checking. Furthermore, it has not been possible to subject the manuscripts to a very thorough editorial examination. Some obvious errors in the manuscripts have been corrected; other errors undoubtedly have been introduced. Figures have been redrawn only when such a step was essential for reproduction purposes. Sincere apologies are offered to authors and readers for any errors which remain; however, in the circumstances neither the IUPAC Commissions who organized the Symposium, nor the U. S. Government Agencies who assisted in the preparation of this book can accept responsibility for the errors.

  20. A thermodynamic framework for the study of crystallization in polymers

    Science.gov (United States)

    Rao, I. J.; Rajagopal, K. R.

    In this paper, we present a new thermodynamic framework within the context of continuum mechanics, to predict the behavior of crystallizing polymers. The constitutive models that are developed within this thermodynamic setting are able to describe the main features of the crystallization process. The model is capable of capturing the transition from a fluid like behavior to a solid like behavior in a rational manner without appealing to any adhoc transition criterion. The anisotropy of the crystalline phase is built into the model and the specific anisotropy of the crystalline phase depends on the deformation in the melt. These features are incorporated into a recent framework that associates different natural configurations and material symmetries with distinct microstructural features within the body that arise during the process under consideration. Specific models are generated by choosing particular forms for the internal energy, entropy and the rate of dissipation. Equations governing the evolution of the natural configurations and the rate of crystallization are obtained by maximizing the rate of dissipation, subject to appropriate constraints. The initiation criterion, marking the onset of crystallization, arises naturally in this setting in terms of the thermodynamic functions. The model generated within such a framework is used to simulate bi-axial extension of a polymer film that is undergoing crystallization. The predictions of the theory that has been proposed are consistent with the experimental results (see [28] and [7]).