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Sample records for non-local thermodynamic equilibrium

  1. The Non-local Thermodynamical Equilibrium Effects on Opacity

    Institute of Scientific and Technical Information of China (English)

    WU Ze-Qing; ZHANG Ben-Ai; QIU Yu-Bo

    2001-01-01

    Based on the detailed configuration accounting (DCA) model, a method is developed to include the resonant photoionization and the excitation-autoionization in the non-local thermodynamical equilibrium (NLTE) average atom(AA) model. Using this new model, the mean charge states and the opacity are calculated for NLTE high-Z plasmas and compared with other results. The agreement w ith AA model is poor at low electron density. The present results agree well with those of DCA model within 10%. The calculations show that the NLTE effects on opacity are strong.

  2. Opacity Calculations for Non-Local Thermodynamic Equilibrium Mixtures

    Institute of Scientific and Technical Information of China (English)

    吴泽清; 韩国兴; 逄锦桥

    2002-01-01

    Based on the average atom model, a non-local thermodynamic equilibrium (non-LTE) model is developed to calculate opacity for mixtures. This model could be applied to high-Z problems. The mean ionization degrees of SiO2 of the present calculation are slightly higher compared with another model for mixtures. As an example, the opacity of Au and Nd mixture is calculated. The results show concrete non-LTE effects and the increase in opacity of the mixture is shown clearly.

  3. Opacity calculations for Non-Local-Thermodynamic-Equilibrium plasmas

    Institute of Scientific and Technical Information of China (English)

    PANG Jin-qiao; WU Ze-qing; YAN Jun; HAN Guo-xing

    2004-01-01

    In this paper, we presented a method to calculate the spectral-resolved opacity for Non-Local-Thermodynamic-Equilibrium (non-LTE) plasmas. By solving the rate equations, we get the population. In the rate equations, configuration-averaged rate coefficients are used and the cross sections are calculated based on the first-perturbation theory. Using the detailed configuration accounting with the term structures treated by the unresolved transition array model, we calculated the spectral-resolved opacity of Al plasmas. The results are compared with those of other theoretical models. From the comparison, we can see that the present results fit well with other models for low-Z plasmas. For high-Z plasmas, we will give detailed discussion in the future.

  4. Modeling non local thermodynamic equilibrium plasma using the Flexible Atomic Code data

    CERN Document Server

    Han, Bo; Salzmann, David; Zhao, Gang

    2015-01-01

    We present a new code, RCF("Radiative-Collisional code based on FAC"), which is used to simulate steady-state plasmas under non local thermodynamic equilibrium condition, especially photoinization dominated plasmas. RCF takes almost all of the radiative and collisional atomic processes into rate equation to interpret the plasmas systematically. The Flexible Atomic Code (FAC) supplies all the atomic data RCF needed, which insures calculating completeness and consistency of atomic data. With four input parameters relating to the radiation source and target plasma, RCF calculates the population of levels and charge states, as well as potentially emission spectrum. In preliminary application, RCF successfully reproduces the results of a photoionization experiment with reliable atomic data. The effects of the most important atomic processes on the charge state distribution are also discussed.

  5. Non-local thermodynamic equilibrium inversions from a 3D MHD chromospheric model

    CERN Document Server

    Rodríguez, Jaime de la Cruz; Carlsson, Mats; Leenaarts, Jorrit

    2012-01-01

    The structure of the solar chromosphere is believed to be governed by magnetic fields, even in quiet-Sun regions that have a relatively weak photospheric field. During the past decade inversion methods have emerged as powerful tools for analyzing the chromosphere of active regions. The applicability of inversions to infer the stratification of the physical conditions in a dynamic 3D solar chromosphere has not yet been studied in detail. This study aims to establish the diagnostic capabilities of non-local thermodynamical equilibrium (NLTE) inversion techniques of Stokes profiles induced by the Zeeman effect in the Ca II 8542 line. We computed the Ca II atomic level populations in a snapshot from a 3D radiation-MHD simulation of the quiet solar atmosphere in non-LTE using the 3D radiative transfer code Multi3d. These populations were used to compute synthetic full-Stokes profiles in the Ca II 8542 line using 1.5D radiative transfer and the inversion code Nicole. The profiles were then spectrally degraded to ac...

  6. He I lines in B stars - Comparison of non-local thermodynamic equilibrium models with observations

    Science.gov (United States)

    Heasley, J. N.; Timothy, J. G.; Wolff, S. C.

    1982-01-01

    Profiles of He gamma-gamma 4026, 4387, 4471, 4713, 5876, and 6678 have been obtained in 17 stars of spectral type B0-B5. Parameters of the nonlocal thermodynamic equilibrium models appropriate to each star are determined from the Stromgren index and fits to H-alpha line profiles. These parameters yield generally good fits to the observed He I line profiles, with the best fits being found for the blue He I lines where departures from local thermodynamic equilibrium are relatively small. For the two red lines it is found that, in the early B stars and in stars with log g less than 3.5, both lines are systematically stronger than predicted by the nonlocal thermodynamic equilibrium models.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-12-15

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

  8. Effects of non-local thermodynamic equilibrium conditions on numerical simulations of inertial confinement fusion plasmas

    Indian Academy of Sciences (India)

    N K Gupta; B K Godwal

    2002-07-01

    Effects of non-local thermodynamic equilibrium (non-LTE) condition on emission and hydrodynamics of typical inertial confinement fusion (ICF) plasmas are studied. The average degree of ionization at high temperatures is seen to be much lower compared to the values obtained from Thomas–Fermi scaling or Saha equation for high- element like gold. LTE and non-LTE predictions for emitted radiation from laser-driven gold foil are compared with the experimental results and it is seen that non-LTE simulations show a marked improvement over LTE results. The effects of one group and multigroup, LTE and non-LTE approximations of radiation transport on hydrodynamic parameters are studied for laser-driven aluminium and gold foils. It is further seen that non-LTE and multigroup effects play an important role in predicting conversion efficiency of laser light to X-rays

  9. NON-LOCAL THERMODYNAMICAL EQUILIBRIUM EFFECTS ON THE IRON ABUNDANCE OF ASYMPTOTIC GIANT BRANCH STARS IN 47 TUCANAE

    Energy Technology Data Exchange (ETDEWEB)

    Lapenna, E.; Mucciarelli, A.; Lanzoni, B.; Ferraro, F. R.; Dalessandro, E.; Massari, D. [Dipartimento di Fisica e Astronomia, Università degli Studi di Bologna, Viale Berti Pichat 6/2, I-40127 Bologna (Italy); Origlia, L. [INAF- Osservatorio Astronomico di Bologna, Via Ranzani, 1, 40127 Bologna (Italy)

    2014-12-20

    We present the iron abundance of 24 asymptotic giant branch (AGB) stars, members of the globular cluster 47 Tucanae, obtained with high-resolution spectra collected with the FEROS spectrograph at the MPG/ESO 2.2 m Telescope. We find that the iron abundances derived from neutral lines (with a mean value [Fe I/H] =–0.94 ± 0.01, σ = 0.08 dex) are systematically lower than those derived from single ionized lines ([Fe II/H] =–0.83 ± 0.01, σ = 0.05 dex). Only the latter are in agreement with those obtained for a sample of red giant branch (RGB) cluster stars, for which the Fe I and Fe II lines provide the same iron abundance. This finding suggests that non-local thermodynamical equilibrium (NLTE) effects driven by overionization mechanisms are present in the atmosphere of AGB stars and significantly affect the Fe I lines while leaving Fe II features unaltered. On the other hand, the very good ionization equilibrium found for RGB stars indicates that these NLTE effects may depend on the evolutionary stage. We discuss the impact of this finding on both the chemical analysis of AGB stars and on the search for evolved blue stragglers.

  10. 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....../Fe] ratios close to solar even at [Fe/H] ~ -2. This is at variance with results of classical abundance analyses based on local thermodynamic equilibrium (LTE) and 1D model stellar atmospheres, which argue for a constant elevated [Mg/Fe] in metal-poor stars of the Galactic thick disk and halo....

  11. Parameterization of the Non-Local Thermodynamic Equilibrium Source Function with Chemical Production by an Equivalent Two-Level Model

    Institute of Scientific and Technical Information of China (English)

    Xun ZHU

    2003-01-01

    The classic two-level or equivalent two-level model that includes only the statistical equilibriumof radiative and thermal processes of excitation and quenching between two vibrational energy levelsis extended by adding chemical production to the rate equations. The modifications to the non-localthermodynamic equilibrium source function and cooling rate are parameterized by φc, which characterizesthe ratio of chemical production to collisional quenching. For applications of broadband emission of O3 at9.6 μm, the non-LTE effect of chemical production on the cooling rate and limb emission is proportionalto the ratio of O to O3. For a typical [O]/[O3], the maximum enhancements of limb radiance and coolingrate are about 15%-30% and 0.03-0.05 K day-1, respectively, both occurring near the mesopause regions.This suggests that the broadband limb radiance above ~80 km is sensitive to O3 density but not sensitiveto the direct cooling rate along the line-of-sight, which makes O3 retrieval feasible but the direct coolingrate retrieval difficult by using the O3 9.6 μm band limb emission.

  12. A non-local thermodynamical equilibrium line formation for neutral and singly ionized titanium in model atmospheres of reference A-K stars

    Science.gov (United States)

    Sitnova, T. M.; Mashonkina, L. I.; Ryabchikova, T. A.

    2016-09-01

    We construct a model atom for Ti I-II using more than 3600 measured and predicted energy levels of Ti I and 1800 energy levels of Ti II, and quantum mechanical photoionization cross-sections. Non-local thermodynamical equilibrium (NLTE) line formation for Ti I and Ti II is treated through a wide range of spectral types from A to K, including metal-poor stars with [Fe/H] down to -2.6 dex. NLTE leads to weakened Ti I lines and positive abundance corrections. The magnitude of NLTE corrections is smaller compared to the literature data for FGK atmospheres. NLTE leads to strengthened Ti II lines and negative NLTE abundance corrections. For the first time, we have performed NLTE calculations for Ti I-II in the 6500 ≤ Teff ≤ 13 000 K range. For four A-type stars, we derived in LTE an abundance discrepancy of up to 0.22 dex between Ti I and Ti II, which vanishes in NLTE. For four other A-B stars, with only Ti II lines observed, NLTE leads to a decrease of line-to-line scatter. An efficiency of inelastic Ti I + H I collisions was estimated from an analysis of Ti I and Ti II lines in 17 cool stars with -2.6 ≤ [Fe/H] ≤ 0.0. Consistent NLTE abundances from Ti I and Ti II were obtained by applying classical Drawinian rates for the stars with log g ≥ 4.1, and neglecting inelastic collisions with H I for the very metal-poor (VMP) giant HD 122563. For the VMP turn-off stars ([Fe/H] ≤ -2 and log g ≤ 4.1), we obtained the positive abundance difference Ti I-II already in LTE, which increases in NLTE. Accurate collisional data for Ti I and Ti II are necessary to help solve this problem.

  13. Experimental benchmark of non-local-thermodynamic-equilibrium plasma atomic physics codes; Validation experimentale des codes de physique atomique des plasmas hors equilibre thermodynamique local

    Energy Technology Data Exchange (ETDEWEB)

    Nagels-Silvert, V

    2004-09-15

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

  14. 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...

  15. Equilibrium thermodynamics

    CERN Document Server

    Oliveira, Mário J

    2013-01-01

    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 textbo...

  16. Non-local Thermodynamic Equilibrium Stellar Spectroscopy with 1D and >3DChemical Properties of the Galactic Metal-poor Disk and the Halo

    Science.gov (United States)

    Bergemann, Maria; Collet, Remo; Schönrich, Ralph; Andrae, Rene; Kovalev, Mikhail; Ruchti, Greg; Hansen, Camilla Juul; Magic, Zazralt

    2017-09-01

    From exploratory studies and theoretical expectations it is known that simplifying approximations in spectroscopic analysis (local thermodynamic equilibrium (LTE), 1D) lead to systematic biases of stellar parameters and abundances. These biases depend strongly on surface gravity, temperature and, in particular, for LTE versus non-LTE (NLTE), on metallicity of the stars. Here we analyze the [Mg/Fe] and [Fe/H] plane of a sample of 326 stars, comparing LTE and NLTE results obtained using 1D hydrostatic models and averaged models. We show that compared to the NLTE benchmark, the other three methods display increasing biases toward lower metallicities, resulting in false trends of [Mg/Fe] against [Fe/H], which have profound implications for interpretations by chemical evolution models. In our best NLTE model, the halo and disk stars show a clearer behavior in the [Mg/Fe]–[Fe/H] plane, from the knee in abundance space down to the lowest metallicities. Our sample has a large fraction of thick disk stars and this population extends down to at least [Fe/H] ∼ ‑1.6 dex, further than previously proven. The thick disk stars display a constant [Mg/Fe] ≈ 0.3 dex, with a small intrinsic dispersion in [Mg/Fe] that suggests that a fast SN Ia channel is not relevant for the disk formation. The halo stars reach higher [Mg/Fe] ratios and display a net trend of [Mg/Fe] at low metallicities, paired with a large dispersion in [Mg/Fe]. These indicate the diverse origin of halo stars from accreted low-mass systems to stochastic/inhomogeneous chemical evolution in the Galactic halo.

  17. Errors in Sounding of the Atmosphere Using Broadband Emission Radiometry (SABER) Kinetic Temperature Caused by Non-Local Thermodynamic Equilibrium Model Parameters

    Science.gov (United States)

    Garcia-Comas, Maya; Lopez-Puertas, M.; Funke, B.; Bermejo-Pantaleon, D.; Marshall, Benjamin T.; Mertens, Christopher J.; Remsberg, Ellis E.; Mlynczak, Martin G.; Gordley, L. L.; Russell, James M.

    2008-01-01

    The vast set of near global and continuous atmospheric measurements made by the SABER instrument since 2002, including daytime and nighttime kinetic temperature (T(sub k)) from 20 to 105 km, is available to the scientific community. The temperature is retrieved from SABER measurements of the atmospheric 15 micron CO2 limb emission. This emission separates from local thermodynamic equilibrium (LTE) conditions in the rarefied mesosphere and thermosphere, making it necessary to consider the CO2 vibrational state non-LTE populations in the retrieval algorithm above 70 km. Those populations depend on kinetic parameters describing the rate at which energy exchange between atmospheric molecules take place, but some of these collisional rates are not well known. We consider current uncertainties in the rates of quenching of CO2 (v2 ) by N2 , O2 and O, and the CO2 (v2 ) vibrational-vibrational exchange to estimate their impact on SABER T(sub k) for different atmospheric conditions. The T(sub k) is more sensitive to the uncertainty in the latter two and their effects depend on altitude. The T(sub k) combined systematic error due to non-LTE kinetic parameters does not exceed +/- 1.5 K below 95 km and +/- 4-5 K at 100 km for most latitudes and seasons (except for polar summer) if the Tk profile does not have pronounced vertical structure. The error is +/- 3 K at 80 km, +/- 6 K at 84 km and +/- 18 K at 100 km under the less favourable polar summer conditions. For strong temperature inversion layers, the errors reach +/- 3 K at 82 km and +/- 8 K at 90 km. This particularly affects tide amplitude estimates, with errors of up to +/- 3 K.

  18. Thermodynamics "beyond" local equilibrium

    Science.gov (United States)

    Vilar, Jose; Rubi, Miguel

    2002-03-01

    Nonequilibrium thermodynamics has shown its applicability in a wide variety of different situations pertaining to fields such as physics, chemistry, biology, and engineering. As successful as it is, however, its current formulation considers only systems close to equilibrium, those satisfying the so-called local equilibrium hypothesis. Here we show that diffusion processes that occur far away from equilibrium can be viewed as at local equilibrium in a space that includes all the relevant variables in addition to the spatial coordinate. In this way, nonequilibrium thermodynamics can be used and the difficulties and ambiguities associated with the lack of a thermodynamic description disappear. We analyze explicitly the inertial effects in diffusion and outline how the main ideas can be applied to other situations. [J.M.G. Vilar and J.M. Rubi, Proc. Natl. Acad. Sci. USA 98, 11081-11084 (2001)].

  19. 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

  20. 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

  1. Fundamental functions in equilibrium thermodynamics

    NARCIS (Netherlands)

    Horst, H.J. ter

    1987-01-01

    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

  2. Estimation Using an Enhancement Factor on Non Local Thermodynamic Equilibrium Behavior of High-lying Energy Levels of Neutral Atom in Argon Radio-Frequency Inductively-Coupled Plasma.

    Science.gov (United States)

    Wagatsuma, Kazuaki; Satoh, Kozue

    2016-01-01

    This paper describes a plasma-diagnostic method using an enhancement factor on the Boltzmann distribution among emission lines of iron atom in an argon radio-frequency inductively-coupled plasma (ICP). It indicated that Boltzmann plots of the atomic lines having lower excitation energies (3.4 to 4.8 eV) were well fitted on a straight line while those having more than 5.5 eV deviated upwards from a linear relationship. This observation could be explained by the fact that ICP is not in a complete thermodynamic equilibrium between direct excitation to energy levels of iron atom, ionization of iron atom, and radiative decay processes to the ground state. Especially, the recombination of iron ion with captured electron should accompany cascade de-excitations between closely-spaced excited levels just below the ionization limit, the rates of which become slower as a whole; as a result, these high-lying levels might be more populated than the low-lying levels as if a different LTE condition coexists on the high energy side. This overpopulation could be quantitatively estimated using an enhancement factor (EF), which was a ratio of the observed intensity to the expected value extrapolated from the normal distribution on the low energy side. The EFs were generally small (less than 3); therefore, the cascade de-excitation process would slightly contribute to the population of these excited levels. It could be considered from variations of the EF that the overpopulation proceeded to a larger extent at lower radio-frequency forward powers, at higher flow rates of the carrier gas, or at higher observation heights. The reason for this is that the kinetic energy of energetic particles, such as electrons, becomes reduced under all of these plasma conditions, thus enabling the high-lying levels to be more populated by cascade de-excitation processes from iron ion rather than by collisional excitation processes with the energetic particles. A similar Boltzmann analysis using the EF

  3. Equilibrium thermodynamics - Callen’s postulational approach

    NARCIS (Netherlands)

    Jongschaap, Robert 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

  4. Mesoscopic non-equilibrium thermodynamics

    Directory of Open Access Journals (Sweden)

    Rubi, Jose' Miguel

    2008-02-01

    Full Text Available Basic concepts like energy, heat, and temperature have acquired a precise meaning after the development of thermodynamics. Thermodynamics provides the basis for understanding how heat and work are related and with the general rules that the macroscopic properties of systems at equilibrium follow. Outside equilibrium and away from macroscopic regimes most of those rules cannot be applied directly. In this paper we present recent developments that extend the applicability of thermodynamic concepts deep into mesoscopic and irreversible regimes. We show how the probabilistic interpretation of thermodynamics together with probability conservation laws can be used to obtain kinetic equations describing the evolution of the relevant degrees of freedom. This approach provides a systematic method to obtain the stochastic dynamics of a system directly from the knowledge of its equilibrium properties. A wide variety of situations can be studied in this way, including many that were thought to be out of reach of thermodynamic theories, such as non-linear transport in the presence of potential barriers, activated processes, slow relaxation phenomena, and basic processes in biomolecules, like translocation and stretching.

  5. Local non-equilibrium thermodynamics.

    Science.gov (United States)

    Jinwoo, Lee; Tanaka, Hajime

    2015-01-16

    Local Shannon entropy lies at the heart of modern thermodynamics, with much discussion of trajectory-dependent entropy production. When taken at both boundaries of a process in phase space, it reproduces the second law of thermodynamics over a finite time interval for small scale systems. However, given that entropy is an ensemble property, it has never been clear how one can assign such a quantity locally. Given such a fundamental omission in our knowledge, we construct a new ensemble composed of trajectories reaching an individual microstate, and show that locally defined entropy, information, and free energy are properties of the ensemble, or trajectory-independent true thermodynamic potentials. We find that the Boltzmann-Gibbs distribution and Landauer's principle can be generalized naturally as properties of the ensemble, and that trajectory-free state functions of the ensemble govern the exact mechanism of non-equilibrium relaxation.

  6. Stochastic approach to equilibrium and nonequilibrium thermodynamics.

    Science.gov (United States)

    Tomé, Tânia; de Oliveira, Mário J

    2015-04-01

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

  7. Non-Equilibrium Thermodynamics in Multiphase Flows

    CERN Document Server

    Mauri, Roberto

    2013-01-01

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

  8. Thermodynamics and fluctuations far from equilibrium

    CERN Document Server

    Ross, John

    2008-01-01

    This book deals with the formulation of the thermodynamics of chemical and other systems far from equilibrium, including connections to fluctuations. It contains applications to non-equilibrium stationary states and approaches to such states, systems with multiple stationary states, stability and equi-stability conditions, reaction diffusion systems, transport properties, and electrochemical systems. The theoretical treatment is complemented by experimental results to substantiate the formulation. Dissipation and efficiency are analyzed in autonomous and externally forced reactions, including several biochemical systems.

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

    Directory of Open Access Journals (Sweden)

    Hameed Metghalchi

    2012-01-01

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

  10. Equilibrium thermodynamics in modified gravitational theories

    CERN Document Server

    Bamba, Kazuharu; Tsujikawa, Shinji

    2009-01-01

    We show that it is possible to obtain a picture of equilibrium thermodynamics on the apparent horizon in the expanding cosmological background for a wide class of modified gravity theories with the Lagrangian density $f(R, \\phi, X)$, where $R$ is the Ricci scalar and $X=-(\

  11. Cosmological particle production and generalized thermodynamic equilibrium

    CERN Document Server

    Zimdahl, W

    1998-01-01

    With the help of a conformal, timelike Killing-vector we define generalized equilibrium states for cosmological fluids with particle production. For massless particles the generalized equilibrium conditions require the production rate to vanish and the well known ``global'' equilibrium of standard relativistic thermodynamics is recovered as a limiting case. The equivalence between the creation rate for particles with nonzero mass and an effective viscous fluid pressure follows as a consequence of the generalized equilibrium properties. The implications of this equivalence for the cosmological dynamics are discussed, including the possibility of a power-law inflationary behaviour. For a simple gas a microscopic derivation for such kind of equilibrium is given on the basis of relativistic kinetic theory.

  12. Contact angle measurements under thermodynamic equilibrium conditions.

    Science.gov (United States)

    Lages, Carol; Méndez, Eduardo

    2007-08-01

    The precise control of the ambient humidity during contact angle measurements is needed to obtain stable and valid data. For a such purpose, a simple low-cost device was designed, and several modified surfaces relevant to biosensor design were studied. Static contact angle values for these surfaces are lower than advancing contact angles published for ambient conditions, indicating that thermodynamic equilibrium conditions are needed to avoid drop evaporation during the measurements.

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

    Science.gov (United States)

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

    1973-01-01

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

  14. Chemical Equilibrium as Balance of the Thermodynamic Forces

    OpenAIRE

    Zilbergleyt, B.

    2004-01-01

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

  15. Equilibrium molecular thermodynamics from Kirkwood sampling.

    Science.gov (United States)

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

    2015-05-21

    We present two methods for barrierless equilibrium sampling of molecular systems based on the recently proposed Kirkwood method (J. Chem. Phys. 2009, 130, 134102). Kirkwood sampling employs low-order correlations among internal coordinates of a molecule for random (or non-Markovian) sampling of the high dimensional conformational space. This is a geometrical sampling method independent of the potential energy surface. The first method is a variant of biased Monte Carlo, where Kirkwood sampling is used for generating trial Monte Carlo moves. Using this method, equilibrium distributions corresponding to different temperatures and potential energy functions can be generated from a given set of low-order correlations. Since Kirkwood samples are generated independently, this method is ideally suited for massively parallel distributed computing. The second approach is a variant of reservoir replica exchange, where Kirkwood sampling is used to construct a reservoir of conformations, which exchanges conformations with the replicas performing equilibrium sampling corresponding to different thermodynamic states. Coupling with the Kirkwood reservoir enhances sampling by facilitating global jumps in the conformational space. The efficiency of both methods depends on the overlap of the Kirkwood distribution with the target equilibrium distribution. We present proof-of-concept results for a model nine-atom linear molecule and alanine dipeptide.

  16. Classical or equilibrium thermodynamics: basic conceptual aspects

    Directory of Open Access Journals (Sweden)

    Luiz Augusto Calvo Tiritan

    2008-08-01

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

  17. A non-local Richards equation to model infiltration into highly heterogeneous media under macroscopic non-equilibrium pressure conditions

    Science.gov (United States)

    Neuweiler, I.; Dentz, M.; Erdal, D.

    2012-04-01

    Infiltration into dry strongly heterogeneous media, such as fractured rocks, can often not be modelled by a standard Richards equation with homogeneous parameters, as the averaged water content is not in equilibrium with the averaged pressure. Often, double continua approaches are used for such cases. We describe infiltration into strongly heterogeneous media by a Richards model for the mobile domain, that is characterized by a memory kernel that encodes the local mass transfer dynamics as well as the geometry of the immobile zone. This approach is based on the assumption that capillary flow can be approximated as diffusion. We demonstrate that this approximation is in many cases justified. Comparison of the model predictions to the results of numerical simulations of infiltration into vertically layered media shows that the non-local approach describes well non-equilibrium effects due to mass transfer between high and low conductivity zones.

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

    Science.gov (United States)

    Banerjee, Anil C.

    1995-01-01

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

  19. Global equilibrium and local thermodynamics in stationary spacetimes

    CERN Document Server

    Panerai, R

    2015-01-01

    In stationary spacetimes global equilibrium states can be defined, applying the maximum entropy principle, by the introduction of local thermodynamic fields determined solely by geometry. As an example, we study a class of equilibrium states for a scalar field in the Einstein's static universe, characterized by inhomogeneous thermodynamic properties and non-vanishing angular momentum.

  20. Far-from-equilibrium measurements of thermodynamic length

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Edward H.; Crooks, Gavin E.

    2008-11-05

    Thermodynamic length is a path function that generalizes the notion of length to the surface of thermodynamic states. Here, we show how to measure thermodynamic length in far-from-equilibrium experiments using the work fluctuation relations. For these microscopic systems, it proves necessary to define the thermodynamic length in terms of the Fisher information. Consequently, the thermodynamic length can be directly related to the magnitude of fluctuations about equilibrium. The work fluctuation relations link the work and the free energy change during an external perturbation on a system. We use this result to determine equilibrium averages at intermediate points of the protocol in which the system is out-of-equilibrium. This allows us to extend Bennett's method to determine the potential of mean force, as well as the thermodynamic length, in single molecule experiments.

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

    Science.gov (United States)

    Silverberg, Lee J.; Raff, Lionel M.

    2015-01-01

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

  2. GURTIN-TYPE VARIATIONAL PRINCIPLES FOR DYNAMICS OF A NON-LOCAL THERMAL EQUILIBRIUM SATURATED POROUS MEDIUM

    Institute of Scientific and Technical Information of China (English)

    Yang Xiao

    2005-01-01

    Based on the porous media theory and by taking into account the effects of the pore fluid viscidity, energy exchanges due to the additional thermal conduction and convection between solid and fluid phases, a mathematical model for the dynamic-thermo-hydro-mechanical coupling of a non-local thermal equilibrium fluid-saturated porous medium, in which the two constituents are assumed to be incompressible and immiscible, is established under the assumption of small deformation of the solid phase, small velocity of the fluid phase and small temperature changes of the two constituents. The mathematical model of a local thermal equilibrium fluid-saturated porous medium can be obtained directly from the above one. Several Gurtin-type variational principles,especially Hu-Washizu type variational principles, for the initial boundary value problems of dynamic and quasi-static responses are presented. It should be pointed out that these variational principles can be degenerated easily into the case of isothermal incompressible fluid-saturated elastic porous media, which have been discussed previously.

  3. Non-Equilibrium Thermodynamics of Self-Replicating Protocells

    DEFF Research Database (Denmark)

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

    2017-01-01

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

  4. Thermodynamics of chemical systems far from equilibrium

    Energy Technology Data Exchange (ETDEWEB)

    Ross, J. (Stanford Univ., CA (USA)); Garcia-Colin, L.S. (UAM-Iztapalapa, Postal (Mexico))

    1989-03-09

    A critique is presented of some recent work in this and other journals on the relation of thermodynamics to the mass action law of kinetics. For most chemical reactions, the thermodynamic variables change on the same time scale as the progress variable and there is no need for an extended thermodynamics.

  5. Geometry and symmetry in non-equilibrium thermodynamic systems

    Science.gov (United States)

    Sonnino, Giorgio

    2017-06-01

    The ultimate aim of this series of works is to establish the closure equations, valid for thermodynamic systems out from the Onsager region, and to describe the geometry and symmetry in thermodynamic systems far from equilibrium. Geometry of a non-equilibrium thermodynamic system is constructed by taking into account the second law of thermodynamics and by imposing the validity of the Glansdorff-Prigogine Universal Criterion of Evolution. These two constraints allow introducing the metrics and the affine connection of the Space of the Thermodynamic Forces, respectively. The Lie group associated to the nonlinear Thermodynamic Coordinate Transformations (TCT) leaving invariant both the entropy production σ and the Glansdorff-Prigogine dissipative quantity P, is also described. The invariance under TCT leads to the formulation of the Thermodynamic Covariance Principle (TCP): The nonlinear closure equations, i.e. the flux-force relations, must be covariant under TCT. In other terms, the fundamental laws of thermodynamics should be manifestly covariant under transformations between the admissible thermodynamic forces (i.e. under TCT). The symmetry properties of a physical system are intimately related to the conservation laws characterizing the thermodynamic system. Noether's theorem gives a precise description of this relation. The macroscopic theory for closure relations, based on this geometrical description and subject to the TCP, is referred to as the Thermodynamic Field Theory (TFT). This theory ensures the validity of the fundamental theorems for systems far from equilibrium.

  6. Mesoscopic thermodynamics of stationary non-equilibrium states

    Energy Technology Data Exchange (ETDEWEB)

    SantamarIa-Holek, I [Facultad de Ciencias, Universidad Nacional Autonoma de Mexico, Circuito exterior de Ciudad Universitaria, 04510 DF (Mexico); RubI, J M [Facultad de FIsica, Universitat de Barcelona, Av. Diagonal 647, 08028, Barcelona (Spain); Perez-Madrid, A [Facultad de FIsica, Universitat de Barcelona, Av. Diagonal 647, 08028, Barcelona (Spain)

    2005-01-01

    Thermodynamics for systems at non-equilibrium stationary states have been formulated, based on the assumption of the existence of a local equilibrium in phase space which enables one to interpret the probability density and its conjugated non-equilibrium chemical potential as mesoscopic thermodynamic variables. The probability current is obtained from the entropy production related to the probability diffusion process and leads to the formulation of the Fokker-Planck equation. For the case of a gas of Brownian particles under steady flow in the dilute and concentrated regimes, we derive non-equilibrium equations of state.

  7. Kinetic, equilibrium and thermodynamic modelling of the sorption of ...

    African Journals Online (AJOL)

    Kinetic, equilibrium and thermodynamic modelling of the sorption of metals ... Batch sorption studies were conducted to assess the potential of a ... negative Ea values, indicating their preference to bind to low-energy sites. ... Article Metrics.

  8. Non-equilibrium thermodynamics of small-scale systems

    Energy Technology Data Exchange (ETDEWEB)

    Rubi, J. Miguel [Departament de Fisica Fonamental, Facultat de Fisica, Universitat de Barcelona, Marti i Franques, 1, 08028-Barcelona (Spain)]. E-mail: mrubi@ub.edu

    2007-04-15

    Small thermodynamic systems exhibit peculiar behavior different from that observed in long-scale systems. Non-equilibrium processes taking place in those systems are strongly influenced by the presence of fluctuations which can be large. Contributions to the free energy which vanish at the infinite number of particles limit cannot be neglected and may exert an important influence on the dynamics. We show that in spite of these important differences, the method of non-equilibrium thermodynamics still applies when reducing the size of the system. By using this method, assumption of local equilibrium at the mesoscale thereby leads to the formulation of a mesoscopic non-equilibrium thermodynamics from which expressions for the non-equilibrium currents and kinetic equations for the probability density can be obtained.

  9. Methane on Mars: Thermodynamic Equilibrium and Photochemical Calculations

    Science.gov (United States)

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

    2010-01-01

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

  10. Composition and Thermodynamic Properties of Air in Chemical Equilibrium

    Science.gov (United States)

    Moeckel, W E; Weston, Kenneth C

    1958-01-01

    Charts have been prepared relating the thermodynamic properties of air in chemical equilibrium for temperatures to 15,000 degrees k and for pressures 10(-5) to 10 (plus 4) atmospheres. Also included are charts showing the composition of air, the isentropic exponent, and the speed of sound. These charts are based on thermodynamic data calculated by the National Bureau of Standards.

  11. Considerations on non equilibrium thermodynamics of interactions

    Science.gov (United States)

    Lucia, Umberto

    2016-04-01

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

  12. Relativistic non-equilibrium thermodynamics revisited

    CERN Document Server

    García-Colin, L S

    2006-01-01

    Relativistic irreversible thermodynamics is reformulated following the conventional approach proposed by Meixner in the non-relativistic case. Clear separation between mechanical and non-mechanical energy fluxes is made. The resulting equations for the entropy production and the local internal energy have the same structure as the non-relativistic ones. Assuming linear constitutive laws, it is shown that consistency is obtained both with the laws of thermodynamics and causality.

  13. Non-Equilibrium Thermodynamics in Conformal Field Theory

    CERN Document Server

    Hollands, Stephan

    2016-01-01

    We present a model independent, operator algebraic approach to non-equilibrium quantum thermodynamics within the framework of two-dimensional Conformal Field Theory. Two infinite reservoirs in equilibrium at their own temperatures and chemical potentials are put in contact through a defect line, possibly by inserting a probe. As time evolves, the composite system then approaches a non-equilibrium steady state that we describe. In particular, we re-obtain recent formulas of Bernard and Doyon.

  14. Effect of Resonant Photoionization in Non-Local Thermodynamical Equilibrium Plasmas

    Institute of Scientific and Technical Information of China (English)

    WU Ze-Qing; ZHANG Ben-Ai; QIU Yu-Bo

    2000-01-01

    Based on the detailed configuration accounting model(DCA), a method is developed to calculate the rate of the resonant photoionization(RP) in the average atom(AA) model. Using this method, the RP rates are calculated for an average ion and compared with DCA calculation. The comparison shows the reasonableness of the proposed method. The RP process is included in the AA rate equations and the numerical results show that RP can cause an additional ionization up to 10% or so in some cases.

  15. EFFECT OF EXCITATION-AUTOIONIZATION IN NON-LOCAL THERMODYNAMIC EQUILIBRIUM PLASMAS

    Institute of Scientific and Technical Information of China (English)

    Wu Ze-qing; Zhang Ben-ai; Qiu Yu-bo

    2000-01-01

    Based on the detailed configuration accounting model, the authros havedeveloped a method to calculate the rate of excitation-autoionization(EA) in the average atom model and used it in the rate equations. Thenumerical results show that EA effect is signifficant in hightemperature low density plasma and can cause an additional ionization upto 15% of an ionization stage.

  16. Non-equilibrium thermodynamics and physical kinetics

    CERN Document Server

    Bikkin, Halid

    2014-01-01

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

  17. Non-equilibrium thermodynamics of gravitational screens

    CERN Document Server

    Freidel, Laurent

    2014-01-01

    We study the Einstein gravity equations projected on a timelike surface, which represents the time evolution of what we call a gravitational screen. We show that such a screen possesses a surface tension and an internal energy, and that the Einstein equations reduce to the thermodynamic equations of a viscous bubble. We also provide a complete dictionary between gravitational and thermodynamical variables. In the non-viscous cases there are three thermodynamic equations which characterise a bubble dynamics: These are the first law, the Marangoni flow equation and the Young-Laplace equation. In all three equations the surface tension plays a central role: In the first law it appears as a work term per unit area, in the Marangoni flow its gradient drives a force, and in the Young-Laplace equation it contributes to a pressure proportional to the surface curvature. The gravity equations appear as a natural generalization of these bubble equations when the bubble itself is viscous and dynamical. In particular, it ...

  18. Elucidation of Reaction Mechanisms Far from Thermodynamic Equilibrium.

    Science.gov (United States)

    Nagao, Raphael

    2016-04-01

    Far from equilibrium: This thesis provides a deep mechanistic analysis of the electrooxidation of methanol when the system is kept far from the thermodynamic equilibrium. Under an oscillatory regime, interesting characteristics between the elementary reaction steps were observed. We were able to elucidate the effect of the intrinsic drift in a potential time-series responsible for spontaneous transition of temporal patterns and the carbon dioxide decoupling from direct and indirect pathways.

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

    NARCIS (Netherlands)

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

    1982-01-01

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

  20. Equilibrium sampling for a thermodynamic assessment of contaminated sediments

    DEFF Research Database (Denmark)

    of the biota relative to the sediment. Furthermore, concentrations in lipid at thermodynamic equilibrium with sediment (Clip?Sed) can be calculated via lipid/silicone partition ratios CSil × KLip:Sil, which has been done in studies with limnic, river and marine sediments. The data can then be compared to lipid...

  1. Thermodynamic Derivation of the Equilibrium Distribution Functions of Statistical Mechanics.

    Science.gov (United States)

    Stoeckly, Beth

    1979-01-01

    Presents a simplified derivation of the equilibrium distribution functions. The derivation proceeds from the change in the Helmholtz free energy when a particle is added to a system of fixed temperature, volume, and chemical potential. The derivations show the relationship between statistical mechanics and macroscopic thermodynamics. (Author/GA)

  2. Local thermodynamic equilibrium for globally disequilibrium open systems under stress

    Science.gov (United States)

    Podladchikov, Yury

    2016-04-01

    Predictive modeling of far and near equilibrium processes is essential for understanding of patterns formation and for quantifying of natural processes that are never in global equilibrium. Methods of both equilibrium and non-equilibrium thermodynamics are needed and have to be combined. For example, predicting temperature evolution due to heat conduction requires simultaneous use of equilibrium relationship between internal energy and temperature via heat capacity (the caloric equation of state) and disequilibrium relationship between heat flux and temperature gradient. Similarly, modeling of rocks deforming under stress, reactions in system open for the porous fluid flow, or kinetic overstepping of the equilibrium reaction boundary necessarily needs both equilibrium and disequilibrium material properties measured under fundamentally different laboratory conditions. Classical irreversible thermodynamics (CIT) is the well-developed discipline providing the working recipes for the combined application of mutually exclusive experimental data such as density and chemical potential at rest under constant pressure and temperature and viscosity of the flow under stress. Several examples will be presented.

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

    Energy Technology Data Exchange (ETDEWEB)

    Glavatskiy, K. S. [School of Chemical Engineering, The University of Queensland, St. Lucia QLD 4072 (Australia)

    2015-10-28

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

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

    Science.gov (United States)

    Glavatskiy, K S

    2015-10-28

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

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

    Directory of Open Access Journals (Sweden)

    G. L. Dotto

    2013-03-01

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

  6. Non-equilibrium Thermodynamics of Rayleigh-Taylor instability

    Science.gov (United States)

    Sengupta, Tapan K.; Sengupta, Aditi; Shruti, K. S.; Sengupta, Soumyo; Bhole, Ashish

    2016-10-01

    Rayleigh-Taylor instability (RTI) has been studied here as a non-equilibrium thermodynamics problem. Air masses with temperature difference of 70K, initially with heavier air resting on lighter air isolated by a partition, are allowed to mix by impulsively removing the partition. This results in interface instabilities, which are traced here by solving two dimensional (2D) compressible Navier-Stokes equation (NSE), without using Boussinesq approximation (BA henceforth). The non-periodic isolated system is studied by solving NSE by high accuracy, dispersion relation preserving (DRP) numerical methods described in Sengupta T.K.: High Accuracy Computing Method (Camb. Univ. Press, USA, 2013). The instability onset is due to misaligned pressure and density gradients and is evident via creation and evolution of spikes and bubbles (when lighter fluid penetrates heavier fluid and vice versa, associated with pressure waves). Assumptions inherent in compressible formulation are: (i) Stokes' hypothesis that uses zero bulk viscosity assumption and (ii) the equation of state for perfect gas which is a consequence of equilibrium thermodynamics. Present computations for a non-equilibrium thermodynamic process do not show monotonic rise of entropy with time, as one expects from equilibrium thermodynamics. This is investigated with respect to the thought-experiment. First, we replace Stokes' hypothesis, with another approach where non-zero bulk viscosity of air is taken from an experiment. Entropy of the isolated system is traced, with and without the use of Stokes' hypothesis. Without Stokes' hypothesis, one notes the rate of increase in entropy to be higher as compared to results with Stokes' hypothesis. We show this using the total entropy production for the thermodynamically isolated system. The entropy increase from the zero datum is due to mixing in general; punctuated by fluctuating entropy due to creation of compression and rarefaction fronts originating at the interface

  7. Equilibrium sampling for a thermodynamic assessment of contaminated sediments

    DEFF Research Database (Denmark)

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

    valid equilibrium sampling (method incorporated QA/QC). The measured equilibrium concentrations in silicone (Csil) can then be divided by silicone/water partition ratios to yield Cfree. CSil can also be compared to CSil from silicone equilibrated with biota in order to determine the equilibrium status...... 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.......Hydrophobic organic contaminants (HOCs) reaching the aquatic environment are largely stored in sediments. The risk of contaminated sediments is challenging to assess since traditional exhaustive extraction methods yield total HOC concentrations, whereas freely dissolved concentrations (Cfree...

  8. A Characterization of Conserved Quantities in Non-Equilibrium Thermodynamics

    Directory of Open Access Journals (Sweden)

    Ignacio Romero

    2013-12-01

    Full Text Available The well-known Noether theorem in Lagrangian and Hamiltonian mechanics associates symmetries in the evolution equations of a mechanical system with conserved quantities. In this work, we extend this classical idea to problems of non-equilibrium thermodynamics formulated within the GENERIC (General Equations for Non-Equilibrium Reversible-Irreversible Coupling framework. The geometric meaning of symmetry is reviewed in this formal setting and then utilized to identify possible conserved quantities and the conditions that guarantee their strict conservation. Examples are provided that demonstrate the validity of the proposed definition in the context of finite and infinite dimensional thermoelastic problems.

  9. Gravitational Energy, Local Holography and Non-equilibrium Thermodynamics

    CERN Document Server

    Freidel, Laurent

    2013-01-01

    We study the properties of gravitational system in finite regions bounded by gravitational screens. We present the detail construction of the total energy of such regions and of the energy and momentum balance equations due to the flow of matter and gravitational radiation through the screen. We establish that the gravitational screen possesses analogs of surface tension, internal energy and viscous stress tensor, while the conservations are analogs of non-equilibrium balance equations for a viscous system. This gives a precise correspondence between gravity in finite regions and non-equilibrium thermodynamics.

  10. Scalar Fluctuations from Extended Non-equilibrium Thermodynamic States

    Science.gov (United States)

    Nettleton, R. E.

    1985-10-01

    In the framework of extended non-equilibrium thermodynamics, the local non-equilibrium state of a liquid is described by the density, temperature, and a structural variable, ζ, and its rate-of-change. ζ is the ensemble average of a function A (Q) of the configuration co-ordinates, and it is assumed to relax to local equilibrium in a time short compared to the time for diffusion of an appreciable number of particles into the system. By a projection operator technique of Grabert, an equation is derived from the Liouville equation for the distribution of fluctuations in TV, the particle number, and in A and Ȧ. An approximate solution is proposed which exhibits nonequilibrium corrections to the Einstein function in the form of a sum of thermodynamic forces. For a particular structural model, the corresponding non-Einstein contributions to correlation functions are estimated to be very small. For variables of the type considered here, the thermodynamic pressure is found to equal the pressure trace.

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

    CERN Document Server

    Jou, David; Lebon, Georgy

    2007-01-01

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

  12. Universal thermodynamics in different gravity theories: Conditions for generalized second law of thermodynamics and thermodynamical equilibrium on the horizons

    CERN Document Server

    Mitra, Saugata; Chakraborty, Subenoy

    2016-01-01

    The present work deals with a detailed study of universal thermodynamics in different modified gravity theories. The validity of the generalized second law of thermodynamics (GSLT) and thermodynamical equilibrium (TE) of the Universe bounded by a horizon (apparent/event) in f(R)-gravity, Einstein-Gauss-Bonnet gravity, RS-II brane scenario and DGP brane model has been investigated. In the perspective of recent observational evidences, the matter in the Universe is chosen as interacting holographic dark energy model. The entropy on the horizons are evaluated from the validity of the unified first law and as a result there is a correction (in integral form) to the usual Bekenstein entropy. The other thermodynamical parameter namely temperature on the horizon is chosen as the recently introduced corrected Hawking temperature. The above thermodynamical analysis is done for homogeneous and isotropic flat FLRW model of the Universe. The restrictions for the validity of GSLT and the TE are presented in tabular form f...

  13. Mesoscopic non-equilibrium thermodynamic analysis of molecular motors.

    Science.gov (United States)

    Kjelstrup, S; Rubi, J M; Pagonabarraga, I; Bedeaux, D

    2013-11-28

    We show that the kinetics of a molecular motor fueled by ATP and operating between a deactivated and an activated state can be derived from the principles of non-equilibrium thermodynamics applied to the mesoscopic domain. The activation by ATP, the possible slip of the motor, as well as the forward stepping carrying a load are viewed as slow diffusion along a reaction coordinate. Local equilibrium is assumed in the reaction coordinate spaces, making it possible to derive the non-equilibrium thermodynamic description. Using this scheme, we find expressions for the velocity of the motor, in terms of the driving force along the spacial coordinate, and for the chemical reaction that brings about activation, in terms of the chemical potentials of the reactants and products which maintain the cycle. The second law efficiency is defined, and the velocity corresponding to maximum power is obtained for myosin movement on actin. Experimental results fitting with the description are reviewed, giving a maximum efficiency of 0.45 at a myosin headgroup velocity of 5 × 10(-7) m s(-1). The formalism allows the introduction and test of meso-level models, which may be needed to explain experiments.

  14. Non-equilibrium Thermodynamics of the Longitudinal Spin Seebeck Effect

    Science.gov (United States)

    Basso, Vittorio; Ferraro, Elena; Sola, Alessandro; Magni, Alessandro; Kuepferling, Michaela; Pasquale, Massimo

    In this paper we employ non equilibrium thermodynamics of fluxes and forces to describe magnetization and heat transport. By the theory we are able to identify the thermodynamic driving force of the magnetization current as the gradient of the effective field ▿H*. This definition permits to define the spin Seebeck coefficient ɛM which relates ▿H* and the temperature gradient ▿T. By applying the theory to the geometry of the longitudinal spin Seebeck effect we are able to obtain the optimal conditions for generating large magnetization currents. Furthermore, by using the results of recent experiments, we obtain an order of magnitude for the value of ɛM ∼ 10-2 TK-1 for yttrium iron garnet (Y3Fe5O12).

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

    Science.gov (United States)

    Sousa, Tânia; Domingos, Tiago

    2006-11-01

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

  16. Quantum relativistic fluid at global thermodynamic equilibrium in curved spacetime

    CERN Document Server

    Becattini, F

    2015-01-01

    We present a new approach to the problem of the thermodynamical equilibrium of a quantum relativistic fluid in a curved spacetime in the limit of small curvature. We calculate the mean value of local operators by expanding the four-temperature Killing vector field in Riemann normal coordinates about the same spacetime point and we derive corrections with respect to the flat spacetime expressions. Thereby, we clarify the origin of the terms proportional to Riemann and Ricci tensors introduced in general hydrodynamic expansion of the stress-energy tensor.

  17. Extended irreversible thermodynamics and non-equilibrium temperature

    Directory of Open Access Journals (Sweden)

    Casas-Vazquez, Jose'

    2008-02-01

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

  18. Engine efficiency: The Curzon-Ahlborn engine and equilibrium thermodynamics

    CERN Document Server

    Bhattacharyya, Kamal

    2014-01-01

    The Carnot engine sets an upper limit to the efficiency of a practical heat engine. An arbitrary variety of the latter, however, is believed to behave closely as the Curzon-Ahlborn engine. Efficiency of this engine is obtained commonly by invoking the maximum power principle in a non-equilibrium framework. We outline here some plausible routes within the domain of classical thermodynamics to arrive at the same expression for efficiency. Further, studies on the performances of quite a few practical engines lead us to a simpler approximate formula with better bounds, on the basis of just the second law.

  19. Thermodynamic equilibrium calculation on preparation of copper oxalate precursor powder

    Institute of Scientific and Technical Information of China (English)

    FAN You-qi; ZHANG Chuan-fu; ZHAN Jing; WU Jian-hui

    2008-01-01

    According to the principles of simultaneous equilibrium and mass balance, a series of thermodynamic equilibrium equations of Cu2+ -C2O2-4 -NH3-NH4+-H2O system at ambient temperature were deduced theoretically and the logarithm concentration versus pH value (lg[Cu2+]T-pH) diagrams at different solution compositions were drawn. The results show that when pH is below 5.0, copper ion reacts with C2O42- directly and the morphology of copper precursor powder is of pie-shape; when pH is above 5.0, copper ion coordinates with ammonia, and the precipitation proceeds slowly accompanying with the release of copper ions from the multi-coordinated Cu(NH3)n2+ (n =1, 2, …, 5) and the morphologies of copper precursor powder are respectively of rod aggregation shape (when 5.0<pH<8.0) and of rod-shape (when pH>8.0). Some experiments were performed to confirm the relation between the total concentration of copper ion and pH value. It is shown that the thermodynamic mathematical model is correct and the calculated values are basically accurate.

  20. Thermodynamic equilibrium of bismuth hydrometallurgy in chloride and nitrate solutions

    Institute of Scientific and Technical Information of China (English)

    王云燕; 彭文杰; 柴立元

    2004-01-01

    Simultaneous equilibrium was applied to the thermodynamic analysis and calculation of Bi( Ⅲ )-X(Cl- ,NO3- )-H2O systems, based on which the diagrams of the logarithm of equilibrium concentration of Bi( Ⅲ ) of series precipitation vs pH value of these two systems at 25 ℃ were obtained, and the pH ranges of the stable zones of various precipitations were analyzed and determined. In Bi( Ⅲ )-Cl -H2O system, the variations of c0 (Bi3+) and c0 (Cl-) have little effect on the equilibria of Bi(OH)3-solution and BiOOH-solution, but has great influence on the equilibrium of BiOCl-solution. However, in Bi( Ⅲ )-NO3-H2O system, the variations of c0 (Bi3+) and C0 (NO3-)have little effect on equilibria of Bi(OH)3-solution, BiOOH-solution and Bi2O3-solution. When pH value is high,Bi2O3 is the thermodynamic stable phase, its stable zone is the widest, almost including the stable zones of BiOCl or BiONO3, Bi(OH)3 and BiOOH. Bi(OH)3 cannot be obtained from Bi( Ⅲ )-Cl--H2O system, even strong alkaline media. Bi2O3 can be obtained from the solution directly, and highly pure BiOCl or BiONO3 can also be obtained through strictly controlling pH value.

  1. Thermodynamic Stability and Structure of Oxidized Cu(110) Surfaces: The Critical Role of non-Local Interactions

    Science.gov (United States)

    Bamidele, Joseph; Brndiar, Jan; Stich, Ivan; Kantorovitch, Lev

    2013-03-01

    Thermodynamic stability of oxidized Cu(110) surface is studied using DFT techniques. At high oxygen exposures standard techniques predict more phases to be quasi-isoenergetic, whereas experiments observe only the c(6 × 2) phase at high oxygen exposures clearly indicating this phase to be the ground-state separated by considerable energy differences from other candidates. We show that this surface system is stabilized by a delicate coexistence and balance of chemi- and physi-sorption. Agreement with experiments is only achieved if the van der Waals interaction between the surface templates is accounted for in DFT thermodynamics. Moreover, van der Waals stabilization of the surface structure is anticipated to be a general feature present also in the cases of other related surfaces.

  2. Weakly nonlocal non-equilibrium thermodynamics - variational principles and Second Law

    OpenAIRE

    Ván, P.

    2009-01-01

    A general, uniform, rigorous and constructive thermodynamic approach to weakly nonlocal non-equilibrium thermodynamics is reviewed. A method is given to construct and restrict the evolution equations of physical theories according to the Second Law of thermodynamics and considering weakly nonlocal constitutive state spaces. The evolution equations of internal variables, the classical irreversible thermodynamics and Korteweg fluids are treated.

  3. Computation of thermodynamic equilibrium in systems under stress

    Science.gov (United States)

    Vrijmoed, Johannes C.; Podladchikov, Yuri Y.

    2016-04-01

    Metamorphic reactions may be partly controlled by the local stress distribution as suggested by observations of phase assemblages around garnet inclusions related to an amphibolite shear zone in granulite of the Bergen Arcs in Norway. A particular example presented in fig. 14 of Mukai et al. [1] is discussed here. A garnet crystal embedded in a plagioclase matrix is replaced on the left side by a high pressure intergrowth of kyanite and quartz and on the right side by chlorite-amphibole. This texture apparently represents disequilibrium. In this case, the minerals adapt to the low pressure ambient conditions only where fluids were present. Alternatively, here we compute that this particular low pressure and high pressure assemblage around a stressed rigid inclusion such as garnet can coexist in equilibrium. To do the computations we developed the Thermolab software package. The core of the software package consists of Matlab functions that generate Gibbs energy of minerals and melts from the Holland and Powell database [2] and aqueous species from the SUPCRT92 database [3]. Most up to date solid solutions are included in a general formulation. The user provides a Matlab script to do the desired calculations using the core functions. Gibbs energy of all minerals, solutions and species are benchmarked versus THERMOCALC, PerpleX [4] and SUPCRT92 and are reproduced within round off computer error. Multi-component phase diagrams have been calculated using Gibbs minimization to benchmark with THERMOCALC and Perple_X. The Matlab script to compute equilibrium in a stressed system needs only two modifications of the standard phase diagram script. Firstly, Gibbs energy of phases considered in the calculation is generated for multiple values of thermodynamic pressure. Secondly, for the Gibbs minimization the proportion of the system at each particular thermodynamic pressure needs to be constrained. The user decides which part of the stress tensor is input as thermodynamic

  4. Thermodynamic State Variables in Quasi-Equilibrium Ultracold Neutral Plasma

    CERN Document Server

    Tiwari, Sanat Kumar; Baalrud, Scott D

    2016-01-01

    The pressure and internal energy of an ultracold plasma in a state of quasi-equilibrium are evaluated using classical molecular dynamics simulations. Coulomb collapse is avoided by modeling electron-ion interactions using an attractive Coulomb potential with a repulsive core. We present a method to separate the contribution of classical bound states, which form due to recombination, from the contribution of free charges when evaluating these thermodynamic state variables. It is found that the contribution from free charges is independent of the choice of repulsive core length-scale when it is sufficiently short-ranged. The partial pressure associated with the free charges is found to closely follow that of the one-component plasma model, reaching negative values at strong coupling, while the total system pressure remains positive. This pseudo-potential model is also applied to Debye-H\\"{u}ckel theory to describe the weakly coupled regime.

  5. Constraints on Contact Angles for Multiple Phases in Thermodynamic Equilibrium.

    Science.gov (United States)

    Blunt, Martin J.

    2001-07-01

    For three or more fluid phases in thermodynamic equilibrium and in contact with a solid surface, the Young equation can be used to find relations between the contact angles for different pairs of fluids. For an n-fluid-phase system, n(n-1)/2 contact angles can be defined, but there are (n-1)(n-2)/2 constraints between them, leaving only n-1 independent values of the contact angle. These constraints are very powerful in limiting and determining possible types of wetting behavior. The consequences are discussed for three- and four-phase flow. They have important applications for the understanding of gas injection processes in petroleum reservoirs. Copyright 2001 Academic Press.

  6. Coronal and Local Thermodynamic Equilibriums in a Hollow Cathode Discharge

    Institute of Scientific and Technical Information of China (English)

    ZHENG Xu-Tao

    2005-01-01

    @@ A characteristic two-section profile of excited-state populations is observed in a hollow cathode discharge and is explained by coexistence of the coronal equilibrium (CE) and the local thermodynamic equilibrium (LTE).At helium pressure 0.1 Torr and cathode current 200-300 mA, vacuum ultraviolet radiations from He I 1snp 1 P (n = 2-16) and He Ⅱ np2P (n = 2-14) axe resolved with a 2.2-M McPherson spectrometer. Relative populations of these states are deduced from the discrete line intensities and are plotted against energy levels. For both the He Ⅰ and He Ⅱ series, as energy level increases, populations of high-n (n > 10) states are found to decrease much more quickly than low-n (n < 7) populations. While low-n populations are described with the CE dominated by direct electron-impact excitations, high-n populations are fitted with the LTE to calculate the population temperatures of gas atoms and ions. Validities of the CE and LTE in different n-ranges are considered on the competition between radiative decays of the excited states and their collisions with gas atoms.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1995-12-31

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

  8. Non-local equilibrium two-phase flow model with phase change in porous media and its application to reflooding of a severely damaged reactor core

    Science.gov (United States)

    Bachrata, A.; Fichot, F.; Quintard, M.; Repetto, G.; Fleurot, J.

    2012-05-01

    A generalized non local-equilibrium, three-equation model was developed for the macroscopic description of two-phase flow heat and mass transfer in porous media subjected to phase change. Six pore-scale closure problems were proposed to determine all the effective transport coefficients for representative unit cells. An improved model is presented in this paper with the perspective of application to intense boiling phenomena. The objective of this paper is to present application of this model to the simulation of reflooding of severely damaged nuclear reactor cores. In case of accident at a nuclear power plant, water sources may not be available for a long period of time and the core heats up due to the residual power. Any attempt to inject water during core degradation can lead to quenching and further fragmentation of the core material. The fragmentation of fuel rods and melting of reactor core materials may result in the formation of a "debris bed". The typical particle size in a debris bed might reach few millimeters (characteristic length-scale: 1 to 5 mm), which corresponds to a high permeability porous medium. The proposed two-phase flow model is implemented in the ICARECATHARE code, developed by IRSN to study severe accident scenarios in pressurized water reactors. Currently, the French IRSN has set up two experimental facilities to study debris bed reflooding, PEARL and PRELUDE, with the objective to validate safety models. The PRELUDE program studies the complex two phase flow of water and steam in a porous medium (diameter 180 mm, height 200 mm), initially heated to a high temperature (400°C or 700°C). The series of PRELUDE experiments achieved in 2010 constitute a significant complement to the database of high temperature bottom reflood experimental data. They provide relevant data to understand the progression of the quench front and the intensity of heat transfer. Modeling accurately these experiments required improvements to the reflooding model

  9. Non-local equilibrium two-phase flow model with phase change in porous media and its application to reflooding of a severely damaged reactor core

    Energy Technology Data Exchange (ETDEWEB)

    Bachrata, A.; Fichot, F.; Quintard, M.; Repetto, G.; Fleurot, J. [Institut de Radioprotection et de Surete Nucleaire, Cadarache (France); Universite de Toulouse (France); INPT, UPS (France); IMFT - Institut de Mecanique des Fluides de Toulouse, Allee Camille Soula, F-31400 Toulouse (France) and CNRS (France); IMFT, F-31400 Toulouse (France); Institut de Radioprotection et de Surete Nucleaire, Cadarache (France)

    2012-05-15

    A generalized non local-equilibrium, three-equation model was developed for the macroscopic description of two-phase flow heat and mass transfer in porous media subjected to phase change. Six pore-scale closure problems were proposed to determine all the effective transport coefficients for representative unit cells. An improved model is presented in this paper with the perspective of application to intense boiling phenomena. The objective of this paper is to present application of this model to the simulation of reflooding of severely damaged nuclear reactor cores. In case of accident at a nuclear power plant, water sources may not be available for a long period of time and the core heats up due to the residual power. Any attempt to inject water during core degradation can lead to quenching and further fragmentation of the core material. The fragmentation of fuel rods and melting of reactor core materials may result in the formation of a {sup d}ebris bed{sup .} The typical particle size in a debris bed might reach few millimeters (characteristic length-scale: 1 to 5 mm), which corresponds to a high permeability porous medium. The proposed two-phase flow model is implemented in the ICARECATHARE code, developed by IRSN to study severe accident scenarios in pressurized water reactors. Currently, the French IRSN has set up two experimental facilities to study debris bed reflooding, PEARL and PRELUDE, with the objective to validate safety models. The PRELUDE program studies the complex two phase flow of water and steam in a porous medium (diameter 180 mm, height 200 mm), initially heated to a high temperature (400 deg. C or 700 deg. C). The series of PRELUDE experiments achieved in 2010 constitute a significant complement to the database of high temperature bottom reflood experimental data. They provide relevant data to understand the progression of the quench front and the intensity of heat transfer. Modeling accurately these experiments required improvements to the

  10. A Unified Graphical Representation of Chemical Thermodynamics and Equilibrium

    Science.gov (United States)

    Hanson, Robert M.

    2012-01-01

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

  11. Experimental determination of thermodynamic equilibrium in biocatalytic transamination

    DEFF Research Database (Denmark)

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

    2012-01-01

    , in this communication we suggest a simple experimental methodology which we hope will stimulate more accurate determination of thermodynamic equilibria when reporting the results of transaminase‐catalyzed reactions in order to increase understanding of the relationship between substrate and product molecular structure...... on reaction thermodynamics....

  12. A Unified Graphical Representation of Chemical Thermodynamics and Equilibrium

    Science.gov (United States)

    Hanson, Robert M.

    2012-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-06-10

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

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

    NARCIS (Netherlands)

    Philipse, A.P.; Vrij, A.

    2011-01-01

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

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

    DEFF Research Database (Denmark)

    Shapiro, Alexander; Stenby, Erling Halfdan

    2001-01-01

    , not for the multicomponent mixtures. The importance is emphasized on the space of the intensive variables P, T and mu (i), where the laws of capillary equilibrium have a simple geometrical interpretation. We formulate thermodynamic problems specific to such an equilibrium, and outline changes to be introduced to common...

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

    Science.gov (United States)

    1976-01-01

    The entropy of a gas system with the number of particles subject to external control is maximized to derive relations between the thermodynamic variables that obtain at equilibrium. These relations are described in terms of the chemical potential, defined as equivalent partial derivatives of entropy, energy, enthalpy, free energy, or free enthalpy. At equilibrium, the change in total chemical potential must vanish. This fact is used to derive the equilibrium constants for chemical reactions in terms of the partition functions of the species involved in the reaction. Thus the equilibrium constants can be determined accurately, just as other thermodynamic properties, from a knowledge of the energy levels and degeneracies for the gas species involved. These equilibrium constants permit one to calculate the equilibrium concentrations or partial pressures of chemically reacting species that occur in gas mixtures at any given condition of pressure and temperature or volume and temperature.

  17. Thermodynamic Equilibrium Diagrams of Sulphur-Chromium System

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The chemical and electrochemical equilibria in the presence of gaseous phase were investigated. Many substances, which consisted of sulphur and chromium, were considered. Various thermodynamic equilibria were calculated in different pressures. Calculation results were shown as log p―1/T and E―T diagrams. These diagrams may be used to study the corrosion of chromium in sulphur-containing circumstances. The diagrams are also used to thermodynami-cally determine the existence area of various substances and so on.

  18. Non-Equilibrium Evolutional Thermodynamics of Boundary Friction

    Directory of Open Access Journals (Sweden)

    I.A. Lyashenko

    2010-01-01

    Full Text Available The general thermodynamic model of ultrathin lubricant film melting is proposed. The critical value of shear velocity, at which lubricant melts according to the shear melting mechanism, was found. It was shown that at temperature of rubbing surfaces above the critical value it melts even at zero shear velocity since total thermodynamic melting is realized. Found features coincide qualitatively with experimental data.

  19. Local thermodynamical equilibrium and the β frame for a quantum relativistic fluid

    OpenAIRE

    Becattini, Francesco; Bucciantini, Leda; Grossi, Eduardo; Tinti, Leonardo

    2015-01-01

    We discuss the concept of local thermodynamical equilibrium in relativistic hydrodynamics in flat spacetime in a quantum statistical framework without an underlying kinetic description, suitable for strongly interacting fluids. We show that the appropriate definition of local equilibrium naturally leads to the introduction of a relativistic hydrodynamical frame in which the four-velocity vector is the one of a relativistic thermometer at equilibrium with the fluid, parallel to the inverse tem...

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

    Science.gov (United States)

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

    1992-01-01

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

  1. Local thermodynamical equilibrium and the β frame for a quantum relativistic fluid

    Energy Technology Data Exchange (ETDEWEB)

    Becattini, Francesco; Grossi, Eduardo [Universita di Firenze, Florence (Italy); INFN, Florence (Italy); Bucciantini, Leda [Dipartimento di Fisica, Universita di Pisa (Italy); INFN, Pisa (Italy); Tinti, Leonardo [Jan Kochanowski University, Kielce (Poland)

    2015-05-15

    We discuss the concept of local thermodynamical equilibrium in relativistic hydrodynamics in flat spacetime in a quantum statistical framework without an underlying kinetic description, suitable for strongly interacting fluids. We show that the appropriate definition of local equilibrium naturally leads to the introduction of a relativistic hydrodynamical frame in which the four-velocity vector is the one of a relativistic thermometer at equilibrium with the fluid, parallel to the inverse temperature four-vector β, which then becomes a primary quantity. We show that this frame is the most appropriate for the expansion of the stress-energy tensor from local thermodynamical equilibrium and that therein the local laws of thermodynamics take on their simplest form. We discuss the difference between the β frame and Landau frame and present an instance where they differ. (orig.)

  2. Local thermodynamical equilibrium and the β frame for a quantum relativistic fluid

    Energy Technology Data Exchange (ETDEWEB)

    Becattini, Francesco, E-mail: becattini@fi.infn.it [Università di Firenze and INFN Sezione di Firenze, Florence (Italy); Bucciantini, Leda, E-mail: leda.bucciantini@df.unipi.it [Dipartimento di Fisica dell’Università di Pisa and INFN, 56127, Pisa (Italy); Grossi, Eduardo, E-mail: grossi@fi.infn.it [Università di Firenze and INFN Sezione di Firenze, Florence (Italy); Tinti, Leonardo, E-mail: dr.leonardo.tinti@gmail.com [Jan Kochanowski University, Kielce (Poland)

    2015-05-05

    We discuss the concept of local thermodynamical equilibrium in relativistic hydrodynamics in flat spacetime in a quantum statistical framework without an underlying kinetic description, suitable for strongly interacting fluids. We show that the appropriate definition of local equilibrium naturally leads to the introduction of a relativistic hydrodynamical frame in which the four-velocity vector is the one of a relativistic thermometer at equilibrium with the fluid, parallel to the inverse temperature four-vector β, which then becomes a primary quantity. We show that this frame is the most appropriate for the expansion of the stress-energy tensor from local thermodynamical equilibrium and that therein the local laws of thermodynamics take on their simplest form. We discuss the difference between the β frame and Landau frame and present an instance where they differ.

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

    Energy Technology Data Exchange (ETDEWEB)

    Horowitz, Jordan M., E-mail: jordan.horowitz@umb.edu [Department of Physics, University of Massachusetts at Boston, Boston, Massachusetts 02125 (United States)

    2015-07-28

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

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

    Science.gov (United States)

    Horowitz, Jordan M

    2015-07-28

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

  5. On a variational formulation of the maximum energy dissipation principle for non-equilibrium chemical thermodynamics

    Science.gov (United States)

    Moroz, Adam

    2008-05-01

    In this work we revise the applicability of the optimal control and variational approach to the maximum energy dissipation (MED) principle in non-equilibrium thermodynamics. The optimal control analogies for the kinetical and potential parts of thermodynamic Lagrangian (in the form of a sum of the positively defined thermodynamic potential and positively defined dissipative function) have been considered. An interpretation of thermodynamic momenta is discussed with respect to standard optimal control applications, which employ dynamic constraints. Also included is interpretation in terms of the least action principle.

  6. Generalised equilibrium of cosmological fluids in second-order thermodynamics

    CERN Document Server

    Zimdahl, W; Le Denmat, G; Zimdahl, Winfried

    1999-01-01

    Combining the second-order entropy flow vector of the causal Israel-Stewart theory with the conformal Killing-vector property of $u_{i}/T$, where $u_{i}$ is the four-velocity of the medium and T its equilibrium temperature, we investigate generalized equilibrium states for cosmological fluids with nonconserved particle number. We calculate the corresponding equilibrium particle production rate and show that this quantity is reduced compared with the results of the previously studied first-order theory. Generalized equilibrium for massive particles turns out to be compatible with a dependence of the Robertson-Walker metric and may be regarded as a realization of so-called K-matter.

  7. Thermodynamic equilibrium diagram of the chlorine-titanium system

    Institute of Scientific and Technical Information of China (English)

    DU Ailing; GUO Xiaofei; ZHANG Heming; LIU Jiang

    2005-01-01

    The chemical and electrochemical equilibria of the chlorine-titanium system in the presence of gaseous phase were investigated. Many species, which consisted of chlorine and titanium, were considered. Various thermodynamic equilibria were calculated in the different pressures at different temperatures. The calculated results were shown as log p-1/T and E-T diagrams. These diagrams may be used as important tools for corrosion study and titanium production. The diagrams are also used to thermodynamically determine the existence areas of various species and so on.

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

    DEFF Research Database (Denmark)

    Hosokawa, Yoshifumi; Yamada, Kazuo; Johannesson, Björn

    2008-01-01

    In this paper, a multi-species mass transport model, which can predict time dependent variation of pore solution and solid-phase composition due to the mass transport into the hardened cement paste, has been developed. Since most of the multi-species models established previously, based...... by the penetration of mineral salts during marine seawater exposure conditions. Those phenomena in concrete can be predicted using the coupled multi-species mass transport model and the thermodynamic equilibrium model described in this paper....... on the Poisson-Nernst-Planck theory, did not involve the modeling of chemical process, it has been coupled to thermodynamic equilibrium model in this study. By the coupling of thermodynamic equilibrium model, the multi-species model could simulate many different behaviours in hardened cement paste such as: (i...

  9. Carbon monoxide distributions from the upper troposphere to the mesosphere inferred from 4.7 μm non-local thermal equilibrium emissions measured by MIPAS on Envisat

    Directory of Open Access Journals (Sweden)

    B. Funke

    2009-04-01

    Full Text Available We present global distributions of carbon monoxide (CO from the upper troposphere to the mesosphere observed by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS on Envisat. Vertically resolved volume mixing ratio profiles have been retrieved from 4.7 μm limb emission spectra under consideration of non-local thermodynamic equilibrium. The precision of individual CO profiles is typically 5–30 ppbv (15–40% for altitudes greater than 40 km and lower than 15 km and 30–90% within 15–40 km. Estimated systematic errors are in the order of 8–15%. Below 60 km, the vertical resolution is 4–7 km. The data set which covers 54 days from September 2003 to March 2004 has been derived with an improved retrieval version including (i the retrieval of log(vmr, (ii the consideration of illumination-dependent vibrational population gradients along the instrument's line of sight, and (iii joint-fitted vmr horizontal gradients in latitudinal and longitudinal directions. A detailed analysis of spatially resolved CO distributions during the 2003/2004 Northern Hemisphere major warming event demonstrate the potential of MIPAS CO observations to obtain new information on transport processes during dynamical active episodes, particularly on those acting in the vertical. From the temporal evolution of zonally averaged CO abundances, we derived extraordinary polar winter descent velocities of 1200 m per day inside the recovered polar vortex in January 2004. Middle stratospheric CO abundances show a well established correlation with the chemical source CH4, particularly in the tropics. In the upper troposphere, a moderate CO decrease from September 2003 to March 2004 was observed. Upper tropospheric CO observations provide a detailed picture of long-range transport of polluted air masses and uplift events. MIPAS observations taken on 9–11 September 2003 confirm the trapping of convective outflow of polluted CO-rich air from

  10. Temporal Non-locality

    Science.gov (United States)

    Filk, Thomas

    2013-04-01

    In this article I investigate several possibilities to define the concept of "temporal non-locality" within the standard framework of quantum theory. In particular, I analyze the notions of "temporally non-local states", "temporally non-local events" and "temporally non-local observables". The idea of temporally non-local events is already inherent in the standard formalism of quantum mechanics, and Basil Hiley recently defined an operator in order to measure the degree of such a temporal non-locality. The concept of temporally non-local states enters as soon as "clock-representing states" are introduced in the context of special and general relativity. It is discussed in which way temporally non-local measurements may find an interesting application for experiments which test temporal versions of Bell inequalities.

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

    CERN Document Server

    Kleidon, Axel

    2005-01-01

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

  12. Thermodynamic equilibrium calculations of dimethyl ether steam reforming and dimethyl ether hydrolysis

    Science.gov (United States)

    Semelsberger, Troy A.; Borup, Rodney L.

    The production of a hydrogen-rich fuel-cell feed by dimethyl ether (DME) steam reforming was investigated using calculations of thermodynamic equilibrium as a function of steam-to-carbon ratio (0.00-4.00), temperature (100-600 °C), pressure (1-5 atm), and product species. Species considered were acetone, acetylene, carbon dioxide, carbon monoxide, dimethyl ether, ethane, ethanol, ethylene, formaldehyde, formic acid, hydrogen, isopropanol, methane, methanol, methyl-ethyl ether, n-propanol and water. Thermodynamic equilibrium calculations of DME steam reforming indicate complete conversion of dimethyl ether to hydrogen, carbon monoxide and carbon dioxide at temperatures greater than 200 °C and steam-to-carbon ratios greater than 1.25 at atmospheric pressure ( P = 1 atm). Increasing the operating pressure shifts the equilibrium toward the reactants; increasing the pressure from 1 to 5 atm decreases the conversion of dimethyl ether from 99.5 to 76.2%. The trend of thermodynamically stable products in decreasing mole fraction is methane, ethane, isopropyl alcohol, acetone, n-propanol, ethylene, ethanol, methyl-ethyl ether and methanol-formaldehyde, formic acid, and acetylene were not observed. Based on the equilibrium calculations, the optimal processing conditions for dimethyl ether steam reforming occur at a steam-to-carbon ratio of 1.50, a pressure of 1 atm, and a temperature of 200 °C. These thermodynamic equilibrium calculations show dimethyl ether processed with steam will produce hydrogen-rich fuel-cell feeds—with hydrogen concentrations exceeding 70%. The conversion of dimethyl ether via hydrolysis (considering methanol as the only product) is limited by thermodynamic equilibrium. Equilibrium conversion increases with temperature and steam-to-carbon ratio. A maximum dimethyl ether conversion of 62% is achieved at a steam-to-carbon ratio of 5.00 and a processing temperature of 600 °C.

  13. Thermodynamic equilibrium in relativity: four-temperature, Killing vectors and Lie derivatives

    CERN Document Server

    Becattini, F

    2016-01-01

    The main concepts of general relativistic thermodynamics and general relativistic statistical mechanics are reviewed. The main building block of the proper relativistic extension of the classical thermodynamics laws is the four-temperature vector \\beta, which plays a major role in the quantum framework and defines a very convenient hydrodynamic frame. The general relativistic thermodynamic equilibrium condition demands \\beta to be a Killing vector field. We show that a remarkable consequence is that all Lie derivatives of all physical observables along the four-temperature flow must then vanish.

  14. Entropy Production: Its Role in Non-Equilibrium Thermodynamics

    Directory of Open Access Journals (Sweden)

    Rosa Maria Velasco

    2011-01-01

    Full Text Available It is unquestionable that the concept of entropy has played an essential role both in the physical and biological sciences. However, the entropy production, crucial to the second law, has also other features not clearly conceived. We all know that the main difficulty is concerned with its quantification in non-equilibrium processes and consequently its value for some specific cases is limited. In this work we will review the ideas behind the entropy production concept and we will give some insights about its relevance.

  15. The matrix model, a driven state variables approach to non-equilibrium thermodynamics

    NARCIS (Netherlands)

    Jongschaap, R.J.J.

    2001-01-01

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

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

    Science.gov (United States)

    Khantuleva, Tatiana A.; Shalymov, Dmitry S.

    2017-03-01

    The application of the speed-gradient (SG) principle to the non-equilibrium distribution systems far away from thermodynamic equilibrium is investigated. The options for applying the SG principle to describe the non-equilibrium transport processes in real-world environments are discussed. Investigation of a non-equilibrium system's evolution at different scale levels via the SG principle allows for a fresh look at the thermodynamics problems associated with the behaviour of the system entropy. Generalized dynamic equations for finite and infinite number of constraints are proposed. It is shown that the stationary solution to the equations, resulting from the SG principle, entirely coincides with the locally equilibrium distribution function obtained by Zubarev. A new approach to describe time evolution of systems far from equilibrium is proposed based on application of the SG principle at the intermediate scale level of the system's internal structure. The problem of the high-rate shear flow of viscous fluid near the rigid plane plate is discussed. It is shown that the SG principle allows closed mathematical models of non-equilibrium processes to be constructed. This article is part of the themed issue 'Horizons of cybernetical physics'.

  17. Natural gas at thermodynamic equilibrium. Implications for the origin of natural gas.

    Science.gov (United States)

    Mango, Frank D; Jarvie, Daniel; Herriman, Eleanor

    2009-06-16

    It is broadly accepted that so-called 'thermal' gas is the product of thermal cracking, 'primary' thermal gas from kerogen cracking, and 'secondary' thermal gas from oil cracking. Since thermal cracking of hydrocarbons does not generate products at equilibrium and thermal stress should not bring them to equilibrium over geologic time, we would not expect methane, ethane, and propane to be at equilibrium in subsurface deposits. Here we report compelling evidence of natural gas at thermodynamic equilibrium. Molecular compositions are constrained to equilibrium, [Formula in text] and isotopic compositions are also under equilibrium constraints: [Formula in text].The functions [(CH4)*(C3H8)] and [(C2H6)2] exhibit a strong nonlinear correlation (R2 = 0.84) in which the quotient Q progresses to K as wet gas progresses to dry gas. There are striking similarities between natural gas and catalytic gas generated from marine shales. A Devonian/Mississippian New Albany shale generates gas with Q converging on K over time as wet gas progresses to dry gas at 200 degrees C. The position that thermal cracking is the primary source of natural gas is no longer tenable. It is challenged by its inability to explain the composition of natural gas, natural gases at thermodynamic equilibrium, and by the existence of a catalytic path to gas that better explains gas compositions.

  18. Natural gas at thermodynamic equilibrium Implications for the origin of natural gas

    Directory of Open Access Journals (Sweden)

    Jarvie Daniel

    2009-06-01

    Full Text Available Abstract It is broadly accepted that so-called 'thermal' gas is the product of thermal cracking, 'primary' thermal gas from kerogen cracking, and 'secondary' thermal gas from oil cracking. Since thermal cracking of hydrocarbons does not generate products at equilibrium and thermal stress should not bring them to equilibrium over geologic time, we would not expect methane, ethane, and propane to be at equilibrium in subsurface deposits. Here we report compelling evidence of natural gas at thermodynamic equilibrium. Molecular compositions are constrained to equilibrium, and isotopic compositions are also under equilibrium constraints: The functions [(CH4*(C3H8] and [(C2H62] exhibit a strong nonlinear correlation (R2 = 0.84 in which the quotient Q progresses to K as wet gas progresses to dry gas. There are striking similarities between natural gas and catalytic gas generated from marine shales. A Devonian/Mississippian New Albany shale generates gas with Q converging on K over time as wet gas progresses to dry gas at 200°C. The position that thermal cracking is the primary source of natural gas is no longer tenable. It is challenged by its inability to explain the composition of natural gas, natural gases at thermodynamic equilibrium, and by the existence of a catalytic path to gas that better explains gas compositions.

  19. On the Effectiveness of Nature-Inspired Metaheuristic Algorithms for Performing Phase Equilibrium Thermodynamic Calculations

    Directory of Open Access Journals (Sweden)

    Seif-Eddeen K. Fateen

    2014-01-01

    Full Text Available The search for reliable and efficient global optimization algorithms for solving phase stability and phase equilibrium problems in applied thermodynamics is an ongoing area of research. In this study, we evaluated and compared the reliability and efficiency of eight selected nature-inspired metaheuristic algorithms for solving difficult phase stability and phase equilibrium problems. These algorithms are the cuckoo search (CS, intelligent firefly (IFA, bat (BA, artificial bee colony (ABC, MAKHA, a hybrid between monkey algorithm and krill herd algorithm, covariance matrix adaptation evolution strategy (CMAES, magnetic charged system search (MCSS, and bare bones particle swarm optimization (BBPSO. The results clearly showed that CS is the most reliable of all methods as it successfully solved all thermodynamic problems tested in this study. CS proved to be a promising nature-inspired optimization method to perform applied thermodynamic calculations for process design.

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

    DEFF Research Database (Denmark)

    Shapiro, Alexander; Stenby, Erling Halfdan

    2001-01-01

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

  1. Kinetics, equilibrium and thermodynamics of the sorption of tetrabromobisphenol A on multiwalled carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Fasfous, Ismail I., E-mail: ismailf@hu.edu.jo [Department of Chemistry, College of Science, Hashemite University, Zarka, Jordan, P.O. Box 330001, Zarka 13133 (Jordan); Radwan, Enas S.; Dawoud, Jamal N. [Department of Chemistry, College of Science, Hashemite University, Zarka, Jordan, P.O. Box 330001, Zarka 13133 (Jordan)

    2010-09-15

    Tetrabromobisphenol A (TBBPA) is widely used as a flame retardant and is relatively persistent in the environment. This study reports the sorption kinetics, equilibrium and thermodynamics of TBBPA on multiwalled carbon nanotubes (MWCNTs). The equilibrium sorption capacity has been significantly improved by increasing the initial TBBPA concentration and contact time. In alkaline conditions and at high temperatures, a large reduction of TBBPA uptake was observed. The equilibrium between TBBPA and MWCNTs was achieved in approximately 60 min with removal of 96% of the TBBPA. The sorption kinetics were well described by a pseudo-second-order rate model, while both Langmuir and Freundlich models described the sorption isotherms well at different temperatures. Thermodynamic parameters suggested that the sorption of TBBPA is exothermic and spontaneous at the temperatures studied.

  2. A Non-equilibrium Thermodynamic Framework for the Dynamics and Stability of Ecosystems

    CERN Document Server

    Michaelian, K

    2002-01-01

    The population dynamics and stability of ecosystems of interacting species is studied from the perspective of non-equilibrium thermodynamics by assuming that species, through their biotic and abiotic interactions, are units of entropy production and exchange in an open thermodynamic system with constant external constraints. Within the context of the linear theory of irreversible thermodynamics, such a system will naturally evolve towards a stable stationary state in which the production of entropy within the ecosystem is at a local minimum value. It is shown that this extremal condition leads to equations for the stationary (steady) state population dynamics of interacting species, more general than those of Lotka-Volterra, and to conditions on the parameters of the community interaction matrix guaranteeing ecosystem stability. The paradoxical stability of real complex ecosystems thus has a simple explanation within the proposed framework. Furthermore, it is shown that the second law of thermodynamics constr...

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

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Wei [Department of Physics and Astronomy and Department of Chemistry, State University of New York at Stony Brook, Stony Brook, New York 11794 (United States); Wang, Jin, E-mail: jin.wang.1@stonybrook.edu [Department of Physics and Astronomy and Department of Chemistry, State University of New York at Stony Brook, Stony Brook, New York 11794 (United States); State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 130022 Changchun, China and College of Physics, Jilin University, 130021 Changchun (China)

    2014-09-14

    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.

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

    Science.gov (United States)

    Philipse, A; Vrij, A

    2011-05-18

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

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

    Science.gov (United States)

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

    2013-12-01

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

  6. Equilibrium, kinetic and thermodynamic study of the biosorption of uranium onto Cystoseria indica algae

    Energy Technology Data Exchange (ETDEWEB)

    Khani, M.H. [Department of Chemical Engineering, Faculty of Engineering, University of Tarbiat Modares, P.O. Box 14115-111, Tehran (Iran, Islamic Republic of); Nuclear Science Research school, Nuclear Science and Technology Research Institute, P.O. Box 11365, 8486 Tehran (Iran, Islamic Republic of)], E-mail: mhkhani@modares.ac.ir; Keshtkar, A.R.; Ghannadi, M. [Nuclear Science Research school, Nuclear Science and Technology Research Institute, P.O. Box 11365, 8486 Tehran (Iran, Islamic Republic of); Pahlavanzadeh, H. [Department of Chemical Engineering, Faculty of Engineering, University of Tarbiat Modares, P.O. Box 14115-111, Tehran (Iran, Islamic Republic of)

    2008-02-11

    Biosorption equilibrium, kinetics and thermodynamics of binding of uranium ions to Cystoseria indica were studied in a batch system with respect to temperature and initial metal ion concentration. Algae biomass exhibited the highest uranium uptake capacity at 15 deg. C at an initial uranium ion concentration of 500 mg l{sup -1} and an initial pH of 4. Biosorption capacity increased from 198 to 233 mg g{sup -1} with an decrease in temperature from 45 to 15 deg. C at this initial uranium concentration. The Langmuir isotherm model were applied to experimental equilibrium data of uranium biosorption depending on temperature. Equilibrium data fitted very well to the Langmuir model C. indica algae in the studied concentration range of Uranium ions at all the temperatures studied. The saturation type kinetic model was applied to experimental data at different temperatures changing from 15 to 45 deg. C to describe the batch biosorption kinetics assuming that the external mass transfer limitations in the system can be neglected and biosorption is chemical sorption controlled. The activation energy of biosorption (E{sub A}) was determined as -6.15 using the Arrhenius equation. Using the thermodynamic equilibrium coefficients obtained at different temperatures, the thermodynamic constants of biosorption ({delta}G{sup o}, {delta}H{sup o} and {delta}S{sup o}) were also evaluated.

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

    Institute of Scientific and Technical Information of China (English)

    RANA Mukhtar Ahmed

    2009-01-01

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

  8. Non-equilibrium thermodynamics of dark energy on the power-law entropy corrected apparent horizon

    CERN Document Server

    Farooq, M Umar

    2011-01-01

    We investigate the Friedmann-Robertson-Walker (FRW) universe (containing dark energy) as a non-equilibrium (irreversible) thermodynamical system by considering the power-law correction to the horizon entropy. By taking power-law entropy area law which appear in dealing with the entanglement of quantum fields in and out the horizon, we determine the power-law entropy corrected apparent horizon of the FRW universe.

  9. Lipid domains in giant unilamellar vesicles and their correspondence with equilibrium thermodynamic phases: A quantitative fluorescence microscopy imaging approach

    DEFF Research Database (Denmark)

    Fidorra, Matthias; Garcia, Alejandra; Ipsen, John Hjort

    2009-01-01

    membrane domains correspond to equilibrium thermodynamic phases (i.e., solid ordered and liquid disordered phases). In addition, the fact that the lever rule is validated from 11 to 14 randomly selected GUVs per molar fraction indicates homogeneity in the lipid composition among the explored GUV...... lipid phase diagram's tie lines and to test whether or not the coexistence of lipid domains in GUVs correspond to equilibrium thermodynamic phases. The analysis was applied to DLPC/DPPC GUVs displaying coexistence of lipid domains. Our results confirm the lever rule, demonstrating that the observed...... populations. In conclusion, our study shows that GUVs are reliable model systems to perform equilibrium thermodynamic studies of membranes....

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

    CERN Document Server

    Becattini, F

    2015-01-01

    We show that the stress-energy tensor has additional terms with respect to the ideal form in states of global thermodynamic equilibrium in flat spacetime with non-vanishing acceleration and vorticity. These corrections are of quantum origin and their leading terms are of second order in the gradients of the thermodynamic fields. The relevant coefficients can be expressed in terms of correlators of the stress-energy tensor operator and the generators of the Lorentz group. With respect to previous assessments, we find that there are more second order coefficients and that all thermodynamic functions including energy density receive acceleration and vorticity dependent corrections. Notably, also the relation between \\rho and p, that is the equation of state, is affected by acceleration and vorticity. We have calculated the corrections for a free real scalar field -- both massive and massless -- and we have found that they increase, particularly for a massive field, at very high acceleration and vorticity and ver...

  11. Thermodynamic Consistency Test for Binary Gas+Water Equilibrium Data at Low and High Pressures

    Institute of Scientific and Technical Information of China (English)

    Claudio A. Fandez; Felipe A. Quiero; Jos O. Valderrama

    2013-01-01

    Phase equilibrium in binary gas+water mixtures over wide ranges of temperatures and pressures are modeled and tested for thermodynamic consistency. For modeling, the Peng-Robinson equation of state was used and the Wong-Sandler mixing rules were incorporated into the equation of state parameters. In the Wong-Sandler mixing rules the van Laar model for the excess Gibbs en-ergy was applied. In addition, a reasonable and flexible method is applied to test the thermody-namic consistency of pressure-temperature-concentration (P-T-x) data of these binary mixtures. Modeling is found acceptable in all cases, meaning that deviations in correlating the pressure and the gas phase concentration are low. For all cases the thermodynamic consistency method gives a clear conclusion about consistency or inconsistency of a set of experimental P-T-x data.

  12. Radiative interactions in molecular gases under local and nonlocal thermodynamic equilibrium conditions

    Science.gov (United States)

    Tiwari, S. N.; Jha, M. K.

    1993-01-01

    Basic formulations, analyses, and numerical procedures are presented to investigate radiative heat interactions in diatomic and polyatomic gases under local and nonlocal thermodynamic equilibrium conditions. Essential governing equations are presented for both gray and nongray gases. Information is provided on absorption models, relaxation times, and transfer equations. Radiative flux equations are developed which are applicable under local and nonlocal thermodynamic equilibrium conditions. The problem is solved for fully developed laminar incompressible flows between two parallel plates under the boundary condition of a uniform surface heat flux. For specific applications, three diatomic and three polyatomic gases are considered. The results are obtained numerically by employing the method of variation of parameters. The results are compared under local and nonlocal thermodynamic equilibrium conditions at different temperature and pressure conditions. Both gray and nongray studies are conducted extensively for all molecular gases considered. The particular gases selected for this investigation are CO, NO, OH, CO2, H2O, and CH4. The temperature and pressure range considered are 300-2000 K and 0.1-10 atmosphere, respectively. In general, results demonstrate that the gray gas approximation overestimates the effect of radiative interaction for all conditions. The conditions of NLTE, however, result in underestimation of radiative interactions. The method developed for this study can be extended to solve complex problems of radiative heat transfer involving nonequilibrium phenomena.

  13. Beyond the Knudsen number: assessing thermodynamic non-equilibrium in gas flows

    CERN Document Server

    Meng, Jianping; Reese, Jason M; Zhang, Yonghao

    2012-01-01

    For more than 150 years the Navier-Stokes equations for thermodynamically quasi-equilibrium flows have been the cornerstone of modern computational fluid dynamics that underpins new fluid technologies. However, the applicable regime of the Navier-Stokes model in terms of the level of thermodynamic non-equilibrium in the local flowfield is not clear especially for hypersonic and low-speed micro/nano flows. Here, we re-visit the Navier-Stokes model in the framework of Boltzmann statistics, and propose a new and more appropriate way of assessing non-equilibrium in the local flowfield, and the corresponding appropriateness of the Navier-Stokes model. Our theoretical analysis and numerical simulations confirm our proposed method. Through molecular dynamics simulations we reveal that the commonly-used Knudsen number, or a parametric combination of Knudsen and Mach numbers, may not be sufficient to accurately assess the departure of flowfields from equilibrium, and the applicability of the Navier-Stokes model.

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

    DEFF Research Database (Denmark)

    Jahnke, Annika; MacLeod, Matthew; Wickström, Håkan

    2014-01-01

    Equilibrium partitioning (EqP) theory is currently the most widely used approach for linking sediment pollution by persistent hydrophobic organic chemicals to bioaccumulation. Most applications of the EqP approach assume (I) a generic relationship between organic carbon-normalized chemical...... chemical concentrations in the silicone, and applying lipid/silicone partition ratios to yield concentrations in lipid at thermodynamic equilibrium with the sediment (CLip⇌Sed). Furthermore, we evaluated the validity of assumption II by comparing CLip⇌Sed of selected persistent, bioaccumulative and toxic...... pollutants (polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB)) to lipid-normalized concentrations for a range of biota from a Swedish background lake. PCBs in duck mussels, roach, eel, pikeperch, perch and pike were mostly below the equilibrium partitioning level relative to the sediment, i...

  15. Emergence of equilibrium thermodynamic properties in quantum pure states. I. Theory.

    Science.gov (United States)

    Fresch, Barbara; Moro, Giorgio J

    2010-07-21

    Investigation on foundational aspects of quantum statistical mechanics recently entered a renaissance period due to novel intuitions from quantum information theory and to increasing attention on the dynamical aspects of single quantum systems. In the present contribution a simple but effective theoretical framework is introduced to clarify the connections between a purely mechanical description and the thermodynamic characterization of the equilibrium state of an isolated quantum system. A salient feature of our approach is the very transparent distinction between the statistical aspects and the dynamical aspects in the description of isolated quantum systems. Like in the classical statistical mechanics, the equilibrium distribution of any property is identified on the basis of the time evolution of the considered system. As a consequence equilibrium properties of quantum system appear to depend on the details of the initial state due to the abundance of constants of the motion in the Schrodinger dynamics. On the other hand the study of the probability distributions of some functions, such as the entropy or the equilibrium state of a subsystem, in statistical ensembles of pure states reveals the crucial role of typicality as the bridge between macroscopic thermodynamics and microscopic quantum dynamics. We shall consider two particular ensembles: the random pure state ensemble and the fixed expectation energy ensemble. The relation between the introduced ensembles, the properties of a given isolated system, and the standard quantum statistical description are discussed throughout the presentation. Finally we point out the conditions which should be satisfied by an ensemble in order to get meaningful thermodynamical characterization of an isolated quantum system.

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

    Science.gov (United States)

    Qian, Hong

    2014-01-01

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

  17. The solubility of (Ba,Sr)SO 4 precipitates: Thermodynamic equilibrium and reaction path analysis

    Science.gov (United States)

    Felmy, Andrew R.; Rai, Dhanpat; Moore, Dean A.

    1993-09-01

    The solubility of (Ba,Sr)SO 4 precipitates, varying in SrSO 4 mole fraction from 0.05-0.90, was investigated at room temperature with an equilibration period extending to almost three years. The data show that on or before 315 days of equilibration the precipitates reach a reversible equilibrium with the aqueous solution. The reversibility of this equilibrium was verified both by the attainment of steady-state concentrations with time and by heating the samples to perturb the equilibrium and then observing the slow return to the initial equilibrium state. The dissolution of the (Ba,Sr)SO 4 precipitates does not, in general, follow limiting reaction paths as defined by the Lippmann solutus or stoichiometric dissolution curves. In addition, activity coefficient calculations for the BaSO 4 and SrSO 4 components of the solid phase, using either total bulk analysis or near-surface analysis of the component mole fractions, do not satisfy the Gibbs-Duhem equation, demonstrating that a single solid-solution phase does not control both the aqueous Ba and Sr concentrations. Instead, our long-term equilibration data can be explained by the unavoidable formation of small amounts of barite and substitution of Sr into a solid-solution phase with the BaSO 4 component of the solid-solution phase never reaching thermodynamic equilibrium with the aqueous phase.

  18. Quantum Thermodynamics: Non-equilibrium 3D Description of an Unbounded System at an Atomistic Level

    Directory of Open Access Journals (Sweden)

    Vittorio Verda

    2010-03-01

    Full Text Available Quantum thermodynamics (QT provides a general framework for the description of non-equilibrium phenomena at any level, particularly the atomistic one. This theory and its dynamical postulate are used here to extend the work reported in previous papers of modeling the storage of hydrogen in an isolated system, by extending the modeling to 3D. The system is prepared in a state with the hydrogen molecules initially far from stable equilibrium after which the system is allowed to relax (evolve to a state of stable equilibrium. The so-called energy eigenvalue problem, which entails a many-body problem that for dilute and moderately dense gases can be solved using virial expansion theory, is used to determine the energy eigenvalues and eigenstates of the system. This information is then used in the nonlinear Beretta equation of motion of QT to determine the evolution of the thermodynamic state of the system as well as the spatial distributions of the hydrogen molecules in time. The results of our simulations provide a quantification of the entropy generated due to irreversibilities at an atomistic level and show in detail the trajectory of the state of the system as the hydrogen molecules, which are initially arranged to be far from the carbon nanotube, spread out in the system and eventually become more concentrated near the carbon atoms which make up the nanotube.

  19. Molecular simulation of the thermodynamic, structural, and vapor-liquid equilibrium properties of neon.

    Science.gov (United States)

    Vlasiuk, Maryna; Frascoli, Federico; Sadus, Richard J

    2016-09-14

    The thermodynamic, structural, and vapor-liquid equilibrium properties of neon are comprehensively studied using ab initio, empirical, and semi-classical intermolecular potentials and classical Monte Carlo simulations. Path integral Monte Carlo simulations for isochoric heat capacity and structural properties are also reported for two empirical potentials and one ab initio potential. The isobaric and isochoric heat capacities, thermal expansion coefficient, thermal pressure coefficient, isothermal and adiabatic compressibilities, Joule-Thomson coefficient, and the speed of sound are reported and compared with experimental data for the entire range of liquid densities from the triple point to the critical point. Lustig's thermodynamic approach is formally extended for temperature-dependent intermolecular potentials. Quantum effects are incorporated using the Feynman-Hibbs quantum correction, which results in significant improvement in the accuracy of predicted thermodynamic properties. The new Feynman-Hibbs version of the Hellmann-Bich-Vogel potential predicts the isochoric heat capacity to an accuracy of 1.4% over the entire range of liquid densities. It also predicts other thermodynamic properties more accurately than alternative intermolecular potentials.

  20. Equilibrium p-T Phase Diagram of Boron: Experimental Study and Thermodynamic Analysis

    Science.gov (United States)

    Solozhenko, Vladimir L.; Kurakevych, Oleksandr O.

    2013-01-01

    Solid-state phase transformations and melting of high-purity crystalline boron have been in situ and ex situ studied at pressures to 20 GPa in the 1500–2500 K temperature range where diffusion processes become fast and lead to formation of thermodynamically stable phases. The equilibrium phase diagram of boron has been constructed based on thermodynamic analysis of experimental and literature data. The high-temperature part of the diagram contains p-T domains of thermodynamic stability of rhombohedral β-B106, orthorhombic γ-B28, pseudo-cubic (tetragonal) t'-B52, and liquid boron (L). The positions of two triple points have been experimentally estimated, i.e. β–t'–L at ~ 8.0 GPa and ~ 2490 K; and β–γ–t' at ~ 9.6 GPa and ~ 2230 K. Finally, the proposed phase diagram explains all thermodynamic aspects of boron allotropy and significantly improves our understanding of the fifth element. PMID:23912523

  1. Molecular simulation of the thermodynamic, structural, and vapor-liquid equilibrium properties of neon

    Science.gov (United States)

    Vlasiuk, Maryna; Frascoli, Federico; Sadus, Richard J.

    2016-09-01

    The thermodynamic, structural, and vapor-liquid equilibrium properties of neon are comprehensively studied using ab initio, empirical, and semi-classical intermolecular potentials and classical Monte Carlo simulations. Path integral Monte Carlo simulations for isochoric heat capacity and structural properties are also reported for two empirical potentials and one ab initio potential. The isobaric and isochoric heat capacities, thermal expansion coefficient, thermal pressure coefficient, isothermal and adiabatic compressibilities, Joule-Thomson coefficient, and the speed of sound are reported and compared with experimental data for the entire range of liquid densities from the triple point to the critical point. Lustig's thermodynamic approach is formally extended for temperature-dependent intermolecular potentials. Quantum effects are incorporated using the Feynman-Hibbs quantum correction, which results in significant improvement in the accuracy of predicted thermodynamic properties. The new Feynman-Hibbs version of the Hellmann-Bich-Vogel potential predicts the isochoric heat capacity to an accuracy of 1.4% over the entire range of liquid densities. It also predicts other thermodynamic properties more accurately than alternative intermolecular potentials.

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

    Directory of Open Access Journals (Sweden)

    naghmouchi nahed

    2016-04-01

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

  3. Equilibrium, kinetic and thermodynamic studies on the biosorption of Cu(II) onto chestnut shell

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Z.-Y., E-mail: zengyuyao@126.com [Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang, Liaoning 110016 (China); Qi, J.-H. [College of Life Sciences, Northwest A and F University, Yangling, Shaanxi 712100 (China); Wang, L.-H. [Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang, Liaoning 110016 (China)

    2010-02-15

    The biosorption of Cu(II) onto chestnut shell, a residue of the food processing industry, in a batch adsorber has been studied. Equilibrium isotherms, kinetic data, and thermodynamic parameters have been evaluated. Equilibrium data agreed well with Langmuir isotherm and Redlich-Peterson isotherm models. The adsorption capacity of chestnut shell for Cu(II) was determined with the Langmuir model and was found to be 12.56 mg g{sup -1} at 293 K. The kinetic data were found to follow the pseudo-second-order model. Intra-particle diffusion is not the sole rate-controlling factor. Gibbs free energy was spontaneous for all interactions, and the adsorption process exhibited exothermic enthalpy values. Chestnut shell was shown to be a promising biosorbent for Cu(II) removal from aqueous solutions.

  4. A new way to measure the departure from thermodynamic equilibrium in stellar atmospheres

    Institute of Scientific and Technical Information of China (English)

    Zhong-Quan Qu; Long-Fei Hao; Xiao-Li Yan; Cheng-Lin Xu

    2009-01-01

    A new way to measure the departure from thermodynamic equilibrium is proposed based on the departure factor which evaluates the deviation from a Boltzmann level distribution, used by Short and Hauschildt (2005) and others. The way is based on an explicit relationship describing the departure factor as a function of line to continuum source, dynamic temperature and line photon frequency, under three assumptions that the scattering can be neglected, the background continuum can be treated as a Planck function, and finally the complete redistribution can be true. It has the advantage that the departure can be very conveniently evaluated from the spectral analysis with only the radiative transfer involved. Some physical insights are recovered for some extreme cases.Some example calculations of the departure are presented for the quiet Sun, faint solar flare and strong solar flare for the generally used solar chromospheric lines: Hα, Hβ,CaII H, K and triplet. It is revealed that in the case of solar flares, the departure is less than thermodynamic equilibrium along the larger depth range than in the quiet sun due to chromospheric condensation. It becomes hard to distinguish the departures for the different lines of the same atom or ion. It is expected that this investigation can be constructive for studying stellar atmospheres in cases where the three assumptions are close to reality.

  5. Local thermodynamic equilibrium modeling of ionization of impurities in argon inductively coupled plasma

    Energy Technology Data Exchange (ETDEWEB)

    Serapinas, Petras, E-mail: serapinas@pfi.l [Institute of Theoretical Physics and Astronomy, Vilnius University, A. Gostauto 12, 01108 Vilnius (Lithuania); Salkauskas, Julius; Ezerinskis, Zilvinas; Acus, Arturas [Institute of Theoretical Physics and Astronomy, Vilnius University, A. Gostauto 12, 01108 Vilnius (Lithuania)

    2010-01-15

    Essentially higher ionization degree of small concentrations of elements in inductively coupled plasma in comparison to the ionization of pure elements is emphasized. This conclusion is used to determine the relative dependence of the sensitivity of the inductively coupled plasma mass spectrometer on the atomic mass. The possibility of evaluation of the ionization temperature and electron density from mass spectrometric signals is proposed. Temperatures about 7000 K and 8000 K were obtained from the ionization ratio dependences on ionization potentials. Electron densities of the order of magnitude 10{sup 15} cm{sup -3}, in excess to the local thermodynamic equilibrium values, follow from the application of the Saha equation to the measurement results and indicate the recombining character of the plasma in the mass spectrometer measurement region. Effects due to additional ionization from matrix were discussed. The effect is largest on minor abundant ionization state components. Matrix effect is restricted to some temperature interval, which depends on the whole matrix composition and the plasma state. The results show that the local thermodynamic equilibrium modeling, if adequately matching the sample composition, can be useful as a quantitative basis for both description of the plasma state and indication of the character of the nonequilibrium effects.

  6. Equilibrium, kinetic and thermodynamic study of cesium adsorption onto nanocrystalline mordenite from high-salt solution.

    Science.gov (United States)

    Lee, Keun-Young; Park, Minsung; Kim, Jimin; Oh, Maengkyo; Lee, Eil-Hee; Kim, Kwang-Wook; Chung, Dong-Yong; Moon, Jei-Kwon

    2016-05-01

    In this study, the equilibrium, kinetics and thermodynamics of cesium adsorption by nanocrystalline mordenite were investigated under cesium contamination with high-salt solution, simulating the case of an operation and decommissioning of nuclear facilities or an accident during the processes. The adsorption rate constants were determined using a pseudo second-order kinetic model. The kinetic results strongly demonstrated that the cesium adsorption rate of nano mordenite is extremely fast, even in a high-salt solution, and much faster than that of micro mordenite. In the equilibrium study, the Langmuir isotherm model fit the cesium adsorption data of nano mordenite better than the Freundlich model, which suggests that cesium adsorption onto nano mordenite is a monolayer homogeneous adsorption process. The obtained thermodynamic parameters indicated that the adsorption involved a very stable chemical reaction. In particular, the combination of rapid particle dispersion and rapid cesium adsorption of the nano mordenite in the solution resulted in a rapid and effective process for cesium removal without stirring, which may offer great advantages for low energy consumption and simple operation.

  7. Adsorption of Congo Red by Ni/Al-CO3: Equilibrium, Thermodynamic and Kinetic Studies

    Directory of Open Access Journals (Sweden)

    N. Ayawei

    2015-09-01

    Full Text Available Experimental investigations were carried out using Ni/Al-CO3 layered double hydroxide as adsorbent for removal of toxic anionic dye namely Congo red from aqueous solutions. The effect of contact time, initial dye concentration and temperature were experimentally studied in batch mode to evaluate the kinetic, equilibrium and thermodynamic parameters of the adsorption process. Experimental results revealed that the degradation of the dye is mostly dependent on temperature. The dye degradation process obeyed the zero-order kinetic model, first-order kinetic model, second-order kinetic model, pseudo second order kinetic and third order kinetic model with correlation coefficient values 1, 0.9998, 0.9999, 0.9999 and 0.9997 respectively. Langmuir, Freundlich, Temkin and Dubinin-Kaganer-Radushkevic isotherms were applied to the equilibrium data and was well described by all. Thermodynamic studies showed congo red adsorption on the layered double hydroxide was endothermic and spontaneous in nature. The results indicate that layered double hydroxide could be employed as alternative for removal of anionic dyes from industrial wastewater.

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

    Science.gov (United States)

    Bharate, Sonali S; Vishwakarma, Ram A

    2015-04-01

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

  9. Adsorption laboratory experiment for undergraduate chemical engineering: Introducing kinetic, equilibrium and thermodynamic concepts

    Science.gov (United States)

    Muryanto, S.; Djatmiko Hadi, S.

    2016-11-01

    Adsorption laboratory experiment for undergraduate chemical engineering program is discussed. The experiment demonstrated adsorption of copper ions commonly found in wastewater using bio-sorbent, i.e. agricultural wastes. The adsorption was performed in a batch mode under various parameters: adsorption time (up to 120 min), initial pH (2 to 6), adsorbent dose (2.0 to 12.0 g L-1), adsorbent size (50 to 170 mesh), initial Cu2+ concentration (25 to 100 ppm) and temperatures (room temp to 40°C). The equilibrium and kinetic data of the experiments were calculated using the two commonly used isotherms: Langmuir and Lagergren pseudo-first-order kinetics. The maximum adsorption capacity for Cu2+ was found as 94.34 mg g-1. Thermodynamically, the adsorption process was spontaneous and endothermic. The calculated activation energy for the adsorption was observed as high as 127.94 kJ mol-1. Pedagogically, the experiment was assumed to be important in increasing student understanding of kinetic, equilibrium and thermodynamic concepts.

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

    Science.gov (United States)

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

    2015-05-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Qian, Hong, E-mail: hqian@u.washington.edu

    2014-01-31

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

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

    Science.gov (United States)

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

    2010-12-15

    Adsorption can be used as a cost effective and efficient technique for the removal of toxic heavy metals from wastewater. Waste materials with no further treatment such as coffee grounds from cafeterias may act as adsorbents for the removal of cadmium. Batch kinetic and equilibrium experiments were conducted to study the effects of contact time, adsorbent dose, initial pH, particle size, initial concentration of cadmium and temperature. Three adsorption isotherm models namely, Langmuir, Freundlich and Dubinin-Radushkevich were used to analyse the equilibrium data. The Langmuir isotherm which provided the best correlation for Cd(2+) adsorption onto coffee grounds, shows that the adsorption was favourable and the adsorption capacity found was equal to 15.65 mg g(-1). Thermodynamic parameters were evaluated and the adsorption was exothermic. The equilibrium was achieved less than 120 min. The adsorption kinetic data was fitted with first and second order kinetic models. Finally it was concluded that the cadmium adsorption kinetic onto coffee grounds was well fitted by second order kinetic model rather than first order model. The results suggest that coffee grounds have high possibility to be used as effective and economical adsorbent for Cd(2+) removal. Copyright © 2010 Elsevier B.V. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-12-15

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

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

    Science.gov (United States)

    Kleidon, A

    2010-05-12

    The Earth system is remarkably different from its planetary neighbours in that it shows pronounced, strong global cycling of matter. These global cycles result in the maintenance of a unique thermodynamic state of the Earth's atmosphere which is far from thermodynamic equilibrium (TE). Here, I provide a simple introduction of the thermodynamic basis to understand why Earth system processes operate so far away from TE. I use a simple toy model to illustrate the application of non-equilibrium thermodynamics and to classify applications of the proposed principle of maximum entropy production (MEP) to such processes into three different cases of contrasting flexibility in the boundary conditions. I then provide a brief overview of the different processes within the Earth system that produce entropy, review actual examples of MEP in environmental and ecological systems, and discuss the role of interactions among dissipative processes in making boundary conditions more flexible. I close with a brief summary and conclusion.

  15. Biosorption of nickel(II) from aqueous solution by brown algae: Equilibrium, dynamic and thermodynamic studies

    Energy Technology Data Exchange (ETDEWEB)

    Pahlavanzadeh, H., E-mail: pahlavzh@modares.ac.ir [Department of Chemical Engineering, Faculty of Engineering, Tarbiat Modares University, P.O. Box 14115-111, Tehran (Iran, Islamic Republic of); Keshtkar, A.R.; Safdari, J. [Atomic Energy Organization of Iran, Nuclear Science and Technology Research Institute, P.O. Box 11365, 8486 Tehran (Iran, Islamic Republic of); Abadi, Z. [Department of Chemical Engineering, Faculty of Engineering, Tarbiat Modares University, P.O. Box 14115-111, Tehran (Iran, Islamic Republic of)

    2010-03-15

    The biosorption characteristics of nickel(II) ions using the brown algae (Cystoseria indica, Nizmuddinia zanardini, Sargassum glaucescens and Padina australis) were investigated. Experimental parameters affecting the biosorption process such as pH level, contact time, initial metal concentration and temperature were studied. The equilibrium data fitted very well to the Langmuir adsorption model in the concentration range of nickel(II) ions and at all the temperatures studied. Evaluation of the experimental data in terms of biosorption dynamics showed that the biosorption of nickel(II) onto algal biomass followed the pseudo-second-order dynamics well. The calculated thermodynamic parameters ({Delta}G{sup o}, {Delta}H{sup o} and {Delta}S{sup o}) showed that the biosorption of nickel(II) ions were feasible, spontaneous and endothermic at the temperature ranges of 293-313 K.

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

    Science.gov (United States)

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

    2017-07-01

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

  17. Cortical phase transitions, non-equilibrium thermodynamics and the time-dependent Ginzburg-Landau equation

    CERN Document Server

    Freeman, W J; Obinata, M; Vitiello, G

    2011-01-01

    The formation of amplitude modulated and phase modulated assemblies of neurons is observed in the brain functional activity. The study of the formation of such structures requires that the analysis has to be organized in hierarchical levels, microscopic, mesoscopic, macroscopic, each with its characteristic space-time scales and the various forms of energy, electric, chemical, thermal produced and used by the brain. In this paper, we discuss the microscopic dynamics underlying the mesoscopic and the macroscopic levels and focus our attention on the thermodynamics of the non-equilibrium phase transitions. We obtain the time-dependent Ginzburg-Landau equation for the non-stationary regime and consider the formation of topologically non-trivial structures such as the vortex solution. The power laws observed in functional activities of the brain is also discussed and related to coherent states characterizing the many-body dissipative model of brain.

  18. Investigation of the local thermodynamic equilibrium of laser-induced aluminum plasma by Thomson scattering technique

    Energy Technology Data Exchange (ETDEWEB)

    Mendys, A., E-mail: agata.mendys@uj.edu.pl [Instytut Fizyki im. M. Smoluchowskiego, Uniwersytet Jagielloński, ul. Reymonta 4, 30-059 Kraków (Poland); Kański, M. [Instytut Fizyki im. M. Smoluchowskiego, Uniwersytet Jagielloński, ul. Reymonta 4, 30-059 Kraków (Poland); Farah-Sougueh, A. [Instytut Fizyki im. M. Smoluchowskiego, Uniwersytet Jagielloński, ul. Reymonta 4, 30-059 Kraków (Poland); GREMI — site de Bourges, Université d' Orléans, CNRS, rue Gaston Berger BP 4043, 18028 Bourges (France); Pellerin, S. [GREMI — site de Bourges, Université d' Orléans, CNRS, rue Gaston Berger BP 4043, 18028 Bourges (France); Pokrzywka, B. [Obserwatorium Astronomiczne na Suhorze, Uniwersytet Pedagogiczny, ul. Podchorażych 2, 30-084 Kraków (Poland); Dzierżęga, K. [Instytut Fizyki im. M. Smoluchowskiego, Uniwersytet Jagielloński, ul. Reymonta 4, 30-059 Kraków (Poland)

    2014-06-01

    A laser Thomson scattering method was applied to investigate the local Saha–Boltzmann equilibrium in aluminum laser-induced plasma. Plasma was created in ambient air using 4.5 ns pulses from a Nd:YAG laser at 532 nm, focused on an Al target. Spatially resolved measurements, performed for the time interval between 600 ns and 3 μs, show electron density and temperature to decrease from 3.4 × 10{sup 23} m{sup −3} to 0.5 × 10{sup 23} m{sup −3} and from 61,000 K to 13,000 K in the plasma core. The existence of local thermodynamic equilibria in the plasma was verified by comparing the rates of the collisional to radiative processes (the McWhirter criterion), as well as relaxation times and diffusion lengths of different plasma species, with the appropriate rate of electron density evolution and its gradients at given, experimentally determined, electron temperatures. We found these criteria to be much easier to satisfy for metallic plasma species than for nitrogen. The criteria are also easier to satisfy in the plasma core of higher electron density. - Highlights: • Laser Thomson scattering method was applied to investigate aluminum laser-induced plasma. • Spatio-temporal evolution of electron temperature and density was determined. • Three criteria for existence of local thermodynamic equilibrium were verified. • Criteria are much easier to satisfy for metallic plasma species than for nitrogen. • Criteria are easier to satisfy at earlier times and in the plasma core.

  19. Non-Perfect-Fluid Space-Times in Thermodynamic Equilibrium and Generalized Friedmann Equations

    Directory of Open Access Journals (Sweden)

    Konrad Schatz

    2016-01-01

    Full Text Available We determine the energy-momentum tensor of nonperfect fluids in thermodynamic equilibrium and, respectively, near to it. To this end, we derive the constitutive equations for energy density and isotropic and anisotropic pressure as well as for heat-flux from the corresponding propagation equations and by drawing on Einstein’s equations. Following Obukhov on this, we assume the corresponding space-times to be conform-stationary and homogeneous. This procedure provides these quantities in closed form, that is, in terms of the structure constants of the three-dimensional isometry group of homogeneity and, respectively, in terms of the kinematical quantities expansion, rotation, and acceleration. In particular, we find a generalized form of the Friedmann equations. As special cases we recover Friedmann and Gödel models as well as nontilted Bianchi solutions with anisotropic pressure. All of our results are derived without assuming any equations of state or other specific thermodynamic conditions a priori. For the considered models, results in literature are generalized to rotating fluids with dissipative fluxes.

  20. Non-perfect-fluid space-times in thermodynamic equilibrium and generalized Friedmann equations

    CERN Document Server

    Schatz, Konrad; Chrobok, Thoralf

    2014-01-01

    Assuming homogeneous and parallax-free space-times, in the case of thermodynamic equilibrium, we construct the energy-momentum tensor of non-perfect fluids. To this end we derive the constitutive equations for energy density, isotropic and anisotropic pressure as well as heat-flux from the respective propagation equations. This provides these quantities in closed form, i. e. in terms of the structure constants of the three-dimensional isometry group of homogeneity and, respectively, of the kinematical quantities expansion, rotation and acceleration. Using Einstein's equations, the thereby occurring constants of integration can be determined such that one gets bounds on the kinematical quantities and finds a generalized form of the Friedmann equations. As a consequence, it is shown that, e. g., for a perfect fluid the Friedmann and G\\"odel models can be recovered. All this is derived without assuming any equations of state or other specific thermodynamic conditions, and, in principle, allows one to go beyond t...

  1. Characterization of local thermodynamic equilibrium in a laser-induced aluminum alloy plasma.

    Science.gov (United States)

    Zhang, Yong; Zhao, Zhenyang; Xu, Tao; Niu, GuangHui; Liu, Ying; Duan, Yixiang

    2016-04-01

    The electron temperature was evaluated using the line-to-continuum ratio method, and whether the plasma was close to the local thermodynamic equilibrium (LTE) state was investigated in detail. The results showed that approximately 5 μs after the plasma formed, the changes in the electron and excitation temperatures, which were determined using a Boltzmann plot, overlapped in the 15% error range, which indicated that the LTE state was reached. The recombination of electrons and ions and the free electron expansion process led to the deviation from the LTE state. The plasma's expansion rate slowed over time, and when the expansion time was close to the ionization equilibrium time, the LTE state was almost reached. The McWhirter criterion was adopted to calculate the threshold electron density for different species, and the results showed that experimental electron density was greater than the threshold electron density, which meant that the LTE state may have existed. However, for the nonmetal element N, the threshold electron density was greater than the value experimental value approximately 0.8 μs after the plasma formed, which meant that LTE state did not exist for N.

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

    Science.gov (United States)

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

    2017-05-01

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

  3. Adsorption of bentazon on activated carbon prepared from Lawsonia inermis wood: Equilibrium, kinetic and thermodynamic studies

    Directory of Open Access Journals (Sweden)

    Abdessalem Omri

    2016-11-01

    Full Text Available The adsorption of bentazon onto Lawsonia inermis wood-based activated carbon (LWAC was carried out in this work. The effects of different reaction parameters such as the initial bentazon concentration, contact time, activated carbon dosage, stirring rate, temperature and pH on bentazon adsorption were investigated in a batch process mode. Equilibrium data were analyzed by the Langmuir, Freundlich and Temkin isotherm model. Langmuir isotherm provided the best fit to the equilibrium data with maximum adsorption capacity of 169.49 mg/g at 20 °C. Adsorption kinetic was found to follow the pseudo-second-order kinetic model. The mechanism of the adsorption process was determined from the intraparticle diffusion model. The calculated thermodynamic parameters such as ΔG°, ΔH° and ΔS° showed that the adsorption of bentazon onto LWAC was feasible, spontaneous and exothermic at 20–40 °C. Desorption of the used LWAC was studied using ethanol as solvent and a percent desorption efficiency of bentazon equalizes 73.8% was obtained after three cycles.

  4. Non-equilibrium thermodynamics and collective vibrational modes of liquid water in an inhomogeneous electric field.

    Science.gov (United States)

    Wexler, Adam D; Drusová, Sandra; Woisetschläger, Jakob; Fuchs, Elmar C

    2016-06-28

    In this experiment liquid water is subject to an inhomogeneous electric field (∇(2)Ea≈ 10(10) V m(2)) using a high voltage (20 kV) point-plane electrode system. Using interferometry it was found that the application of a strong electric field gradient to water generates local changes in the refractive index of the liquid, polarizes the surface and creates a downward moving electro-convective jet. A maximum temperature difference of 1 °C is measured in the immediate vicinity of the point electrode. Raman spectroscopy performed on water reveals an enhancement of the vibrational collective modes (3250 cm(-1)) as well as an increase in the local mode (3490 cm(-1)) energy. This bimodal enhancement indicates that the spectral changes are not due to temperature changes. The intense field gradient thus establishes an excited subpopulation of vibrational oscillators far from thermal equilibrium. Delocalization of the collective vibrational mode spatially expands this excited population beyond the microscale. Hindered rotational freedom due to electric field pinning of molecular dipoles retards the heat flow and generates a chemical potential gradient. These changes are responsible for the observed changes in the refractive index and temperature. It is demonstrated that polar liquids can thus support local non-equilibrium thermodynamic transient states critical to biochemical and environmental processes.

  5. Equilibrium and thermodynamic studies on biosorption of Pb(II) onto Candida albicans biomass

    Energy Technology Data Exchange (ETDEWEB)

    Baysal, Zuebeyde [Department of Chemistry, Faculty of Science-Art, Dicle University, Diyarbakir (Turkey)], E-mail: zbaysal@dicle.edu.tr; Cinar, Ercan; Bulut, Yasemin; Alkan, Hueseyin; Dogru, Mehmet [Department of Chemistry, Faculty of Science-Art, Dicle University, Diyarbakir (Turkey)

    2009-01-15

    Biosorption of Pb(II) ions from aqueous solutions was studied in a batch system by using Candida albicans. The optimum conditions of biosorption were determined by investigating the initial metal ion concentration, contact time, temperature, biosorbent dose and pH. The extent of metal ion removed increased with increasing contact time, initial metal ion concentration and temperature. Biosorption equilibrium time was observed in 30 min. The Freundlich and Langmuir adsorption models were used for the mathematical description of biosorption equilibrium and isotherm constants were also evaluated. The maximum biosorption capacity of Pb(II) on C. albicans was determined as 828.50 {+-} 1.05, 831.26 {+-} 1.30 and 833.33 {+-} 1.12 mg g{sup -1}, respectively, at different temperatures (25, 35 and 45 deg. C). Biosorption showed pseudo second-order rate kinetics at different initial concentration of Pb(II) and different temperatures. The activation energy of the biosorption (E{sub a}) was estimated as 59.04 kJ mol{sup -1} from Arrhenius equation. Using the equilibrium constant value obtained at different temperatures, the thermodynamic properties of the biosorption ({delta}G{sup o}, {delta}H{sup o} and {delta}S{sup o}) were also determined. The results showed that biosorption of Pb(II) ions on C. albicans were endothermic and spontaneous. The optimum initial pH for Pb(II) was determined as pH 5.0. FTIR spectral analysis of Pb(II) adsorbed and unadsorbed C. albicans biomass was also discussed.

  6. Linear thermodynamic analysis of the reversible Selkov model: An interpretation of the Chatelier-like principle for local concentration fluctuations near thermodynamic equilibrium

    Science.gov (United States)

    Dutt, Arun K.

    1990-03-01

    Thermodynamic analysis of the reversible Selkov model (a simple kinetic model describing glycolytic oscillations) has been done by an entropy production technique of Prigogine and it is shown that only the autocatalytic step can destabilize the steady state in this model. It is derived that at thermodynamic equilibrium, the product δS δP is always a positive quantity which appears to be a Chatelier-like principle for local concentration fluctuation applicable to the autocatalytic step S ⇄ P of this model.

  7. Effect of deviation from local thermodynamic equilibrium on the Goldberg-Unno method. [turbulence effects on optical density in the solar photosphere

    Science.gov (United States)

    Troyan, V. I.

    1974-01-01

    The dependence of turbulent velocity on optical depth was studied by use of the Goldberg-Unno method, with allowance made for the influence of deviation from the local thermodynamic equilibrium. It was found that allowance for deviation from local thermodynamic equilibrium displaces the curve of dependence of turbulent velocity on optical depth along two axes.

  8. Analysis of Hydrogen Generation through Thermochemical Gasification of Coconut Shell Using Thermodynamic Equilibrium Model Considering Char and Tar.

    Science.gov (United States)

    Rupesh, Shanmughom; Muraleedharan, Chandrasekharan; Arun, Palatel

    2014-01-01

    This work investigates the potential of coconut shell for air-steam gasification using thermodynamic equilibrium model. A thermodynamic equilibrium model considering tar and realistic char conversion was developed using MATLAB software to predict the product gas composition. After comparing it with experimental results the prediction capability of the model is enhanced by multiplying equilibrium constants with suitable coefficients. The modified model is used to study the effect of key process parameters like temperature, steam to biomass ratio, and equivalence ratio on product gas yield, composition, and heating value of syngas along with gasification efficiency. For a steam to biomass ratio of unity, the maximum mole fraction of hydrogen in the product gas is found to be 36.14% with a lower heating value of 7.49 MJ/Nm(3) at a gasification temperature of 1500 K and equivalence ratio of 0.15.

  9. Analysis of Hydrogen Generation through Thermochemical Gasification of Coconut Shell Using Thermodynamic Equilibrium Model Considering Char and Tar

    Science.gov (United States)

    Rupesh, Shanmughom; Muraleedharan, Chandrasekharan; Arun, Palatel

    2014-01-01

    This work investigates the potential of coconut shell for air-steam gasification using thermodynamic equilibrium model. A thermodynamic equilibrium model considering tar and realistic char conversion was developed using MATLAB software to predict the product gas composition. After comparing it with experimental results the prediction capability of the model is enhanced by multiplying equilibrium constants with suitable coefficients. The modified model is used to study the effect of key process parameters like temperature, steam to biomass ratio, and equivalence ratio on product gas yield, composition, and heating value of syngas along with gasification efficiency. For a steam to biomass ratio of unity, the maximum mole fraction of hydrogen in the product gas is found to be 36.14% with a lower heating value of 7.49 MJ/Nm3 at a gasification temperature of 1500 K and equivalence ratio of 0.15. PMID:27433487

  10. The non-equilibrium thermodynamics and kinetics of focal adhesion dynamics.

    Directory of Open Access Journals (Sweden)

    Joseph E Olberding

    Full Text Available BACKGROUND: We consider a focal adhesion to be made up of molecular complexes, each consisting of a ligand, an integrin molecule, and associated plaque proteins. Free energy changes drive the binding and unbinding of these complexes and thereby controls the focal adhesion's dynamic modes of growth, treadmilling and resorption. PRINCIPAL FINDINGS: We have identified a competition among four thermodynamic driving forces for focal adhesion dynamics: (i the work done during the addition of a single molecular complex of a certain size, (ii the chemical free energy change associated with the addition of a molecular complex, (iii the elastic free energy change associated with deformation of focal adhesions and the cell membrane, and (iv the work done on a molecular conformational change. We have developed a theoretical treatment of focal adhesion dynamics as a nonlinear rate process governed by a classical kinetic model. We also express the rates as being driven by out-of-equilibrium thermodynamic driving forces, and modulated by kinetics. The mechanisms governed by the above four effects allow focal adhesions to exhibit a rich variety of behavior without the need to introduce special constitutive assumptions for their response. For the reaction-limited case growth, treadmilling and resorption are all predicted by a very simple chemo-mechanical model. Treadmilling requires symmetry breaking between the ends of the focal adhesion, and is achieved by driving force (i above. In contrast, depending on its numerical value (ii causes symmetric growth, resorption or is neutral, (iii causes symmetric resorption, and (iv causes symmetric growth. These findings hold for a range of conditions: temporally-constant force or stress, and for spatially-uniform and non-uniform stress distribution over the FA. The symmetric growth mode dominates for temporally-constant stress, with a reduced treadmilling regime. SIGNIFICANCE: In addition to explaining focal adhesion

  11. Equilibrium, kinetic and thermodynamic studies on aluminum biosorption by a mycelial biomass (Streptomyces rimosus)

    Energy Technology Data Exchange (ETDEWEB)

    Tassist, Amina, E-mail: aminatassist@yahoo.fr [Laboratory of Environmental Biotechnologies and Process Engineering, BIOGEP, Polytechnic National School of Algiers, Hacen Badi, El Harrach, Algiers (Algeria); Lounici, Hakim; Abdi, Nadia; Mameri, Nabil [Laboratory of Environmental Biotechnologies and Process Engineering, BIOGEP, Polytechnic National School of Algiers, Hacen Badi, El Harrach, Algiers (Algeria)

    2010-11-15

    This work focused on kinetic, equilibrium and thermodynamic studies on aluminum biosorption by Streptomyces rimosus biomass. Infrared spectroscopy analysis shows that S. rimosus present some groups: hydroxyl, methyl, carboxyl, amine, thiol and phosphate. The maximum biosorption capacity of S. rimosus biomass was found to be 11.76 mg g{sup -1} for the following optimum conditions: particle size,]250-560] {mu}m, pH 4-4.25, biomass content of 25 g L{sup -1}, agitation of 250 rpm and temperature of 25 deg. C. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models were applied to describe the biosorption isotherms at free pH (pH{sub i} 4) and fixed pH (pH{sub f} 4). Langmuir model is the most adequate. With fixed pH, the maximum biosorption capacity is enhanced from 6.62 mg g{sup -1} to 11.76 mg g{sup -1}. The thermodynamic parameters ({Delta}G{sup o}, {Delta}H{sup o} and {Delta}S{sup o}) showed the feasibility, endothermic and spontaneous nature of the biosorption at 10-80 deg. C. The activation energy (Ea) was determined as 52.18 kJ mol{sup -1} using the Arrhenius equation and the rate constant of pseudo-second-order model (the most adequate kinetic model). The mean free energy was calculated as 12.91 kJ mol{sup -1} using the D-R isotherm model. The mechanism of Al(III) biosorption on S. rimosus could be a chemical ion exchange and carboxyl groups are mainly involved in this mechanism.

  12. Equilibrium, kinetic and thermodynamic studies on aluminum biosorption by a mycelial biomass (Streptomyces rimosus).

    Science.gov (United States)

    Tassist, Amina; Lounici, Hakim; Abdi, Nadia; Mameri, Nabil

    2010-11-15

    This work focused on kinetic, equilibrium and thermodynamic studies on aluminum biosorption by Streptomyces rimosus biomass. Infrared spectroscopy analysis shows that S. rimosus present some groups: hydroxyl, methyl, carboxyl, amine, thiol and phosphate. The maximum biosorption capacity of S. rimosus biomass was found to be 11.76 mg g(-1) for the following optimum conditions: particle size, [250-560] μm, pH 4-4.25, biomass content of 25 g L(-1), agitation of 250 rpm and temperature of 25 °C. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models were applied to describe the biosorption isotherms at free pH (pH(i) 4) and fixed pH (pH(f) 4). Langmuir model is the most adequate. With fixed pH, the maximum biosorption capacity is enhanced from 6.62 mg g(-1) to 11.76 mg g(-1). The thermodynamic parameters (ΔG°, ΔH° and ΔS°) showed the feasibility, endothermic and spontaneous nature of the biosorption at 10-80 °C. The activation energy (Ea) was determined as 52.18 kJ mol(-1) using the Arrhenius equation and the rate constant of pseudo-second-order model (the most adequate kinetic model). The mean free energy was calculated as 12.91 kJ mol(-1) using the D-R isotherm model. The mechanism of Al(III) biosorption on S. rimosus could be a chemical ion exchange and carboxyl groups are mainly involved in this mechanism.

  13. Determination of the thermodynamic properties of liquid Ag-Sb-Sn system by equilibrium saturation method

    Directory of Open Access Journals (Sweden)

    J. Romanowska

    2011-09-01

    Full Text Available Purpose: The interaction of lead-free solders with a copper substrate is an essential issue for the reliability of solder joints. In order to understand this interaction, the knowledge of thermodynamic and other physical properties of several ternary systems such as Ag-Sb-Sn system is necessary. The aim of this work was to determine the activities of all components in Ag-Sb-Sn alloy.Design/methodology/approach: The investigation of this system was carried out using the equilibrium saturation (ES method. The ES measurements were performed at 1273, 1373 and 1473 K. As the latter method is a comparative one, a Sn-Sb alloy was accepted as a reference alloy, where a formula for the Sb activity proposed by Jönsson and verified by Vassiliev was accepted.Findings: In the frame of the presented experiments the activity of Sb was determined by ES method.Research limitations/implications: The activity of Sb was obtained by ES and fitted to the Redlich-Kister-Muggianu (RKM model.Practical implications: A knowledge of multi-component phase equilibrium can provide the alloy developer with specific data enabling finding alloys that meet certain criteria. Phase diagrams are built on the basis of experimental data and the reliability of phase diagrams depends on the reliability of the experimental data used for the optimisation. Hence it is advantageous to use various source of data obtained by several methods and when the data of different source agree (like the ones presented in this paper it proves their reliability. Data presented in this paper will be used for Ag-Sb-Sn phase diagram optimisation in the frame of the COST Action MP0602.Originality/value: Sb activity values in Ag-Sb-Sn alloys obtained by ES and activity values of Sb, Ag and Sn calculated using the RKM model.

  14. Assessing life's effects on the interior dynamics of planet Earth using non-equilibrium thermodynamics

    Directory of Open Access Journals (Sweden)

    J. G. Dyke

    2010-09-01

    Full Text Available Vernadsky described life as the geologic force, while Lovelock noted the role of life in driving the Earth's atmospheric composition to a unique state of thermodynamic disequilibrium. Here, we use these notions in conjunction with thermodynamics to quantify biotic activity as a driving force for geologic processes. Specifically, we explore the hypothesis that biologically-mediated processes operating on the surface of the Earth, such as the biotic enhancement of weathering of continental crust, affect interior processes such as mantle convection and have therefore shaped the evolution of the whole Earth system beyond its surface and atmosphere. We set up three simple models of mantle convection, oceanic crust recycling and continental crust recycling. We describe these models in terms of non-equilibrium thermodynamics in which the generation and dissipation of gradients is central to driving their dynamics and that such dynamics can be affected by their boundary conditions. We use these models to quantify the maximum power that is involved in these processes. The assumption that these processes, given a set of boundary conditions, operate at maximum levels of generation and dissipation of free energy lead to reasonable predictions of core temperature, seafloor spreading rates, and continental crust thickness. With a set of sensitivity simulations we then show how these models interact through the boundary conditions at the mantle-crust and oceanic-continental crust interfaces. These simulations hence support our hypothesis that the depletion of continental crust at the land surface can affect rates of oceanic crust recycling and mantle convection deep within the Earth's interior. We situate this hypothesis within a broader assessment of surface-interior interactions by setting up a work budget of the Earth's interior to compare the maximum power estimates that drive interior processes to the power that is associated with biotic activity

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

    Science.gov (United States)

    Lebon, G.; Jou, D.

    2015-06-01

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

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

    Science.gov (United States)

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

    2014-05-01

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

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

    Directory of Open Access Journals (Sweden)

    V. Gunasekar

    2013-01-01

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

  18. Phase equilibriums and thermodynamic properties of the system Bi-Te-I

    Energy Technology Data Exchange (ETDEWEB)

    Babanly, M.B. [Baku State University, Baku, AZ 1148, Z.Khalilov str, 23, BSU (Azerbaijan)], E-mail: Babanly_mb@rambler.ru; Tedenac, J.-C. [PMOF, ICGM UMR 5253 CNRS UM2, ENSCM, UM1, Place Eugene Bataillon, 34095 Montpellier (France)], E-mail: tedenac@univ-montp2.fr; Aliyev, Z.S. [Baku State University, Baku, AZ 1148, Z.Khalilov str, 23, BSU (Azerbaijan); Balitsky, D.V. [PMOF, ICGM UMR 5253 CNRS UM2, ENSCM, UM1, Place Eugene Bataillon, 34095 Montpellier (France)

    2009-07-29

    The system Bi-Te-I was studied by methods of differential thermal analysis and the X-ray diffraction, and also by measurements of electromotive forces (EMF) of concentration chains of type (-) Bi (s) | liquid electrolytic conductor, Bi{sup 3+} | (Bi-Te-I) (s) (+) in the temperatures range of 300-400 K. The series of polythermal sections and isothermal section of the phase diagram at 300 K, and a projection of the liquidus surface were constructed. Earlier indicated ternary compounds BiTeI, Bi{sub 2}TeI and Bi{sub 4}TeI{sub 1.25} were confirmed, the position of phase areas and their relationships was established. Areas of primary crystallization fields, types and coordinates of the non- and mono-variant equilibriums were determined. The measurements of EMF have allowed calculation of partial molar functions ({delta}G-bar,{delta}H-bar,{delta}S-bar) of bismuth in alloys, standard thermodynamic functions of formation and standard entropies of the indicated ternary compounds.

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

    Directory of Open Access Journals (Sweden)

    J. G. Dyke

    2011-06-01

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

  20. EQUILIBRIUM, KINETIC, AND THERMODYNAMIC STUDIES OF HAZARDOUS DYE NEUTRAL RED BIOSORPTION BY SPENT CORNCOB SUBSTRATE

    Directory of Open Access Journals (Sweden)

    Xiuwu Yu

    2011-04-01

    Full Text Available This study focuses on the possible use of spent corncob substrate (SCS, an agricultural waste utilized after the cultivation of white rot fungus Pleurotus ostreatus, to adsorb the hazardous dye Neutral Red (NR from aqueous solutions. Natural SCS was initially characterized by using a combination of Fourier Transform Infrared Spectrometry (FTIR and Brunauer-Emmett-Teller (BET techniques. A batch adsorption study was carried out with varied solution pH, adsorption time, temperature, and initial NR concentration. It was found that NR uptake was favorable over a pH range of 4.0 to 7.0, and the equilibrium adsorption capacity can be reached within about 180 min. The biosorption data were also calculated by the pseudo-second-order kinetic model and Langmuir isotherm model. The maximum adsorption capacity was 139.1, 140.0, and 143.3 mg g-1 at 20, 30, and 40 °C, respectively. Thermodynamic parameters showed that the adsorption was a spontaneous and endothermic process. The study highlighted a new pathway to develop potential low-cost biosorbent for the removal of dye pollutants from wastewater.

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

    Directory of Open Access Journals (Sweden)

    Israa G. Zainal

    2010-01-01

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

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

    Science.gov (United States)

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

    2016-09-01

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

  3. Adsorption of hydrogen fluoride onto activated carbon under vacuum conditions: Equilibrium, kinetic and thermodynamic investigations

    Directory of Open Access Journals (Sweden)

    Bahrami Hussein

    2012-01-01

    Full Text Available In this study, the adsorption of HF gas by three types of activated carbon has been investigated under vacuum condition. The effects of experimental parameters such as initial pressure of the HF gas, contact time and temperature on adsorption process have been investigated. The results showed that the adsorption of the HF gas onto activated carbon increased by increasing initial pressure of gas, while it decreased with increase in temperature. The Freundlich isotherm model fitted the equilibrium data better than the other isotherm models. Using Langmuir isotherm model, the maximum adsorption capacities of the first type, the second type and third type of activated carbon were 226.4, 268.8 and 258.9 mg/g, respectively. Experimental data were also evaluated in terms of kinetic characteristics of adsorption and it was found that the adsorption process followed well pseudo-second-order kinetics. Thermodynamic parameters, the change of free energy (ΔG°, enthalpy (ΔH° and entropy (ΔS° of adsorption were calculated at the temperature range of 28-55°C. The results showed that the adsorption of HF on activated carbon is feasible, spontaneous and exothermic.

  4. A thermodynamic study of silica-saturated iron silicate slags in equilibrium with liquid copper

    Science.gov (United States)

    Oishi, Toshio; Kamuo, Morinori; Ono, Katsutoshi; Moriyama, Joichiro

    1983-03-01

    The thermodynamic properties of silica-saturated iron silicate slags in equilibrium with liquid copper have been studied from oxygen partial pressure measurements in the temperature range from 1490 to 1580 K by means of a solid electrolyte galvanic cell. The following cells were used: Pt, Ni-NiO/O=/slag-Cu(l), Cr2O3, Pt; Pt, Fe-FeO/O=/slag-Cu(Fe sat.), Fe. A strong correlation was found between oxygen pressure and the copper content of the slag; the copper content increased from less than 1 pct near iron saturation to about 4 pct at an oxygen partial pressure of 7.2 x 10-3 Pa. A similar correlation was found between the ferric iron/total iron ratio and the oxygen pressure. The oxygen content in liquid copper decreased with increasing iron content in liquid copper and increased slightly near iron saturation. This behavior could be explained qualitatively by using the standard free energy of formation of FeO and the activities of components.

  5. Deviation of Carbon Dioxide-Water Gas-Liquid Balance from Thermodynamic Equilibrium in Turbulence I:Experiment and Correlation

    Institute of Scientific and Technical Information of China (English)

    ZHANG Zhenzhen; QIAN Zhi; XU Lianbin; WU Caiyan; GUO Kai

    2013-01-01

    The carbon dioxide-water system was used to investigate the flowing gas-liquid metastable state.The experiment was carried out in a constant volume vessel with a horizontal circulation pipe and a peristaltic pump forced CO2 saturated water to flow.The temperature and pressure were recorded.The results showed that some CO2 escaped from the water in the flow process and the pressure increased,indicating that the gas-liquid equilibrium was broken.The amount of escaped CO2 varied with flow speed and reached a limit in a few minutes,entitled dynamic equilibrium.Temperature and liquid movement played the same important role in breaking the phase equilibrium.Under the experimental conditions,the ratio of the excessive carbon dioxide in the gas phase to its thermodynamic equilibrium amount in the liquid could achieve 15%.

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

    CERN Document Server

    Nosonovsky, Michael

    2013-01-01

    Many scientists and engineers do not realize that, under certain conditions, friction can lead to the formation of new structures at the interface, including in situ tribofilms and various patterns. In turn, these structures-usually formed by destabilization of the stationary sliding regime-can lead to the reduction of friction and wear. Friction-Induced Vibrations and Self-Organization: Mechanics and Non-Equilibrium Thermodynamics of Sliding Contact combines the mechanical and thermodynamic methods in tribology, thus extending the field of mechanical friction-induced vibrations to non-mechani

  7. Theoretical Aspects of Differential Scanning Calorimetry as a Tool for the Studies of Equilibrium Thermodynamics in Pharmaceutical Solid Phase Transitions.

    Science.gov (United States)

    Faroongsarng, Damrongsak

    2016-06-01

    Although differential scanning calorimetry (DSC) is a non-equilibrium technique, it has been used to gain energetic information that involves phase equilibria. DSC has been widely used to characterize the equilibrium melting parameters of small organic pharmaceutical compounds. An understanding of how DSC measures an equilibrium event could make for a better interpretation of the results. The aim of this mini-review was to provide a theoretical insight into the DSC measurement to obtain the equilibrium thermodynamics of a phase transition especially the melting process. It was demonstrated that the heat quantity obtained from the DSC thermogram (ΔH) was related to the thermodynamic enthalpy of the phase transition (ΔH (P) ) via: ΔH = ΔH (P) /(1 + K (- 1)) where K was the equilibrium constant. In melting, the solid and liquefied phases presumably coexist resulting in a null Gibbs free energy that produces an infinitely larger K. Thus, ΔH could be interpreted as ΔH (P). Issues of DSC investigations on melting behavior of crystalline solids including polymorphism, degradation impurity due to heating in situ, and eutectic melting were discussed. In addition, DSC has been a tool for determination of the impurity based on an ideal solution of the melt that is one of the official methods used to establish the reference standard.

  8. Randomness and Non-Locality

    Science.gov (United States)

    Senno, Gabriel; Bendersky, Ariel; Figueira, Santiago

    2016-07-01

    The concepts of randomness and non-locality are intimately intertwined outcomes of randomly chosen measurements over entangled systems exhibiting non-local correlations are, if we preclude instantaneous influence between distant measurement choices and outcomes, random. In this paper, we survey some recent advances in the knowledge of the interplay between these two important notions from a quantum information science perspective.

  9. Chromium Biosorption from Cr(VI) Aqueous Solutions by Cupressus lusitanica Bark: Kinetics, Equilibrium and Thermodynamic Studies

    Science.gov (United States)

    Netzahuatl-Muñoz, Alma Rosa; Cristiani-Urbina, María del Carmen; Cristiani-Urbina, Eliseo

    2015-01-01

    The present study investigated the kinetics, equilibrium and thermodynamics of chromium (Cr) ion biosorption from Cr(VI) aqueous solutions by Cupressus lusitanica bark (CLB). CLB total Cr biosorption capacity strongly depended on operating variables such as initial Cr(VI) concentration and contact time: as these variables rose, total Cr biosorption capacity increased significantly. Total Cr biosorption rate also increased with rising solution temperature. The pseudo-second-order model described the total Cr biosorption kinetic data best. Langmuir´s model fitted the experimental equilibrium biosorption data of total Cr best and predicted a maximum total Cr biosorption capacity of 305.4 mg g-1. Total Cr biosorption by CLB is an endothermic and non-spontaneous process as indicated by the thermodynamic parameters. Results from the present kinetic, equilibrium and thermodynamic studies suggest that CLB biosorbs Cr ions from Cr(VI) aqueous solutions predominantly by a chemical sorption phenomenon. Low cost, availability, renewable nature, and effective total Cr biosorption make CLB a highly attractive and efficient method to remediate Cr(VI)-contaminated water and wastewater. PMID:26352933

  10. Lipid domains in giant unilamellar vesicles and their correspondence with equilibrium thermodynamic phases: a quantitative fluorescence microscopy imaging approach.

    Science.gov (United States)

    Fidorra, M; Garcia, A; Ipsen, J H; Härtel, S; Bagatolli, L A

    2009-10-01

    We report a novel analytical procedure to measure the surface areas of coexisting lipid domains in giant unilamellar vesicles (GUVs) based on image processing of 3D fluorescence microscopy data. The procedure involves the segmentation of lipid domains from fluorescent image stacks and reconstruction of 3D domain morphology using active surface models. This method permits the reconstruction of the spherical surface of GUVs and determination of the area fractions of coexisting lipid domains at the level of single vesicles. Obtaining area fractions enables the scrutiny of the lever rule along lipid phase diagram's tie lines and to test whether or not the coexistence of lipid domains in GUVs correspond to equilibrium thermodynamic phases. The analysis was applied to DLPC/DPPC GUVs displaying coexistence of lipid domains. Our results confirm the lever rule, demonstrating that the observed membrane domains correspond to equilibrium thermodynamic phases (i.e., solid ordered and liquid disordered phases). In addition, the fact that the lever rule is validated from 11 to 14 randomly selected GUVs per molar fraction indicates homogeneity in the lipid composition among the explored GUV populations. In conclusion, our study shows that GUVs are reliable model systems to perform equilibrium thermodynamic studies of membranes.

  11. Chromium Biosorption from Cr(VI Aqueous Solutions by Cupressus lusitanica Bark: Kinetics, Equilibrium and Thermodynamic Studies.

    Directory of Open Access Journals (Sweden)

    Alma Rosa Netzahuatl-Muñoz

    Full Text Available The present study investigated the kinetics, equilibrium and thermodynamics of chromium (Cr ion biosorption from Cr(VI aqueous solutions by Cupressus lusitanica bark (CLB. CLB total Cr biosorption capacity strongly depended on operating variables such as initial Cr(VI concentration and contact time: as these variables rose, total Cr biosorption capacity increased significantly. Total Cr biosorption rate also increased with rising solution temperature. The pseudo-second-order model described the total Cr biosorption kinetic data best. Langmuir´s model fitted the experimental equilibrium biosorption data of total Cr best and predicted a maximum total Cr biosorption capacity of 305.4 mg g(-1. Total Cr biosorption by CLB is an endothermic and non-spontaneous process as indicated by the thermodynamic parameters. Results from the present kinetic, equilibrium and thermodynamic studies suggest that CLB biosorbs Cr ions from Cr(VI aqueous solutions predominantly by a chemical sorption phenomenon. Low cost, availability, renewable nature, and effective total Cr biosorption make CLB a highly attractive and efficient method to remediate Cr(VI-contaminated water and wastewater.

  12. Chromium Biosorption from Cr(VI) Aqueous Solutions by Cupressus lusitanica Bark: Kinetics, Equilibrium and Thermodynamic Studies.

    Science.gov (United States)

    Netzahuatl-Muñoz, Alma Rosa; Cristiani-Urbina, María del Carmen; Cristiani-Urbina, Eliseo

    2015-01-01

    The present study investigated the kinetics, equilibrium and thermodynamics of chromium (Cr) ion biosorption from Cr(VI) aqueous solutions by Cupressus lusitanica bark (CLB). CLB total Cr biosorption capacity strongly depended on operating variables such as initial Cr(VI) concentration and contact time: as these variables rose, total Cr biosorption capacity increased significantly. Total Cr biosorption rate also increased with rising solution temperature. The pseudo-second-order model described the total Cr biosorption kinetic data best. Langmuir´s model fitted the experimental equilibrium biosorption data of total Cr best and predicted a maximum total Cr biosorption capacity of 305.4 mg g(-1). Total Cr biosorption by CLB is an endothermic and non-spontaneous process as indicated by the thermodynamic parameters. Results from the present kinetic, equilibrium and thermodynamic studies suggest that CLB biosorbs Cr ions from Cr(VI) aqueous solutions predominantly by a chemical sorption phenomenon. Low cost, availability, renewable nature, and effective total Cr biosorption make CLB a highly attractive and efficient method to remediate Cr(VI)-contaminated water and wastewater.

  13. Thermodynamics and equilibrium structure of Ne38 cluster: quantum mechanics versus classical.

    Science.gov (United States)

    Predescu, Cristian; Frantsuzov, Pavel A; Mandelshtam, Vladimir A

    2005-04-15

    The equilibrium properties of classical Lennard-Jones (LJ38) versus quantum Ne38 Lennard-Jones clusters are investigated. The quantum simulations use both the path-integral Monte Carlo (PIMC) and the recently developed variational-Gaussian wave packet Monte Carlo (VGW-MC) methods. The PIMC and the classical MC simulations are implemented in the parallel tempering framework. The classical heat capacity Cv(T) curve agrees well with that of Neirotti et al. [J. Chem. Phys. 112, 10340 (2000)], although a much larger confining sphere is used in the present work. The classical Cv(T) shows a peak at about 6 K, interpreted as a solid-liquid transition, and a shoulder at approximately 4 K, attributed to a solid-solid transition involving structures from the global octahedral (Oh) minimum and the main icosahedral (C5v) minimum. The VGW method is used to locate and characterize the low energy states of Ne38, which are then further refined by PIMC calculations. Unlike the classical case, the ground state of Ne38 is a liquidlike structure. Among the several liquidlike states with energies below the two symmetric states (Oh and C5v), the lowest two exhibit strong delocalization over basins associated with at least two classical local minima. Because the symmetric structures do not play an essential role in the thermodynamics of Ne38, the quantum heat capacity is a featureless curve indicative of the absence of any structural transformations. Good agreement between the two methods, VGW and PIMC, is obtained. The present results are also consistent with the predictions by Calvo et al. [J. Chem. Phys. 114, 7312 (2001)] based on the quantum superposition method within the harmonic approximation. However, because of its approximate nature, the latter method leads to an incorrect assignment of the Ne38 ground state as well as to a significant underestimation of the heat capacity.

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

    Science.gov (United States)

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

    2017-07-01

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

  15. Adsorption properties of tetracycline onto graphene oxide: equilibrium, kinetic and thermodynamic studies.

    Directory of Open Access Journals (Sweden)

    Ehsan Ezzatpour Ghadim

    Full Text Available Graphene oxide (GO nanoparticle is a high potential effective absorbent. Tetracycline (TC is a broad-spectrum antibiotic produced, indicated for use against many bacterial infections. In the present research, a systematic study of the adsorption and release process of tetracycline on GO was performed by varying pH, sorption time and temperature. The results of our studies showed that tetracycline strongly loads on the GO surface via π-π interaction and cation-π bonding. Investigation of TC adsorption kinetics showed that the equilibrium was reached within 15 min following the pseudo-second-order model with observed rate constants of k2 = 0.2742-0.5362 g/mg min (at different temperatures. The sorption data has interpreted by the Langmuir model with the maximum adsorption of 323 mg/g (298 K. The mean energy of adsorption was determined 1.83 kJ/mol (298 K based on the Dubinin-Radushkevich (D-R adsorption isotherm. Moreover, the thermodynamic parameters such as ΔH°, ΔS° and ΔG° values for the adsorption were estimated which indicated the endothermic and spontaneous nature of the sorption process. The electrochemistry approved an ideal reaction for the adsorption under electrodic process. Simulation of GO and TC was done by LAMMPS. Force studies in z direction showed that tetracycline comes close to GO sheet by C8 direction. Then it goes far and turns and again comes close from amine group to the GO sheet.

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

    Energy Technology Data Exchange (ETDEWEB)

    Stout, R B

    2001-04-01

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

  17. Natural gas at thermodynamic equilibrium Implications for the origin of natural gas

    OpenAIRE

    Jarvie Daniel; Mango Frank D; Herriman Eleanor

    2009-01-01

    Abstract It is broadly accepted that so-called 'thermal' gas is the product of thermal cracking, 'primary' thermal gas from kerogen cracking, and 'secondary' thermal gas from oil cracking. Since thermal cracking of hydrocarbons does not generate products at equilibrium and thermal stress should not bring them to equilibrium over geologic time, we would not expect methane, ethane, and propane to be at equilibrium in subsurface deposits. Here we report compelling evidence of natural gas at ther...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-11-01

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

  19. Thermodynamic equilibrium calculations of sulfur poisoning in Ce-O-S and La-O-S systems

    Energy Technology Data Exchange (ETDEWEB)

    Karjalainen, Heidi; Lassi, Ulla; Rahkamaa-Tolonen, Katariina; Kroeger, Virpi; Keiski, Riitta L. [University of Oulu, Department of Process and Environmental Engineering, P.O. Box 4300, FIN-90014 Oulu (Finland)

    2005-02-28

    Sulfur poisoning is still a problem in many application areas of exhaust gas catalysts despite the fact that the sulfur levels, e.g. in gasoline are being continuously reduced. The aim of this study was to calculate thermodynamic equilibrium compositions of sulfur in Ce-O-S and La-O-S systems in the presence of precious metals (Pt, Pd, and Rh), which all were considered as bulk materials, in order to understand the experimentally observed sulfur poisoning under the real applications of exhaust gas catalysts. Depending on temperature and oxygen partial pressure, sulfur can be present in the form of sulfates, sulfides and oxysulfides. It is thermodynamically favorable that cerium oxide reacts with SO{sub 2} to form cerium sulfate at low temperatures and cerium oxysulfides at high temperatures. Lanthanum oxide reacts with SO{sub 2} to form sulfate under oxidizing conditions and sulfides under reducing conditions.

  20. How Many Types of Thermodynamical Equilibrium are There: Relation to Information Theory and Holism

    CERN Document Server

    Koleva, M K

    2006-01-01

    Major revision of the thermodynamics is made in order to provide rigorous fundament for functional diversity of holistic type. It turns out that the new approach ensures reproducibility of the information as well.

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

    DEFF Research Database (Denmark)

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

    2004-01-01

    Vacuum membrane distillation (VMD) has been studied as a separation process to remove volatile organic compounds from aqueous streams. A vapour pressure difference across a microporous hydrophobic membrane is the driving force for the mass transport through the membrane pores (this transport take...... values; membrane type: PTFE/PP/PVDF; feed flow rate; feed temperature. A comparison is made between different thermodynamic models for calculating the vapour-liquid equilibrium at the membrane/pore interface. (C) 2004 Elsevier B.V. All rights reserved....

  2. Partition functions 1: Improved partition functions and thermodynamic quantities for normal, equilibrium, and ortho and para molecular hydrogen

    CERN Document Server

    Popovas, Andrius

    2016-01-01

    Aims. In this work we rigorously show the shortcomings of various simplifications that are used to calculate the total internal partition function. These shortcomings can lead to errors of up to 40 percent or more in the estimated partition function. These errors carry on to calculations of thermodynamic quantities. Therefore a more complicated approach has to be taken. Methods. Seven possible simplifications of various complexity are described, together with advantages and disadvantages of direct summation of experimental values. These were compared to what we consider the most accurate and most complete treatment (case 8). Dunham coefficients were determined from experimental and theoretical energy levels of a number of electronically excited states of H$_2$ . Both equilibrium and normal hydrogen was taken into consideration. Results. Various shortcomings in existing calculations are demonstrated, and the reasons for them are explained. New partition functions for equilibrium, normal, and ortho and para hyd...

  3. The non-local oscillator

    Energy Technology Data Exchange (ETDEWEB)

    Maccari, A. [Istituto Tecnico `G. Cardano`, Monterotondo, Rome (Italy)

    1996-08-01

    The most important characteristics of the non-local oscillator, an oscillator subjected to an additional non-local force, are extensively studied by means of a new asymptotic perturbation method that is able to furnish an approximate solution of weakly non-linear differential equations. The resulting motion is doubly periodic, because a second little frequency appears, in addition to the fundamental harmonic frequency. Comparison with the numerical solution obtained by the Runge-Kitta method confirms the validity of the asymptotic perturbation method and its importance for the study of non-linear dynamical systems.

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

    Directory of Open Access Journals (Sweden)

    Samson Abramsky

    2015-11-01

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

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

    Science.gov (United States)

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

    2016-02-01

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

  6. Thermodynamic Investigation of the Effect of Interface Curvature on the Solid-Liquid Equilibrium and Eutectic Point of Binary Mixtures.

    Science.gov (United States)

    Liu, Fanghui; Zargarzadeh, Leila; Chung, Hyun-Joong; Elliott, Janet A W

    2017-09-29

    Thermodynamic phase behavior is affected by curved interfaces in micro- and nanoscale systems. For example, capillary freezing point depression is associated with the pressure difference between the solid and liquid phases caused by interface curvature. In this study, the thermal, mechanical, and chemical equilibrium conditions are derived for binary solid-liquid equilibrium with a curved solid-liquid interface due to confinement in a capillary. This derivation shows the equivalence of the most general forms of the Gibbs-Thomson and Ostwald-Freundlich equations. As an example, the effect of curvature on solid-liquid equilibrium is explained quantitatively for the water/glycerol system. Considering the effect of a curved solid-liquid interface, a complete solid-liquid phase diagram is developed over a range of concentrations for the water/glycerol system (including the freezing of pure water or precipitation of pure glycerol depending on the concentration of the solution). This phase diagram is compared with the traditional phase diagram in which the assumption of a flat solid-liquid interface is made. We show the extent to which nanoscale interface curvature can affect the composition-dependent freezing and precipitating processes, as well as the change in the eutectic point temperature and concentration with interface curvature. Understanding the effect of curvature on solid-liquid equilibrium in nanoscale capillaries has applications in the food industry, soil science, cryobiology, nanoporous materials, and various nanoscience fields.

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

    Science.gov (United States)

    Popovas, A.; Jørgensen, U. G.

    2016-11-01

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

  8. Equilibrium and thermodynamic parameters for heterogeneous esterification of butyric acid with methanol under microwave irradiation

    Directory of Open Access Journals (Sweden)

    P.N. Dange

    2017-03-01

    Full Text Available Synthesis of methyl butyrate was investigated in a microwave irradiated batch reactor in presence of acid ion-exchange resin catalyst, amberlyst-15. Methyl ester was heterogeneously produced by the reaction between butyric acid and methanol. Effect of reaction parameters of temperature (323–343 K, catalyst loading (0–10.5% w/w, alcohol to acid ratio, M (1–5, and amount of molecular sieves added (0–13.5% w/w on conversion were studied. Equilibrium conversion of 92.6% was achieved in 60 minutes under microwave irradiation. Equilibrium constants at varied temperatures and dependency of equilibrium constant on temperature were studied. Equilibrium constant and equilibrium conversion showed increase with the increase in temperature as expected as per le-Chatelier principle. Van't Hoff plot for esterification of butyric acid was linear with negative slope indicating that reaction was endothermic. Comparative study showed that microwave irradiated method for methyl butyrate synthesis to be very efficient and fast compared with conventional and ultrasound assisted routes under optimized reaction conditions.

  9. Adsorption of Remazol Brilliant Blue R using ZnO fine powder: Equilibrium, kinetic and thermodynamic modeling studies

    Energy Technology Data Exchange (ETDEWEB)

    Ada, Kezban [Department of Chemistry, Faculty of Arts and Sciences, Kirikkale University, 71450 Yahsihan-Kirikkale (Turkey); Ergene, Aysun, E-mail: ayergene@yahoo.com [Department of Biology, Faculty of Arts and Sciences, Kirikkale University, 71450 Yahsihan-Kirikkale (Turkey); Tan, Sema; Yalcin, Emine [Department of Biology, Faculty of Arts and Sciences, Kirikkale University, 71450 Yahsihan-Kirikkale (Turkey)

    2009-06-15

    Zinc oxide powders with six-sided flake-like particles were prepared by homogeneous precipitation from boiling aqueous solutions that contained excess urea and 0.075 (Z075) and 0.300 (Z300) M Zn{sup 2+}. The average sizes of the particles are 37 and 46 {mu}m, while the average sizes of the crystals are {approx}45 for Z075 and Z300 at 1000 deg. C. Equilibrium, kinetic and thermodynamic studies were carried out for the adsorption of RBBR dye from aqueous solution using both types of ZnO in the form of fine powders. The effects of pH, initial dye concentration, contact time and temperature of solution on the adsorption were studied. Langmuir, Temkin and Dubinin-Radushkevich (D-R) isotherm models were used to describe the adsorption of RBBR onto ZnO powders. The Langmuir and D-R isotherm models fit the equilibrium data better than the Temkin isotherm model. The monomolecular adsorption capacity of Z075 and Z300 was determined to be 190 and 345 mg g{sup -1} for RBBR, respectively. The Lagergren first-order, Ritchie second-order kinetic and intra-particle diffusion models were used for the adsorption of the dye onto ZnO powders. The Ritchie second-order model was suitable for describing the adsorption kinetics for the removal of RBBR from aqueous solution onto Z075 and Z300. Thermodynamic parameters, such as the Gibbs free energy ({Delta}G{sup numbersign}), enthalpy ({Delta}H{sup numbersign}), entropy ({Delta}S{sup numbersign}) and equilibrium constant of activation (K{sup numbersign}) were calculated. These parameters showed that the adsorption process of RBBR onto Z075 and Z300 was an endothermic process of a chemical nature under the studied conditions.

  10. Adsorption of Remazol Brilliant Blue R using ZnO fine powder: equilibrium, kinetic and thermodynamic modeling studies.

    Science.gov (United States)

    Ada, Kezban; Ergene, Aysun; Tan, Sema; Yalçin, Emine

    2009-06-15

    Zinc oxide powders with six-sided flake-like particles were prepared by homogeneous precipitation from boiling aqueous solutions that contained excess urea and 0.075 (Z075) and 0.300 (Z300)M Zn(2+). The average sizes of the particles are 37 and 46 microm, while the average sizes of the crystals are approximately 45 for Z075 and Z300 at 1000 degrees C. Equilibrium, kinetic and thermodynamic studies were carried out for the adsorption of RBBR dye from aqueous solution using both types of ZnO in the form of fine powders. The effects of pH, initial dye concentration, contact time and temperature of solution on the adsorption were studied. Langmuir, Temkin and Dubinin-Radushkevich (D-R) isotherm models were used to describe the adsorption of RBBR onto ZnO powders. The Langmuir and D-R isotherm models fit the equilibrium data better than the Temkin isotherm model. The monomolecular adsorption capacity of Z075 and Z300 was determined to be 190 and 345 mg g(-1) for RBBR, respectively. The Lagergren first-order, Ritchie second-order kinetic and intra-particle diffusion models were used for the adsorption of the dye onto ZnO powders. The Ritchie second-order model was suitable for describing the adsorption kinetics for the removal of RBBR from aqueous solution onto Z075 and Z300. Thermodynamic parameters, such as the Gibbs free energy (DeltaG(#)), enthalpy (DeltaH(#)), entropy (DeltaS(#)) and equilibrium constant of activation (K(#)) were calculated. These parameters showed that the adsorption process of RBBR onto Z075 and Z300 was an endothermic process of a chemical nature under the studied conditions.

  11. Non-local models for ductile failure

    Science.gov (United States)

    César de Sá, José; Azinpour, Erfan; Santos, Abel

    2016-08-01

    Ductile damage can be dealt with continuous descriptions of material, resorting, for example, to continuous damage mechanic descriptions or micromechanical constitutive models. When it comes to describe material behaviour near and beyond fracture these approaches are no longer sufficient or valid and continuous/discontinuous approaches can be adopted to track fracture initiation and propagation. Apart from more pragmatic solutions like element erosion or remeshing techniques more advanced approaches based on the X-FEM concept, in particular associated with non-local formulations, may be adopted to numerically model these problems. Nevertheless, very often, for practical reasons, some important aspects are somewhat left behind, specially energetic requirements to promote the necessary transition of energy release associated with material damage and fracture energy associated to a crack creation and evolution. Phase-field methods may combine advantages of regularised continuous models by providing a similar description to non-local thermodynamical continuous damage mechanics, as well as, a "continuous" approach to numerically follow crack evolution and branching

  12. Thermodynamic Study of the Role of Interface Curvature on Multicomponent Vapor-Liquid Phase Equilibrium.

    Science.gov (United States)

    Shardt, Nadia; Elliott, Janet A W

    2016-04-14

    The effect of interface curvature on phase equilibrium has been much more studied for single-component than multicomponent systems. We isolate the effect of curvature on multicomponent vapor-liquid equilibrium (VLE) phase envelopes and phase composition diagrams using the ideal system methanol/ethanol and the nonideal system ethanol/water as illustrative examples. An important finding is how nanoscale interface curvature shifts the azeotrope (equal volatility point) of nonideal systems. Understanding of the effect of curvature on VLE can be exploited in future nanoscale prediction and design.

  13. Generalized thermodynamic relations for a system experiencing heat and mass diffusion in the far-from-equilibrium realm based on steepest entropy ascent.

    Science.gov (United States)

    Li, Guanchen; von Spakovsky, Michael R

    2016-09-01

    This paper presents a nonequilibrium thermodynamic model for the relaxation of a local, isolated system in nonequilibrium using the principle of steepest entropy ascent (SEA), which can be expressed as a variational principle in thermodynamic state space. The model is able to arrive at the Onsager relations for such a system. Since no assumption of local equilibrium is made, the conjugate fluxes and forces are intrinsic to the subspaces of the system's state space and are defined using the concepts of hypoequilibrium state and nonequilibrium intensive properties, which describe the nonmutual equilibrium status between subspaces of the thermodynamic state space. The Onsager relations are shown to be a thermodynamic kinematic feature of the system independent of the specific details of the micromechanical dynamics. Two kinds of relaxation processes are studied with different constraints (i.e., conservation laws) corresponding to heat and mass diffusion. Linear behavior in the near-equilibrium region as well as nonlinear behavior in the far-from-equilibrium region are discussed. Thermodynamic relations in the equilibrium and near-equilibrium realm, including the Gibbs relation, the Clausius inequality, and the Onsager relations, are generalized to the far-from-equilibrium realm. The variational principle in the space spanned by the intrinsic conjugate fluxes and forces is expressed via the quadratic dissipation potential. As an application, the model is applied to the heat and mass diffusion of a system represented by a single-particle ensemble, which can also be applied to a simple system of many particles. Phenomenological transport coefficients are also derived in the near-equilibrium realm.

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

    Science.gov (United States)

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

    2016-06-01

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

  15. The mechanism of inward rectification in Kir channels: A novel kinetic model with non-equilibrium thermodynamics approach.

    Science.gov (United States)

    Hsieh, Chi-Pan; Chiang, Cheng-Chin; Huang, Chiung-Wei

    2016-05-01

    The mechanisms of the strong inward rectification in inward rectifier K(+) (Kir) channels are controversial because the drop in electrical potential due to the movement of the blocker and coupling ions is insufficient to explain the steep voltage-dependent block near the equilibrium potential. Here, we study the "driving force"-dependent block in Kir channels with a novel approach incorporating concepts from the non-equilibrium thermodynamics of small systems, and computer kinetic simulations based on the experimental data of internal Ba(2+) block on Kir2.1 channels. The steep exponential increase in the apparent binding rate near the equilibrium potential is explained, when the encounter frequency is construed as the likelihood of transfer events down or against the electrochemical potential gradient. The exponent of flux ratio, nf=2.62, implies that the blockage of the internal blocker may be coupled with the outward transport of 2 to 3K(+) ions. The flux-coupled block in the single-file multi-ion pore can be demonstrated by the concentration gradient alone, as well as when the driving force is the electrochemical potential difference across the membrane.

  16. Non-Local Euclidean Medians.

    Science.gov (United States)

    Chaudhury, Kunal N; Singer, Amit

    2012-11-01

    In this letter, we note that the denoising performance of Non-Local Means (NLM) can be improved at large noise levels by replacing the mean by the Euclidean median. We call this new denoising algorithm the Non-Local Euclidean Medians (NLEM). At the heart of NLEM is the observation that the median is more robust to outliers than the mean. In particular, we provide a simple geometric insight that explains why NLEM performs better than NLM in the vicinity of edges, particularly at large noise levels. NLEM can be efficiently implemented using iteratively reweighted least squares, and its computational complexity is comparable to that of NLM. We provide some preliminary results to study the proposed algorithm and to compare it with NLM.

  17. Gravity and non-locality

    CERN Document Server

    Diaz, Pablo; Walton, Mark

    2016-01-01

    With the aim of investigating the relation between gravity and non-locality at the classical level, we study a bilocal scalar field model. Bilocality introduces new (internal) degrees of freedom that can potentially reproduce gravity. We show that the equations of motion of the massless branch of the free bilocal model match those of linearized gravity. We also discuss higher orders of perturbation theory, where there is self-interaction in both gravity and the bilocal field sectors.

  18. Thermodynamic equilibrium calculations of hydrogen production from the combined processes of dimethyl ether steam reforming and partial oxidation

    Science.gov (United States)

    Semelsberger, Troy A.; Borup, Rodney L.

    Thermodynamic analyses of producing a hydrogen-rich fuel-cell feed from the combined processes of dimethyl ether (DME) partial oxidation and steam reforming were investigated as a function of oxygen-to-carbon ratio (0.00-2.80), steam-to-carbon ratio (0.00-4.00), temperature (100 °C-600 °C), pressure (1-5 atm) and product species. Thermodynamically, dimethyl ether processed with air and steam generates hydrogen-rich fuel-cell feeds; however, the hydrogen concentration is less than that for pure DME steam reforming. Results of the thermodynamic processing of dimethyl ether indicate the complete conversion of dimethyl ether to hydrogen, carbon monoxide and carbon dioxide for temperatures greater than 200 °C, oxygen-to-carbon ratios greater than 0.00 and steam-to-carbon ratios greater than 1.25 at atmospheric pressure (P = 1 atm). Increasing the operating pressure has negligible effects on the hydrogen content. Thermodynamically, dimethyl ether can produce concentrations of hydrogen and carbon monoxide of 52% and 2.2%, respectively, at a temperature of 300 °C, and oxygen-to-carbon ratio of 0.40, a pressure of 1 atm and a steam-to-carbon ratio of 1.50. The order of thermodynamically stable products (excluding H 2, CO, CO 2, DME, NH 3 and H 2O) in decreasing mole fraction is methane, ethane, isopropyl alcohol, acetone, n-propanol, ethylene, ethanol and methyl-ethyl ether; trace amounts of formaldehyde, formic acid and methanol are observed. Ammonia and hydrogen cyanide are also thermodynamically favored products. Ammonia is favored at low temperatures in the range of oxygen-to-carbon ratios of 0.40-2.50 regardless of the steam-to-carbon ratio employed. The maximum ammonia content (i.e., 40%) occurs at an oxygen-to-carbon ratio of 0.40, a steam-to-carbon ratio of 1.00 and a temperature of 100 °C. Hydrogen cyanide is favored at high temperatures and low oxygen-to-carbon ratios with a maximum of 3.18% occurring at an oxygen-to-carbon ratio of 0.40 and a steam

  19. Thermodynamics of open nonlinear systems far from equilibrium: The continuously stirred tank reactor

    Science.gov (United States)

    Yoshida, Nobuo

    1993-11-01

    A thermodynamic analysis is made of a continuously stirred tank reactor (CSTR) which is fed with ideal gases and in which arbitrary types of chemical reactions take place. For stationary states and oscillatory ones in which limit cycles are established, expressions are derived which describe the change of entropy of the reactor contents relative to the feed in terms of explicit quantities, including the rate of entropy production due to the chemical reactions. This entropy change is shown to be always greater than what would be observed in closed systems under comparable circumstances. It is pointed out that this statement is beyond what the second law of thermodynamics can predict. In previous articles, entropy and entropy production have been found to follow certain systematic trends in some specific models based on the CSTR. That work is compared with the present theory.

  20. Non-local massive gravity

    CERN Document Server

    Modesto, Leonardo

    2013-01-01

    We present a general covariant action for massive gravity merging together a class of "non-polynomial" and super-renormalizable or finite theories of gravity with the non-local theory of gravity recently proposed by Jaccard, Maggiore and Mitsou (arXiv:1305.3034 [hep-th]). Our diffeomorphism invariant action gives rise to the equations of motion appearing in non-local massive massive gravity plus quadratic curvature terms. Not only the massive graviton propagator reduces smoothly to the massless one without a vDVZ discontinuity, but also our finite theory of gravity is unitary at tree level around the Minkowski background. We also show that, as long as the graviton mass $m$ is much smaller the today's Hubble parameter $H_0$, a late-time cosmic acceleration can be realized without a dark energy component due to the growth of a scalar degree of freedom. In the presence of the cosmological constant $\\Lambda$, the dominance of the non-local mass term leads to a kind of "degravitation" for $\\Lambda$ at the late cos...

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

    OpenAIRE

    Horowitz, Jordan M.

    2015-01-01

    The stochastic thermodynamics of a dilute, well-stirred mixture of chemically-reacting species is built on the stochastic trajectories of reaction events obtained from the Chemical Master Equation. However, when the molecular populations are large, the discrete Chemical Master Equation can be approximated with a continuous diffusion process, like the Chemical Langevin Equation or Low Noise Approximation. In this paper, we investigate to what extent these diffusion approximations inherit the s...

  2. 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

  3. Thermodynamic Bethe ansatz for non-equilibrium steady states: exact energy current and fluctuations in integrable QFT

    Science.gov (United States)

    Castro-Alvaredo, Olalla; Chen, Yixiong; Doyon, Benjamin; Hoogeveen, Marianne

    2014-03-01

    We evaluate the exact energy current and scaled cumulant generating function (related to the large-deviation function) in non-equilibrium steady states with energy flow, in any integrable model of relativistic quantum field theory (IQFT) with diagonal scattering. Our derivations are based on various recent results of Bernard and Doyon. The steady states are built by connecting homogeneously two infinite halves of the system thermalized at different temperatures Tl, Tr, and waiting for a long time. We evaluate the current J(Tl, Tr) using the exact QFT density matrix describing these non-equilibrium steady states and using Zamolodchikov’s method of the thermodynamic Bethe ansatz (TBA). The scaled cumulant generating function is obtained from the extended fluctuation relations which hold in integrable models. We verify our formula in particular by showing that the conformal field theory (CFT) result is obtained in the high-temperature limit. We analyze numerically our non-equilibrium steady-state TBA equations for three models: the sinh-Gordon model, the roaming trajectories model, and the sine-Gordon model at a particular reflectionless point. Based on the numerics, we conjecture that an infinite family of non-equilibrium c-functions, associated with the scaled cumulants, can be defined, which we interpret physically. We study the full scaled distribution function and find that it can be described by a set of independent Poisson processes. Finally, we show that the ‘additivity’ property of the current, which is known to hold in CFT and was proposed to hold more generally, does not hold in general IQFT—that is, J(Tl, Tr) is not of the form f(Tl) - f(Tr).

  4. The thermodynamic equilibrium of gas in a box divided by a piston

    CERN Document Server

    Herrera-Gomez, Alberto

    2010-01-01

    The equilibrium conditions of a system consisting of a box with gas divided by a piston are revised. The apparent indetermination of the problem is solved by explicitly imposing the constancy of the internal energy when the Entropy Maximum Principle is applied. The equality of the pressures is naturally concluded from this principle when the piston is allowed to spontaneously move. The application of the Energy Minimum Principle is also revised.

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

    OpenAIRE

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

    2007-01-01

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

  6. Non-Equilibrium and Classical Thermodynamics for Practical Systems: Today Closer Together Than Ever Before

    Directory of Open Access Journals (Sweden)

    Stanislaw Sieniutycz

    1998-06-01

    Full Text Available We deal with applications of thermodynamics and availability theory to practical systems where a certain external control is possible in order to achieve improved performance. In particular, results of optimization of endoreversible processes which yield mechanical work are discussed. Equations of dynamics which follow from energy balance and transfer equations are difference constraints for optimizing work. Irreversibilities caused by the energy transport are essential. A model system is developed which incorporates finite heat resistances for an energy conversion process, and may be extended to take into account friction, heat leakage, mixing and other effects decreasing the thermodynamic efficiency. Deviation of efficiencies from their limiting Carnot values are analyzed in terms of the finite heat flux. The variational calculus and optimal control theories are shown to be the basic tools when formulating and solving problems with maximizing work. For a finite-time passage of a resource body between two given temperatures, optimality of an irreversible process manifests itself as a connection between the process duration and an optimal intensity. Extremal performance functions which describe extremal work are found in terms of final states and process duration measured in terms of the number of the heat transfer units. An extended exergy that has an irreversible component and simplifies to the classical thermal exergy in the limit of infinite duration is discussed. With this exergy performance criteria and bounds are defined for real processes occurring in a finite time. Enhanced bounds for the work released from an engine system or added to a heat-pump system are evaluated. A comparison between the optimization in thermodynamics (with exergy and in economics (with costs is made. Examples of exergy analysis to seek the best adjustable parameters of solar collectors, separation processes (distillation and a chemical process with catalyst

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

    Science.gov (United States)

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

    2015-01-01

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

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

    KAUST Repository

    Pump, Eva

    2015-02-24

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

  9. Non-Equilibrium Thermodynamic Analysis of Transport Properties in the Nanofiltration of Ionic Liquid-Water Solutions

    Directory of Open Access Journals (Sweden)

    Hua P. Wang

    2009-05-01

    Full Text Available Thenanofiltration of aqueous solutions of the ionic liquids (ILs 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF4, and 1-butyl-3-methylimidazolium bromide ([Bmim]Br with a polyamide nanofiltration membrane was investigated. The practical transport coefficients, including hydrodynamic permeability (Lp, reflection (σ and solute permeability (ω were calculated in terms of a non-equilibrium thermodynamics approach. It was found that Lp and σ diminished as the concentration of the IL solutions increased. These characteristics are similar to those observed in inorganic electrolyte-water systems. In addition, it was shown that the rejection and volume flux for both ionic liquid solutions rose with feed pressure, while it decreased with feed concentration. The maximum rejection efficiencies for [Bmim]Br and [Bmim]BF4 are 67 % and 60 %, respectively, on our experimental scale. All the data suggests that a highly efficient process for IL separation could be developed when the operating conditions are optimized further.

  10. Thermodynamic equilibrium studies of nanocrystallite SrTiO3 grain boundaries by high temperature photoelectron spectroscopy

    Institute of Scientific and Technical Information of China (English)

    刘振祥; 谢侃

    2000-01-01

    Nanostructured strontium titanate (SrTiO3) thin films are studied by high temperature pho-toelectron spectroscopy and thermal gravimetric analysis. The results indicate that ion migration and redistribution as well as transformation between lattice oxygen and gas phase oxygen take place near the grain boundaries during thermodynamic equilibrium process, which lead to obvious variation of the surface composition with temperature. The lattice oxygen ions migrate from bulk to grain surface with temperature rising up; meanwhile Ti ions also migrate to grain surface and combine with oxygen ions forming Ti-O complex. An opposite process takes place during temperature falling down, but the latter process is much slower than the former one. A primary model is proposed to explain this phenomenon.

  11. Thermodynamic equilibrium studies of nanocrystallite SrTiO3 grain boundaries by high temperature photoelectron spectroscopy

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Nanostructured strontium titanate (SrTiO3) thin films are studied by high temperature photoelectron spectroscopy and thermal gravimetric analysis. The results indicate that ion migration and redistribution as well as transformation between lattice oxygen and gas phase oxygen take place near the grain boundaries during thermodynamic equilibrium process, which lead to obvious variation of the surface composition with temperature. The lattice oxygen ions migrate from bulk to grain surface with temperature rising up; meanwhile Ti ions also migrate to grain surface and combine with oxygen ions forming Ti-O complex. An opposite process takes place during temperature falling down, but the latter process is much slower than the former one. A primary model is proposed to explain this phenomenon.

  12. Lipid domains in giant unilamellar vesicles and their correspondence with equilibrium thermodynamic phases: A quantitative fluorescence microscopy imaging approach

    DEFF Research Database (Denmark)

    Fidorra, Matthias; Garcia, Alejandra; Ipsen, John Hjort

    2009-01-01

    and reconstruction of 3D domain morphology using active surface models. This method permits the reconstruction of the spherical surface of GUVs and determination of the area fractions of coexisting lipid domains at the level of single vesicles. Obtaining area fractions enables the scrutiny of the lever rule along...... lipid phase diagram's tie lines and to test whether or not the coexistence of lipid domains in GUVs correspond to equilibrium thermodynamic phases. The analysis was applied to DLPC/DPPC GUVs displaying coexistence of lipid domains. Our results confirm the lever rule, demonstrating that the observed......We report a novel analytical procedure to measure the surface areas of coexisting lipid domains in giant unilamellar vesicles (GUVs) based on image processing of 3D fluorescence microscopy data. The procedure involves the segmentation of lipid domains from fluorescent image stacks...

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

    Energy Technology Data Exchange (ETDEWEB)

    Aksakal, Ozkan [Department of Biology, Faculty of Science, Ataturk University, Erzurum 25240 (Turkey); Ucun, Handan, E-mail: hanucun@yahoo.com [Department of Environmental Engineering, Faculty of Engineering, Bartin University, Bartin 74100 (Turkey)

    2010-09-15

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

  14. Non-Local Means Denoising

    Directory of Open Access Journals (Sweden)

    Antoni Buades

    2011-09-01

    Full Text Available We present in this paper a new denoising method called non-local means. The method is based on a simple principle: replacing the color of a pixel with an average of the colors of similar pixels. But the most similar pixels to a given pixel have no reason to be close at all. It is therefore licit to scan a vast portion of the image in search of all the pixels that really resemble the pixel one wants to denoise. The paper presents two implementations of the method and displays some results.

  15. Stochastic dynamics and non-equilibrium thermodynamics of a bistable chemical system: the Schlögl model revisited.

    Science.gov (United States)

    Vellela, Melissa; Qian, Hong

    2009-10-06

    Schlögl's model is the canonical example of a chemical reaction system that exhibits bistability. Because the biological examples of bistability and switching behaviour are increasingly numerous, this paper presents an integrated deterministic, stochastic and thermodynamic analysis of the model. After a brief review of the deterministic and stochastic modelling frameworks, the concepts of chemical and mathematical detailed balances are discussed and non-equilibrium conditions are shown to be necessary for bistability. Thermodynamic quantities such as the flux, chemical potential and entropy production rate are defined and compared across the two models. In the bistable region, the stochastic model exhibits an exchange of the global stability between the two stable states under changes in the pump parameters and volume size. The stochastic entropy production rate shows a sharp transition that mirrors this exchange. A new hybrid model that includes continuous diffusion and discrete jumps is suggested to deal with the multiscale dynamics of the bistable system. Accurate approximations of the exponentially small eigenvalue associated with the time scale of this switching and the full time-dependent solution are calculated using Matlab. A breakdown of previously known asymptotic approximations on small volume scales is observed through comparison with these and Monte Carlo results. Finally, in the appendix section is an illustration of how the diffusion approximation of the chemical master equation can fail to represent correctly the mesoscopically interesting steady-state behaviour of the system.

  16. Thermodynamic Equilibrium Analysis of Methanol Conversion to Hydrocarbons Using Cantera Methodology

    Directory of Open Access Journals (Sweden)

    Duminda A. Gunawardena

    2012-01-01

    Full Text Available Reactions associated with removal of oxygen from oxygenates (deoxygenation are an important aspect of hydrocarbon fuels production process from biorenewable substrates. Here we report the equilibrium composition of methanol-to-hydrocarbon system by minimizing the total Gibbs energy of the system using Cantera methodology. The system was treated as a mixture of 14 components which had CH3OH, C6H6, C7H8, C8H10 (ethyl benzene, C8H10 (xylenes, C2H4, C2H6, C3H6, CH4, H2O, C, CO2, CO, H2. The carbon in the equilibrium mixture was used as a measure of coke formation which causes deactivation of catalysts that are used in aromatization reaction(s. Equilibrium compositions of each species were analyzed for temperatures ranging from 300 to 1380 K and pressure at 0–15 atm gauge. It was observed that when the temperature increases the mole fractions of benzene, toluene, ethylbenzene, and xylene pass through a maximum around 1020 K. At 300 K the most abundant species in the system were CH4, CO2, and H2O with mole fractions 50%, 16.67%, and 33.33%, respectively. Similarly at high temperature (1380 K, the most abundant species in the system were H2 and CO with mole fractions 64.5% and 32.6% respectively. The pressure in the system shows a significant impact on the composition of species.

  17. Adsorptive removal of acrylonitrile by commercial grade activated carbon: kinetics, equilibrium and thermodynamics.

    Science.gov (United States)

    Kumar, Arvind; Prasad, B; Mishra, I M

    2008-04-01

    The potential of activated carbons--powdered (PAC) and granular (GAC), for the adsorption of acrylonitrile (AN) at different initial AN concentrations (50PAC and GAC, respectively. Error analysis also confirmed the efficacy of the R-P isotherm to best fit the experimental data. The pseudo-second order kinetic model best represents the kinetics of the adsorption of AN onto PAC and GAC. Maximum adsorption capacity of PAC and GAC at optimum conditions of AN removal (adsorbent dose approximately 20 g/l of solution, and equilibrium time approximately 5 h) was found to be 51.72 and 46.63 mg/g, respectively.

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

    Science.gov (United States)

    Abdolali, Atefeh; Ngo, Huu Hao; Guo, Wenshan; Lu, Shaoyong; Chen, Shiao-Shing; Nguyen, Nguyen Cong; Zhang, Xinbo; Wang, Jie; Wu, Yun

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-12-21

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

  20. Modelling on the Equilibrium, Kinetics and Thermodynamics for Zinc (II Ions Removal from Solution by “Aloji” Kaolinite Clay

    Directory of Open Access Journals (Sweden)

    G. K. Akpomie

    2014-09-01

    Full Text Available This study reports the use of Aloji kaolinite clay as an adsorbent for Zinc (II ions from solution. The aim of this research was the use of the kaolinite mineral as a low cost adsorbent for the removal of zinc (II ions from aqueous stream. The adsorption was performed by the use of batch method and the dependence of pH, initial metal ion concentration, contact time and temperature on adsorption were investigated. Maximum adsorption of zinc ions was achieved at an optimum pH of 4.0. Equilibrium sorption was achieved within 60 minutes of the experiment. Equilibrium sorption data were analyzed by the Langmuir and Freundlich isotherm. The Freundlich isotherm gave a better fit to the data than the Langmuir isotherm based on the comparison of their linear regression R2 values. Kinetic studies revealed the applicability of the Pseudo-second order kinetic model than the Pseudo-first order model based on their R2 values. Thermodynamic parameters such as changes in Gibbs free energy, ΔG0, enthalpy, ΔH0 and entropy, ΔS0 were evaluated and showed the adsorption process to be spontaneous, feasible and exothermic in nature. These results showed the potential of Aloji kaolinite clay as a suitable low-cost adsorbent for Zinc (II ions from aqueous stream

  1. Insights into the equilibrium, kinetic and thermodynamics of nickel removal by environmental friendly Lansium domesticum peel biosorbent.

    Science.gov (United States)

    Lam, Yun Fung; Lee, Lai Yee; Chua, Song Jun; Lim, Siew Shee; Gan, Suyin

    2016-05-01

    Lansium domesticum peel (LDP), a waste material generated from the fruit consumption, was evaluated as a biosorbent for nickel removal from aqueous media. The effects of dosage, contact time, initial pH, initial concentration and temperature on the biosorption process were investigated in batch experiments. Equilibrium data were fitted by the Langmuir, Freundlich, Temkin and Dubinin-Radushkevich models using nonlinear regression method with the best-fit model evaluated based on coefficient of determination (R(2)) and Chi-square (χ(2)). The best-fit isotherm was found to be the Langmuir model exhibiting R(2) very close to unity (0.997-0.999), smallest χ(2) (0.0138-0.0562) and largest biosorption capacity (10.1mg/g) at 30°C. Kinetic studies showed that the initial nickel removal was rapid with the equilibrium state established within 30min. Pseudo-second-order model was the best-fit kinetic model indicating the chemisorption nature of the biosorption process. Further data analysis by the intraparticle diffusion model revealed the involvement of several rate-controlling steps such as boundary layer and intraparticle diffusion. Thermodynamically, the process was exothermic, spontaneous and feasible. Regeneration studies indicated that LDP biosorbent could be regenerated using hydrochloric acid solution with up to 85% efficiency. The present investigation proved that LDP having no economic value can be used as an alternative eco-friendly biosorbent for remediation of nickel contaminated water.

  2. Equilibrium Isotherm Modeling, Kinetics and Thermodynamics Study for Removal of Lead from Waste Water

    Directory of Open Access Journals (Sweden)

    Z. Chowdhury

    2011-01-01

    Full Text Available The low cost adsorbent palm oil fuel ash (POFA derived from an agricultural waste material was investigated as a replacement of current expensive methods for treating wastewater contaminated by Pb(II cation. Adsorption studies were carried out to delineate the effect of contact time, temperature, pH and initial metal ion concentration. The experimental data followed pseudo second order kinetics which confirms chemisorptions. The values of Langmuir dimensionless constant, RL and Freundlich constant, 1/n were less than 1 representing favorable process for adsorption. Thermodynamic parameters such as ΔG°, ΔH° and ΔS°, related to Gibbs free energy, enthalpy and entropy were evaluated. It was concluded that, chemically treated palm oil fuel ash (POFA can be used successfully for adsorption of Pb(II from aqueous solution.

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

    Science.gov (United States)

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

    2012-06-01

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

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

    Science.gov (United States)

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

    1951-01-01

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

  5. Reaching equilibrium: the role of dissipation in analogous systems, within a thermodynamic-like perspective

    Science.gov (United States)

    Bonanno, A.; Camarca, M.; Sapia, P.

    2012-11-01

    Isomorphic problems play an acknowledged pedagogical role in the physics teaching/learning process. In this context, we describe a unified approach to a wide class of physical systems formally analogous to the well-known ‘two-capacitor system’. The proposed learning path, specifically addressed to university students, provides the opportunity to introduce a unitary graphical representation that is very suitable to describe the system energy evolution, as well as allowing the highlighting of the mutually exclusive roles of dissipation and reversibility when the system approaches its equilibrium conditions (where ‘equilibrium’ must be interpreted in its most general meaning, either as ‘static equilibrium’ or as ‘steady state’). Moreover, a new quantitative modeling is introduced for two representative systems, in order to show that the energy ‘missed’ during the equilibrium achievement is just equal to the negative work an external agent should make to let the system reach its final state quasi-statically and reversibly.

  6. Phase equilibrium data and thermodynamic modelling of the system (propane + DMF + methanol) at high pressures

    Energy Technology Data Exchange (ETDEWEB)

    Charin, Rafael M. [Department of Chemical Engineering, Federal University of Parana (UFPR), Polytechnic Center (DTQ/ST/UFPR), Jardim das Americas, Curitiba 82530-990, PR (Brazil); Department of Food Engineering, URI - Campus de Erechim, Av. Sete de Setembro, 1621, Erechim 99700-000, RS (Brazil); Corazza, Marcos L.; Ndiaye, Papa M. [Department of Chemical Engineering, Federal University of Parana (UFPR), Polytechnic Center (DTQ/ST/UFPR), Jardim das Americas, Curitiba 82530-990, PR (Brazil); Rigo, Aline A.; Mazutti, Marcio A. [Department of Food Engineering, URI - Campus de Erechim, Av. Sete de Setembro, 1621, Erechim 99700-000, RS (Brazil); Vladimir Oliveira, J., E-mail: vladimir@uricer.edu.b [Department of Food Engineering, URI - Campus de Erechim, Av. Sete de Setembro, 1621, Erechim 99700-000, RS (Brazil)

    2011-03-15

    Reported in this work are phase equilibrium data at high pressures for the binary and ternary systems formed by {l_brace}propane + N,N-dimethylformamide (DMF) + methanol{r_brace}. Phase equilibrium measurements were performed in a high-pressure, variable-volume view cell, following the static synthetic method for obtaining the experimental bubble and dew points transition data over the temperature range of (363 to 393) K, pressures up to 11.5 MPa and overall mole fraction of the lighter component varying from 0.1 to 0.995. For the systems investigated, vapour-liquid (VLE), liquid-liquid (LLE) and vapour-liquid-liquid (VLLE) phase transitions were visually recorded. Results show that the systems investigated present UCST (upper critical solution temperature) phase transition curves with an UCEP (upper critical end point) at a temperature higher than the propane critical temperature. The experimental data were modelled using the Peng-Robinson equation of state with the Wong-Sandler and the classical quadratic mixing rules, affording a satisfactory representation of the experimental data.

  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. Reactivity, characterization, equilibrium thermodynamics and hetero-bimetallic studies of tridentate and tetradentate complexes relevant to syngas catalysis

    Science.gov (United States)

    Imler, Gregory H.

    The unifying objective of this work is the study of model systems that will assist in the development of new metal catalysts capable of converting carbon monoxide and hydrogen (syngas) into organic oxygenates at mild temperature and pressure. The selective catalytic transformation of carbon monoxide and hydrogen to liquid fuels and chemical feedstocks represents a major "Grand Challenge" of catalysis science. A core objective is the study of a macrocycle that is related to a porphyrin ligand in order to circumvent some of the disadvantages of utilizing porphyrins in catalysis. The rhodium complex of the macrocycle dibenzotetramethylaza[14]annulene ([(tmtaa)Rh]2]) was reacted with a series of small molecules relevant to CO reduction and hydrogenation. Several complexes were formed that demonstrated the ability to partially reduce and hydrogenate carbon monoxide, including the dirhodium ketone (Rh-C(O)-Rh) and an example of a thermodynamically favorable metal formyl complex ((tmtaa)Rh-C(O)H). An important feature of this work is the measurement of thermodynamic data to provide experimental benchmarks for obtaining key species in CO reduction and hydrogenation. A thorough study of the (tmtaa)Rh system will help in identifying structural features that assist or hinder CO hydrogenation. All reactions are monitored by 1H NMR which permits determination of solution thermodynamics from equilibrium constants obtained by NMR peak integrations. DFT calculations have supplemented experimental results by providing estimates to compare with the experimentally determined thermodynamic data. These computations also provide insight into the structures and thermodynamics of species that cannot be observed directly such as short lived intermediates and thermodynamically unfavorable products. Heterobimetallic complexes of (tmtaa)Rh• with a second metal radical have been utilized to attempt to convert CO to organic products. Reactivity with CO and H2 has been accomplished, with most

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

    Science.gov (United States)

    Pashai Gatabi, Maliheh; Milani Moghaddam, Hossain; Ghorbani, Mohsen

    2016-07-01

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

  10. Non equilibrium thermodynamics and the city: a new approach to urban studies.

    Science.gov (United States)

    Pulselli, Riccardo Maria; Ciampalini, Francesca; Galli, Alessandro; Pulselli, Federico Maria

    2006-01-01

    A city can be conceived as a complex self-adaptive system. The multiple interactions among its structural elements and dynamic agents, its organization on multiple time-space scales, its exchanges with the external context, its irreversible dynamics, are signs of complexity. Some concepts from the evolutionary thermodynamics, such us the theory of dissipative structures, could be extended to the city in order to investigate its behaviour. This theoretical framework suggests to analyze the city in terms of entropy and negentropy production. An emergy analysis (spelled with an "m") of an urban region is presented in order to investigate how cities maintain their organization (and decrease their entropy) by virtue of constant energy inflows from the external environment. As a result, a non-homogeneous spatial pattern of emergy density is shown as an attempt to investigate the multiple relations and energy exchanges that take place in an urban region. This approach to urban studies introduces a new energy-based vision to understand cities.

  11. Equilibrium, kinetic and thermodynamic studies of mercury adsorption on almond shell.

    Science.gov (United States)

    Khaloo, Shokooh Sadat; Matin, Amir Hossein; Sharifi, Sahar; Fadaeinia, Masoumeh; Kazempour, Narges; Mirzadeh, Shaghayegh

    2012-01-01

    The application of almond shell as a low cost natural adsorbent to remove Hg(2+) from aqueous solution was investigated. Batch experiments were carried out to evaluate the adsorption capacity of the material. The chemical and physical parameters such as pH, sorbent amount, initial ion concentration, and contact time were optimized for the maximum uptake of mercury onto the solid surface. Adsorption isotherms were expressed by Langmuir and Freundlich adsorption models, and the experimental data were found to fit the Langmuir model rather than the Freundlich. The maximum adsorption capacity obtained from the Langmuir isotherm was 135.13 mg/g. A kinetic study was carried out with pseudo-first-order and pseudo-second-order reaction equations and it was found that the Hg(2+) uptake process followed the pseudo-second-order rate expression. The thermodynamic values, ΔG(0), ΔH(0) and ΔS(0), indicated that adsorption was an endothermic and spontaneous process. The potential of this material for mercury elimination was demonstrated by efficient Hg(2+) removal from a synthetic effluent.

  12. Removal of methylene blue by adsorption on aluminosilicate waste: equilibrium, kinetic and thermodynamic parameters.

    Science.gov (United States)

    Policiano Almeida, Carlos Alberto; Zanela, Tânia Marina Palhano; Machado, Clodoaldo; Altamirano Flores, Juan Antônio; Scheibe, Luiz Fernando; Hankins, Nicholas P; Debacher, Nito Angelo

    2016-11-01

    An aluminosilicate waste (AW) was investigated as adsorbent for methylene blue (MB) dye. AW was characterized by petrography, X-ray diffractometry, X-ray fluorescence, scanning electron microscopy, thermogravimetry and zeta potential measurements. It was found that AW contains kaolinite, and other minor components such as quartz, muscovite, smectite, siderite, pyrite and organic compounds. The chemical composition of AW is mainly SiO2 (49%) and Al2O3 (23%) and it has negative superficial charge above pH 1.73. Adsorption of MB dye was studied in a batch system under different conditions of initial dye concentration, contact time and temperature. The isothermal data from batch experiments were fitted to Langmuir and Freundlich equations, with a better fit shown by the Langmuir isotherm equation. Also, pseudo-first-order, pseudo-second-order and intraparticle diffusion models were considered to evaluate the rate parameters. The experimental data fitted the pseudo-first-order kinetic model best. Thermodynamic parameters were calculated, showing the adsorption to be an endothermic yet spontaneous process, with the activation energy of +37.8 kJ mol(-1). The results indicate that AW adsorbs MB efficiently, and can be employed as a low-cost alternative in wastewater treatment for the removal of cationic dyes.

  13. EQUILIBRIUM, KINETIC, AND THERMODYNAMIC STUDIES OF LEAD (II BIOSORPTION ON SESAME LEAF

    Directory of Open Access Journals (Sweden)

    Li-e Liu,

    2012-06-01

    Full Text Available Sesame leaf, an agricultural solid waste, was used as low cost adsorbent for removal of Pb(II from aqueous solution in batch mode. The biosorbent was characterized by thermo-gravimetric analysis and Fourier transform infrared spectroscopy. The influences of phase contact time, solution pH, adsorbent dosage, and initial concentrations were investigated to optimize the conditions for maximum adsorption. The experimental data were analyzed by Langmuir, Freundlich, and Koble-Corrigan isotherm models. The Koble-Corrigan and Langmuir isotherms best represented the measured biosorption data. According to an evaluation using the Langmuir equation, the adsorption capacity of the biosorbent was found to be 279.86 mg g-1, which was higher or comparable to the adsorption capacity of various adsorbents reported in the literature. The kinetics of adsorption of Pb(II was evaluated by pseudo-first order, pseudo-second order, and intra-particle diffusion kinetic models. The experimental data fitted very well with the pseudo-second order kinetic model. The intra-particle diffusion model is not a dominant rate controlling mechanism in the sorption of Pb(II. Thermodynamic analysis showed that the adsorption was a spontaneous and endothermic process. The results indicated that sesame leaf can be used as an effective biosorbent for Pb(II removal from aqueous solutions.

  14. Physical Properties Models for Simulation of Processes to Treat INEEL Tank Farm Waste: Thermodynamic Equilibrium

    Energy Technology Data Exchange (ETDEWEB)

    Nichols, T.T.; Taylor, D.D.

    2002-07-18

    A status is presented of the development during FY2002 of a database for physical properties models for the simulation of the treatment of Sodium-Bearing Waste (SBW) at the Idaho National Engineering and Environmental Laboratory. An activity coefficient model is needed for concentrated, aqueous, multi-electrolyte solutions that can be used by process design practitioners. Reasonable first-order estimates of activity coefficients in the relevant media are needed rather than an incremental improvement in theoretical approaches which are not usable by practitioners. A comparison of the Electrolyte Non-Random Two-Liquid (ENRTL) and Pitzer ion-interaction models for the thermodynamic representation of SBW is presented. It is concluded that Pitzer's model is superior to ENRTL in modeling treatment processes for SBW. The applicability of the Pitzer treatment to high concentrations of pertinent species and to the determination of solubilities and chemical equilibria is addressed. Alternate values of Pitzer parameters for HCl, H2SO4, and HNO3 are proposed, applicable up to 16m, and 12m, respectively. Partial validation of the implementation of Pitzer's treatment within the commercial process simulator ASPEN Plus was performed.

  15. Fluctuation theorems and inequalities generalizing the second law of thermodynamics out of equilibrium.

    Science.gov (United States)

    Verley, Gatien; Lacoste, David

    2012-11-01

    We present a general framework for systems which are prepared in a nonstationary nonequilibrium state in the absence of any perturbation and which are then further driven through the application of a time-dependent perturbation. By assumption, the evolution of the system must be described by Markovian dynamics. We distinguish two different situations depending on the way the nonequilibrium state is prepared; either it is created by some driving or it results from a relaxation following some initial nonstationary conditions. Our approach is based on a recent generalization of the Hatano-Sasa relation for nonstationary probability distributions. We also investigate whether a form of the second law holds for separate parts of the entropy production and for any nonstationary reference process, a question motivated by the work of M. Esposito et al. [Phys. Rev. Lett. 104, 090601 (2010)]. We find that although the special structure of the theorems derived in this reference is not recovered in the general case, detailed fluctuation theorems still hold separately for parts of the entropy production. These detailed fluctuation theorems contain interesting generalizations of the second law of thermodynamics for nonequilibrium systems.

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

    Science.gov (United States)

    Svoboda, J.; Fischer, F. D.

    2014-01-01

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

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

    Science.gov (United States)

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

    2017-08-15

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

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

    Directory of Open Access Journals (Sweden)

    Zonghua Wang

    2013-05-01

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

  19. Physical Properties Models for Simulation of Processes to Treat INEEL Tank Farm Waste: Thermodynamic Equilibrium

    Energy Technology Data Exchange (ETDEWEB)

    Nichols, Todd Travis; Taylor, Dean Dalton

    2002-07-01

    A status is presented of the development during FY2002 of a database for physical properties models for the simulation of the treatment of Sodium-Bearing Waste (SBW) at the Idaho National Engineering and Environmental Laboratory. An activity coefficient model is needed for concentrated, aqueous, multi-electrolyte solutions that can be used by process design practitioners. Reasonable first-order estimates of activity coefficients in the relevant media are needed rather than an incremental improvement in theoretical approaches which are not usable by practitioners. A comparison of the Electrolyte Non-Random Two-Liquid (ENRTL) and Pitzer ion-interaction models for the thermodynamic representation of SBW is presented. It is concluded that Pitzer's model is superior to ENRTL in modeling treatment processes for SBW. The applicability of the Pitzer treatment to high concentrations of pertinent species and to the determination of solubilities and chemical equilibria is addressed. Alternate values of Pitzer parameters for HCl, H2SO4, and HNO3 are proposed, applicable up to 16m, and 12m, respectively. Partial validation of the implementation of Pitzer's treatment within the commercial process simulator ASPEN Plus was performed.

  20. Adsorption equilibrium and thermodynamics of CO2 and CH4 on carbon molecular sieves

    Science.gov (United States)

    Song, Xue; Wang, Li'ao; Ma, Xu; Zeng, Yunmin

    2017-02-01

    Carbon molecular sieves (CMS) are widely used in the separation of dioxide carbon and methane. In this research, three commercial CMS were utilized to analyze the pore structure and chemical properties. The adsorption isotherms of CO2 and CH4 were studied at 298 K, 308 K and 318 K over the pressure range of 0-1 MPa by an Intelligent Gravimetric analysis (IGA-100B, UK). Langmuir model was adopted to fit the experimental data. The working capacity and selectivity were employed to evaluate the adsorbents. The adsorption thermodynamics were discussed. The adsorbed amounts of both CO2 and CH4 are found to be highly related with the BET specific surface area and the volume of micropores, and also are interrelated with the total pore volume and micropore surface area. The standard enthalpy change (ΔHΘ), standard Gibbs free energy (ΔGΘ) and standard entropy change (ΔSΘ) at zero surface loading are negative, manifesting the adsorption process is exothermic and spontaneous, and the system tends to be ordered. With the increasing surface coverage, the absolute values of Gibbs free energy (ΔG) decrease whereas the absolute values of enthalpy change (ΔH) and entropy change(ΔS) increase. This indicates that as the adsorbed amount increases, the degree of the spontaneity reduces, the intermolecular forces among the adsorbate molecules increase, the orderliness of the system improves and the adsorbed amount approaches the maximum adsorbed capacity.

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

    Directory of Open Access Journals (Sweden)

    Piar Chand

    2013-01-01

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

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

    Science.gov (United States)

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

    2017-08-15

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

  3. Oxygen nonstoichiometry, the defect equilibrium model and thermodynamic quantities of the Ruddlesden-Popper oxide Sr3Fe2O(7-δ).

    Science.gov (United States)

    Ling, Yihan; Wang, Fang; Budiman, Riyan Achmad; Nakamura, Takashi; Amezawa, Koji

    2015-03-21

    Oxygen nonstoichiometry of the Ruddlesden-Popper oxide Sr3Fe2O7-δ was measured at intermediate temperatures (773-1073 K) by coulometric titration and high temperature gravimetry. The oxygen nonstoichiometric behavior was analyzed using the defect equilibrium model with localized electrons. From the defect chemical analysis, estimated oxygen vacancy concentration at the O3 sites increases and at the O1 sites decreases with the increasing temperature. This characteristic behavior is considered to be caused by the redistribution of oxygen and vacancies between the O1 and O3 sites. The obtained thermodynamic quantities of the partial molar enthalpy of oxygen, h(O) - h°(O), and the partial molar entropy of oxygen, s(O) - s°(O), calculated from the Gibbs-Helmholtz equation are in good agreement with those from the statistical thermodynamic calculation based on the defect equilibrium model, indicating that the proposed defect equilibrium model is reasonable.

  4. Equilibrium, kinetic and thermodynamic studies of acid Orange 52 dye biosorption by Paulownia tomentosa Steud. leaf powder as a low-cost natural biosorbent.

    Science.gov (United States)

    Deniz, Fatih; Saygideger, Saadet D

    2010-07-01

    The biosorption of Acid Orange 52 onto the leaf powder of Paulownia tomentosa Steud. was studied in a batch adsorption system to estimate the equilibrium, kinetic and thermodynamic parameters as a function of solution pH, biosorbent concentration, dye concentration, biosorbent size, temperature and contact time. The Langmuir, Freundlich and Temkin isotherm models were used for modeling the biosorption equilibrium. The experimental equilibrium data could be well interpreted by the Temkin and Langmuir isotherms with maximum adsorption capacity of 10.5 mg g(-1). In order to state the sorption kinetics, the fits of pseudo-first order, pseudo-second order, Elovich and intraparticle diffusion kinetic models were investigated. It was obtained that the biosorption process followed the pseudo-second order rate kinetics. Thermodynamic studies indicated that this system was exothermic process. The results revealed that P. tomentosa leaf powder could be an efficient biosorbent for the treatment of wastewater containing Acid Orange 52.

  5. Vapor-Liquid Equilibrium of Carbon Dioxide + Ethanol: Experimental Measurements with Acoustic Method and Thermodynamic Modeling

    Directory of Open Access Journals (Sweden)

    Ana Mehl

    2011-01-01

    Full Text Available Phase behavior of systems composed by supercritical carbon dioxide and ethanol is of great interest, especially in the processes involving supercritical extraction in which ethanol is used as a cosolvent. The development of an apparatus, which is able to perform the measurements of vapor-liquid equilibrium (VLE at high pressure using a combination of the visual and the acoustic methods, was successful and was proven to be suited for determining the isothermal VLE data of this system. The acoustic method, based on the variation of the amplitude of an ultra-sound signal passing through a mixture during a phase transition, was applied to investigate the phase equilibria of the system carbon dioxide + ethanol at temperatures ranging from 298.2 K to 323.2 K and pressures from 3.0 MPa to 9.0 MPa. The VLE data were correlated with Peng-Robinson equation of state combined with two different mixing rules and the SAFT equations of state as well. The compositions calculated with the models are in good agreement with the experimental data for the isotherms evaluated.

  6. Thermodynamic Equilibrium Morphology Prediction of Polyurethane/Polyacrylate Composite Latex Particles

    Institute of Scientific and Technical Information of China (English)

    CHAI Shu-Ling; JIN Ming-Martin

    2008-01-01

    Composite particles were prepared by seeded surfactant-free batch emulsion polymerization at 80 ℃ using K2S2O8 as an initiator, and polyurethane aqueous dispersion as seed particles. The acrylate monomers were continuously added into the reactor under a starving condition in the second stage polymerization. The synthesized hybrid emulsions were found to form an inverted core-shell structure with polyacrylate as the core and with polyurethane as the shell from the observation with a transmission electron microscope. The interfacial tensions between polymer and polymer as well as polymer and water were calculated with a simple method according to harmonic mean equation and used in a mathematical model based on the minimum interfacial energy change principle to predict the equilibrium morphology. The observed particle morphologies were in good agreement with the predicted ones. The surface properties of the dried films formed from polyurethane (PU)/polyacrylate (PA) composite emulsions were also studied by contact angle measurements, showing that the shell part of the composite emulsions is preferentially oriented toward the surface layers of the dried films.

  7. Improved calorimetric procedure for monitoring the approach to thermodynamic equilibrium in glassy polymers

    Energy Technology Data Exchange (ETDEWEB)

    Lagasse, R.R.

    1982-02-01

    Techniques for measuring the enthalpy change during isothermal aging of polymer glasses are discussed. Critical analysis of conventional scanning calorimetry reveals that its accuracy may be suspect under certain circumstances due to the thermal lag inherent in a temperature scanning experiment. An additional problem is that the conventional technique is restricted to certain kinds of paths for reaching the aging temperature. It is proposed that both problems can be overcome by analyzing the output of a scanning calorimeter not only during the steady heating but also during an extension of a method used previously by others in accurate measurements of the much larger heat of fusion of crystalline polymers. Practical feasibility of the improved technique is demonstrated by preliminary measurements of enthalpy relaxation during aging of well-characterized polystyrene at 80/sup 0/C. In particular, the initial departure from equilibrium of a glass prepared by 5/sup 0/C/min cooling from the liquid state is found to be 6.9 +- 0.6 J/g. This measured value agrees with a value calculated on the basis of the glass transition temperature corresponding to 5/sup 0/C/min cooling and at-capacity data from the literature.

  8. On the compatibility of thermodynamic equilibrium conditions with the non-perturbative lattice propagators

    CERN Document Server

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

    2016-01-01

    In this paper it is analyzed the compatibility of the non-perturbative equations of state of quarks and gluons arising from the lattice with some natural requirements for self gravitating objects at equilibrium: the existence of an equation of state (namely, the possibility to define the pressure as a function of the energy density), the absence of superluminal propagation and Le Chatelier's principle. It is discussed under which conditions it is possible to extract an equation of state (in the above sense) from the non-perturbative propagators arising from the fits of the last lattice data. In particular, in the quarks case, there is a small but non vanishing range of temperatures in which it is not possible to define a single-valued functional relation between density and pressure. Interestingly enough, a small change of the parameters appearing in the fit of the lattice quark propagator (of around 10\\%) can guarantee the fulfillment of all the three conditions (keeping alive, at the same time, the violatio...

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

    Science.gov (United States)

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

    2016-08-01

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

  10. Contribution of the entropy on the thermodynamic equilibrium of vacancies in nickel

    Energy Technology Data Exchange (ETDEWEB)

    Metsue, Arnaud, E-mail: arnaud.metsue@univ-lr.fr; Oudriss, Abdelali; Bouhattate, Jamaa; Feaugas, Xavier [Laboratoire des Sciences de l’Ingénieur pour l’Environnement, UMR CNRS 7356, Université de La Rochelle, Avenue Michel Crépeau, 17000 La Rochelle (France)

    2014-03-14

    The equilibrium vacancy concentration in nickel was determined from ab initio calculations performed with both generalized gradient approximation and local density approximation up to the melting point. We focus the study on the vacancy formation entropy expressed as a sum of a vibration and an electronic contribution, which were determined from the vibration modes and the electronic densities of states. Applying a method based on the quasi-harmonic approximation, the temperature dependence of the defect formation energy and entropy were calculated. We show that the vibrations of the first shell of atoms around the defect are predominant to the vibration formation entropy. On the other hand, the electronic formation entropy is very sensitive to the exchange-correlation potential used for the calculations. Finally, the vacancy concentration is computed at finite temperature with the calculated values for the defect formation energy and entropy. In order to reconcile point-defects concentration obtained with our calculations and experimental data, we conducted complementary calorimetric measurements of the vacancy concentration in the 1073–1273 K temperature range. Close agreement between theory and experiments at high temperature is achieved if the calculations are performed with the generalized gradient approximation and both vibration and electronic contributions to the formation entropy are taken into account.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-08-15

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

  12. Acarbose Isolation with Gel Type Strong Acid Cation Exchange Resin:Equilibrium, Kinetic and Thermodynamic Studies

    Institute of Scientific and Technical Information of China (English)

    王亚军; 于蕾; 郑裕国; 王远山; 沈寅初

    2013-01-01

    Acarbose, a potentα-glucosidase inhibitor, is widely used as an oral anti-diabetic drug for the treatment of the type 2, non-insulin-dependent diabetes. In this work, a gel type strong acid cation exchange resin 001×4 was applied to isolate acarbose from fermentation broth. It was demonstrated that cation exchanger 001×4 displayed a large adsorption capacity and quick exchange rate for acarbose. The static adsorption equilibrium data were well fitted to the Langmuir equation. Column adsorption experiments demonstrated that high dynamic adsorption capacity was reached at bed height of 104.4 mm, feed flow rate of 1.0 ml·min-1 and acarbose concentration of 4.0 mg·ml-1. Under the optimized conditions, the column chromatography packed with cation exchanger 001×4 recovered 74.3%(by mass) of acarbose from Actinoplanes utahensis ZJB-08196 fermentation broth with purity of 80.1%(by mass), demonstrating great potential in the practical applications in acarbose separation.

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

    Directory of Open Access Journals (Sweden)

    Shanmugam Arivoli

    2009-08-01

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

  14. Adsorption of Chromium Ions by Acid Activated Low Cost Carbon-Kinetic,Thermodynamic and Equilibrium Studies

    Directory of Open Access Journals (Sweden)

    B. R. Venkatraman

    2009-01-01

    Full Text Available A carbonaceous adsorbent prepared from an indigenous waste, by acid treatment was tested for its efficiency in removing metal ions. The process parameters studied include agitation time, initial metal ions concentration, carbon dose, pH and temperature. The adsorption followed first order reaction equation and the rate is mainly controlled by intra-particle diffusion. Freundlich and Langmuir isotherm models were applied to the equilibrium data. The adsorption capacity (Qm obtained from the Langmuir isotherm plot were found to around 30 mg/g at an initial pH of 7.0. The temperature variation study showed that the metal ions adsorption is endothermic and spontaneous with increased randomness at the solid solution interface. Significant effect on adsorption was observed on varying the pH of the metal ion solutions. The Langmuir and Freundlich adsorption isotherms obtained, positive ΔH0 value, pH dependent results and desorption of metal ions in mineral acid suggest that the adsorption of metal ions on BBC involves chemisorption as well as physisorption mechanism.

  15. Adsorption of Nickel Ion by Low Cost Carbon-Kinetic, Thermodynamic and Equilibrium Studies

    Directory of Open Access Journals (Sweden)

    V. Vijayakumaran

    2009-01-01

    Full Text Available A carbonaceous adsorbent prepared from an indigenous waste, by acid treatment was tested for its efficiency in removing nickel ion. The process parameters studied include agitation time, initial metal ion concentration, carbon dose, pH and temperature. The adsorption followed first order reaction equation and the rate is mainly controlled by intraparticle diffusion. Freundlich and Langmuir isotherm models were applied to the equilibrium data. The adsorption capacity (Qm obtained from the Langmuir isotherm plot were found to around 43 mg/g at an initial pH of 7.0. The temperature variation study showed that the nickel ions adsorption is endothermic and spontaneous with increased randomness at the solid solution interface. Significant effect on adsorption was observed on varying the pH of the nickel ion solutions. The Langmuir and Freundlich adsorption isotherms obtained, positive ΔH0 value, pH dependent results and desorption of metal ions in mineral acid suggest that the adsorption of nickel ion on MCC involves chemisorption as well as physisorption mechanism.

  16. A Tightly Coupled Non-Equilibrium Magneto-Hydrodynamic Model for Inductively Coupled RF Plasmas

    Science.gov (United States)

    2016-02-29

    effects are described based on a hybrid State-to-State (StS) approach. A multi-temperature formulation is used to account for thermal non-equilibrium...for Inductively Coupled Radio-Frequency (RF) Plasmas. Non Local Thermodynamic Equilibrium (NLTE) effects are described based on a hybrid State-to-State...usually obtained through quantum chemistry calculations51–56 or through phenomenological models providing a simplified descrip- tion of the kinetic

  17. Prediction of coal slag foaming under gasification conditions by thermodynamic equilibrium calculations

    Energy Technology Data Exchange (ETDEWEB)

    Lim, S.; Oh, M. [Hongik University, Seoul (Republic of Korea). School of Chemical Engineering

    2007-09-15

    In slagging gasifiers, slag foaming can cause serious operational problems, so there is a need for investigation into the conditions causing slag foaming. Viscosity experiments were carried out examining viscosity, extent of swelling and Fe formation. Although extensive swelling was not observed, FeO reduction was observed under an N{sub 2}/CO gas atmosphere, but not under CO{sub 2}/CO. In order to predict FeO reduction conditions in the gasifier, a model for an adiabatic equilibrium gasifier was developed. The gas composition, the amount of gas to slag, and PO{sub 2} were calculated for a slurry-feed gasifier, and the results of the calculation were used to predict the reduction of FeO in slag by using FactSage. Under typical gasification conditions for Denisovsky coal, the predicted -O{sub 2} in the gasifier was not low enough to cause FeO reduction. The FactSage simulation for the viscometer conditions predicted no FeO reduction under a CO/CO{sub 2} atmosphere, but did predict Fe formation under CO/N{sub 2} conditions. At a 20% CO concentration, FeO reduction starts at temperatures above 1,600{sup o}C. Since the slag has a low viscosity at 1,600{sup o}C, the oxygen bubble may have escaped as it formed. Therefore, slag foaming, caused by FeO reduction in the slag, can only occur when the right conditions of viscosity and oxygen partial pressure are met.

  18. Non-local Optical Potentials

    Science.gov (United States)

    Thompson, Ian

    2010-11-01

    In all direct reactions to probe the structure of exotic nuclei at FRIB, optical potentials will be needed in the entrance and exit channels. At high energies Glauber approximations may be useful, but a low energies (5 to 20 MeV/nucleon) other approaches are required. Recent work of the UNEDF project [1] has shown that reaction cross sections at these energies can be accounted for by calculating all inelastic and transfer channels reachable by one particle-hole transitions from the elastic channel. In this model space, we may also calculate the two-step dynamic polarization potential (DPP) that adds to the bare folded potential to form the complex optical potential. Our calculations of the DPP, however, show that its non-localities are very significant, as well as the partial-wave dependence of both its real and imaginary components. The Perey factors (the wave function ratio to that from an equivalent local potential) are more than 20% different from unity, especially for partial waves inside grazing. These factors combine to suggest a reexamination of the validity of local and L-independent fitted optical potentials, especially for capture reactions that are dominated by low partial waves. Prepared by LLNL under Contract DE-AC52-07NA27344. [1] G.P.A. Nobre, F.S. Dietrich, J.E. Escher, I.J. Thompson, M. Dupuis, J. Terasaki and J. Engel, submitted to Phys. Rev. Letts., 2010.

  19. Adsorption of Zn2+ ions onto NaA and NaX zeolites: kinetic, equilibrium and thermodynamic studies.

    Science.gov (United States)

    Nibou, D; Mekatel, H; Amokrane, S; Barkat, M; Trari, M

    2010-01-15

    The adsorption of Zn(2+) onto NaA and NaX zeolites was investigated. The samples were synthesized according to a hydrothermal crystallization using aluminium isopropoxide (Al[OCH(CH(3))(2)](3)) as a new alumina source. The effects of pH, initial concentration, solid/liquid ratio and temperature were studied in batch experiments. The Freundlich and the Langmuir models were applied and the adsorption equilibrium followed Langmuir adsorption isotherm. The uptake distribution coefficient (K(d)) indicated that the Zn(2+) removal was the highest at minimum concentration. Thermodynamic parameters were calculated. The negative values of standard enthalpy of adsorption revealed the exothermic nature of the adsorption process whereas the negative activation entropies reflected that no significant change occurs in the internal structure of the zeolites solid matrix during the sorption of Zn(2+). The negative values of Gibbs free energy were indicative of the spontaneity of the adsorption process. Analysis of the kinetic and rate data revealed that the pseudo second-order sorption mechanism is predominant and the intra particle diffusion was the determining step for the sorption of zinc ions. The obtained optimal parameters have been applied to wastewater from the industrial zone (Algeria) in order to remove the contained zinc effluents.

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

    Energy Technology Data Exchange (ETDEWEB)

    Das, Devlina [School of Biosciences and Technology, VIT University, Vellore, Tamil Nadu (India); Das, Nilanjana, E-mail: nilanjana00@lycos.com [School of Biosciences and Technology, VIT University, Vellore, Tamil Nadu (India); Mathew, Lazar [School of Biosciences and Technology, VIT University, Vellore, Tamil Nadu (India)

    2010-12-15

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

  1. Equilibrium, Kinetic, and Thermodynamic Studies on the Adsorption of Cadmium from Aqueous Solution by Modified Biomass Ash

    Science.gov (United States)

    Zheng, Xuebo; Cui, Hongbiao; Zhu, Zhenqiu; Liang, Jiani

    2017-01-01

    Natural biomass ash of agricultural residuals was collected from a power plant and modified with hexagonal mesoporous silica and functionalized with 3-aminopropyltriethoxysilane. The physicochemical and morphological properties of the biomass ash were analyzed by ICP-OES, SEM, TEM-EDS, FTIR, and BET analysis. The adsorption behavior of the modified product for Cd2+ in aqueous solution was studied as a function of pH, initial metal concentration, equilibrium time, and temperature. Results showed that the specific surface area of the modified product was 9 times that of the natural biomass ash. The modified biomass ash exhibited high affinity for Cd2+ and its adsorption capacity increased sharply with increasing pH from 4.0 to 6.0. The maximum adsorption capacity was 23.95 mg/g in a pH 5 solution with an initial metal concentration of 50 mg/L and a contact time of 90 min. The adsorption of Cd2+ onto the modified biomass ash was well fitted to the Langmuir model and it followed pseudo-second-order kinetics. Thermodynamic analysis results showed that the adsorption of Cd2+ was spontaneous and endothermic in nature. The results suggest that the modified biomass ash is promising for use as an inexpensive and effective adsorbent for Cd2+ removal from aqueous solution.

  2. Equilibrium, kinetic and thermodynamic studies for sorption of Ni (II from aqueous solution using formaldehyde treated waste tea leaves

    Directory of Open Access Journals (Sweden)

    Jasmin Shah

    2015-05-01

    Full Text Available The sorption characteristic of Ni (II from aqueous solution using formaldehyde treated waste tea leaves as a low cost sorbent has been studied. The effect of pH, contact time, sorbent dose, initial metal ion concentration and temperature were investigated in batch experiments. The equilibrium data were fitted into four most common isotherm models; Freundlich, Langmuir, Tempkin and Dubinin–Radushkevich (D–R. The Langmuir model described the sorption isotherm best with maximum monolayer sorption capacity of 120.50 mg g−1. Four kinetic models, pseudo-first-order, pseudo-second-order, intraparticle diffusion and Elovich were employed to explain the sorption mechanism. The kinetics of sorption data showed that the pseudo-second-order model is the best with correlation coefficient of 0.9946. The spontaneous and exothermic nature of the sorption process was revealed from thermodynamic investigations. The effect of some common alkali and alkaline earth metal ions were also studied which showed that the presence of these ions have no effect on the sorption of Ni (II. The results showed that waste tea leaves have the potential to be used as a low cost sorbent for the removal of Ni (II from aqueous solutions.

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

    Science.gov (United States)

    Sengupta, Tapan K.; Sengupta, Aditi; Sharma, Nidhi; Sengupta, Soumyo; Bhole, Ashish; Shruti, K. S.

    2016-09-01

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

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

    Science.gov (United States)

    Basha, Shaik; Jaiswar, Santlal; Jha, Bhavanath

    2010-09-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-09-15

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-02-01

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

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

    Science.gov (United States)

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

    2009-02-01

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

  8. Biosorption of palladium(II) from aqueous solution by moss (Racomitrium lanuginosum) biomass: Equilibrium, kinetic and thermodynamic studies

    Energy Technology Data Exchange (ETDEWEB)

    Sari, Ahmet; Mendil, Durali; Tuzen, Mustafa [Department of Chemistry, Gaziosmanpasa University, Tokat 60250 (Turkey); Soylak, Mustafa [Department of Chemistry, Erciyes University, Kayseri 38039 (Turkey)], E-mail: soylak@erciyes.edu.tr

    2009-03-15

    The biosorption potential of Racomitrium lanuginosum as aquatic moss biosorbent for the removal of Pd(II) from aqueous solution was investigated. The effects of pH, biomass dosage, contact time, and temperature on the biosorption processes were systematically studied. Experimental data were modeled by Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherms. Langmuir isotherm model (R{sup 2} = 0.994) fitted the equilibrium data better than the Freundlich isotherm model (R{sup 2} = 0.935). The monolayer biosorption capacity of R. lanuginosum biomass for Pd(II) was found to be 37.2 mg/g at pH 5. The mean free energy was calculated as 9.2 kJ/mol using the D-R isotherm model (R{sup 2} = 0.996). This result indicated that the biosorption of Pd(II) was taken place by chemical ion-exchange. The calculated thermodynamic parameters, {delta}G{sup o}, {delta}H{sup o} and {delta}S{sup o} showed that the biosorption of Pd(II) on R. lanuginosum biomass was feasible, spontaneous and exothermic under examined conditions. Experimental data were also tested using the biosorption kinetic models. The results showed that the biosorption processes of Pd(II) on R. lanuginosum followed well pseudo-second-order kinetics at 20-50 deg. C (R{sup 2} = 0.999)

  9. A kinetic, equilibrium and thermodynamic study of l-phenylalanine adsorption using activated carbon based on agricultural waste (date stones

    Directory of Open Access Journals (Sweden)

    Badreddine Belhamdi

    2016-10-01

    Full Text Available The main purpose of this work is to produce low cost activated carbons from date stones wastes for the adsorption of l-phenylalanine. The activated carbons were prepared by chemical activation with KOH (ACK and ZnCl2 (ACZ and characterized by scanning electron microscopy, N2 adsorption–desorption isotherms and FT-IR spectroscopy. Both The activated carbons ACK and ACZ have high specific surface areas and large pore volumes, favorable for the adsorption. Batch experiments were conducted to determine the adsorption capacities. A Strong dependence of the adsorption capacity on pH was observed, the capacity decreases with increasing pH up to optimal value of 5.7. The adsorption follows a pseudo-second order kinetic model. Additionally, the equilibrium adsorption data were well fitted to the Langmuir isotherm, and the maximum adsorption capacities of l-phenylalanine onto ACK and ACZ were 188.3 and 133.3 mg g−1 at pH 5.7, respectively. The thermodynamic study revealed that the adsorption of l-phenylalanine onto activated carbons was exothermic in nature. The proposed adsorption mechanisms take into account the hydrophobic and electrostatic interactions which played the critical roles in the l-phenylalanine adsorption.

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

    Directory of Open Access Journals (Sweden)

    SLOBODAN P. SERBANOVIC

    2000-12-01

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

  11. Origin of Dynamical Quantum Non-locality

    Science.gov (United States)

    Pachon, Cesar E.; Pachon, Leonardo A.

    2014-03-01

    Non-locality is one of the hallmarks of quantum mechanics and is responsible for paradigmatic features such as entanglement and the Aharonov-Bohm effect. Non-locality comes in two ``flavours'': a kinematic non-locality- arising from the structure of the Hilbert space- and a dynamical non-locality- arising from the quantum equations of motion-. Kinematic non-locality is unable to induce any change in the probability distributions, so that the ``action-at-a-distance'' cannot manifest. Conversely, dynamical non-locality does create explicit changes in probability, though in a ``causality-preserving'' manner. The origin of non-locality of quantum measurements and its relations to the fundamental postulates of quantum mechanics, such as the uncertainty principle, have been only recently elucidated. Here we trace the origin of dynamical non-locality to the superposition principle. This relation allows us to establish and identify how the uncertainty and the superposition principles determine the non-local character of the outcome of a quantum measurement. Being based on group theoretical and path integral formulations, our formulation admits immediate generalizations and extensions to to, e.g., quantum field theory. This work was supported by the Departamento Administrativo de Ciencia, Tecnologia e Innovacion -COLCIENCIAS- of Colombia under the grant number 111556934912.

  12. Causality, Non-Locality and Negative Refraction

    CERN Document Server

    Forcella, Davide; Carminati, Rémi

    2016-01-01

    The importance of spatial non-locality in the description of negative refraction in electromagnetic materials has been put forward recently. We develop a theory of negative refraction in homogeneous and isotropic media, based on first principles, and that includes non-locality in its full generality. The theory shows that both dissipation and spatial non-locality are necessary conditions for the existence of negative refraction. It also provides a sufficient condition in materials with weak spatial non-locality. These fundamental results should have broad implications in the theoretical and practical analyses of negative refraction of electromagnetic and other kinds of waves.

  13. Biosorption of Ni(II), Cr(III), and Co(II) from Solutions Using Acalypha hispida Leaf: Kinetics, Equilibrium, and Thermodynamics

    OpenAIRE

    Adesola Babarinde; J. Oyebamiji Babalola; John Adegoke; Osundeko, Adebola O.; Susan Olasehinde; Adetayo Omodehin; Emmanuel Nurhe

    2013-01-01

    Biosorption studies were conducted to study the removal of Ni(II), Cr(III), and Co(II) from aqueous solution of Acalypha hispida leaf. The FTIR spectral characteristics of Acalypha hispida leaf revealed the presence of ioniazable groups that could participate in the binding of metal ions in solution. The kinetic, equilibrium, and thermodynamic studies of the biosorption of the metal ions were investigated using various physicochemical parameters; each parameter was found to affect the biosorp...

  14. Thermodynamics of ion exchange equilibrium for some uni-univalent and divalent reaction systems using strongly basic anion exchange resin Indion FF-IP

    Directory of Open Access Journals (Sweden)

    P.U. Singare

    2008-12-01

    Full Text Available The study on thermodynamics of ion exchange equilibrium for uni-univalent Cl-/I-, Cl-/Br-, and uni-divalent Cl-/SO42-, Cl-/C2O42- reaction systems was carried out using ion exchange resin Indion FF-IP. The equilibrium constant K was calculated by taking into account the activity coefficient of ions both in solution as well as in the resin phase. For uni-univalent ion exchange reaction systems, the equilibrium constant K’ were also calculated by considering mole fraction of ions in the resin phase. The K values calculated for uni-univalent and uni-divalent anion exchange reaction systems were observed to increase with rise in temperature, indicating the endothermic exchange reactions having enthalpy values of 22.45, 28.57, 17.84, 15.97 kJ/mol, respectively.

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

    Science.gov (United States)

    Mavris, Dimitri; Roth, Bryce; McDonald, Rob

    2002-01-01

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

  16. Non-local parallel transport in BOUT++

    CERN Document Server

    Omotani, J T; Havlickova, E; Umansky, M

    2015-01-01

    Non-local closures allow kinetic effects on parallel transport to be included in fluid simulations. This is especially important in the scrape-off layer, but to be useful there the non-local model requires consistent kinetic boundary conditions at the sheath. A non-local closure scheme based on solution of a kinetic equation using a diagonalized moment expansion has been previously reported. We derive a method for imposing kinetic boundary conditions in this scheme and discuss their implementation in BOUT++. To make it feasible to implement the boundary conditions in the code, we are lead to transform the non-local model to a different moment basis, better adapted to describe parallel dynamics. The new basis has the additional benefit of enabling substantial optimization of the closure calculation, resulting in an O(10) speedup of the non-local code.

  17. [Non-equilibrium thermodynamic separation theory of nonlinear chromatography. II. The 0-1 model for nonlinear-mass transfer kinetic processes].

    Science.gov (United States)

    Liang, Heng; Jia, Zhenbin

    2007-11-01

    In the optimal design and control of preparative chromatographic processes, the obstacles appear when one tries to link the Wilson' s framework of chromatographic theories based on partial differential equations (PDEs) with the Eulerian presentation to optimal control approaches based on discrete time states, such as Markov decision processes (MDP) or Model predictive control (MPC). In this paper, the 0-1 model is presented to overcome the obstacles for nonlinear transport chromatography (NTC). With the Lagrangian-Eulerian description (L-ED), one solute cell unit is split into two solute cells, one (SCm) in the mobile phase with the linear velocity of the mobile phase, and the other (SCs) in the stationary phase with zero-velocity. The thermodynamic state vector, S(k), which comprises four vector components, i.e., the sequence number, the position and the local solute concentrations in both SCms and SCses, is introduced to describe the local thermodynamic path (LTP) and the macroscopical thermodynamic path (MTP). For the NTC, the LTP is designed for a solute zone to evolve from the state, S(k), to the virtual migration state, S(M), undergoing the virtual net migration sub-process, and then to the state, S(k+1), undergoing the virtual net inter phase mass transfer sub-process in a short time interval. Complete thermodynamic state iterations with the Markov characteristics are derived by using the local equilibrium isotherm and the local lumped mass transfer coefficient. When the local thermodynamic equilibrium is retained, excellent properties, such as consistency, stability, conservation, accuracy, etc., of the numerical solution of the 0-1 model are observed in the theoretical analysis and in the numerical experiments of the nonlinear ideal chromatography. It is found that the 0-1 model could properly link up with the MDP or optimal control approaches based on discrete time states.

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

    Energy Technology Data Exchange (ETDEWEB)

    Pinto, Leandro F.; Segalen da Silva, Diogo Italo [Department of Chemical Engineering, Federal University of Parana, CEP 81531-990, Curitiba, PR (Brazil); Rosa da Silva, Fabiano; Ramos, Luiz P. [Department of Chemistry, Federal University of Parana, CEP 81531-990, Curitiba, PR (Brazil); Ndiaye, Papa M. [Department of Chemical Engineering, Federal University of Parana, CEP 81531-990, Curitiba, PR (Brazil); Corazza, Marcos L., E-mail: corazza@ufpr.br [Department of Chemical Engineering, Federal University of Parana, CEP 81531-990, Curitiba, PR (Brazil)

    2012-01-15

    Highlights: > We measured phase behavior for the system involving {l_brace}CO{sub 2} + biodiesel + methanol{r_brace}. > The saturation pressures were obtained using a variable-volume view cell. > The experimental data were modeled using PR-vdW2 and PR-WS equations of state. - Abstract: The main objective of this work was to investigate the high pressure phase behavior of the binary systems {l_brace}CO{sub 2}(1) + methanol(2){r_brace} and {l_brace}CO{sub 2}(1) + soybean methyl esters (biodiesel)(2){r_brace} and the ternary system {l_brace}CO{sub 2}(1) + biodiesel(2) + methanol(3){r_brace} were determined. Biodiesel was produced from soybean oil, purified, characterized and used in this work. The static synthetic method, using a variable-volume view cell, was employed to obtain the experimental data in the temperature range of (303.15 to 343.15) K and pressures up to 21 MPa. The mole fractions of carbon dioxide were varied according to the systems as follows: (0.2383 to 0.8666) for the binary system {l_brace}CO{sub 2}(1) + methanol(2){r_brace}; (0.4201 to 0.9931) for the binary system {l_brace}CO{sub 2}(1) + biodiesel(2){r_brace}; (0.4864 to 0.9767) for the ternary system {l_brace}CO{sub 2}(1) + biodiesel(2) + methanol(3){r_brace} with a biodiesel to methanol molar ratio of (1:3); and (0.3732 to 0.9630) for the system {l_brace}CO{sub 2} + biodiesel + methanol{r_brace} with a biodiesel to methanol molar ratio of (8:1). For these systems, (vapor + liquid), (liquid + liquid), (vapor + liquid + liquid) transitions were observed. The phase equilibrium data obtained for the systems were modeled using the Peng-Robinson equation of state with the classical van der Waals (PR-vdW2) and Wong-Sandler (PR-WS) mixing rules. Both thermodynamic models were able to satisfactorily correlate the phase behavior of the systems investigated and the PR-WS presented the best performance.

  19. Can EPR non-locality be geometrical?

    Energy Technology Data Exchange (ETDEWEB)

    Ne`eman, Y. [Tel-Aviv Univ. (Israel). Raymond and Beverly Sackler Faculty of Exact Sciences]|[Univ. of Texas, Austin, TX (United States). Center for Particle Physics; Botero, A. [Texas Univ., Austin, TX (United States)

    1995-10-01

    The presence in Quantum Mechanics of non-local correlations is one of the two fundamentally non-intuitive features of that theory. The non-local correlations themselves fall into two classes: EPR and Geometrical. The non-local characteristics of the geometrical type are well-understood and are not suspected of possibly generating acausal features, such as faster-than-light propagation of information. This has especially become true since the emergence of a geometrical treatment for the relevant gauge theories, i.e. Fiber Bundle geometry, in which the quantum non-localities are seen to correspond to pure homotopy considerations. This aspect is reviewed in section 2. Contrary-wise, from its very conception, the EPR situation was felt to be paradoxical. It has been suggested that the non-local features of EPR might also derive from geometrical considerations, like all other non-local characteristics of QM. In[7], one of the authors was able to point out several plausibility arguments for this thesis, emphasizing in particular similarities between the non-local correlations provided by any gauge field theory and those required by the preservation of the quantum numbers of the original EPR state-vector, throughout its spatially-extended mode. The derivation was, however, somewhat incomplete, especially because of the apparent difference between, on the one hand, the closed spatial loops arising in the analysis of the geometrical non-localities, from Aharonov-Bohm and Berry phases to magnetic monopoles and instantons, and on the other hand, in the EPR case, the open line drawn by the positions of the two moving decay products of the disintegrating particle. In what follows, the authors endeavor to remove this obstacle and show that as in all other QM non-localities, EPR is somehow related to closed loops, almost involving homotopy considerations. They develop this view in section 3.

  20. Employee Travel Data (Non-Local)

    Data.gov (United States)

    Montgomery County of Maryland — ‘This dataset provides information regarding the total approved actual expenses incurred by Montgomery County government employees traveling non-locally (over 75...

  1. Robust non-local median filter

    Science.gov (United States)

    Matsuoka, Jyohei; Koga, Takanori; Suetake, Noriaki; Uchino, Eiji

    2017-04-01

    This paper describes a novel image filter with superior performance on detail-preserving removal of random-valued impulse noise superimposed on natural gray-scale images. The non-local means filter is in the limelight as a way of Gaussian noise removal with superior performance on detail preservation. By referring the fundamental concept of the non-local means, we had proposed a non-local median filter as a specialized way for random-valued impulse noise removal so far. In the non-local processing, the output of a filter is calculated from pixels in blocks which are similar to the block centered at a pixel of interest. As a result, aggressive noise removal is conducted without destroying the detailed structures in an original image. However, the performance of non-local processing decreases enormously in the case of high noise occurrence probability. A cause of this problem is that the superimposed noise disturbs accurate calculation of the similarity between the blocks. To cope with this problem, we propose an improved non-local median filter which is robust to the high level of corruption by introducing a new similarity measure considering possibility of being the original signal. The effectiveness and validity of the proposed method are verified in a series of experiments using natural gray-scale images.

  2. A method of calculating of the thermodynamic properties and the composition of the explosion products of hydrocarbons and air under partial chemical equilibrium

    Science.gov (United States)

    Shargatov, V. A.

    2016-11-01

    We examined the approximate method to calculate composition and thermodynamic parameters of hydrocarbons-air nonequilibrium explosion products based on the assumption of the existence of a partial chemical equilibrium. With excellent accuracy of calculating thermodynamic properties and species mass fraction the respective stiff system of detailed kinetics differential equations can be replaced by the one differential equation or the two differential equations and a system of algebraic equations. This method is always consistent with the detailed kinetic mechanism. The constituent equations of the method were derived and the respective computer code written. We examine the applicability of the method by solving the test problem. The proposed method simulation results are in excellent agreement with the detailed kinetics model results corresponding the stiff ordinary differential equation solver including NO time histories.

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

    Science.gov (United States)

    Grossman, B.; Cinella, P.

    1988-01-01

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

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

    Science.gov (United States)

    Grossman, B.; Cinella, P.

    1988-01-01

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

  5. Thermodynamics of the equilibrium of the reaction between (5,10,15,20-tetra(2-methoxyphenyl)porphinato)chloroindium(III) and pyridine

    Science.gov (United States)

    Bichan, N. G.; Ovchenkova, E. N.; Mozhzhukhina, E. G.; Lomova, T. N.

    2017-07-01

    The results from thermodynamic and quantum-chemical studies of the reversible reaction between (5,10,15,20-tetra(2-methoxyphenyl)porphinato)chloroindium(III) and pyridine are reported. The main physicochemical parameters of properties of its supramolecular products are obtained and analyzed. The addition of pyridine molecules to metalloporphyrin proceeds in one step to attain an equilibrium state with the formation of supramolecules with a stoichiometry of 2: 1; spectral characteristics and parameters of the stability of the latter are identified. The possibility of using substituted indium(III)porphyrin for further research in the field of hybrid solar cells is discussed.

  6. Investigation of thermodynamic equilibrium in laser-induced aluminum plasma using the H{sub α} line profiles and Thomson scattering spectra

    Energy Technology Data Exchange (ETDEWEB)

    Cvejić, M., E-mail: marko.cvejic@ipb.ac.rs, E-mail: krzysztof.dzierzega@uj.edu.pl [Institute of Physics, University of Belgrade, P.O. Box 68, 11080 Belgrade (Serbia); Faculty of Physics, Weizmann Institute of Science, Rehovot 7610001 (Israel); Dzierżęga, K., E-mail: marko.cvejic@ipb.ac.rs, E-mail: krzysztof.dzierzega@uj.edu.pl; Pięta, T. [M. Smoluchowski Institute of Physics, Jagellonian University, ul. Łojasiewicza 11, 30-348 Kraków (Poland)

    2015-07-13

    We have studied isothermal equilibrium in the laser-induced plasma from aluminum pellets in argon at pressure of 200 mbar by using a method which combines the standard laser Thomson scattering and analysis of the H{sub α}, Stark-broadened, line profiles. Plasma was created using 4.5 ns, 4 mJ pulses from a Nd:YAG laser at 1064 nm. While electron density and temperature were determined from the electron feature of Thomson scattering spectra, the heavy particle temperature was obtained from the H{sub α} full profile applying computer simulation including ion-dynamical effects. We have found strong imbalance between these two temperatures during entire plasma evolution which indicates its non-isothermal character. At the same time, according to the McWhirter criterion, the electron density was high enough to establish plasma in local thermodynamic equilibrium.

  7. Thermodynamic extension of density-functional theory. I. Canonical Massieu-Planck function, its Legendre and Massieu-Planck transforms for equilibrium state in terms of density matrix

    CERN Document Server

    Balawender, Robert

    2009-01-01

    A unified formulation of the equilibrium state of a many-electron system in terms of an ensemble (mixed-state) density matrix, which applies the maximum entropy principle combined with the use of Massieu-Planck function, is presented. The properties of the characteristic functionals for macrocanonical ensemble are established. Their extension to other ensembles is accomplished via a Legendre transform. The relations between equilibrium states defined by a formal mathematical procedure and by criteria adopted for traditional (Gibbs, Helmholtz) potentials are investigated using Massieu-Planck transform. The preeminence of the Massieu-Planck function over the traditional thermodynamic potentials is discussed in detail on an example of their second derivatives. Introduced functions are suitable for application to the extensions of the density functional theory, both at finite and zero temperatures.

  8. Thermodynamic study of binary system Propafenone Hydrocloride with Metoprolol Tartrate: solid-liquid equilibrium and compatibility with α-lactose monohydrate and corn starch.

    Science.gov (United States)

    Marinescu, Daniela-Crina; Pincu, Elena; Meltzer, Viorica

    2013-05-20

    Solid-liquid equilibrium (SLE) for binary mixture of Propafenone Hydrocloride (PP) with Metoprolol Tartrate (MT) was investigated using differential scanning calorimetry (DSC) and corresponding activity coefficients were calculated. Simple eutectic behavior for this system was observed. The excess thermodynamic functions: G(E) and S(E) for the pre-, post-, and eutectic composition have been obtained using the computed activity coefficients data of the eutectic phase with their excess chemical potentials μi(E) (i=1, 2). The experimental solid-liquid phase temperatures were compared with predictions obtained from available eutectic equilibrium models. The results indicate non-ideality in this mixture. Also, the compatibility of each component and their eutectic mixture with usual excipients was investigated, and the DSC experiments indicate possible weak interactions with α-lactose monohydrate and compatibility with corn starch. The results obtained were confirmed by FT-IR measurements.

  9. Phase equilibrium engineering

    CERN Document Server

    Brignole, Esteban Alberto

    2013-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-02-15

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

  11. Biosorption of Ni(II, Cr(III, and Co(II from Solutions Using Acalypha hispida Leaf: Kinetics, Equilibrium, and Thermodynamics

    Directory of Open Access Journals (Sweden)

    Adesola Babarinde

    2013-01-01

    Full Text Available Biosorption studies were conducted to study the removal of Ni(II, Cr(III, and Co(II from aqueous solution of Acalypha hispida leaf. The FTIR spectral characteristics of Acalypha hispida leaf revealed the presence of ioniazable groups that could participate in the binding of metal ions in solution. The kinetic, equilibrium, and thermodynamic studies of the biosorption of the metal ions were investigated using various physicochemical parameters; each parameter was found to affect the biosorption process. The kinetic studies showed that the biosorption process was best represented by pseudo-second-order kinetics among four kinetic models tested. Equilibrium data were better represented by Freundlich isotherm among Langmuir and Freundlich adsorption isotherms. The study on the effect of dosage showed that the dosage of the biomass significantly affected the uptake of the metal ions from solution. Thermodynamic parameters such as standard Gibbs-free energy (, standard enthalpy (, standard entropy (, and the activation energy were calculated. The order of spontaneity of the biosorption process was found to be Cr(III > Ni(II > Co(II. The activation energy for the biosorption of each of the metal ions was less than 42 kJmol−1 at 323 K indicating that each was a diffusion-controlled process.

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

    Science.gov (United States)

    Williams, Donald F.; Glasser, David

    1991-01-01

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

  13. Statistical Thermodynamics of an "Open" Hard Sphere System on the Equilibrium Fluid Isotherm: Study of Properties of the Freezing Transition Without Direct Involvement of the Equilibrium Solid Phase

    Science.gov (United States)

    Reiss, Howard; Manzanares, José A.

    2016-09-01

    Using several theoretical toolsldots (i) the nucleation theorem, (ii) an equivalent cavity, (iii) the reversible work of adding a cavity to an open hard sphere system, and (iv) the theory of "stability"... the authors estimated the density at which the hard sphere freezing transition occurs. No direct involvement of the equilibrium solid phase is involved. The reduced density \\uppi a^3ρ _f/6 (where a is the hard sphere diameter and ρ _f is the actual density at which freezing occurs) is found to be 0.4937 while the value obtained by computer simulation is 0.494. The agreement is good, but the new method still contains some approximation. However, the approximation is based on the idea that at a density just below ρ _f the fluid adopts a distorted structure resembling the solid, but different enough so that long-range order vanishes. Initial loss of stability may not be involved in every fluid-solid transition, but it may be an early step in the hard sphere and related systems.

  14. Kinetic, equilibrium and thermodynamic investigations of Ni(II, Cd(II, Cu(II and Co(II adsorption on barley straw ash

    Directory of Open Access Journals (Sweden)

    M. Arshadi

    2014-08-01

    Full Text Available This work reports the application of a straw ash from barley as a novel bioadsorbent for the removal of several heavy metals: Ni(II, Cd(II, Cu(II, and Co(II. Equilibrium and kinetic models for heavy metals sorption were developed by considering the effect of the contact time, initial heavy metal ion concentrations, effect of temperature, and initial pH. The adsorption of heavy metal ions have been studied in terms of pseudo-first- and -second-order kinetics, and the Freundlich, Langmuir and Langmuir–Freundlich isotherms models have also been used to the equilibrium adsorption data. The equilibrium data fitted well with the Langmuir–Freundlich model and showed the following affinity order of the material: Ni(II>Cu(II>Co(II>Cd(II. The adsorption kinetics followed the mechanism of the pseudo-second-order equation for all systems studied, confirming chemical sorption as the rate-limiting step of adsorption mechanisms. The thermodynamic parameters (ΔG°, ΔH° and ΔS° indicated that the adsorption of heavy metals ions were feasible, spontaneous and endothermic at 15–80 °C.

  15. Large-scale screening of metal hydrides for hydrogen storage from first-principles calculations based on equilibrium reaction thermodynamics.

    Science.gov (United States)

    Kim, Ki Chul; Kulkarni, Anant D; Johnson, J Karl; Sholl, David S

    2011-04-21

    Systematic thermodynamics calculations based on density functional theory-calculated energies for crystalline solids have been a useful complement to experimental studies of hydrogen storage in metal hydrides. We report the most comprehensive set of thermodynamics calculations for mixtures of light metal hydrides to date by performing grand canonical linear programming screening on a database of 359 compounds, including 147 compounds not previously examined by us. This database is used to categorize the reaction thermodynamics of all mixtures containing any four non-H elements among Al, B, C, Ca, K, Li, Mg, N, Na, Sc, Si, Ti, and V. Reactions are categorized according to the amount of H(2) that is released and the reaction's enthalpy. This approach identifies 74 distinct single step reactions having that a storage capacity >6 wt.% and zero temperature heats of reaction 15 ≤ΔU(0)≤ 75 kJ mol(-1) H(2). Many of these reactions, however, are likely to be problematic experimentally because of the role of refractory compounds, B(12)H(12)-containing compounds, or carbon. The single most promising reaction identified in this way involves LiNH(2)/LiH/KBH(4), storing 7.48 wt.% H(2) and having ΔU(0) = 43.6 kJ mol(-1) H(2). We also examined the complete range of reaction mixtures to identify multi-step reactions with useful properties; this yielded 23 multi-step reactions of potential interest.

  16. Measuring Thermodynamic Length

    Energy Technology Data Exchange (ETDEWEB)

    Crooks, Gavin E

    2007-09-07

    Thermodynamic length is a metric distance between equilibrium thermodynamic states. Among other interesting properties, this metric asymptotically bounds the dissipation induced by a finite time transformation of a thermodynamic system. It is also connected to the Jensen-Shannon divergence, Fisher information, and Rao's entropy differential metric. Therefore, thermodynamic length is of central interestin understanding matter out of equilibrium. In this Letter, we will consider how to denethermodynamic length for a small system described by equilibrium statistical mechanics and how to measure thermodynamic length within a computer simulation. Surprisingly, Bennett's classic acceptance ratio method for measuring free energy differences also measures thermodynamic length.

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

    Science.gov (United States)

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

    2017-01-01

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

  18. Development of a multi-species mass transport model for concrete with account to thermodynamic phase equilibriums

    DEFF Research Database (Denmark)

    Hosokawa, Yoshifumi; Yamada, Kazuo; Johannesson, Björn

    2011-01-01

    In this study, a coupled multi-species transport and chemical equilibrium model has been established. The model is capable of predicting time dependent variation of pore solution and solid-phase composition in concrete. Multi-species transport approaches, based on the Poisson–Nernst–Planck (PNP......) theory alone, not involving chemical processes, have no real practical interest since the chemical action is very dominant for cement based materials. Coupled mass transport and chemical equilibrium models can be used to calculate the variation in pore solution and solid-phase composition when using...... by using the PHREEQC program. The coupling between the transport part and chemical part of the problem is tackled by using a sequential operator splitting technique and the calculation results are verified by comparing the elemental spacial distribution in concrete measured by the electron probe...

  19. Equilibrium, kinetic and thermodynamic studies for sorption of Ni (II) from aqueous solution using formaldehyde treated waste tea leaves

    OpenAIRE

    2015-01-01

    The sorption characteristic of Ni (II) from aqueous solution using formaldehyde treated waste tea leaves as a low cost sorbent has been studied. The effect of pH, contact time, sorbent dose, initial metal ion concentration and temperature were investigated in batch experiments. The equilibrium data were fitted into four most common isotherm models; Freundlich, Langmuir, Tempkin and Dubinin–Radushkevich (D–R). The Langmuir model described the sorption isotherm best with maximum monolayer sorpt...

  20. Equilibrium, Kinetics, and Thermodynamics of Remazol Brilliant Blue R Dye Adsorption onto Activated Carbon Prepared from Pinang Frond

    OpenAIRE

    Mohd Azhar Ahmad; Safarudin Gazali Herawan; Ahmad Anas Yusof

    2014-01-01

    The adsorption of remazol brilliant blue R (RBBR) dye on pinang frond based activated carbon (PF-AC) was investigated in a batch process. The effects of initial dye concentration, contact time, solution temperature, and solution pH were evaluated. The adsorption equilibrium and kinetic were found to follow Freundlich isotherm models and pseudo-second-order kinetic model, respectively. The mechanism of the adsorption process was found from the intraparticle diffusion model. Result from adsorpt...

  1. Models of Non-Stationary Thermodynamic Processes in Rocket Engines Taking into Account a Chemical Equilibrium of Combustion Products

    Directory of Open Access Journals (Sweden)

    A. V. Aliev

    2015-01-01

    Full Text Available The paper considers the two approach-based techniques for calculating the non-stationary intra-chamber processes in solid-propellant rocket engine (SPRE. The first approach assumes that the combustion products are a mechanical mix while the other one supposes it to be the mix, which is in chemical equilibrium. To enhance reliability of solution of the intra ballistic tasks, which assume a chemical equilibrium of combustion products, the computing algorithms to calculate a structure of the combustion products are changed. The algorithm for solving a system of the nonlinear equations of chemical equilibrium, when determining the iterative amendments, uses the orthogonal QR method instead of a method of Gauss. Besides, a possibility to apply genetic algorithms in a task about a structure of combustion products is considered.It is shown that in the tasks concerning the prediction of non-stationary intra ballistic characteristics in a solid propellant rocket engine, application of models of mechanical mix and chemically equilibrium structure of combustion products leads to qualitatively and quantitatively coinciding results. The maximum difference in parameters is 5-10%, at most. In tasks concerning the starting operation of a solid sustainer engine with high-temperature products of combustion difference in results is more essential, and can reach 20% and more.A technique to calculate the intra ballistic parameters, in which flotation of combustion products is considered in the light of a spatial statement, requires using the high-performance computer facilities. For these tasks it is offered to define structure of products of combustion and its thermo-physical characteristics, using the polynoms coefficients of which should be predefined.

  2. Towards an emerging understanding of non-locality phenomena and non-local transport

    Science.gov (United States)

    Ida, K.; Shi, Z.; Sun, H. J.; Inagaki, S.; Kamiya, K.; Rice, J. E.; Tamura, N.; Diamond, P. H.; Dif-Pradalier, G.; Zou, X. L.; Itoh, K.; Sugita, S.; Gürcan, O. D.; Estrada, T.; Hidalgo, C.; Hahm, T. S.; Field, A.; Ding, X. T.; Sakamoto, Y.; Oldenbürger, S.; Yoshinuma, M.; Kobayashi, T.; Jiang, M.; Hahn, S. H.; Jeon, Y. M.; Hong, S. H.; Kosuga, Y.; Dong, J.; Itoh, S.-I.

    2015-01-01

    In this paper, recent progress on experimental analysis and theoretical models for non-local transport (non-Fickian fluxes in real space) is reviewed. The non-locality in the heat and momentum transport observed in the plasma, the departures from linear flux-gradient proportionality, and externally triggered non-local transport phenomena are described in both L-mode and improved-mode plasmas. Ongoing evaluation of ‘fast front’ and ‘intrinsically non-local’ models, and their success in comparisons with experimental data, are discussed

  3. Sorption of Cu2+ and Co2+ from aqueous solutions onto sepiolite: an equilibrium, kinetic and thermodynamic study

    Directory of Open Access Journals (Sweden)

    SLAVICA LAZAREVIĆ

    2011-01-01

    Full Text Available The efficiency of natural sepiolite for the removal of Cu2+ and Co2+ from aqueous solution was determined using the batch method. The sorption experiments were performed as a function of the initial metal concentration, the equilibration time and temperature. Thermodynamic parameters, such as enthalpy, free energy and entropy, were calculated from the temperature dependent sorption isotherms and these values showed that the sorption of the investigated metals onto sepiolite was endothermic. The pseudo-second order kinetic model provides the best correlation of the experimental kinetic data.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-06-15

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

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

    Science.gov (United States)

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

    2014-06-01

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

  6. Analysis of Entropy Generation of Combined Heat and Mass Transfer in Internal and External Flows with the Assumption of Local Thermodynamic Equilibrium

    Institute of Scientific and Technical Information of China (English)

    ShouguangYao

    1994-01-01

    In this paper,the control volume method is used to establish the general expression of entropy generation due to combined convective heat and mass transfer in internal and external fluid streams.The expression accounts for irreversibilities due to the presence of heat transfer across a finite temperature difference,mass transfer across a finite difference in the chemical potential of a species,and due to flow friction.Based on the assumption of local thermodynamic equilibrium,the generalized form of the Gibbs equation is used in this analysis.The results are applied to two fundamental problems of forced convection heat and mass transfer in internal and external flows.After minimizing the entropy generation,useful conclusions are derived that are typical of the second law viewpoint for the definition of the optimum operation conditions for the specified applications.which is a valuable criterion for optimum design of heat and fluid flow devices.

  7. A computationally efficient and accurate numerical representation of thermodynamic properties of steam and water for computations of non-equilibrium condensing steam flow in steam turbines

    Directory of Open Access Journals (Sweden)

    Hrubý Jan

    2012-04-01

    Full Text Available Mathematical modeling of the non-equilibrium condensing transonic steam flow in the complex 3D geometry of a steam turbine is a demanding problem both concerning the physical concepts and the required computational power. Available accurate formulations of steam properties IAPWS-95 and IAPWS-IF97 require much computation time. For this reason, the modelers often accept the unrealistic ideal-gas behavior. Here we present a computation scheme based on a piecewise, thermodynamically consistent representation of the IAPWS-95 formulation. Density and internal energy are chosen as independent variables to avoid variable transformations and iterations. On the contrary to the previous Tabular Taylor Series Expansion Method, the pressure and temperature are continuous functions of the independent variables, which is a desirable property for the solution of the differential equations of the mass, energy, and momentum conservation for both phases.

  8. Thermodynamic Equilibrium Studies of Nanocrystallite CeO2 Grain Boundaries by High Temperature X-Ray Photoelectron Spectroscopy and Thermal Gravimetric Analysis

    Institute of Scientific and Technical Information of China (English)

    LIU Zhen-Xiang; XIE Kan

    2000-01-01

    Nanostructured CeO2 thin films and powders are studied by high temperature x-ray photoelectron spectroscopy and thermal gravimetric analysis. The results indicate that the surface composition strongly depends on temperature, the surface O/Ce ratio initially increases with increasing temperature, then decreases with the further increase of temperature, the maximum surface O/Ce ratio is at about 300℃ C. The variation of the surface composition with temperature arises from the ion migration, redistribution and transformation between lattice oxygen and gas phase oxygen near the grain boundaries during the thermodynamic equilibrium process. The results also show that CeO2 has a weakly bond oxygen, high oxygen mobility in the bulk and a high molecular dissociation rate at the surface, especially for the sol-gel prepared nanocrystallite CeO2.

  9. Quantum Loops in Non-Local Gravity

    CERN Document Server

    Talaganis, Spyridon

    2015-01-01

    In this proceedings, I will consider quantum aspects of a non-local, infinite-derivative scalar field theory - a ${\\it toy \\, model}$ depiction of a covariant infinite-derivative, non-local extension of Einstein's general relativity which has previously been shown to be free from ghosts around the Minkowski background. The graviton propagator in this theory gets an exponential suppression making it ${\\it asymptotically \\, free}$, thus providing strong prospects of resolving various classical and quantum divergences. In particular, I will find that at $1$-loop, the $2$-point function is still divergent, but once this amplitude is renormalized by adding appropriate counter terms, the ultraviolet (UV) behavior of all other $1$-loop diagrams as well as the $2$-loop, $2$-point function remains well under control. I will go on to discuss how one may be able to generalize our computations and arguments to arbitrary loops.

  10. Non-local geometry inside Lifshitz horizon

    Science.gov (United States)

    Hu, Qi; Lee, Sung-Sik

    2017-07-01

    Based on the quantum renormalization group, we derive the bulk geometry that emerges in the holographic dual of the fermionic U( N ) vector model at a nonzero charge density. The obstruction that prohibits the metallic state from being smoothly deformable to the direct product state under the renormalization group flow gives rise to a horizon at a finite radial coordinate in the bulk. The region outside the horizon is described by the Lifshitz geometry with a higher-spin hair determined by microscopic details of the boundary theory. On the other hand, the interior of the horizon is not described by any Riemannian manifold, as it exhibits an algebraic non-locality. The non-local structure inside the horizon carries the information on the shape of the filled Fermi sea.

  11. Experimental thermodynamic study of the equilibrium phase AgBi{sub 3}S{sub 5} by an improved EMF method

    Energy Technology Data Exchange (ETDEWEB)

    Tesfaye, Fiseha, E-mail: fiseha.tesfaye@aalto.fi; Taskinen, Pekka, E-mail: pekka.taskinen@aalto.fi

    2013-06-20

    Highlights: • A new method for constructing and measuring on galvanic cells has been employed. • Galvanic cells including AgI and RbAg{sub 4}I{sub 5} solid electrolytes were measured accurately. • Thermodynamics of the phase assemblages AgBi{sub 3}S{sub 5}–Bi{sub 2}S{sub 3}–S/Bi have been investigated. • Δ{sub f}G° values for sulfur- and bismuth-saturated pavonite (AgBi{sub 3}S{sub 5}) have been determined. • New experimental thermodynamic data for bismuth-saturated pavonite were generated. - Abstract: A thermodynamic study of the equilibrium phase assemblages AgBi{sub 3}S{sub 5}–Bi{sub 2}S{sub 3}–S/Bi was made by an EMF-technique. The ternary phase was synthesized from the pure Ag{sub 2}S and Bi{sub 2}S{sub 3} in an evacuated silica ampoule, and ground into powder before mixing with appropriate compositions of Bi{sub 2}S{sub 3} and S or Bi. The phase mixtures were pressed into different pellets, in a series of experiments. Together with pieces of pure Ag-foil and the electrolytic pellets of superionic conductor RbAg{sub 4}I{sub 5} or AgI, the pellets were assembled to form the galvanic cells Pt(−) | Ag | RbAg{sub 4}I{sub 5} | AgBi{sub 3}S{sub 5} + Bi{sub 2}S{sub 3} + S + (C) | Pt(+) and Pt(−) | Ag | AgI | AgBi{sub 3}S{sub 5} + Bi{sub 2}S{sub 3} + Bi | C | Pt(+). The EMF-measurements were made in a temperature range 299.15–594.15 K. In this paper, the thermodynamic functions for the formation of pavonite (AgBi{sub 3}S{sub 5}) at sulfur and bismuth saturation have been determined. The obtained results are in agreement with some of the available literature values. Furthermore, new experimental thermodynamic data of bismuth-saturated pavonite (AgBi{sub 3+x}S{sub 5}; 0 < x < 0.14), in the temperature range 299.15–594.15 K, were determined.

  12. Relativistic three-partite non-locality

    CERN Document Server

    Montakhab, A

    2015-01-01

    Bell-like inequalities have been used in order to distinguish non-local quantum pure states by various authors. The behavior of such inequalities under Lorentz transformation has been a source of debate and controversies in the past. In this paper, we consider the two most commonly studied three-particle pure states, that of W and GHZ states which exhibit distinctly different type of entanglement. We discuss the various types of three-particle inequalities used in previous studies and point to their corresponding shortcomings and strengths. Our main result is that if one uses Svetlichny's inequality as the main measure of non-locality and uses the same angles in the rest frame ($S$) as well as the moving frame ($S^{\\prime}$), then maximally violated inequality in $S$ will decrease in the moving frame, and will eventually lead to lack of non-locality ( i.e. satisfaction of inequality) in the $v \\rightarrow c$ limit. This is shown for both GHZ and W states and in two different configurations which are commonly ...

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

    Directory of Open Access Journals (Sweden)

    Ruth Alfaro-Cuevas-Villanueva

    2014-01-01

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

  14. Removal of cadmium(II) ions from aqueous solution using Ni (15 wt.%)-doped α-Fe2O3 nanocrystals: equilibrium, thermodynamic, and kinetic studies.

    Science.gov (United States)

    OuldM'hamed, Mohamed; Khezami, L; Alshammari, Abdulrahman G; Ould-Mame, S M; Ghiloufi, I; Lemine, O M

    2015-01-01

    The present publication investigates the performance of nanocrystalline Ni (15 wt.%)-doped α-Fe2O3 as an effective nanomaterial for the removal of Cd(II) ions from aqueous solutions. The nanocrystalline Ni-doped α-Fe2O3 powders were prepared by mechanical alloying, and characterized by X-ray diffraction and a vibrating sample magnetometer. Batch-mode experiments were realized to determine the adsorption equilibrium, kinetics, and thermodynamic parameters of toxic heavy metal ions by Ni (15 wt.%)-doped α-Fe2O3. The adsorption isotherms data were found to be in good agreement with the Langmuir model. The adsorption capacity of Cd(II) ion reached a maximum value of about 90.91 mg g(-1) at 328 K and pH 7. The adsorption process kinetics was found to comply with pseudo-second-order rate law. Thermodynamic parameters related to the adsorption reaction, free energy change, enthalpy change and entropy change, were evaluated. The found values of free energy and enthalpy revealed a spontaneous endothermic adsorption-process. Moreover, the positive entropy suggests an increase of randomness during the process of heavy metal removal at the adsorbent-solution interface.

  15. The Adsorption of Pb, Zn, Cu, Ni, and Cd by Modified Ligand in a Single Component Aqueous Solution: Equilibrium, Kinetic, Thermodynamic, and Desorption Studies

    Directory of Open Access Journals (Sweden)

    E. Igberase

    2017-01-01

    Full Text Available In this investigation, an amino functionalized adsorbent was developed by grafting 4-aminobenzoic acid onto the backbone of cross-linked chitosan beads. The 3 sets of beads including chitosan (CX, glutaraldehyde cross-linked chitosan (CCX, and 4-aminobenzoic acid grafted cross-linked chitosan (FGCX were characterized by FTIR, XRD, SEM, and TGA. The water content and amine concentration of FGCX were determined. The effect of adsorption parameters was studied and the optimum was used for further studies. Equilibrium data was obtained from the adsorption experiment carried out at different initial concentration; the data were applied in isotherm, thermodynamics, and kinetic studies. The Langmuir and Dubinin-Kaganer-Radushkevich (DKR models were successful in describing the isotherm data for the considered metal ions while the Freundlich and Temkin model fit some of the considered metal ions. Pseudo-second-order and intraparticle model described the kinetic data quite well. Thermodynamic parameters such as Gibb’s free energy change (ΔGo, enthalpy change (ΔHo, and entropy change (ΔSo were calculated and the results showed that the adsorption of Pb, Cu, Ni, Zn, and Cd ions onto FGCX is spontaneous and endothermic in nature. Regeneration of the spent adsorbent was efficient for the considered metal ions.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-07-15

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

  17. 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.

  18. Thermodynamic modelling of phase equilibrium for water + poly(Ethylene glycol + salt aqueous two-phase systems

    Directory of Open Access Journals (Sweden)

    R.A.G. Sé

    2002-04-01

    Full Text Available The NRTL (nonrandom, two-liquid model, expressed in mass fraction instead of mole fraction, was used to correlate liquid-liquid equilibria for aqueous two-phase polymer-salt solutions. New interaction energy parameters for this model were determined using reported data on the water + poly(ethylene glycol + salt systems, with different molecular masses for PEG and the salts potassium phosphate, sodium sulfate, sodium carbonate and magnesium sulfate. The correlation of liquid-liquid equilibrium is quite satisfactory.

  19. Thermodynamics at the nanoscale: phase diagrams of nickel-carbon nanoclusters and equilibrium constants for phase transitions.

    Science.gov (United States)

    Engelmann, Yannick; Bogaerts, Annemie; Neyts, Erik C

    2014-10-21

    Using reactive molecular dynamics simulations, the melting behavior of nickel-carbon nanoclusters is examined. The phase diagrams of icosahedral and Wulff polyhedron clusters are determined using both the Lindemann index and the potential energy. Formulae are derived for calculating the equilibrium constants and the solid and liquid fractions during a phase transition, allowing more rational determination of the melting temperature with respect to the arbitrary Lindemann value. These results give more insight into the properties of nickel-carbon nanoclusters in general and can specifically be very useful for a better understanding of the synthesis of carbon nanotubes using the catalytic chemical vapor deposition method.

  20. Steepest-entropy-ascent quantum thermodynamic framework for describing the non-equilibrium behavior of a chemically reactive system at an atomistic level

    CERN Document Server

    Beretta, Gian Paolo

    2015-01-01

    Steepest-Entropy-Ascent Quantum Thermodynamics (SEAQT) provides a general framework for the description of non-equilibrium phenomena at any level, particularly the atomistic one. This theory and its dynamical postulate are used here to develop a general mathematical framework, which at an atomistic level, in particular, can be used to predict the non-equilibrium evolution in state of a closed, chemically reactive mixture such as the one examined here, i.e., a mixture of hydrogen (H2) and flourine (F) contained in an isolated tank of fixed volume. The general framework provided, however, is written for a reactive system subject to multiple reaction mechanisms. To predict this evolution in state, both the energy and particle number eigenvalue problems for a dilute gas are set up and solved analytically. Wall and non-ideal-gas behavior effects are neglected, although the extension to dense gases is straightforward but left for a future paper. The system-level energy and particle number eigenvalues and eigenstate...

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

    Science.gov (United States)

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

    2013-10-15

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

  2. On non-local representations of the ageing algebra

    Energy Technology Data Exchange (ETDEWEB)

    Henkel, Malte, E-mail: henkel@lpm.u-nancy.f [Groupe de Physique Statistique, Departement de Physique de la Matiere et des Materiaux, Institut Jean Lamour, Nancy Universite (UMR 7198-CNRS-UHP-INPL-UPVM) B.P. 70239, F-54506 Vandoeuvre les Nancy Cedex (France); Stoimenov, Stoimen [Institute of Nuclear Research and Nuclear Energy, Bulgarian Academy of Sciences, 72 Tsarigradsko chaussee, Blvd., BG-1784 Sofia (Bulgaria)

    2011-06-21

    The ageing algebra is a local dynamical symmetry of many ageing systems, far from equilibrium, and with a dynamical exponent z=2. Here, new representations for an integer dynamical exponent z=n are constructed, which act non-locally on the physical scaling operators. The new mathematical mechanism which makes the infinitesimal generators of the ageing algebra dynamical symmetries, is explicitly discussed for an n-dependent family of linear equations of motion for the order-parameter. Finite transformations are derived through the exponentiation of the infinitesimal generators and it is proposed to interpret them in terms of the transformation of distributions of spatio-temporal coordinates. The two-point functions which transform co-variantly under the new representations are computed, which quite distinct forms for n even and n odd. Depending on the sign of the dimensionful mass parameter, the two-point scaling functions either decay monotonously or in an oscillatory way towards zero.

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

    Directory of Open Access Journals (Sweden)

    Fazel Mohammadi-Moghadam

    2013-01-01

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

  4. Application of Glycyrrhiza glabra root as a novel adsorbent in the removal of toluene vapors: equilibrium, kinetic, and thermodynamic study.

    Science.gov (United States)

    Mohammadi-Moghadam, Fazel; Amin, Mohammad Mehdi; Khiadani Hajian, Mehdi; Momenbeik, Fariborz; Nourmoradi, Heshmatollah; Hatamipour, Mohammad Sadegh

    2013-01-01

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

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

    Science.gov (United States)

    Mohammadi-Moghadam, Fazel; Amin, Mohammad Mehdi; Khiadani (Hajian), Mehdi; Momenbeik, Fariborz; Nourmoradi, Heshmatollah; Hatamipour, Mohammad Sadegh

    2013-01-01

    The aim of this paper is to investigate the removal of toluene from gaseous solution through Glycyrrhiza glabra root (GGR) as a waste material. The batch adsorption experiments were conducted at various conditions including contact time, adsorbate concentration, humidity, and temperature. The adsorption capacity was increased by raising the sorbent humidity up to 50 percent. The adsorption of toluene was also increased over contact time by 12 h when the sorbent was saturated. The pseudo-second-order kinetic model and Freundlich model fitted the adsorption data better than other kinetic and isotherm models, respectively. The Dubinin-Radushkevich (D-R) isotherm also showed that the sorption by GGR was physical in nature. The results of the thermodynamic analysis illustrated that the adsorption process is exothermic. GGR as a novel adsorbent has not previously been used for the adsorption of pollutants. PMID:23554821

  6. Phase equilibrium in argon films stabilized by homogeneous surfaces and thermodynamics of two-stage melting transition

    Energy Technology Data Exchange (ETDEWEB)

    Ustinov, E. A., E-mail: eustinov@mail.wplus.net [Ioffe Physical Technical Institute, 26 Polytechnicheskaya, St. Petersburg 194021 (Russian Federation)

    2014-02-21

    Freezing of gases adsorbed on open surfaces (e.g., graphite) and in narrow pores is a widespread phenomenon which is a subject of a large number of publications. Modeling of the gas/liquid–solid transition is usually accomplished with a molecular simulation technique. However, quantitative analysis of the gas/liquid–solid coexistence and thermodynamic properties of the solid layer still encounters serious difficulties. This is mainly due to the effect of simulation box size on the lattice constant. Since the lattice constant is a function of loading and temperature, once the ordering transition has occurred, the simulation box size must be corrected in the course of simulation according to the Gibbs–Duhem equation. A significant problem is also associated with accurate prediction of the two-dimensional liquid–solid coexistence because of a small difference in densities of coexisting phases. The aim of this study is thermodynamic analysis of the two-dimensional phase coexistence in systems involving crystal-like free of defects layers in narrow slit pores. A special attention was paid to the determination of triple point temperatures. It is shown that intrinsic properties of argon monolayer adsorbed on the graphite surface are similar to those of isolated monolayer accommodated in the slit pore having width of two argon collision diameters. Analysis of the latter system is shown to be clearer and less time-consuming than the former one, which has allowed for explanation of the experimentally observed two-stage melting transition of argon monolayer on graphite without invoking the periodic surface potential modulation and orientational transition.

  7. 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…

  8. On the 2D-transition, hysteresis and thermodynamic equilibrium of Kr adsorption on a graphite surface.

    Science.gov (United States)

    Diao, Rui; Fan, Chunyan; Do, D D; Nicholson, D

    2015-12-15

    The adsorption and desorption of Kr on graphite at temperatures in the range 60-88K, was systematically investigated using a combination of several simulation techniques including: Grand Canonical Monte Carlo (GCMC), Canonical kinetic-Monte Carlo (C-kMC) and the Mid-Density Scheme (MDS). Particular emphasis was placed on the gas-solid, gas-liquid and liquid-solid 2D phase transitions. For temperatures below the bulk triple point, the transition from a 2D-liquid-like monolayer to a 2D-solid-like state is manifested as a sub-step in the isotherm. A further increase in the chemical potential leads to another rearrangement of the 2D-solid-like state from a disordered structure to an ordered structure that is signalled by (1) another sub-step in the monolayer region and (2) a spike in the plot of the isosteric heat versus density at loadings close to the dense monolayer coverage concentration. Whenever a 2D transition occurs in a grand canonical isotherm it is always associated with a hysteresis, a feature that is not widely recognised in the literature. We studied in details this hysteresis with the analysis of the canonical isotherm, obtained with C-kMC, which exhibits a van der Waals (vdW) type loop with a vertical segment in the middle. We complemented the hysteresis loop and the vdW curve with the analysis of the equilibrium transition obtained with the MDS, and found that the equilibrium transition coincides exactly with the vertical segment of the C-kMC isotherm, indicating the co-existence of two phases at equilibrium. We also analysed adsorption at higher layers and found that the 2D-coexistence is also observed, provided that the temperature is well below the triple point. Finally the 2D-critical temperatures were obtained for the first three layers and they are in good agreement with the experimental data in the literature.

  9. Non-local modeling of materials

    DEFF Research Database (Denmark)

    Niordson, Christian Frithiof

    2002-01-01

    Numerical studies of non-local plasticity effects on different materials and problems are carried out. Two different theories are used. One is of lower order in that it retains the structure of a conventional plasticity boundary value problem, while the other is of higher order and employs higher...... order stresses as work conjugates to higher order strains and uses higher order boundary conditions. The influence of internal material length parameters is studied, and the effects of higher order boundary conditions are analyzed. The focus of the thesis is on metal-matrix composites, and non...

  10. Uncertainty, non-locality and Bell's inequality

    CERN Document Server

    Pati, A K

    1998-01-01

    We derive a Bell-like inequality involving all correlations in local observables with uncertainty free states and show that the inequality is violated in quantum mechanics for EPR and GHZ states. If the uncertainties are allowed in local observables then the statistical predictions of hidden variable theory is well respected in quantum world. We argue that the uncertainties play a key role in understanding the non-locality issues in quantum world. Thus we can not rule out the possibility that a local, realistic hidden variable theory with statistical uncertainties in the observables might reproduce all the results of quantum theory.

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

    Directory of Open Access Journals (Sweden)

    R. Bhaumik

    2012-01-01

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

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

    Science.gov (United States)

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

    2015-01-01

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

  13. Nested Markov chain Monte Carlo sampling of a density functional theory potential: equilibrium thermodynamics of dense fluid nitrogen.

    Science.gov (United States)

    Coe, Joshua D; Sewell, Thomas D; Shaw, M Sam

    2009-08-21

    An optimized variant of the nested Markov chain Monte Carlo [n(MC)(2)] method [J. Chem. Phys. 130, 164104 (2009)] is applied to fluid N(2). In this implementation of n(MC)(2), isothermal-isobaric (NPT) ensemble sampling on the basis of a pair potential (the "reference" system) is used to enhance the efficiency of sampling based on Perdew-Burke-Ernzerhof density functional theory with a 6-31G(*) basis set (PBE6-31G(*), the "full" system). A long sequence of Monte Carlo steps taken in the reference system is converted into a trial step taken in the full system; for a good choice of reference potential, these trial steps have a high probability of acceptance. Using decorrelated samples drawn from the reference distribution, the pressure and temperature of the full system are varied such that its distribution overlaps maximally with that of the reference system. Optimized pressures and temperatures then serve as input parameters for n(MC)(2) sampling of dense fluid N(2) over a wide range of thermodynamic conditions. The simulation results are combined to construct the Hugoniot of nitrogen fluid, yielding predictions in excellent agreement with experiment.

  14. Breadnut peel as a highly effective low-cost biosorbent for methylene blue: Equilibrium, thermodynamic and kinetic studies

    Directory of Open Access Journals (Sweden)

    Linda B.L. Lim

    2017-05-01

    Full Text Available This work reports the potential use of peel of breadnut, Artocarpus camansi, as an effective low-cost biosorbent for the removal of methylene blue (MB. Oven dried A. camansi peel (ACP, which had a point of zero charge at pH = 4.8, showed maximum biosorption capacity which was far superior to most literature reported fruit biomasses, including samples that have been activated. Isotherm studies on biosorption of MB onto ACP gave a maximum biosorption capacity of 409 mg g−1. The Langmuir model was found to give the best fit among various isotherm models investigated and error analyses performed. Kinetics studies were fast with 50% dye being removed in less than 8 min from a 50 mg L−1 dye solution and further, kinetics followed the pseudo second order. Thermodynamic studies indicated that the biosorption process was both spontaneous and exothermic. Fourier transform infrared (FT-IR of ACP before and after MB adsorption was investigated. It can be concluded that oven dried breadnut peel is a highly promising low-cost biosorbent with great potential for the removal of MB.

  15. Removal of Methylene Blue from Aqueous Solution Using Agricultural Residue Walnut Shell: Equilibrium, Kinetic, and Thermodynamic Studies

    Directory of Open Access Journals (Sweden)

    Ranxiao Tang

    2017-01-01

    Full Text Available Walnut shell (WS, as an economic and environmental-friendly adsorbent, was utilized to remove methylene blue (MB from aqueous solutions. The effects of WS particle size, solution pH, adsorbent dosage and contact time, and concentration of NaCl on MB removal were systematically investigated. Under the optimized conditions (i.e., contact time ~ 2 h, pH ~ 6, particle size ~ 80 mesh, dye concentration 20 mg/L, and 1.25 g/L adsorbent, the removal percentages can achieve ~97.1%, indicating WS was a promising absorbent to remove MB. Other supplementary experiments, such as Fourier transform infrared spectroscopy (FTIR, dynamic light scattering (DLS, and Brunauer-Emmett-Teller (BET method, were also employed to understand the adsorption mechanisms. FTIR confirmed that the successful adsorption of MB on WS particles was through functional groups of WS. Using DLS method, the interactions between WS particles and dyes under various pH were investigated, which can be ascribed to the electrostatic forces. Kinetic data can be well fitted by the pseudo-second-order model, indicating a chemical adsorption. The adsorption isotherms were well described by both Langmuir and Freundlich models. Dubinin-Radushkevich model also showed that the adsorption process was a chemical adsorption. Thermodynamic data indicated that the adsorption was spontaneous, exothermic, and favorable at room temperature.

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

    Directory of Open Access Journals (Sweden)

    Susan Azizi

    2017-06-01

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

  17. ADSORPTION CHARACTERIZATION OF CO(II IONS ONTO CHEMICALLY TREATED QUERCUS COCCIFERA SHELL: EQUILIBRIUM, KINETIC AND THERMODYNAMIC STUDIES

    Directory of Open Access Journals (Sweden)

    M. Hamdi Karaoglu

    2011-04-01

    Full Text Available Quercus coccifera shell (QCS, a relatively abundant and inexpensive material, is currently being investigated as an adsorbent to remove cobalt(II from water. Before the adsorption experiments, QCS was subjected to chemical treatment to provide maximum surface area. Then, the kinetics and adsorption mechanism of Co(II ions on QCS were studied using different parameters such as adsorbent dosage, initial concentration, temperature, contact time, and solution pH. The loaded metals could be desorbed effectively with dilute hydrochloric acid, nitric acid, and 0.1 M EDTA. The Langmuir and Freundlich models were used to describe the uptake of cobalt on QCS. The equilibrium adsorption data were better fitted to Langmuir adsorption isotherm model. The maximum adsorption capacity (qm of QCS for Co(II was 33 mg g-1. Various kinetic models were used to describe the adsorption process. The adsorption followed pseudo second-order kinetic model. The intraparticle diffusion was found to be the rate-limiting step in the adsorption process. The diffusion coefficients were calculated and found to be in the range of 3.11×10−6 to 168.78×10−6 cm2s-1. The negative DH* value indicated exothermic nature of the adsorption.

  18. Atomistic study of the thermodynamic equilibrium of nano-sized helium cavities in {beta}SiC

    Energy Technology Data Exchange (ETDEWEB)

    Couet, Adrien [CEA-Saclay, DEN/DMN/SRMP, 91991 Gif-sur-Yvette (France); Crocombette, Jean-Paul, E-mail: jpcrocombette@cea.f [CEA-Saclay, DEN/DMN/SRMP, 91991 Gif-sur-Yvette (France); Chartier, Alain [CEA-Saclay, DEN/DPC/SCP, 91191 Gif-sur-Yvette (France)

    2010-09-01

    The estimation of the number of inert gas atoms contained at equilibrium in microscale bubbles in a solid usually relies on a well-known formula equilibrating the internal pressure of He to the surface energy of the bubble. This approach evidences a strong variation with temperature of He content for a given bubble. At the opposite, at the Angstrom scale, ab initio calculations for He contained in vacancy assemblies neglect temperature effects. In this work, empirical potential molecular dynamics simulations are used to study, in the case of helium inserted in cubic silicon carbide, the variation of the He content of sub-nanoscale cavities with temperature. To do so free energy for He atoms inserted in cavities made of a few vacancies (up to 29) are calculated. One then evidences the existence of a sub-surface segregation in interstitial sites close to the surface of the cavity. The variation of the He content with temperature is observed to be negligible at the nanoscale, thus validating the ab initio approach.

  19. Adsorption of Chromium Ion by Acid Activated Low Cost Carbon-Kinetic, Mechanistic, Thermodynamic and Equilibrium Studies

    Directory of Open Access Journals (Sweden)

    S. Arivoli

    2008-01-01

    Full Text Available A carbonaceous adsorbent prepared from an indigenous waste by acid treatment was tested for its efficiency in removing chromium ion. The parameters studied include agitation time, initial chromium ion concentration, carbon dose, pH and temperature. The adsorption followed first order reaction equation and the rate is mainly controlled by intra-particle diffusion. Freundlich and Langmuir isotherm models were applied to the equilibrium data. The adsorption capacity (Qm obtained from the Langmuir isotherm plots were 27.40, 26.06, 26.06 and 26.17 mg/g respectively at an initial pH of 7.0 at 30, 40, 50 and 60°C. The temperature variation study showed that the chromium ion adsorption is endothermic and spontaneous with increased randomness at the solid solution interface. Significant effect on adsorption was observed on varying the pH of the chromium ion solutions. Almost 70% removal of chromium ion was observed at 60°C. The Langmuir and Freundlich isotherms obtained, positive ∆H0 value, pH dependent results and desorption of dye in mineral acid suggest that the adsorption of chromium ion on PDC involves physisorption mechanism.

  20. Kinetic, Mechanistic, Thermodynamic and Equilibrium Studies on the Adsorption of Rhodamine B by Acid Activated Low Cost Carbon

    Directory of Open Access Journals (Sweden)

    S. Arivoli

    2008-01-01

    Full Text Available A carbonaceous adsorbent prepared from an indigenous waste by acid treatment was tested for its efficiency in removing Rhodamine B (RDB. The parameters studied include agitation time, initial dye concentration, carbon dose, pH and temperature. The adsorption followed first order reaction equation and the rate is mainly controlled by intra-particle diffusion. Freundlich and Langmuir isotherm models were applied to the equilibrium data. The adsorption capacity (Qm obtained from the Langmuir isotherm plots were 51.546, 47.236, 44.072 and 41.841 mg/g respectively at an initial pH of 7.0 at 30, 40, 50 and 60°C. The temperature variation study showed that the Rhodamine B adsorption is endothermic and spontaneous with increased randomness at the solid solution interface. Significant effect on adsorption was observed on varying the pH of the Rhodamine B solutions. Almost 90% removal of Rhodamine B was observed at 60°C. The Langmuir and Freundlich isotherms obtained, positive ΔH0 value, pH dependent results and desorption of dye in mineral acid suggest that the adsorption of Rhodamine B on PSC involves physisorption mechanism.

  1. Biosorptive uptake of arsenic(V) by steam activated carbon from mung bean husk: equilibrium, kinetics, thermodynamics and modeling

    Science.gov (United States)

    Mondal, Sandip; Aikat, Kaustav; Halder, Gopinath

    2017-07-01

    The present investigation emphasizes on the biosorptive removal of toxic pentavalent arsenic from water using steam activated carbon prepared from mung bean husk (SAC-MBH). Characterization of the synthesized sorbent was done using different instrumental techniques, i.e., SEM, BET and point of zero charge. Sorptive uptake of As(V) over steam activated MBH as a function of pH (3-9), agitation speed (40-200 rpm), dosage (50-1000 mg) and temperature (298-313 K) was studied by batch process at arsenic concentration of 2 mg L-1. Lower pH increases the arsenic removal over the pH range of 3-9. Among three adsorption isotherm models examined, Langmuir model was observed to show superior results over Freundlich model. The mean sorption energy (E) estimated by Dubinin-Radushkevich model suggested that the process of adsorption was chemisorption. Thermodynamic parameters confer that the sorption process was spontaneous, exothermic and feasible in nature. The pseudo-second-order rate kinetics of arsenic gave better correlation coefficients as compared to pseudo-first-order kinetics equation. Three process parameters, viz. adsorbent dosage, agitation speed and pH were opted for optimizing As(V) elimination using central composite design matrix of response surface methodology (RSM). The identical design setup was used for artificial neural network (ANN) for comparing its prediction capability with RSM towards As(V) removal. Maximum arsenic removal was observed to be 98.75% at sorbent dosage 0.75 gm L-1, pH 3.0, agitation speed 160 rpm and temperature 308 K. The study concluded that SAC-MBH could be a competent adsorbent for As(V) removal and ANN model was better in arsenic removal predictability results than RSM model.

  2. 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.

  3. Removal of Reactive Red 198 from aqueous solution by combined method multi-walled carbon nanotubes and zero-valent iron:Equilibrium, kinetics, and thermodynamic

    Institute of Scientific and Technical Information of China (English)

    Sudabeh Pourfadakari; Nader Yousefi; Amir Hossein Mahvi

    2016-01-01

    Dyes often include toxic, carcinogenic compounds and are harmful to humans' health. Therefore, removal of dyes from textile industry wastewater is essential. The present study aimed to evaluate the efficiency of the combina-tion of zero valent iron (ZVI) powder and multi-walled carbon nanotubes (MWCNTs) in the removal of Reactive Red 198 (RR198) dye from aqueous solution. This applied research was performed in a batch system in the lab-oratory scale. This study investigated the effect of various factors influencing dye removal, including contact time, pH, adsorbent dose, iron powder dose, initial dye concentration, and temperature. The equilibrium adsorption data were analyzed using three common adsorption models:Langmuir, Freundlich and Temkin. Besides, kinetic and thermodynamic parameters were used to establish the adsorption mechanism. The results showed, in pH=3, contact time=100 min, ZVI dose=5000 mg·L−1, and MWCNTs dose=600 mg·L−1 in 100 mg·L−1 dye con-centration, the adsorption efficiency increased to 99.16%. Also, adsorption kinetics was best described by the pseudo-second-order model. Equilibrium data fitted well with the Freundlich isotherm (R2=0.99). The negative values ofΔG0 and the positive value ofΔH0 (91.76) indicate that the RR198 adsorption process is spontaneous and endothermic. According to the results, the combination of MWCNTs and ZVI was highly efficient in the re-moval of azo dyes.

  4. Experimental studies on equilibrium adsorption isosteres and determination of the thermodynamic quantities of polar media on alumina Al2O3

    Directory of Open Access Journals (Sweden)

    Yonova Albena

    2017-03-01

    Full Text Available The present work is a revieif of theoretical and experimental study on the adsorption performance of the adsorbent Alumina (Al2O3 used in the adsorption system. An experimental investigation on the equilibrium adsorption isosteres at low pressure (< 1 atm of working pairs Al2O3/H2O and Al2O3/C2H6O2 is carried out. The isovolume measurement method is adopted in the test setup to directly measure the saturated vapor pressures of working pairs at vapor-liquid equilibrium (dG=0 and dμi=0. Quantity adsorbed is determined from pressure, volume and temperature using gas law. The isosteric heat of adsorption is calculated from the slope of the plot of lnP versus 1/T different amounts of adsorbate onto adsorbent as follows: 0,01 vol% Al2O3/H2O; 0,03 vol% Al2O3/H2O; 0,1 vol% Al2O3/H2O; 0,01 vol% Al2O3/C2H6O2; 0,03 vol% Al2O3/C2H6O2; 0,1 vol% Al2O3/C2H6O2. This study shows that adsorption working pair Al2O3 C2H6O2 has better adsorption performances than those of the A2O3/H2O. Surface acidity! is a most important property! far both adsorption and catalysis and therefore is examined structure of active sites of alumina surface. Thermodynamic parameters such as isosteric heat of adsorption, isosteric enthalpy and entropy of adsorption are critical design variables in estimating the performance and predicting the mechanism of an adsorption process and are also one of the basic requirements for the characterization and optimization of an adsorption process

  5. 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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-01-15

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

  7. Adsorption of Zn{sup 2+} ions onto NaA and NaX zeolites: Kinetic, equilibrium and thermodynamic studies

    Energy Technology Data Exchange (ETDEWEB)

    Nibou, D., E-mail: dnibou@yahoo.fr [Laboratoire des Sciences et Genie des Materiaux, Universite des Sciences et de la Technologie Houari Boumediene, B.P. 32, El-Alia, Bab-Ezzouar, Alger (Algeria); Mekatel, H.; Amokrane, S. [Laboratoire des Sciences et Genie des Materiaux, Universite des Sciences et de la Technologie Houari Boumediene, B.P. 32, El-Alia, Bab-Ezzouar, Alger (Algeria); Barkat, M. [Centre de Recherche Nucleaire de Draria, B.P. 43, 16003 Draria, Alger (Algeria); Trari, M. [Laboratoire de stockage et de Valorisation des Energies Renouvelables, Universite des Sciences et de la Technologie Houari Boumediene, B.P. 32, El-Alia, Bab-Ezzouar, Alger (Algeria)

    2010-01-15

    The adsorption of Zn{sup 2+} onto NaA and NaX zeolites was investigated. The samples were synthesized according to a hydrothermal crystallization using aluminium isopropoxide (Al[OCH(CH{sub 3}){sub 2}]{sub 3}) as a new alumina source. The effects of pH, initial concentration, solid/liquid ratio and temperature were studied in batch experiments. The Freundlich and the Langmuir models were applied and the adsorption equilibrium followed Langmuir adsorption isotherm. The uptake distribution coefficient (K{sub d}) indicated that the Zn{sup 2+} removal was the highest at minimum concentration. Thermodynamic parameters were calculated. The negative values of standard enthalpy of adsorption revealed the exothermic nature of the adsorption process whereas the negative activation entropies reflected that no significant change occurs in the internal structure of the zeolites solid matrix during the sorption of Zn{sup 2+}. The negative values of Gibbs free energy were indicative of the spontaneity of the adsorption process. Analysis of the kinetic and rate data revealed that the pseudo second-order sorption mechanism is predominant and the intra particle diffusion was the determining step for the sorption of zinc ions. The obtained optimal parameters have been applied to wastewater from the industrial zone (Algeria) in order to remove the contained zinc effluents.

  8. Experimental studies on equilibrium adsorption isosteres and determination of the thermodynamic quantities of polar media on alumina Al2O3

    Science.gov (United States)

    Yonova, Albena

    2017-03-01

    The present work is a revieif of theoretical and experimental study on the adsorption performance of the adsorbent Alumina (Al2O3) used in the adsorption system. An experimental investigation on the equilibrium adsorption isosteres at low pressure (law. The isosteric heat of adsorption is calculated from the slope of the plot of lnP versus 1/T different amounts of adsorbate onto adsorbent as follows: 0,01 vol% Al2O3/H2O; 0,03 vol% Al2O3/H2O; 0,1 vol% Al2O3/H2O; 0,01 vol% Al2O3/C2H6O2; 0,03 vol% Al2O3/C2H6O2; 0,1 vol% Al2O3/C2H6O2. This study shows that adsorption working pair Al2O3 C2H6O2 has better adsorption performances than those of the A2O3/H2O. Surface acidity! is a most important property! far both adsorption and catalysis and therefore is examined structure of active sites of alumina surface. Thermodynamic parameters such as isosteric heat of adsorption, isosteric enthalpy and entropy of adsorption are critical design variables in estimating the performance and predicting the mechanism of an adsorption process and are also one of the basic requirements for the characterization and optimization of an adsorption process

  9. Removal of Pb(II) ions from aqueous solution by a waste mud from copper mine industry: equilibrium, kinetic and thermodynamic study.

    Science.gov (United States)

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

    2009-07-30

    The objective of this study was to assess the adsorption potential of a waste mud (WM) for the removal of lead (Pb(II)) ions from aqueous solutions. The WM was activated with NaOH in order to increase its adsorption capacity. Adsorption studies were conducted in a batch system as a function of solution pH, contact time, initial Pb(II) concentration, activated-waste mud (a-WM) concentration, temperature, etc. Optimum pH was specified as 4.0. The adsorption kinetic studies indicated that the overall adsorption process was best described by pseudo-second-order kinetics. The equilibrium adsorption capacity of a-WM was obtained by using Langmuir and Freundlich isotherm models and both models fitted well. Adsorption capacity for Pb(II) was found to be 24.4 mg g(-1) for 10 g L(-1) of a-WM concentration. Thermodynamic parameters including the Gibbs free energy (Delta G degrees), enthalpy (Delta H degrees), and entropy (DeltaS degrees) indicated that the adsorption of Pb(II) ions on the a-WM was feasible, spontaneous and endothermic, at temperature range of 0-40 degrees C. Desorption studies were carried out successfully with diluted HCl solutions. The results indicate that a-WM can be used as an effective and no-cost adsorbent for the treatment of industrial wastewaters contaminated with Pb(II) ions.

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

    Science.gov (United States)

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

    2015-04-09

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

  11. Adsorption of methylene blue onto activated carbon produced from tea (Camellia sinensis L.) seed shells:kinetics, equilibrium, and thermodynamics studies

    Institute of Scientific and Technical Information of China (English)

    Jun-jie GAO; Ye-bo QIN; Tao ZHOU; Dong-dong CAO; Ping XU; Danielle HOCHSTETTER; Yue-fei WANG

    2013-01-01

    Tea (Camellia sinensis L.) seed shells,the main byproduct of the manufacture of tea seed oil,were used as precursors for the preparation of tea activated carbon (TAC) in the present study.A high yield (44.1%) of TAC was obtained from tea seed shells via a one-step chemical method using ZnCI2 as an agent.The Brunauer-Emmett-Teller (BET) surface area and the total pore volumes of the obtained TAC were found to be 1 530.67 mg2/g and 0.782 6 cm3/g,respectively.The equilibrium adsorption results were complied with Langmuir isotherm model and its maximum monolayer adsorption capacity was 324.7 mg/g for methylene blue.Adsorption kinetics studies indicated that the pseudosecond-order model yielded the best fit for the kinetic data.An intraparticle diffusion model suggested that the intraparticle diffusion was not the only rate-controlling step.Thermodynamics studies revealed the spontaneous and exothermic nature of the sorption process.These results indicate that tea seed shells could be utilized as a renewable resource to develop activated carbon which is a potential adsorbent for methylene blue.

  12. Removal of hazardous azopyrazole dye from an aqueous solution using rice straw as a waste adsorbent: Kinetic, equilibrium and thermodynamic studies.

    Science.gov (United States)

    El-Bindary, Ashraf A; El-Sonbati, Adel Z; Al-Sarawy, Ahmad A; Mohamed, Khaled S; Farid, Mansour A

    2015-02-05

    In this research, activated carbonmade from rice straw (ACRS) was synthesized simply by a low cost and nontoxic procedure and used for the adsorption of hazardous azopyrazole dye. The effect of different variables in the batch method as a function of solution pH, contact time, concentration of adsorbate, adsorbent dosage and temperature were investigated and optimal experimental conditions were ascertaine. Surface modification of ACRS using scanning electron microscopy (SEM) was obtained. More than 75% removal efficiency was obtained within 75min at adsorbent dose of 0.5g for initial dye concentration of 30-100mgL(-1) at pH 3. The experimental equilibrium data were tested by the isotherm models namely, Langmuir and Freundlich adsorption and the isotherm constants were determined. The kinetic data obtained with different initial concentration and temperature were analyzed using a pseudo-first-order and pseudo-second-order equations. The activation energy of adsorption was also evaluated and found to be +13.25kJmol(-1) indicating that the adsorption is physisorption. The thermodynamics of the adsorption indicated spontaneous and exothermic nature of the process. The results indicate that ACRS could be employed as low-cost material for the removal of acid dyes from aqueous solution.

  13. Kinetic modeling, equilibrium isotherm and thermodynamic studies on a batch adsorption of anionic dye onto eco-friendly dried Carpobrotus edulis plant

    Science.gov (United States)

    Aziam, R.; Chiban, M.; Eddaoudi, H.; Soudani, A.; Zerbet, M.; Sinan, F.

    2017-04-01

    In the present study, a low-cost bio-adsorbent is developed from the naturally and abundantly available dried Mediterranean plant which is biodegradable. The bio-adsorbent was characterized by Fourier transform infrared spectroscopy (FTIR) and point of zero charge (PZC). A study on the adsorption kinetics and isotherms was performed applying the optimized conditions. The equilibrium data for the adsorption of acid blue 113 on dried plant is tested with various adsorption isotherm models such as Langmuir, Freundlich, Temkin and Dubinin-Radushkevich equation. The Langmuir isotherm model is found to be the most suitable one for the acid blue 113 (AB113) adsorption using dried C. edulis plant and the theoretical maximum adsorption capacity obtained with the application of Langmuir isotherm model is 8.2 mg.g-1 at room temperature. The adsorption process follows the second-order kinetics and the corresponding rate constants are obtained. The thermodynamic parameters suggest that the adsorption process is spontaneous and exothermic nature. It can be concluded that the dried C. edulis adsorbent studied has good perspective to be used as adsorbent material in anionic dyes removal from industry effluents.

  14. Synthesis and Properties of Fe3O4-Activated Carbon Magnetic Nanoparticles for Removal of Aniline from Aqueous Solution: Equilibrium, Kinetic and Thermodynamic Studies

    Directory of Open Access Journals (Sweden)

    Babak Kakavandi

    2013-02-01

    Full Text Available In this study, powder activated carbon (PAC and magnetic nanoparticles of iron (III oxide were used for synthesis of Fe3O4-activated carbon magnetic nanoparticles (AC-Fe3O4 MNPs as an adsorbent for the removal of aniline. The characteristics of adsorbent were evaluated by SEM, TEM, XRD and BET. Also, the impact of different parameters such as pH, contact time, adsorbent dosage, aniline initials concentration and solution temperature were studied. The experimental data investigated by Langmuir and Freundlich adsorption isotherms and two models kinetically of pseudo first-order and pseudo second-order. The results indicated that the adsorption followed Langmuir and pseudo second-order models with correlation r2 > 0.98 and r2 > 0.99, respectively. The equilibrium time was obtained after 5 h. According to Langmuir model, the maximum adsorption capacity was 90.91 mg/g at pH = 6, and 20°C. The thermodynamic parameters indicated that adsorption of aniline on magnetic activated carbon was exothermic and spontaneous. This synthesized AC-Fe3O4 MNPs due to have advantages such as easy and rapid separation from solution could be applied as an adsorbent effective for removal of pollutants such as aniline from water and wastewater

  15. Synthesis and properties of Fe3O4-activated carbon magnetic nanoparticles for removal of aniline from aqueous solution: equilibrium, kinetic and thermodynamic studies.

    Science.gov (United States)

    Kakavandi, Babak; Jonidi, Ahmad; Rezaei, Roshanak; Nasseri, Simin; Ameri, Ahmad; Esrafily, Ali

    2013-01-01

    In this study, powder activated carbon (PAC) and magnetic nanoparticles of iron (III) oxide were used for synthesis of Fe3O4-activated carbon magnetic nanoparticles (AC-Fe3O4 MNPs) as an adsorbent for the removal of aniline. The characteristics of adsorbent were evaluated by SEM, TEM, XRD and BET. Also, the impact of different parameters such as pH, contact time, adsorbent dosage, aniline initials concentration and solution temperature were studied. The experimental data investigated by Langmuir and Freundlich adsorption isotherms and two models kinetically of pseudo first-order and pseudo second-order. The results indicated that the adsorption followed Langmuir and pseudo second-order models with correlation r(2) > 0.98 and r(2) > 0.99, respectively. The equilibrium time was obtained after 5 h. According to Langmuir model, the maximum adsorption capacity was 90.91 mg/g at pH = 6, and 20°C. The thermodynamic parameters indicated that adsorption of aniline on magnetic activated carbon was exothermic and spontaneous. This synthesized AC-Fe3O4 MNPs due to have advantages such as easy and rapid separation from solution could be applied as an adsorbent effective for removal of pollutants such as aniline from water and wastewater.

  16. Optimization of Cr(VI biosorption onto Aspergillus niger using 3-level Box-Behnken design: Equilibrium, kinetic, thermodynamic and regeneration studies

    Directory of Open Access Journals (Sweden)

    Naba Kumar Mondal

    2017-06-01

    Full Text Available Heavy metal biosorption is an efficient technology for the decontamination of metal from industrial waste water. The present study focused on exploration of Aspergillus niger towards removal of Cr(VI from aqueous solution. The influence of different experimental parameters—initial pH, adsorbent dose, initial concentration, contact time, shaking speed, temperature, and their combined effect during Cr(VI adsorption—was investigated by means of response surface methodology based on four factorial Box–Behnken experimental design. Optimized values of initial Cr(VI concentration, pH, adsorbent dose, and contact time were found as 33.33 mg/L, 4.6, 1.0 g/L, and 48.45 min, respectively. A. niger showed the highest adsorption capacity 11.792 mg/g at initial pH 2.0. Equilibrium data fitted well to the Temkin and Freundlich isotherms. Cr(VI biosorption showed Pseudo-second order rate kinetics. The activation energy of the adsorption was estimated as 2.9 × 10−3 kJ/mol. Thermodynamics properties of the Cr(VI biosorption was spontaneous in nature. Desorption study showed that nearly 94% of the Cr(VI adsorbed on A. niger could be desorbed using 0.5 M EDTA.

  17. Preparation of titanate nanoflower for sorption of {sup 75}Se(IV) radioisotope from aqueous solution. Equilibrium, kinetic and thermodynamic studies

    Energy Technology Data Exchange (ETDEWEB)

    Abd El-Kader Sharaf El-Deen, Sahar El-Sayed; Allan, Karam Fatwhi; Holeil, Mohamed [Atomic Energy Authority, Inshas (Egypt). Dept. of Nuclear Chemistry; Abd El-Kader Sharaf El-Deen, Gehan El-Sayed [Atomic Energy Authority, Inshas (Egypt). Dept. of Radioactive Waste Treatment

    2015-07-01

    In this study, the adsorptive removal of selenium (IV) from aqueous solution by titanate nanoflower (TNF) was prepared via alkaline hydrothermal method. The morphology and crystal phase of the TNF were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscope (EDX), selected area electron diffraction (SAED), thermogravimetric analysis (TGA), fourier transform infrared spectroscopy (FTIR) and specific surface area. This study was conducted to determine the influence of various operating parameters such as pH, adsorbate weight, initial anion concentration, contact time and solution temperature on the adsorptive removal of selenium (IV). Equilibrium adsorption data were analyzed using Freundlich, Langmuir and Dubinin-Radushkevich (D-R) isotherm models. The results demonstrated that the adsorption was well described by the Langmuir adsorption isotherm with the maximum adsorption capacity up to 46.52 mg/g at pH 3.5. The adsorption of Se(IV) anions onto the surface of TNF may proceed through outer sphere electrostatic interactions and/or inner-sphere complexation interaction. The kinetic data indicated that the adsorption fit well with the pseudo-second-order kinetic model. The thermodynamic parameters implied that the adsorption process was spontaneous and endothermic in nature.

  18. Thermophysical properties of SF6-Cu mixtures at temperatures of 300-30 000 K and pressures of 0.01-1.0 MPa: part 1. Equilibrium compositions and thermodynamic properties considering condensed phases

    Science.gov (United States)

    Rong, Mingzhe; Zhong, Linlin; Cressault, Yann; Gleizes, Alain; Wang, Xiaohua; Chen, Feng; Zheng, Hao

    2014-11-01

    The equilibrium compositions and thermodynamic properties of SF6-Cu mixtures with copper proportions up to 50% are calculated as a function of temperature from 300 to 30 000 K and pressure from 0.01 to 1.0 MPa. The condensed phases and Debye-Hückel corrections are both taken into account. The influences of condensed phases, Debye-Hückel corrections, copper proportions and gas pressures on the composition and/or thermodynamic properties are discussed in detail under various conditions. Some results are tabulated for the modelling of SF6 arc plasmas contaminated by Cu.

  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. 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

  1. 藻蓝蛋白静态吸附平衡及热力学研究%Adsorption equilibrium and thermodynamic of c-phycocyanin

    Institute of Scientific and Technical Information of China (English)

    刘杨; 虞永蕾

    2011-01-01

    研究了钝顶螺旋藻中藻蓝蛋白在DEAE-Sephadex A-50离子交换树脂上的静态吸附平衡,考察了无机盐NaCl浓度和聚合物PEG6000质量分数,以及吸附温度对藻蓝蛋白静态吸附平衡的影响,以Langmuir和Freundlich吸附等温方程分别对不同条件下的吸附平衡数据进行拟合,并计算出吸附过程的热力学参数△G,△H和△S.研究表明:NaCl具有显著抑制藻蓝蛋白吸附的作用,而PEG具有明显促进藻蓝蛋白吸附的作用;Freundlich吸附等温方程对藻蓝蛋白的吸附平衡数据具有更好的拟合效果,并判定吸附过程为优惠吸附;在不同的吸附条件下,AG <0,且其绝对值小于20 k J/mol,表明吸附过程可自发进行并为物理吸附,△H>O,表明该吸附过程为吸热过程,△S>0,该吸附过程属于熵增过程.%The adsorption equilibrium of c-phycocyanin from Spirulina platensis on DEAE-Sephadex A-SO was studied. The effects of NaCl concentration and polymer PEG6000 mass fraction, and adsorption temperature on the adsorption equilibrium of c-phycocyanin were investigated. The adsorption data were fitted to the Langmuir and Freundlich equations, and the thermodynamic parameters such as AG, Aif and AS were calculated. The results imply that NaCl can decrease the adsorption while PEC can increase the adsorption. The experimental data can be well fitted by Freundlich equations and the adsorption is verified to be the optimal adsorption. Under the various adsorption conditions, Gibbs free energy change △G0 indicates that the process is endothermic and physical adsorption. The entropy change △S>0 indicates that the adsorption is an entropic increasing process.

  2. Thermodynamics Behavior of Germanium During Equilibrium Reactions between FeOx-CaO-SiO2-MgO Slag and Molten Copper

    Science.gov (United States)

    Shuva, M. A. H.; Rhamdhani, M. A.; Brooks, G. A.; Masood, S.; Reuter, M. A.

    2016-10-01

    The distribution ratio of germanium (Ge), L_{{Ge}}^{s/m} during equilibrium reactions between magnesia-saturated FeOx-CaO-SiO2 (FCS) slag and molten copper has been measured under oxygen partial pressures from 10-10 to 10-7 atm and at temperatures 1473 to 1623 K (1200 to 1350 °C). It was observed that the Ge distribution ratio increases with increasing oxygen partial pressure, and with decreasing temperature. It was also observed that the distribution ratio is strongly dependent on slag basicity. The distribution ratio was observed to increase with increasing optical basicity. At fixed CaO concentration in the slag, the distribution ratio was found to increase with increasing Fe/SiO2 ratio, tending to a plateau at L_{{Ge}}^{s/m} = 0.8. This behavior is consistent with the assessment of ionic bond fraction carried out in this study, and suggested the acidic nature of germanium oxide (GeO2) in the slag system studied. The characterisation results of the quenched slag suggested that Ge is present in the FeOx-CaO-SiO2-MgO slag predominantly as GeO2. At 1573 K (1300 °C) and p_{{{{O}}2 }} = 10-8 atm, the activity coefficient of GeO2 in the slag was calculated to be in the range of 0.24 to 1.50. The results from the current study suggested that less-basic slag, high operating temperature, and low oxygen partial pressure promote a low Ge distribution ratio. These conditions are desired for maximizing Ge recovery, for example, during pyrometallurgical processing of Ge-containing e-waste through secondary copper smelting. Overall, the thermodynamics data generated from this study can be used for process modeling purposes for improving recovery of Ge in primary and secondary copper smelting processes.

  3. The non-local content of quantum operations

    CERN Document Server

    Collins, D; Popescu, S; Collins, Daniel; Linden, Noah; Popescu, Sandu

    2000-01-01

    We show that quantum operations on multi-particle systems have a non-local content; this mirrors the non-local content of quantum states. We introduce a general framework for discussing the non-local content of quantum operations, and give a number of examples. Quantitative relations between quantum actions and the entanglement and classical communication resources needed to implement these actions are also described. We also show how entanglement can catalyse classical communication from a quantum action.

  4. Multipartite non-locality and entanglement signatures of a field-induced quantum phase transition

    Science.gov (United States)

    Batle, Josep; Alkhambashi, Majid; Farouk, Ahmed; Naseri, Mosayeb; Ghoranneviss, Mahmood

    2017-02-01

    Quantum correlation measures are limited in practice to a few number of parties, since no general theory is still capable of reaching the thermodynamic limit. In the present work we study entanglement and non-locality for a cluster of spins belonging to a compound that displays a magnetocaloric effect. A quantum phase transition (QPT) is induced by an external magnetic field B, in such a way that the corresponding quantum fluctuations are reproduced at a much smaller scale than the experimental outcomes, and then described by means of the aforementioned quantum measures.

  5. Braun-Le Chatelier principle in dissipative thermodynamics

    CERN Document Server

    Pavelka, Michal

    2016-01-01

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

  6. Incompressible turbulence as non-local field theory

    Indian Academy of Sciences (India)

    Mahendra K Verma

    2005-03-01

    It is well-known that incompressible turbulence is non-local in real space because sound speed is infinite in incompressible fluids. The equation in Fourier space indicates that it is non-local in Fourier space as well. However, the shell-to-shell energy transfer is local. Contrast this with Burgers equation which is local in real space. Note that the sound speed in Burgers equation is zero. In our presentation we will contrast these two equations using non-local field theory. Energy spectrum and renormalized parameters will be discussed.

  7. 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.

  8. Causal Set theory, non-locality and phenomenology

    CERN Document Server

    Belenchia, Alessio

    2015-01-01

    This proceeding is based on a talk prepared for the XIV Marcel Grossmann meeting. We review some results on causal set inspired non-local theories as well as work in progress concerning their phenomenology.

  9. Noether's theorem in non-local field theories

    CERN Document Server

    Krivoruchenko, M I

    2016-01-01

    Explicit expressions are constructed for a locally conserved vector current associated with a continuous internal symmetry and for energy-momentum and angular-momentum density tensors associated with the Poincar\\'e group in field theories with higher-order derivatives and in non-local field theories. An example of non-local charged scalar field equations with broken C and CPT symmetries is considered. For this case, we find simple analytical expressions for the conserved currents.

  10. Information theory and Thermodynamics

    OpenAIRE

    Kafri, Oded

    2006-01-01

    A communication theory for a transmitter broadcasting to many receivers is presented. In this case energetic considerations cannot be neglected as in Shannon theory. It is shown that, when energy is assigned to the information bit, information theory complies with classical thermodynamic and is part of it. To provide a thermodynamic theory of communication it is necessary to define equilibrium for informatics systems that are not in thermal equilibrium and to calculate temperature, heat, and ...

  11. A Systems-Theoretical Generalization of Non-Local Correlations

    Science.gov (United States)

    von Stillfried, Nikolaus

    Non-local correlations between quantum events are not due to a causal interaction in the sense of one being the cause for the other. In principle, the correlated events can thus occur simultaneously. Generalized Quantum Theory (GQT) formalizes the idea that non-local phenomena are not exclusive to quantum mechanics, e.g. due to some specific properties of (sub)atomic particles, but that they instead arise as a consequence of the way such particles are arranged into systems. Non-local phenomena should hence occur in any system which fulfils the necessary systems-theoretical parameters. The two most important parameters with respect to non-local correlations seem to be a conserved global property of the system as a whole and sufficient degrees of freedom of the corresponding property of its subsystems. Both factors place severe limitations on experimental observability of the phenomena, especially in terms of replicability. It has been suggested that reported phenomena of a so-called synchronistic, parapsychological or paranormal kind could be understood as instances of systems-inherent non-local correlations. From a systems-theoretical perspective, their phenomenology (including the favorable conditions for their occurrence and their lack of replicability) displays substantial similarities to non-local correlations in quantum systems and matches well with systems-theoretical parameters, thus providing circumstantial evidence for this hypothesis.

  12. Evidence of Non-local Chemical, Thermal and Gravitational Effects

    Directory of Open Access Journals (Sweden)

    Hu H.

    2007-04-01

    Full Text Available Quantum entanglement is ubiquitous in the microscopic world and manifests itself macroscopically under some circumstances. But common belief is that it alone cannot be used to transmit information nor could it be used to produce macroscopic non- local effects. Yet we have recently found evidence of non-local effects of chemical substances on the brain produced through it. While our reported results are under independent verifications by other groups, we report here our experimental findings of non-local chemical, thermal and gravitational effects in simple physical systems such as reservoirs of water quantum-entangled with water being manipulated in a remote reservoir. With the aids of high-precision instruments, we have found that the pH value, temperature and gravity of water in the detecting reservoirs can be non-locally affected through manipulating water in the remote reservoir. In particular, the pH value changes in the same direction as that being manipulated; the temperature can change against that of local environment; and the gravity apparently can also change against local gravity. These non-local effects are all reproducible and can be used for non-local signalling and many other purposes. We suggest that they are mediated by quantum entanglement between nuclear and/or electron spins in treated water and discuss the implications of these results.

  13. On the power of non-local boxes

    CERN Document Server

    Broadbent, A J

    2005-01-01

    A non-local box is a virtual device that has the following property: given that Alice inputs a bit at her end of the device and that Bob does likewise, it produces two bits, one at Alice's end and one at Bob's end, such that the XOR of the outputs is equal to the AND of the inputs. This box, inspired from the CHSH inequality, was first proposed by Popescu and Rohrlich to examine the question: given that a maximally entangled pair of qubits is non-local, why is it not maximally non-local? We believe that understanding the power of this box will yield insight into the non-locality of quantum mechanics. It was shown recently by Cerf, Gisin, Massar and Popescu, that this imaginary device is able to simulate correlations from any measurement on a singlet state. Here, we show that the non-local box can in fact do much more: through the simulation of the magic square pseudo-telepathy game and the Mermin-GHZ pseudo-telepathy game, we show that the non-local box can simulate quantum correlations that no entangled pair...

  14. Equilibrium statistical mechanics

    CERN Document Server

    Mayer, J E

    1968-01-01

    The International Encyclopedia of Physical Chemistry and Chemical Physics, Volume 1: Equilibrium Statistical Mechanics covers the fundamental principles and the development of theoretical aspects of equilibrium statistical mechanics. Statistical mechanical is the study of the connection between the macroscopic behavior of bulk matter and the microscopic properties of its constituent atoms and molecules. This book contains eight chapters, and begins with a presentation of the master equation used for the calculation of the fundamental thermodynamic functions. The succeeding chapters highlight t

  15. Thermodynamic Stability of Wormholes

    CERN Document Server

    Sajadi, S N

    2016-01-01

    In the context of GR, we study the thermodynamic stability of evolving Lorentzian wormholes at the apparent horizon. The average pressure of the anisotrropic components is considered as the pressure of the wormhole. According to the requirements of stable equilibrium in conventional thermodynamics, we calculate the heat capacity at constant pressure and Gibbs free energy and analyze the local and global thermodynamic stability of the wormhole.

  16. ISORROPIA II: a computationally efficient thermodynamic equilibrium model for K+─Ca²+─Mg²+─NH4+─Na+─SO4²-─NO3-─Cl-─H2O aerosols

    Directory of Open Access Journals (Sweden)

    C. Fountoukis

    2007-09-01

    Full Text Available This study presents ISORROPIA II, a thermodynamic equilibrium model for the K+–Ca2+–Mg2+–NH4+–Na+–SO42−–NO3−–Cl−–H2O aerosol system. A comprehensive evaluation of its performance is conducted against water uptake measurements for laboratory aerosol and predictions of the SCAPE2 thermodynamic module over a wide range of atmospherically relevant conditions. The two models agree well, to within 13% for aerosol water content and total PM mass, 16% for aerosol nitrate and 6% for aerosol chloride and ammonium. Largest discrepancies were found under conditions of low RH, primarily from differences in the treatment of water uptake and solid state composition. In terms of computational speed, ISORROPIA II was more than an order of magnitude faster than SCAPE2, with robust and rapid convergence under all conditions. The addition of crustal species does not slow down the thermodynamic calculations (compared to the older ISORROPIA code because of optimizations in the activity coefficient calculation algorithm. Based on its computational rigor and performance, ISORROPIA II appears to be a highly attractive alternative for use in large scale air quality and atmospheric transport models.

  17. Fundamental Research in Engineering Education. Development of Concept Questions and Inquiry-Based Activities in Thermodynamics and Heat Transfer: An Example for Equilibrium vs. Steady-State

    Science.gov (United States)

    Vigeant, Margot; Prince, Michael; Nottis, Katharyn

    2011-01-01

    This study examines the use of inquiry-based instruction to promote the understanding of critical concepts in thermodynamics and heat transfer. Significant research shows that students frequently enter our courses with tightly held misconceptions about the physical world that are not effectively addressed through traditional instruction. Students'…

  18. Formation and reactivity of a porphyrin iridium hydride in water: acid dissociation constants and equilibrium thermodynamics relevant to Ir-H, Ir-OH, and Ir-CH2- bond dissociation energetics.

    Science.gov (United States)

    Bhagan, Salome; Wayland, Bradford B

    2011-11-01

    Aqueous solutions of group nine metal(III) (M = Co, Rh, Ir) complexes of tetra(3,5-disulfonatomesityl)porphyrin [(TMPS)M(III)] form an equilibrium distribution of aquo and hydroxo complexes ([(TMPS)M(III)(D(2)O)(2-n)(OD)(n)]((7+n)-)). Evaluation of acid dissociation constants for coordinated water show that the extent of proton dissociation from water increases regularly on moving down the group from cobalt to iridium, which is consistent with the expected order of increasing metal-ligand bond strengths. Aqueous (D(2)O) solutions of [(TMPS)Ir(III)(D(2)O)(2)](7-) react with dihydrogen to form an iridium hydride complex ([(TMPS)Ir-D(D(2)O)](8-)) with an acid dissociation constant of 1.8(0.5) × 10(-12) (298 K), which is much smaller than the Rh-D derivative (4.3 (0.4) × 10(-8)), reflecting a stronger Ir-D bond. The iridium hydride complex adds with ethene and acetaldehyde to form organometallic derivatives [(TMPS)Ir-CH(2)CH(2)D(D(2)O)](8-) and [(TMPS)Ir-CH(OD)CH(3)(D(2)O)](8-). Only a six-coordinate carbonyl complex [(TMPS)Ir-D(CO)](8-) is observed for reaction of the Ir-D with CO (P(CO) = 0.2-2.0 atm), which contrasts with the (TMPS)Rh-D analog which reacts with CO to produce an equilibrium with a rhodium formyl complex ([(TMPS)Rh-CDO(D(2)O)](8-)). Reactivity studies and equilibrium thermodynamic measurements were used to discuss the relative M-X bond energetics (M = Rh, Ir; X = H, OH, and CH(2)-) and the thermodynamically favorable oxidative addition of water with the (TMPS)Ir(II) derivatives.

  19. Liquid-liquid equilibrium of water + PEG 8000 + magnesium sulfate or sodium sulfate aqueous two-phase systems at 35°C: experimental determination and thermodynamic modeling

    Directory of Open Access Journals (Sweden)

    B. D. Castro

    2005-09-01

    Full Text Available Liquid-liquid extraction using aqueous two-phase systems is a highly efficient technique for separation and purification of biomolecules due to the mild properties of both liquid phases. Reliable data on the phase behavior of these systems are essential for the design and operation of new separation processes; several authors reported phase diagrams for polymer-polymer systems, but data on polymer-salt systems are still relatively scarce. In this work, experimental liquid-liquid equilibrium data on water + polyethylene glycol 8000 + magnesium sulfate and water + polyethylene glycol 8000 + sodium sulfate aqueous two-phase systems were obtained at 35°C. Both equilibrium phases were analyzed by lyophilization and ashing. Experimental results were correlated with a mass-fraction-based NRTL activity coefficient model. New interaction parameters were estimated with the Simplex method. The mean deviations between the experimental and calculated compositions in both equilibrium phases is about 2%.

  20. Non-local magnetoresistance in YIG/Pt nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Goennenwein, Sebastian T. B., E-mail: goennenwein@wmi.badw.de; Pernpeintner, Matthias; Gross, Rudolf; Huebl, Hans [Walther-Meißner-Institut, Bayerische Akademie der Wissenschaften, Walther-Meißner-Str. 8, 85748 Garching (Germany); Nanosystems Initiative Munich (NIM), Schellingstraße 4, 80799 München (Germany); Physik-Department, Technische Universität München, James-Franck-Str. 1, 85748 Garching (Germany); Schlitz, Richard; Ganzhorn, Kathrin [Walther-Meißner-Institut, Bayerische Akademie der Wissenschaften, Walther-Meißner-Str. 8, 85748 Garching (Germany); Physik-Department, Technische Universität München, James-Franck-Str. 1, 85748 Garching (Germany); Althammer, Matthias [Walther-Meißner-Institut, Bayerische Akademie der Wissenschaften, Walther-Meißner-Str. 8, 85748 Garching (Germany)

    2015-10-26

    We study the local and non-local magnetoresistance of thin Pt strips deposited onto yttrium iron garnet. The local magnetoresistive response, inferred from the voltage drop measured along one given Pt strip upon current-biasing it, shows the characteristic magnetization orientation dependence of the spin Hall magnetoresistance. We simultaneously also record the non-local voltage appearing along a second, electrically isolated, Pt strip, separated from the current carrying one by a gap of a few 100 nm. The corresponding non-local magnetoresistance exhibits the symmetry expected for a magnon spin accumulation-driven process, confirming the results recently put forward by Cornelissen et al. [“Long-distance transport of magnon spin information in a magnetic insulator at room temperature,” Nat. Phys. (published online 14 September 2015)]. Our magnetotransport data, taken at a series of different temperatures as a function of magnetic field orientation, rotating the externally applied field in three mutually orthogonal planes, show that the mechanisms behind the spin Hall and the non-local magnetoresistance are qualitatively different. In particular, the non-local magnetoresistance vanishes at liquid Helium temperatures, while the spin Hall magnetoresistance prevails.

  1. 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

  2. Quantum theory is classical mechanics with non-local existence

    CERN Document Server

    Hegseth, John

    2009-01-01

    I propose a new and direct connection between classical mechanics and quantum mechanics where I derive the quantum mechanical propagator from a variational principle. This variational principle is Hamilton's modified principle generalized to allow many paths due to the non-local existence of particles in phase space. This principle allows a physical system to evolve non-locally in phase space while still allowing a representation that uses many classical paths. Whereas a point in phase space represents a classical system's state, I represent the state of a non-local system by a mixed trajectory. This formulation naturally leads to the transactional interpretation for resolving the paradoxes of the measurement problem. This principle also suggests a more flexible framework for formulating theories based on invariant actions and provides a single conceptual framework for discussing many areas of science.

  3. Generalized conservation laws in non-local field theories

    Science.gov (United States)

    Kegeles, Alexander; Oriti, Daniele

    2016-04-01

    We propose a geometrical treatment of symmetries in non-local field theories, where the non-locality is due to a lack of identification of field arguments in the action. We show that the existence of a symmetry of the action leads to a generalized conservation law, in which the usual conserved current acquires an additional non-local correction term, obtaining a generalization of the standard Noether theorem. We illustrate the general formalism by discussing the specific physical example of complex scalar field theory of the type describing the hydrodynamic approximation of Bose-Einstein condensates. We expect our analysis and results to be of particular interest for the group field theory formulation of quantum gravity.

  4. Generalised conservation laws in non-local field theories

    CERN Document Server

    Kegeles, Alexander

    2015-01-01

    We propose a geometrical treatment of symmetries in non-local field theories, where the non-locality is due to a lack of identification of field arguments in the action. We show that the existence of a symmetry of the action leads to a generalised conservation law, in which the usual conserved current acquires an additional non-local correction term, obtaining a generalisation of the standard Noether theorem. We illustrate the general formalism by discussing the specific physical example of complex scalar field theory of the type describing the hydrodynamic approximation of Bose-Einstein condensates. We expect our analysis and results to be of particular interest for the group field theory formulation of quantum gravity.

  5. (Chemical thermodynamics)

    Energy Technology Data Exchange (ETDEWEB)

    Mesmer, R.E.

    1990-09-12

    The purpose of this travel was for the traveler to participate in the 11th IUPAC International Conference on Chemical Thermodynamics and to present a paper of which he is co-author entitled The Transition from Strong-to-Weak Electrolyte Behavior Near the Critical Point of Water'' in the session on Solutions. The conference brought together nearly 500 scientists from around the world to discuss broad aspects of experimental thermodynamics and theoretical modeling. The traveler also visited the University of Karlsruhe to discuss current research with E.U. Franck and his collaborators. This institution has been for many years one of the leading centers for experimental studies on phase equilibrium and physical chemical studies especially on pure substances under the direction of Franck.

  6. Accelerating cosmologies from non-local higher-derivative gravity

    CERN Document Server

    Capozziello, Salvatore; Nojiri, Shin'ichi; Odintsov, Sergei D

    2008-01-01

    We study accelerating cosmological solutions of a general class of non-linear gravities which depend on Gauss-Bonnet and other higher derivative invariants. To achieve this goal a local formulation with auxiliary scalars for arbitrary higher-derivative non-local gravity is developed. It is demonstrated that non-local Gauss-Bonnet gravity can be reduced, in the local formulation, to a model of string-inspired scalar-Gauss-Bonnet gravity. A natural unification, in the theory here developed, of the early-time inflation epoch with a late-time acceleration stage can also be realized.

  7. Accelerating cosmologies from non-local higher-derivative gravity

    Energy Technology Data Exchange (ETDEWEB)

    Capozziello, Salvatore [Dipartimento di Scienze Fisiche, Universita di Napoli ' Federico II' , INFN Sez. di Napoli, Compl. Univ. di Monte S. Angelo, Edificio G, Via Cinthia, I-80126 Napoli (Italy); Elizalde, Emilio [Consejo Superior de Investigaciones Cientificas ICE/CSIC-IEEC, Campus UAB, Facultat de Ciencies, Torre C5-Parell-2a pl, E-08193 Bellaterra (Barcelona) (Spain); Nojiri, Shin' ichi [Department of Physics, Nagoya University, Nagoya 464-8602 (Japan)], E-mail: nojiri@phys.nagoya-u.ac.jp; Odintsov, Sergei D. [Institucio Catalana de Recerca i Estudis Avancats (ICREA) and Institut de Ciencies de l' Espai (IEEC-CSIC), Campus UAB, Facultat de Ciencies, Torre C5-Par-2a pl, E-08193 Bellaterra, Barcelona (Spain)

    2009-01-12

    We study accelerating cosmological solutions of a general class of non-linear gravities which depend on Gauss-Bonnet and other higher derivative invariants. To achieve this goal a local formulation with auxiliary scalars for arbitrary higher-derivative non-local gravity is developed. It is demonstrated that non-local Gauss-Bonnet gravity can be reduced, in the local formulation, to a model of string-inspired scalar-Gauss-Bonnet gravity. A natural unification, in the theory here developed, of the early-time inflation epoch with a late-time acceleration stage can also be realized.

  8. To the non-local theory of cold nuclear fusion.

    Science.gov (United States)

    Alexeev, Boris V

    2014-10-01

    In this paper, we revisit the cold fusion (CF) phenomenon using the generalized Bolzmann kinetics theory which can represent the non-local physics of this CF phenomenon. This approach can identify the conditions when the CF can take place as the soliton creation under the influence of the intensive sound waves. The vast mathematical modelling leads to affirmation that all parts of soliton move with the same velocity and with the small internal change of the pressure. The zone of the high density is shaped on the soliton's front. It means that the regime of the 'acoustic CF' could be realized from the position of the non-local hydrodynamics.

  9. Generalized non-local responses and higher harmonic retention in non-local polymerization driven diffusion model based simulations

    Science.gov (United States)

    Sheridan, J. T.; Kelly, J. V.; O'Brien, G.; Gleeson, M. R.; O'Neill, F. T.

    2004-12-01

    Non-local and non-linear models of photopolymer materials, which include diffusion effects, have recently received much attention in the literature. The material response is described as non-local as it is assumed that monomers are polymerized to form polymer chains and that these chains grow away from a point of initiation. The non-locality is defined in terms of a spatial non-local material response function. The material model is non-linear as a general non-linear material response to the incident light is included. Typically the numerical method of solution has involved retaining only up to four harmonics of the Fourier series of monomer concentration in the calculations. In this paper a general set of coupled first-order differential equations is derived which allow the inclusion of a higher number of harmonics. The resulting effect on the convergence of the algorithm, as the number of harmonics retained is increased, is investigated. Special care is taken to note the effect of physical parameters, i.e. the non-local material variance σ, the power-law degree k, and the rates of diffusion, D, and polymerization, F0.

  10. Thermodynamics of Biological Processes

    Science.gov (United States)

    Garcia, Hernan G.; Kondev, Jane; Orme, Nigel; Theriot, Julie A.; Phillips, Rob

    2012-01-01

    There is a long and rich tradition of using ideas from both equilibrium thermodynamics and its microscopic partner theory of equilibrium statistical mechanics. In this chapter, we provide some background on the origins of the seemingly unreasonable effectiveness of ideas from both thermodynamics and statistical mechanics in biology. After making a description of these foundational issues, we turn to a series of case studies primarily focused on binding that are intended to illustrate the broad biological reach of equilibrium thinking in biology. These case studies include ligand-gated ion channels, thermodynamic models of transcription, and recent applications to the problem of bacterial chemotaxis. As part of the description of these case studies, we explore a number of different uses of the famed Monod–Wyman–Changeux (MWC) model as a generic tool for providing a mathematical characterization of two-state systems. These case studies should provide a template for tailoring equilibrium ideas to other problems of biological interest. PMID:21333788

  11. Thermodynamic Simulation of Carbonate Cements-Water-Carbon Dioxide Equilibrium in Sandstone for Prediction of Precipitation/Dissolution of Carbonate Cements

    OpenAIRE

    Duan, Yiping; Feng, Mingshi; Zhong, Xinyan; Shang, Ruishu; Huang, Lihong

    2016-01-01

    Carbonate cements, such as calcite, dolomite, ferrocalcite and ankerite, play important roles in the formation of pores in sandstones: precipitation of carbonate cements modifies pores and inhibits compaction, while dissolution creates secondary pores. This work proposed a precipitation-dissolution model for carbonate cements-CO2-H2O system by means of ion equilibrium concentration ([M2+], M = Ca, Mg, Fe or Mn) with different factors, such as temperature, depth, pH, P CO 2 , variable rock com...

  12. Controlled perturbation of the thermodynamic equilibrium by microfluidic separation of porphyrin-based aggregates in a multi-component self-assembling system.

    Science.gov (United States)

    Helmich, Floris; Meijer, E W

    2013-03-04

    In a microfluidic H-cell, a multi-component self-assembled system is brought out-of-equilibrium by changing the bimodal composition of porphyrin stacks and pyridine-capped dimers. Driven by their different diffusivities, diffusion-controlled separation in methylcyclohexane reveals different compositions when detected in-line and off-line, which demonstrates the kinetic behaviour of this metastable system. The microfluidic technique also proves to be highly equipped to determine diffusion constants of the different assemblies.

  13. Non-local common cause explanations for EPR

    CERN Document Server

    Egg, Matthias

    2013-01-01

    The paper argues that a causal explanation of the correlated outcomes of EPR-type experiments is desirable and possible. It shows how Bohmian mechanics and the GRW mass density theory offer such an explanation in terms of a non-local common cause.

  14. Non-local model analysis of heat pulse propagation

    Energy Technology Data Exchange (ETDEWEB)

    Iwasaki, Takuya [Interdisciplinary Graduate School of Engineering Sciences, Kyushu Univ., Kasuga, Fukuoka (Japan); Itoh, Sanae-I.; Yagi, Masatoshi

    1998-10-01

    A new theoretical model equation which includes the non-local effect in the heat flux is proposed to study the transient transport phenomena. A non-local heat flux, which is expressed in terms of the integral equation, is superimposed on the conventional form of the heat flux. This model is applied to describe the experimental results from the power switching [Stroth U, et al 1996 Plasma Phys. Control. Fusion 38 1087] and the power modulation experiments [Giannone L, et al 1992 Nucl. Fusion 32 1985] in the W7-AS stellarator. A small fraction of non-local component in the heat flux is found to be very effective in modifying the response against an external modulation. The transient feature of the transport property, which are observed in the response of heat pulse propagation, are qualitatively reproduced by the transport simulations based on this model. A possibility is discussed to determine the correlation length of the non-local effect experimentally by use of the results of transport simulations. (author)

  15. Rapid-Equilibrium Enzyme Kinetics

    Science.gov (United States)

    Alberty, Robert A.

    2008-01-01

    Rapid-equilibrium rate equations for enzyme-catalyzed reactions are especially useful because if experimental data can be fit by these simpler rate equations, the Michaelis constants can be interpreted as equilibrium constants. However, for some reactions it is necessary to use the more complicated steady-state rate equations. Thermodynamics is…

  16. Calculation of the rate of nuclear excitation by electron transition in an Rbm84 plasma under the hypothesis of local thermodynamic equilibrium using a multiconfiguration Dirac-Fock approach

    Science.gov (United States)

    Denis-Petit, David; Gosselin, Gilbert; Hannachi, Fazia; Tarisien, Medhi; Bonnet, Thomas; Comet, Maxime; Gobet, Franck; Versteegen, Maud; Morel, Pascal; Méot, Vincent; Matea, Iolanda

    2017-08-01

    One promising candidate for the first detection of nuclear excitation in plasma is the 463-keV, 20.26-min-lifetime isomeric state in 84Rb, which can be excited via a 3.5-keV transition to a higher lying state. According to our preliminary calculations, under specific plasma conditions, nuclear excitation by electron transition (NEET) may be its strongest excitation process. Evaluating a reliable NEET rate requires, in particular, a thorough examination of all atomic transitions contributing to the rate under plasma conditions. We report the results of a detailed evaluation of the NEET rate based on multiconfiguration Dirac Fock (MCDF) atomic calculations, in a rubidium plasma at local thermodynamic equilibrium with a temperature of 400 eV and a density of 10-2g /cm3 and based on a more precise energy measurement of the nuclear transition involved in the excitation.

  17. Molecular thermodynamic analysis for assessing the relationship between reentrant swelling behavior and ternary liquid-liquid equilibrium for poly(N-isopropylacrylamide) nanometer-sized gel particles in a water-tetrahydrofuran cosolvent system.

    Science.gov (United States)

    Jung, Sang Chul; Bae, Young Chan

    2012-02-23

    The influence of phase separation on swelling behavior was investigated based on the thermodynamic framework of reswelling phenomena. The cloud-point for a ternary system of water(1)-tetrahydrofuran (THF)(2)-poly(N-isopropylacrylamide)(3) was examined by thermo-optical analysis (TOA). Nanometer-sized N-isopropylacrylamide (NIPA) gel particles were prepared by precipitation polymerization, and their swelling behaviors were determined using photon correlation spectroscopy (PCS). NIPA gel particles underwent reswelling when the ratio of water to THF was varied. First, the modified double lattice model (MDL) was employed to determine ternary interaction energy parameters for the liquid-liquid equilibrium (LLE) of linear poly-NIPA in a water-THF cosolvent system. The reentrant swelling equilibria of the NIPA gel in the water-THF system were then calculated using the interaction energy parameters. © 2012 American Chemical Society

  18. 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.

  19. Evaluation of the aerothermodynamic field produced by a pseudospheric body of mercury type at M = 22.6 flying in air in thermodynamic equilibrium

    Directory of Open Access Journals (Sweden)

    S. ANGELUCCI

    1963-06-01

    Full Text Available Tlie differential equations valid after tlie shock are first
    given in curvilinear coordinates; the cbosen unknowns are the two velocity
    components and the entropy and enthalpy. A function of entropy and
    enthalpy is then determined, by ineans of wliich ali the thermodynamic
    variables of the fluir are " coherently " approximated. Later on, the density
    and ali the otlier kinematic and thermodynamic variables are calculated
    immediately after the shock, taking the angle a as a parameter. The shape
    of the body is now taken into account and a convenient shape of the shock
    wave is given.
    The differential equations are then integrated with a step-by-step
    procedure, until the stagnation entropy is reached 011 the body.
    Finally the pressure and the temperature on the body are given. A
    sonic-to-stagnation pressure of 0.0 is the result, instead of 0.523 for a perfect
    gas.

  20. Numerical Solution of Transonic Wet Steam Flow in Blade-to-Blade Cascade with Non-equilibrium Condensation and Real Thermodynamics

    Directory of Open Access Journals (Sweden)

    Hric Vladimír

    2015-01-01

    Full Text Available We present an engineering approach to mathematical modeling and numerical solution of 2D inviscid transonic flow of wet steam in a steam turbine cascade channel of penultimate stage at rotor tip section in full Eulerian framework. Our flow model consists of the Euler system for the mixture (dry steam + homogeneously dispersed water droplets and transport equations for moments of droplet number distribution function known as method of moments. Thermodynamic properties of vapor steam are provided by set of IAPWS equations. For equation of state for vapor phase valid both in superheated and wet (meta-stable region we adopted recently developed equation in CFD formulation for low pressures provi1ded by Hrubý et al. [9], [8], [10]. For extraction of vapor parameters from the mixture ones we implemented simple relations in polynomial form describing thermodynamic properties of saturated liquid state. Nucleation model is resorting to modified classical nucleation theory. Linear droplet growth model is implemented for calculation of liquid sources. Numerical method is simple: cell-centered finite volume approach, 1st-order AUSM+ scheme for spatial derivatives, symmetrical fractional step method for separation of convection and condensation part, explicit 2-stage 2nd-order Runge-Kutta method for time integration. Geometry of blade profile and experimental results are provided by Bakhtar’s work [22], [23]. Results were obtained for one subsonic inlet/subsonic outlet regime and gave quite reasonable accordance with experiment.

  1. Thermodynamics of the hydration equilibrium derived from the luminescence spectra of the solid state for the case of the Eu-EDTA system.

    Science.gov (United States)

    Janicki, R; Mondry, A

    2015-11-28

    The luminescence properties of two compounds, [C(NH2)3][Eu(EDTA)(H2O)3] (I) and [C(NH2)3]2[Yb0.97Eu0.03(EDTA)(H2O)2]ClO4·6H2O (II), were determined. The weighted sum of luminescence spectra of I and II was used to reproduce the spectra of the Eu-EDTA system in aqueous solution in the temperature range 276-363 K. By implementing this method it was possible to determine the thermodynamic functions (ΔH = 18113 ± 506 J mole(-1) and ΔS = 62.5 ± 4.9 J mole(-1) K(-1)) of the reaction [Eu(EDTA)(H2O)3](-)⇆ [Eu(EDTA)(H2O)2](-) + H2O, which is difficult using other methods.

  2. Equilibrium thermodynamics to form a rhodium formyl complex from reactions of CO and H2: metal σ donor activation of CO.

    Science.gov (United States)

    Imler, Gregory H; Zdilla, Michael J; Wayland, Bradford B

    2014-04-23

    A rhodium(II) dibenzotetramethylaza[14]annulene dimer ([(tmtaa)Rh]2) (1) reacts with CO and H2 in toluene and pyridine to form equilibrium distributions with hydride and formyl complexes ((tmtaa)Rh-H (2); (tmtaa)Rh-C(O)H (3)). The rhodium formyl complex ((tmtaa)Rh-C(O)H) was isolated under a CO/H2 atmosphere, and the molecular structure was determined by X-ray diffraction. Equilibrium constants were evaluated for reactions of (tmtaa)Rh-H with CO to produce formyl complexes in toluene (K2(298 K)(tol) = 10.8 (1.0) × 10(3)) and pyridine (K2(298 K)(py) = 2.2 (0.2) × 10(3)). Reactions of 1 and 2 in toluene and pyridine are discussed in the context of alternative radical and ionic pathways. The five-coordinate 18-electron Rh(I) complex ([(py)(tmtaa)Rh(I)](-)) is proposed to function as a nucleophile toward CO to give a two-electron activated bent Rh-CO unit. Results from DFT calculations on the (tmtaa)Rh system correlate well with experimental observations. Reactions of 1 with CO and H2 suggest metal catalyst design features to reduce the activation barriers for homogeneous CO hydrogenation.

  3. Thermodynamics of radiation modes

    Energy Technology Data Exchange (ETDEWEB)

    Pina, Eduardo; De la Selva, Sara Maria Teresa [Departamento de Fisica, Universidad Autonoma Metropolitana - Iztapalapa, PO Box 55 534, Mexico, D F, 09340 (Mexico)], E-mail: pge@xanum.uam.mx, E-mail: tere@xanum.uam.mx

    2010-03-15

    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 frequencies. One equation relating frequency and volume is used to define the thermodynamics of one mode, and to explain the mystery of the frequency-dependent quantities having a similar behaviour to the non-frequency-dependent quantities for some thermodynamic equations and different behaviour for others. Besides, this frequency-volume relation is used to count the number of modes in a band of frequency.

  4. 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.

  5. Black hole thermodynamics in finite time

    CERN Document Server

    Gruber, Christine

    2016-01-01

    Finite-time thermodynamics provides the means to revisit ideal thermodynamic equilibrium processes in the light of reality and investigate the energetic "price of haste", i.e. the consequences of carrying out a process in finite time, when perfect equilibrium cannot be awaited due to economic reasons or the nature of the process. Employing the formalism of geometric thermodynamics, a lower bound on the energy dissipated during a process is derived from the thermodynamic length of that process. The notion of length is hereby defined via a metric structure on the space of equilibrium thermodynamics, spanned by a set of thermodynamic variables describing the system. Since the aim of finite-time thermodynamics is to obtain realistic limitations on idealized scenarios, it is a useful tool to reassess the efficiency of thermodynamic processes. We examine its implications for black hole thermodynamics, in particular scenarios inspired by the Penrose process, a thought experiment by which work can be extracted from a...

  6. Understanding quantum non-locality through pseudo-telepathy game

    Science.gov (United States)

    Kunkri, Samir

    2006-11-01

    Usually by quantum non-locality we mean that quantum mechanics can not be replaced by local realistic theory. On the other hand this nonlocal feature of quantum mechanics can not be used for instantaneous communication and hence it respect Einstein's special theory of relativity. But still it is not trivial as proved by various quantum information processing using entangled states. Recently there have been studies of hypothetical non-local system again respecting no-signalling which is beyond quantum mechanics. Here we study the power of such a hypothetical nonlocal box first suggested by Popescu et.al. in the context of recently suggested pseudo-telepathy game constructed from a Kochen-Specker set.

  7. Thermodynamic Simulation of Carbonate Cements-Water-Carbon Dioxide Equilibrium in Sandstone for Prediction of Precipitation/Dissolution of Carbonate Cements.

    Science.gov (United States)

    Duan, Yiping; Feng, Mingshi; Zhong, Xinyan; Shang, Ruishu; Huang, Lihong

    2016-01-01

    Carbonate cements, such as calcite, dolomite, ferrocalcite and ankerite, play important roles in the formation of pores in sandstones: precipitation of carbonate cements modifies pores and inhibits compaction, while dissolution creates secondary pores. This work proposed a precipitation-dissolution model for carbonate cements-CO2-H2O system by means of ion equilibrium concentration ([M2+], M = Ca, Mg, Fe or Mn) with different factors, such as temperature, depth, pH, [Formula: see text], variable rock composition and overpressure. Precipitation-dissolution reaction routes were also analyzed by minimization of the total Gibbs free energy (ΔG). Δ[M2+], the variation of [Ca2+], [Fe2+], [Mg2+] or [Mn2+] for every 100 m of burial depths, is used to predict precipitation or dissolution. The calculation results indicate that the increasing temperature results in decrease of equilibrium constant of reactions, while the increasing pressure results in a relatively smaller increase of equilibrium constant; As a result, with increasing burial depth, which brings about increase of both temperature and pressure, carbonate cements dissolve firstly and produces the maximal dissolved amounts, and then precipitation happens with further increasing depth; For example, calcite is dissolving from 0.0 km to 3.0 km with a maximal value of [Ca2+] at depth of 0.8 km, and then precipitates with depth deeper than 3.0 km. Meanwhile, with an increasing CO2 mole fraction in the gaseous phase from 0.1% to 10.0% in carbonate systems, the aqueous concentration of metal ions increases, e.g., dissolved amount of CaFe0.7Mg0.3(CO3)2 increases and reaches maximum of 1.78 mmol·L-1 and 8.26 mmol·L-1 at burial depth of 0.7 km with CO2 mole fraction of 0.1% and 10.0%, respectively. For the influence of overpressure in the calcite system, with overpressure ranging from 36 MPa to 83 MPa, pH reaches a minimum of 6.8 at overpressure of 51 MPa; meanwhile, Δ[Ca2+] increases slightly from -2.24 mmol·L-1 to

  8. A histories perspective on characterising quantum non-locality

    CERN Document Server

    Dowker, Fay; Wallden, Petros

    2013-01-01

    We introduce a framework for studying non-locality and contextuality inspired by the path integral formulation of quantum theory. We prove that the existence of a strongly positive joint quantum measure -- the quantum analogue of a joint probability measure -- on a set of experimental probabilities implies the Navascues-Pironio-Acin (NPA) condition $Q^1$ and is implied by the stronger NPA condition $Q^{1+AB}$. A related condition is shown to be equivalent to $Q^{1+AB}$.

  9. Ground state solutions for non-local fractional Schrodinger equations

    Directory of Open Access Journals (Sweden)

    Yang Pu

    2015-08-01

    Full Text Available In this article, we study a time-independent fractional Schrodinger equation with non-local (regional diffusion $$ (-\\Delta^{\\alpha}_{\\rho}u + V(xu = f(x,u \\quad \\text{in }\\mathbb{R}^{N}, $$ where $\\alpha \\in (0,1$, $N > 2\\alpha$. We establish the existence of a non-negative ground state solution by variational methods.

  10. Non-local gravity with a Weyl-square term

    CERN Document Server

    Cusin, Giulia; Maggiore, Michele; Mancarella, Michele

    2016-01-01

    Recent work has shown that modifications of General Relativity based on the addition of a non-local term $R\\,\\Box^{-2}R$ produce a dynamical model of dark energy, which is cosmologically viable both at the background level and at the level of cosmological perturbations. We explore a more general class of models based on the addition of terms proportional to $R_{\\mu\

  11. Non-local flow effects on bedform dynamics

    Science.gov (United States)

    Perron, J. Taylor; Kao, Justin; Myrow, Paul

    2013-04-01

    Bedform patterns are sensitive recorders of feedbacks among bed topography, fluid flow, and sediment transport. Some of the most important feedbacks are local. For example, evolution models based on simple flow parameterizations that only incorporate local bed height can reproduce some of the essential features of bedform evolution, including bedform growth and migration. However, non-local effects can also be critically important. For example, field and laboratory measurements have shown that the spacing of most sand ripples generated by wave-driven oscillatory flows is linearly proportional to the amplitude of the flow oscillation, implying that fluid stress and sediment transport at a given location depend on upstream features that perturb the flow. A model that fully captures the coupling of flow and bedform evolution must include such effects, but it is not clear how detailed the description of the flow must be to reproduce the most important aspects of bedform evolution. To account for the most significant non-local flow effects without resorting to a coupled hydrodynamic model, we propose an approximation in which the bed shear stress is expressed as a convolution of the bed topography with a kernel that includes both local effects, such as acceleration over bumps, and non-local effects, such as flow separation and re-attachment. Two-dimensional flow simulations demonstrate that a single, generic kernel gives a good approximation of shear stress over a wide range of bed profiles under oscillatory and some combined flows. Incorporating this approximation into a simple bedform evolution model, we show that non-local effects are required to reproduce the characteristic transient patterns that emerge as wave ripples respond to changes in the flow, which we have documented with time-lapse imagery of laboratory wave tank experiments. We then show how this result informs interpretations of two-dimensional wave ripple patterns preserved in the geologic record.

  12. Response reactions: equilibrium coupling.

    Science.gov (United States)

    Hoffmann, Eufrozina A; Nagypal, Istvan

    2006-06-01

    It is pointed out and illustrated in the present paper that if a homogeneous multiple equilibrium system containing k components and q species is composed of the reactants actually taken and their reactions contain only k + 1 species, then we have a unique representation with (q - k) stoichiometrically independent reactions (SIRs). We define these as coupling reactions. All the other possible combinations with k + 1 species are the coupled reactions that are in equilibrium when the (q - k) SIRs are in equilibrium. The response of the equilibrium state for perturbation is determined by the coupling and coupled equilibria. Depending on the circumstances and the actual thermodynamic data, the effect of coupled equilibria may overtake the effect of the coupling ones, leading to phenomena that are in apparent contradiction with Le Chatelier's principle.

  13. LIQUID-LIQUID EQUILIBRIUM FOR TERNARY SYSTEMS CONTAINING ETHYLIC BIODIESEL + ANHYDROUS ETHANOL + REFINED VEGETABLE OIL (SUNFLOWER OIL, CANOLA OIL AND PALM OIL: EXPERIMENTAL DATA AND THERMODYNAMIC MODELING

    Directory of Open Access Journals (Sweden)

    T. P. V. B. Dias

    2015-09-01

    Full Text Available AbstractPhase equilibria of the reaction components are essential data for the design and process operations of biodiesel production. Despite their importance for the production of ethylic biodiesel, the reaction mixture, reactant (oil and ethanol and the product (fatty acid ethyl esters up to now have received less attention than the corresponding systems formed during the separation and purification phases of biodiesel production using ethanol. In this work, new experimental measurements were performed for the liquid-liquid equilibrium (LLE of the system containing vegetable oil (sunflower oil and canola oil + ethylic biodiesel of refined vegetable oil + anhydrous ethanol at 303.15 and at 323.15 K and the system containing refined palm oil + ethylic biodiesel of refined palm oil + ethanol at 318.15 K. The experimental data were successfully correlated by the nonrandom two-liquid (NRTL model; the average deviations between calculated and experimental data were smaller than 1.00%.

  14. Critical thresholds in flocking hydrodynamics with non-local alignment.

    Science.gov (United States)

    Tadmor, Eitan; Tan, Changhui

    2014-11-13

    We study the large-time behaviour of Eulerian systems augmented with non-local alignment. Such systems arise as hydrodynamic descriptions of agent-based models for self-organized dynamics, e.g. Cucker & Smale (2007 IEEE Trans. Autom. Control 52, 852-862. (doi:10.1109/TAC.2007.895842)) and Motsch & Tadmor (2011 J. Stat. Phys. 144, 923-947. (doi:10.1007/s10955-011-0285-9)) models. We prove that, in analogy with the agent-based models, the presence of non-local alignment enforces strong solutions to self-organize into a macroscopic flock. This then raises the question of existence of such strong solutions. We address this question in one- and two-dimensional set-ups, proving global regularity for subcritical initial data. Indeed, we show that there exist critical thresholds in the phase space of the initial configuration which dictate the global regularity versus a finite-time blow-up. In particular, we explore the regularity of non-local alignment in the presence of vacuum.

  15. Positive cosmological constant, non-local gravity and horizon entropy

    Energy Technology Data Exchange (ETDEWEB)

    Solodukhin, Sergey N., E-mail: Sergey.Solodukhin@lmpt.univ-tours.fr [Laboratoire de Mathematiques et Physique Theorique, Universite Francois-Rabelais Tours, Federation Denis Poisson - CNRS, Parc de Grandmont, 37200 Tours (France)

    2012-08-21

    We discuss a class of (local and non-local) theories of gravity that share same properties: (i) they admit the Einstein spacetime with arbitrary cosmological constant as a solution; (ii) the on-shell action of such a theory vanishes and (iii) any (cosmological or black hole) horizon in the Einstein spacetime with a positive cosmological constant does not have a non-trivial entropy. The main focus is made on a recently proposed non-local model. This model has two phases: with a positive cosmological constant {Lambda}>0 and with zero {Lambda}. The effective gravitational coupling differs essentially in these two phases. Generalizing the previous result of Barvinsky we show that the non-local theory in question is free of ghosts on the background of any Einstein spacetime and that it propagates a standard spin-2 particle. Contrary to the phase with a positive {Lambda}, where the entropy vanishes for any type of horizon, in an Einstein spacetime with zero cosmological constant the horizons have the ordinary entropy proportional to the area. We conclude that, somewhat surprisingly, the presence of any, even extremely tiny, positive cosmological constant should be important for the proper resolution of the entropy problem and, possibly, the information puzzle.

  16. Positive cosmological constant, non-local gravity and horizon entropy

    Science.gov (United States)

    Solodukhin, Sergey N.

    2012-08-01

    We discuss a class of (local and non-local) theories of gravity that share same properties: (i) they admit the Einstein spacetime with arbitrary cosmological constant as a solution; (ii) the on-shell action of such a theory vanishes and (iii) any (cosmological or black hole) horizon in the Einstein spacetime with a positive cosmological constant does not have a non-trivial entropy. The main focus is made on a recently proposed non-local model. This model has two phases: with a positive cosmological constant Λ>0 and with zero Λ. The effective gravitational coupling differs essentially in these two phases. Generalizing the previous result of Barvinsky we show that the non-local theory in question is free of ghosts on the background of any Einstein spacetime and that it propagates a standard spin-2 particle. Contrary to the phase with a positive Λ, where the entropy vanishes for any type of horizon, in an Einstein spacetime with zero cosmological constant the horizons have the ordinary entropy proportional to the area. We conclude that, somewhat surprisingly, the presence of any, even extremely tiny, positive cosmological constant should be important for the proper resolution of the entropy problem and, possibly, the information puzzle.

  17. Positive cosmological constant, non-local gravity and horizon entropy

    CERN Document Server

    Solodukhin, Sergey N

    2012-01-01

    We discuss a class of (local and non-local) theories of gravity that share same properties: i) they admit the Einstein spacetime with arbitrary cosmological constant as a solution; ii) the on-shell action of such a theory vanishes and iii) any (cosmological or black hole) horizon in the Einstein spacetime with a positive cosmological constant does not have a non-trivial entropy. The main focus is made on a recently proposed non-local model. This model has two phases: with a positive cosmological constant $\\Lambda>0$ and with zero $\\Lambda$. The effective gravitational coupling differs essentially in these two phases. Generalizing the previous result of Barvinsky we show that the non-local theory in question is free of ghosts on the background of any Einstein spacetime and that it propagates a standard spin-2 particle. Contrary to the phase with a positive $\\Lambda$, where the entropy vanishes for any type of horizon, in an Einstein spacetime with zero cosmological constant the horizons have the ordinary entro...

  18. Ghezeljeh nanoclay as a new natural adsorbent for the removal of copper and mercury ions:Equilibrium, kinetics and thermodynamics studies

    Institute of Scientific and Technical Information of China (English)

    Majid Soleimani⁎; Zahra Hassanzadeh Siahpoosh

    2015-01-01

    Heavy metal determination was carried out by applying the solid phase extraction (SPE) method in batch mode followed by atomic absorption spectroscopy (AAS) and inductively coupled plasma atomic emission spectrosco-py (ICP-AES) from aqueous solutions using Ghezeljeh montmoril onite nanoclay as a new natural adsorbent. The Ghezeljeh clay is characterized by using Fourier Transform Infrared (FT-IR) Spectroscopy, Scanning Electron Mi-croscopy–Energy Dispersive Spectrometry (SEM–EDS) and X-ray Diffractometry (XRD) and X-ray Fluorescence (XRF). The results of XRD and FT-IR of nanoclay confirm that montmoril onite is the dominant mineral phase. Based on SEM images of Ghezeljeh clay, it can be seen that the distance between the plates is Nano. The effects of varying parameters such as initial concentration of metal ions, pH and type of buffer solutions, amount of ad-sorbent, contact time, and temperature on the adsorption process were examined. The effect of various interfer-ing ions was studied. The adsorption data correlated with Freundlich, Langmuir, Dubinin–Radushkevich (D–R), and Temkin isotherms. The Langmuir and Freundlich isotherms showed the best fit to the equilibrium data for Hg(I ), but the equilibrium nature of Cu(II) adsorption has been described by the Langmuir isotherm. The kinetic data were described with pseudo-first-order, pseudo-second-order and double-exponential models. The adsorp-tion process follows a pseudo-second-order reaction scheme. Calculation ofΔG0,ΔH0 andΔS0 showed that the nature of Hg(II) ion sorption onto the Ghezeljeh nanoclay was endothermic and was favored at higher temper-ature, and the nature of Cu(II) ion sorption was exothermic and was favored at lower temperature.

  19. Equilibrium, Thermodynamics, and Kinetic Sorption Studies for the Removal of Coomassie Brilliant Blue on Wheat Bran as a Low-Cost Adsorbent

    Directory of Open Access Journals (Sweden)

    Sadia Ata

    2012-01-01

    Full Text Available The sorption studies of coomassie brilliant blue (CBB from aqueous solution have been carried out on wheat bran (WB. Coomassie brilliant blue on wheat bran was used to study the adsorption behavior under various parameters such as pH, dosage amount, and contact time. It was observed that under optimized conditions up to 95.70% dye could be removed from solution onto WB. Langmuir and Freundlich adsorption isotherms were used to elaborate the results. Freundlich model was found to be fitted well and favored multilayer adsorption. The Freundlich constants n and KF were determined as 0.53 and 2.5×10−4. Thermodynamic parameters such as ΔG, ΔH, and ΔS studied were taking into account, showed spontaneous and favorable reaction for coomassie brilliant blue on wheat bran. The maximum adsorption capacity qm was found to be 6.410 mg/g. The investigations show that non treated WB is a low-cost adsorbent for the removal of dyes from textile industry effluents.

  20. Enhanced adsorptive removal of Safranine T from aqueous solutions by waste sea buckthorn branch powder modified with dopamine: Kinetics, equilibrium, and thermodynamics

    Science.gov (United States)

    Xu, Xiaohui; Bai, Bo; Wang, Honglun; Suo, Yourui

    2015-12-01

    Polydopamine coated sea buckthorn branch powder (PDA@SBP) was facilely synthesized via a one-pot bio-inspired dip-coating approach. The as-synthesized PDA@SBP was characterized using Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). The adsorption progresses of Safranine T on the surface of PDA@SBP adsorbent were systematically investigated. More specifically, the effects of solution pH, contact time, initial concentration and temperature were evaluated, respectively. The experimental results showed the adsorption capacity of PDA@SBP at 293.15 K could reach up to 54.0 mg/g; the adsorption increased by 201.7% compared to that of native SBP (17.9 mg/g). Besides, kinetics studies showed that pseudo-second-order kinetic model adequately described the adsorption behavior. The adsorption experimental data could be fitted well a Freundlich isotherm model. Thermodynamic analyses showed that the ST adsorption was a physisorption endothermic process. Regeneration of the spent PDA@SBP adsorbent was conducted with 0.1 M HCl without significant reduction in adsorption capacity. On the basis of these investigations, it is believed that the PDA@SBP adsorbent could have potential applications in sewage disposal areas because of their considerable adsorption capacities, brilliant regeneration capability, and cost-effective and eco-friendly preparation and use.

  1. Cauliflower Leave, an Agricultural Waste Biomass Adsorbent, and Its Application for the Removal of MB Dye from Aqueous Solution: Equilibrium, Kinetics, and Thermodynamic Studies

    Science.gov (United States)

    Ansari, Seraj Anwar; Khan, Fauzia

    2016-01-01

    Cauliflower leaf powder (CLP), a biosorbent prepared from seasonal agricultural crop waste material, has been employed as a prospective adsorbent for the removal of a basic dye, methylene blue (MB) from aqueous solution by the batch adsorption method under varying conditions, namely, initial dye concentration, adsorbent dose, solution pH, and temperature. Characterization of the material by FTIR and SEM indicates the presence of functional groups and rough coarse surface suitable for the adsorption of methylene blue over it. Efforts were made to fit the isotherm data using Langmuir, Freundlich, and Temkin equation. The experimental data were best described by Freundlich isotherm model, with an adsorption capacity of 149.22 mg/g at room temperature. To evaluate the rate of methylene blue adsorption onto CLP, pseudo-first-order, pseudo-second-order, and intraparticle diffusion models were employed. The experimental data were best described by the pseudo-second-order kinetic model. Evaluation of thermodynamic parameters such as changes in enthalpy, entropy, and Gibbs' free energy showed the feasible, spontaneous, and exothermic nature of the adsorption process. On the basis of experimental results obtained, it may be concluded that the CLP prepared from agricultural waste has considerable potential as low-cost adsorbent in wastewater treatment for the removal of basic dye, MB. PMID:27974892

  2. Adsorption equilibrium, kinetics and thermodynamics of α-amylase on poly(DVB-VIM)-Cu(+2) magnetic metal-chelate affinity sorbent.

    Science.gov (United States)

    Osman, Bilgen; Kara, Ali; Demirbel, Emel; Kök, Senay; Beşirli, Necati

    2012-09-01

    Designing an immobilised metal ion affinity process on large-scale demands that a thorough understanding be developed regarding the adsorption behaviour of proteins on metal-loaded gels and the characteristic adsorption parameters to be evaluated. In view of this requirement, interaction of α-amylase as a model protein with newly synthesised magnetic-poly(divinylbenzene-1-vinylimidazole) [m-poly(DVB-VIM)] microbeads (average diameter, 53-212 μm) was investigated. The m-poly(DVB-VIM) microbeads were prepared by copolymerising of divinylbenzene (DVB) with 1-vinylimidazole (VIM). The m-poly(DVB-VIM) microbeads were characterised by N(2) adsorption/desorption isotherms, electron spin resonance, elemental analysis, scanning electron microscope and swelling studies. Cu(2+) ions were chelated on the m-poly(DVB-VIM) beads and used in adsorption of α-amylase in a batch system. The maximum α-amylase adsorption capacity of the m-poly(DVB-VIM)-Cu(2+) beads was determined as 10.84 mg/g at pH 6.0, 25 °C. The adsorption data were analyzed using three isotherm models, which are the Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. The pseudo-first-order, pseudo-second-order, modified Ritchie's-second-order and intraparticle diffusion models were used to test dynamic experimental data. The study of temperature effect was quantified by calculating various thermodynamic parameters such as Gibbs free energy, enthalpy and entropy changes.

  3. Spectral non-uniform temperature and non-local heat transfer in the spin Seebeck effect.

    Science.gov (United States)

    Tikhonov, Konstantin S; Sinova, Jairo; Finkel'stein, Alexander M

    2013-01-01

    Recently discovered spin-dependent thermoelectric effects have merged spin, charge, and thermal physics, known as spin caloritronics, of which the spin Seebeck effect is its most puzzling. Here we present a theory of this effect driven by subthermal non-local phonon heat transfer and spectral non-uniform temperature. The theory explains its non-local behaviour from the fact that phonons that store the energy (thermal) and the phonons that transfer it (subthermal) are located in different parts of the spectrum and have different kinetics. This gives rise to a spectral phonon distribution that deviates from local equilibrium along the substrate and is sensitive to boundary conditions. The theory also predicts a non-magnon origin of the effect in ferromagnetic metals in agreement with observations in recent experiments. Equilibration of the heat flow from the substrate to the Pt probe and backwards leads to a vertical spin current produced by the spin-polarized electrons dragged by the thermal phonons.

  4. Fundamentals of engineering thermodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Moran, M.J.; Shapiro, H.N.

    1988-01-01

    This book provides a thorough development of the second law of thermodynamics (featuring the entropy-production concept), an up-to-date discussion of availability analysis (including an introduction to chemical availability), and a sound description of the application areas. Topics covered include control volume energy analysis, vapor power systems, gas power systems, thermodynamic relations for simple compressible substances, nonreacting ideal gas mixtures and psycrometrics, reacting mixtures and combustion, and chemical and phase equilibrium.

  5. Biosorptive uptake of ibuprofen by steam activated biochar derived from mung bean husk: Equilibrium, kinetics, thermodynamics, modeling and eco-toxicological studies.

    Science.gov (United States)

    Mondal, Sandip; Bobde, Kiran; Aikat, Kaustav; Halder, Gopinath

    2016-11-01

    The present study explores the use of steam activated mung bean husk biochar (SA-MBHB) as a potential sorbent for the removal of non-steroidal and anti-inflammatory drug ibuprofen from aqueous solution. SA-MBHB was characterized by SEM, FTIR, BET, TGA, point of zero charge (pHPZC) and UV-Vis spectrophotometer. The relation between removal percentages of ibuprofen and parameters such as adsorbent dose (0.05 g-250 g), contact time (5 min-210 min), pH (2-10), speed of agitation (40-280 rpm), temperature (293-308 K) and initial ibuprofen concentration (5-100 ppm) was investigated and optimized by a series of batch sorption experiments. The optimized conditions achieved were: adsorbent dose 0.1 g/L, agitation speed 200 rpm, pH 2, initial ibuprofen concentration 20 mg L(-1), equilibrium time 120 min and temperature 20 °C for more than 99% adsorptive removal of ibuprofen. The equilibrium adsorption data were well fitted into the Langmuir isotherm model while kinetic data suggested the removal process to follow pseudo second order reaction. The adsorption phenomena were optimized and simulated by using response surface methodology (RSM) and artificial neural network (ANN). Effect of process variables viz. dose, agitation speed and pH on the sorbed amount of IBP was studied through a 2(3) full factorial central composite design (CCD). The comparative analysis was done for ibuprofen removal by constructing ANN model training using same experimental matrix of CCD. The growth of Scenedesmus abundans was also observed to be affected by the IBP solution whereas the biochar treated with IBP solution did not significantly affect the growth of the Scenedesmus abundans. The results revealed that SA-MBHB could be a cost-effective, efficient and non-hazardous adsorbent for the removal of ibuprofen from aqueous solution.

  6. Components in Chemical Thermodynamics

    Science.gov (United States)

    Alberty, Robert A.

    1995-09-01

    Chemical equations are actually matrix equations, and this has important implications for their thermodynamic treatment. The fundamental equation for chemical thermodynamics for a chemical reaction system can be written in terms of species, but at chemical equilibrium, it has to be written in terms of components. The number of components is equal to the number of species minus the number of independent chemical reactions. The fundamental equation for the Gibbs energy of a system containing ethylene, methane, ethane, and propane is discussed. At chemical equilibrium there are two components, which can be taken to be carbon and hydrogen or ethylene and methane. There are advantages in using matrix notation.

  7. Modern thermodynamics - New concepts based on the second law of thermodynamics

    Institute of Scientific and Technical Information of China (English)

    Jitao Wang

    2009-01-01

    Thermodynamics is a core part of science.Nearly all scientists should have a basic knowledge of thermodynamics.Thermodynamics is a science of development,and is a viewpoint of scientific development in natural sciences.Achievement of thermodynamics has influence not only on natural sciences,but also on social sciences and philosophy.Fundamental concepts and definitions are very important for any discipline of science,so what is classical thermodynamics and what is modern thermodynamics have become the key points of puzzledom in thermodynamics.In this paper,after clarification of fundamental concept in thermodynamics,a complete basic modern classification of thermodynamics is naturally obtained.It is suggested that extended Carnot theorem and dissipation decrease theorem,together with the laws of thermodynamics,are the most fundamental theorems in thermodynamics discipline.Nondissipative thermodynamics is a new field besides equilibrium thermodynamics belonging to the equal part of the second law of thermodynamics.

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

    Directory of Open Access Journals (Sweden)

    Saied Bashiri

    2012-11-01

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

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

    Directory of Open Access Journals (Sweden)

    Samarghandi Mohammad

    2012-11-01

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

  10. Kinetics, Equilibrium, and Thermodynamics of the Sorption of Bisphenol A onto N-CNTs-β-Cyclodextrin and Fe/N-CNTs-β-Cyclodextrin Nanocomposites

    Directory of Open Access Journals (Sweden)

    Keletso Mphahlele

    2015-01-01

    Full Text Available We analysed the adsorptive behaviour of Fe/N-CNTs-β-CD nanocomposite in the removal of bisphenol A (BPA from aqueous solution and identified the key influencing parameters. The Fe/N-CNTs-β-CD nanocomposite adsorbent was prepared by dispersing Fe uniformly on N-CNTs-β-CD using a microwave polyol method and characterized using Fourier transform infrared spectroscopy (FTIR, focused ion beam scanning electron microscopy (FIB-SEM, and energy-dispersive X-ray spectroscopy (EDS. The solution pH and temperature had minimal effect on sorption of BPA while the initial concentration and adsorbent mass affected the adsorption of BPA. No leaching of Fe into the water was observed; thus the nanocomposites were found suitable for use in water purification. From equilibrium isotherm studies, the Langmuir isotherm model gave the best description of the experimental data. The Langmuir monolayer adsorption capacities of BPA onto N-CNTs-β-CD and Fe/N-CNTs-β-CD are 38.20 mg·g−1 and 80.65 mg·g−1 at 298 K, respectively. Evidently, these adsorption capacity values gave an indication that uniform dispersion of Fe N-CNTs-β-CD prepared by the microwave polyol method enhances the adsorption of BPA. Meanwhile, the sorption kinetics of BPA onto Fe/N-CNTs-β-CD were best described by the pseudo-second-order model.

  11. Application of novel, low-cost, laterite-based adsorbent for removal of lead from water: Equilibrium, kinetic and thermodynamic studies.

    Science.gov (United States)

    Chatterjee, Somak; De, Sirshendu

    2016-01-01

    Contamination of groundwater by carcinogenic heavy metal, e.g., lead is an important issue and possibility of using a natural rock, laterite, is explored in this work to mitigate this problem. Treated laterite (TL- prepared using hydrochloric acid and sodium hydroxide) was successfully utilized for this purpose. The adsorbent was characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray (EDX), and Fourier Transform Infrared Spectroscopy (FTIR) to highlight its physical and chemical properties. Optimized equilibrium conditions were 1 g L(-1) adsorbent concentration, 0.26 mm size and a pH of 7 ± 0.2. Monolayer adsorption capacity of lead on treated laterite was 15 mg/g, 14.5 and 13 mg g(-1) at temperatures of 303 K, 313 K and 323 K, respectively. The adsorption was exothermic and physical in nature. At 303 K, value of effective diffusivity of (De) and mass transfer co-efficient (Kf) of lead onto TL were 6.5 × 10(-10) m(2)/s and 3.3 × 10(-4) m/s, respectively (solved from shrinking core model of adsorption kinetics). Magnesium and sulphate show highest interference effect on the adsorption of lead by TL. Efficacy of the adsorbent has been verified using real-life contaminated groundwater. Thus, this work demonstrates performance of a cost-effective media for lead removal.

  12. Valorization of two waste streams into activated carbon and studying its adsorption kinetics, equilibrium isotherms and thermodynamics for methylene blue removal

    Directory of Open Access Journals (Sweden)

    Zeid Abdullah AlOthman

    2014-12-01

    Full Text Available Wastes must be managed properly to avoid negative impacts that may result. Open burning of waste causes air pollution which is particularly hazardous. Flies, mosquitoes and rats are major problems in poorly managed surroundings. Uncollected wastes often cause unsanitary conditions and hinder the efforts to keep streets and open spaces in a clean and attractive condition. During final disposal methane is generated, it is much more effective than carbon dioxide as a greenhouse gas, leading to climate change. Therefore, this study describes the possible valorization of two waste streams into activated carbon (AC with added value due to copyrolysis. High efficiency activated carbon was prepared by the copyrolysis of palm stem waste and lubricating oil waste. The effects of the lubricating oil waste to palm stem ratio and the carbonization temperature on the yield and adsorption capacity of the activated carbon were investigated. The results indicated that the carbon yield depended strongly on both the carbonization temperature and the lubricating oil to palm stem ratio. The efficiency of the adsorption of methylene blue (MB onto the prepared carbons increased when the lubricating oil to palm stem ratio increased due to synergistic effect. The effects of pH, contact time, and the initial adsorbate concentration on the adsorption of methylene blue were investigated. The maximum adsorption capacity (128.89 mg/g of MB occurred at pH 8.0. The MB adsorption kinetics were analyzed using pseudo-first order, pseudo-second order and intraparticle diffusion kinetic models. The results indicated that the adsorption of MB onto activated carbon is best described using a second order kinetic model. Adsorption data are well fitted with Langmuir and Freundlich isotherms. The thermodynamic parameters; ΔG°, ΔH° and ΔS° indicate that the adsorption is spontaneous and endothermic.

  13. Optimization, equilibrium, kinetic, thermodynamic and desorption studies on the sorption of Cu(II) from an aqueous solution using marine green algae: Halimeda gracilis.

    Science.gov (United States)

    Jayakumar, R; Rajasimman, M; Karthikeyan, C

    2015-11-01

    The aptitude of marine green algae Helimeda gracilis for sorption of Cu(II) ions from an aqueous solution was studied in batch experiments. The effect of relevant parameters such as function of pH, sorbent dosage, agitation speed and contact time was evaluated by using Response surface methodology (RSM). A maximum percentage removal of Cu (II) by Halimeda gracilis occurs at pH-4.49, sorbent dosage-1.98g/L, agitation speed-119.43rpm and contact time-60.21min. Further, the sorbent was characterized by using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning electron microscope (SEM) analysis. Experimental data were analyzed in terms of pseudo-first order, pseudo-second order, intraparticle diffusion, power function and elovich kinetic models. The results showed that the sorption process of Cu(II) ions followed well pseudo-second order kinetics. The sorption data of Cu(II) ions at 308.15K are fitted to Langmuir, Freundlich, Dubinin-Radushkevich (D-R), Temkin, Sips and Toth isotherms. Sorption of Cu(II) onto marine green algae Helimeda gracilis followed the Langmuir and Toth isotherm models (R(2)=0.998 and R(2)=0.999) with the maximum sorption capacity of 38.46 and 38.07mg/g. The calculated thermodynamic parameters such as ΔG°, ΔH° and ΔS° showed that the sorption of Cu(II) ions onto Helimeda gracilis biomass was feasible, spontaneous and endothermic. Desorption study shows that the sorbent could be regenerated using 0.2M HCl solution, with up to 89% recovery. Copyright © 2015 Elsevier Inc. All rights reserved.

  14. Kinetic, equilibrium and thermodynamic studies of synthetic dye removal using pomegranate peel activated carbon prepared by microwave-induced KOH activation

    Directory of Open Access Journals (Sweden)

    Mohd Azmier Ahmad

    2014-08-01

    Full Text Available Pomegranate peel was converted into activated carbon using microwave induced and KOH activation techniques. The prepared activated carbon (PPAC was characterized using FTIR, TGA, SEM, and nitrogen-adsorption surface area (BET. BET measurements gave remarkable increase in both the surface area (941.02 m2/g and total pore volume (0.470 cm3/g. Various operational parameters such as pH, initial dye concentration, contact time and solution temperature in batch systems were investigated on the use of PPAC in the adsorption of remazol brilliant blue reactive (RBBR dye. At pH 2, the optimum dye removal was 94.36%. The amount of dye removed was dependent on initial dye concentration and solution temperature. Adsorption kinetics was found to follow pseudo-second-order kinetic model. Experimental data were analyzed using eight model equations: Langmuir, Freundlich, Temkin, Dubinin–Radushkevich, Radke Prausnite, Sips, Viet–Sladek and Brouers – Sotolongo isotherms and it was found that the Freundlich isotherm model fitted the adsorption data most with the highest correlation (R2≥0.99 and lowest normalized standard deviation, ∆qe. Both intra-particle and film diffusion governed the adsorption process. Thermodynamic parameters, such as standard Gibbs free energy (∆G0, standard enthalpy (∆H0, standard entropy (∆S0, and the activation energy (Ea were calculated. The adsorption of RBBR dye onto PPAC was found to be spontaneous and exothermic in nature. This study shows that the adsorption follows physisorption mechanism.

  15. ``Statistical treatment of the spectral properties of plasmas in local thermodynamical equilibrium using a screened hydrogenic model``; ``Traitement statistique des proprietes spectrales des plasmas a l`equilibre thermodynamique local dans le cadre du modele hydrogenique ecrante``

    Energy Technology Data Exchange (ETDEWEB)

    Faussurier, G.

    1996-12-31

    A new screened hydrogenic model is presented. The screening constants depend both on the principal n and orbital l quantum numbers. They have been obtained from numerical fits over a large data base containing ionization potentials and one-electron excitation energies of ions. A rapid and original method to compute the bound-bound and bound-free oscillator strengths is proposed. The discrete spectrum and the series continuum are connected by continuity, and the sum rules are respected. The screened hydrogenic average atom is well-adapted to describe multicharged ion plasmas in local thermodynamic equilibrium (LTE). Using the key principle of statistical mechanics, it is shown first that this model is properly defined and thermodynamically coherent. Secondly, a new method of detailed ionization stage accounting of a LTE plasma is explained. It can be used to reconstruct the distribution of integer charge states in such a plasma from any average atom model. The l -splitting allows one-electron transitions between two subshells with the same principal quantum number n. They may be of great importance when the Rosseland opacity is computed. Though, methods of classical statistical mechanics are required to calculate the distribution of the configurations around the average atom one and so to improve the spectral opacities. The splitting in integer ionic stages can be easily included. The formalism is tested by comparisons with theoretical and experimental results published in the literature. From the photoabsorption spectra encountered, the main results are the correct estimations of both the Rosseland opacity and the detailed charge degrees accounting. (author).

  16. AC-conductance of a non-local Thirring model

    Energy Technology Data Exchange (ETDEWEB)

    Trobo, Marta Liliana; Von Reichenbach, Maria Cecilia [Universidad Nacional de La Plata (UNLP) (Argentina); Barci, Daniel G. [Universidade do Estado do Rio de Janeiro (UERJ), RJ (Brazil)]|[Illinois Univ., Urbana, IL (United States); Medeiros Neto, J.F. de [Universidade Estadual de Santa Cruz (UESC), Ilheus, BA (Brazil)

    2000-07-01

    Full text follows: In recent years renewed interest has arisen in the study of low dimensional field theories. In particular, research on the one dimensional (1-d) fermionic gas has been very active, mainly due to the actual nano-fabrication of the so called quantum wires and their relevance for low dimensional condensed matter physics as, for instance, the quantum Hall effect and high-T{sub c} superconductivity. Experimental and theoretical investigations of the AC-transport phenomena in nano-structures are of profound scientific interest since they provide insight into the behavior of quantum systems. In this frame, we consider a field theoretical approach that can be used to describe a system of 1-d strongly correlated particles in the low transferred momentum limit. We study a non-local and non-covariant version of the Thirring model where the fermionic densities and currents are coupled through bilocal, distance-dependent potentials which describe the forward scattering processes. We apply the functional bosonization formalism, a very useful technique to understand the non-perturbative regime of strongly correlated one-dimensional fermionic systems, to this non local Thirring like model (NLTM). We are interesting in the transport properties of the system, in particular in the AC-conductance. To this end, we consider a NLTM in the presence of an external electromagnetic field. We obtain the AC-conductance of the model in terms of non-local potentials used to describe the interactions between fermionic currents. We also analyze the transport properties in the case in which weak couplings between fermionic currents and localized impurities are taken into account. (author)

  17. An Information Theory Approach to Nonlinear, Nonequilibrium Thermodynamics.

    Science.gov (United States)

    Rogers, David M; Beck, Thomas L; Rempe, Susan B

    2011-10-01

    Using the problem of ion channel thermodynamics as an example, we illustrate the idea of building up complex thermodynamic models by successively adding physical information. We present a new formulation of information algebra that generalizes methods of both information theory and statistical mechanics. From this foundation we derive a theory for ion channel kinetics, identifying a nonequilibrium 'process' free energy functional in addition to the well-known integrated work functionals. The Gibbs-Maxwell relation for the free energy functional is a Green-Kubo relation, applicable arbitrarily far from equilibrium, that captures the effect of non-local and time-dependent behavior from transient thermal and mechanical driving forces. Comparing the physical significance of the Lagrange multipliers to the canonical ensemble suggests definitions of nonequilibrium ensembles at constant capacitance or inductance in addition to constant resistance. Our result is that statistical mechanical descriptions derived from a few primitive algebraic operations on information can be used to create experimentally-relevant and computable models. By construction, these models may use information from more detailed atomistic simulations. Two surprising consequences to be explored in further work are that (in)distinguishability factors are automatically predicted from the problem formulation and that a direct analogue of the second law for thermodynamic entropy production is found by considering information loss in stochastic processes. The information loss identifies a novel contribution from the instantaneous information entropy that ensures non-negative loss.

  18. An Information Theory Approach to Nonlinear, Nonequilibrium Thermodynamics

    Science.gov (United States)

    Rogers, David M.; Beck, Thomas L.

    2012-01-01

    Using the problem of ion channel thermodynamics as an example, we illustrate the idea of building up complex thermodynamic models by successively adding physical information. We present a new formulation of information algebra that generalizes methods of both information theory and statistical mechanics. From this foundation we derive a theory for ion channel kinetics, identifying a nonequilibrium ‘process’ free energy functional in addition to the well-known integrated work functionals. The Gibbs-Maxwell relation for the free energy functional is a Green-Kubo relation, applicable arbitrarily far from equilibrium, that captures the effect of non-local and time-dependent behavior from transient thermal and mechanical driving forces. Comparing the physical significance of the Lagrange multipliers to the canonical ensemble suggests definitions of nonequilibrium ensembles at constant capacitance or inductance in addition to constant resistance. Our result is that statistical mechanical descriptions derived from a few primitive algebraic operations on information can be used to create experimentally-relevant and computable models. By construction, these models may use information from more detailed atomistic simulations. Two surprising consequences to be explored in further work are that (in)distinguishability factors are automatically predicted from the problem formulation and that a direct analogue of the second law for thermodynamic entropy production is found by considering information loss in stochastic processes. The information loss identifies a novel contribution from the instantaneous information entropy that ensures non-negative loss. PMID:22966210

  19. Regularity for solutions of non local parabolic equations

    CERN Document Server

    Lara, Héctor A Chang

    2011-01-01

    We study the regularity of solutions of parabolic fully nonlinear nonlocal equations. We proof $C^\\a$ regularity in space and time and for translation invariant equations and under different assumptions on the kernels $C^{1,\\a}$ in space and time regularity. The proofs rely on a weak parabolic ABP inspired in recent work done by L. Silvestre and the classic ideas of K. Tso and L. Wang. Our results remain uniform as $\\s\\to2$ allowing us to understand the non local theory as an extension to the classical one.

  20. Soft Matrix Elements in Non-local Chiral Quark Model

    CERN Document Server

    Kotko, Piotr

    2009-01-01

    Using non-local chiral quark model and currents satisfying Ward-Takahashi identities we analyze Distribution Amplitudes (DA) of photon and pion-to-photon Transition Distribution Amplitudes (TDA) in the low energy regime. Photon DA's are calculated analytically up to twist-4 and reveal several interesting features of photon structure. TDA's calculated in the present model satisfy polynomiality condition. Normalization of vector TDA is fixed by the axial anomaly. We also compute relevant form factors and compare them with existing data. Axial form factor turns out to be much lower then the vector one, what indeed is seen in the experimental data.

  1. Dynamical quenching with non-local alpha and downward pumping

    CERN Document Server

    Brandenburg, A; Käpylä, P J

    2014-01-01

    In light of new results, the one-dimensional mean-field dynamo model of Brandenburg & Kapyla (2007) with dynamical quenching and a nonlocal Babcock-Leighton alpha effect is re-examined for the solar dynamo. We extend the one-dimensional model to include the effects of turbulent downward pumping (Kitchatinov & Olemskoy 2011), and to combine dynamical quenching with shear. We use both the conventional dynamical quenching model of Kleeorin & Ruzmaikin (1982) and the alternate one of Hubbard & Brandenburg (2011), and confirm that with varying levels of non-locality in the alpha effect, and possibly shear as well, the saturation field strength can be independent of the magnetic Reynolds number.

  2. Specific heat of a non-local attractive Hubbard model

    Energy Technology Data Exchange (ETDEWEB)

    Calegari, E.J., E-mail: eleonir@ufsm.br [Laboratório de Teoria da Matéria Condensada, Departamento de Física, UFSM, 97105-900, Santa Maria, RS (Brazil); Lobo, C.O. [Laboratório de Teoria da Matéria Condensada, Departamento de Física, UFSM, 97105-900, Santa Maria, RS (Brazil); Magalhaes, S.G. [Instituto de Física, Universidade Federal Fluminense, Av. Litorânea s/n, 24210, 346, Niterói, Rio de Janeiro (Brazil); Chaves, C.M.; Troper, A. [Centro Brasileiro de Pesquisas Físicas, Rua Xavier Sigaud 150, 22290-180, Rio de Janeiro, RJ (Brazil)

    2013-10-01

    The specific heat C(T) of an attractive (interaction G<0) non-local Hubbard model is investigated within a two-pole approximation that leads to a set of correlation functions, which play an important role as a source of anomalies as the pseudogap. For a giving range of G and n{sub T} (where n{sub T}=n{sub ↑}+n{sub ↓}), the specific heat as a function of the temperature presents a two peak structure. Nevertehelesss, the presence of a pseudogap eliminates the two peak structure. The effects of the second nearest-neighbor hopping on C(T) are also investigated.

  3. Entangling capacities of noisy non-local Hamiltonians

    CERN Document Server

    Bandyopadhyay, S; Bandyopadhyay, Somshubhro; Lidar, Daniel A.

    2003-01-01

    We show that intrinsic Gaussian fluctuations in system control parameters impose limits on the ability of non-local (exchange) Hamiltonians to generate entanglement in the presence of mixed initial states. We find three equivalence classes. For the Ising and XYZ models there are qualitatively distinct sharp entanglement-generation transitions, while the class of Heisenberg, XY, and XXZ Hamiltonians is capable of generating entanglement for any finite noise level. Our findings imply that exchange Hamiltonians are surprisingly robust in their ability to generate entanglement in the presence of noise, thus potentially reducing the need for quantum error correction.

  4. Fast Non-Local Means Algorithm Based on Krawtchouk Moments

    Institute of Scientific and Technical Information of China (English)

    吴一全; 戴一冕; 殷骏; 吴健生

    2015-01-01

    Non-local means (NLM)method is a state-of-the-art denoising algorithm, which replaces each pixel with a weighted average of all the pixels in the image. However, the huge computational complexity makes it impractical for real applications. Thus, a fast non-local means algorithm based on Krawtchouk moments is proposed to improve the denoising performance and reduce the computing time. Krawtchouk moments of each image patch are calculated and used in the subsequent similarity measure in order to perform a weighted averaging. Instead of computing the Euclid-ean distance of two image patches, the similarity measure is obtained by low-order Krawtchouk moments, which can reduce a lot of computational complexity. Since Krawtchouk moments can extract local features and have a good anti-noise ability, they can classify the useful information out of noise and provide an accurate similarity measure. Detailed experiments demonstrate that the proposed method outperforms the original NLM method and other moment-based methods according to a comprehensive consideration on subjective visual quality, method noise, peak signal to noise ratio (PSNR), structural similarity (SSIM) index and computing time. Most importantly, the proposed method is around 35 times faster than the original NLM method.

  5. Thermodynamics of light and sound

    Directory of Open Access Journals (Sweden)

    G. M. Kremer

    1991-05-01

    Full Text Available This paper presents a thermodynamic theory of light and sound. It demonstrates that extended thermodynamics permits the explicit calculation of the main part of the equations of balance of energy for photons and phonons. Wave speeds are calculated and the limiting cases of near-equilibrium and free streaming are discussed.

  6. Thermodynamic aspects of rock friction

    CERN Document Server

    Mitsui, Noa

    2013-01-01

    Rate- and state-dependent friction law for velocity-step tests is analyzed from a thermodynamic point of view. A simple macroscopic non-equilibrium thermodynamic model with a single internal variable reproduces instantaneous jump and relaxation. Velocity weakening appears as a consequence of a plasticity related nonlinear coefficient. Permanent part of displacement corresponds to plastic strain, and relaxation effects are analogous to creep in thermodynamic rheology.

  7. GENERAL EQUILIBRIUM

    Directory of Open Access Journals (Sweden)

    Monique Florenzano

    2008-09-01

    Full Text Available General equilibrium is a central concept of economic theory. Unlike partial equilibrium analysis which study the equilibrium of a particular market under the clause “ceteris paribus” that revenues and prices on the other markets stay approximately unaffected, the ambition of a general equilibrium model is to analyze the simultaneous equilibrium in all markets of a competitive economy. Definition of the abstract model, some of its basic results and insights are presented. The important issues of uniqueness and local uniqueness of equilibrium are sketched; they are the condition for a predictive power of the theory and its ability to allow for statics comparisons. Finally, we review the main extensions of the general equilibrium model. Besides the natural extensions to infinitely many commodities and to a continuum of agents, some examples show how economic theory can accommodate the main ideas in order to study some contexts which were not thought of by the initial model

  8. 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...

  9. Discrete Thermodynamics of Lasers

    CERN Document Server

    Zilbergleyt, B

    2007-01-01

    The paper offers a discrete thermodynamic model of lasers. Laser is an open system; its equilibrium is based on a balance of two thermodynamic forces, one related to the incoming pumping power and another to the emitted light. The basic expression for such equilibrium is a logistic map, graphical solutions to which are pitchfork bifurcation diagrams. As pumping force increases, the relative populations on the ground and lasing branches tend to zero and unity correspondingly. An interesting feature of this model is the line spectrum of the up and down transitions between the branches beyond bifurcation point. Even in a simple case of 2-level laser with only 2 possible transition types (up and down), the spectra look like sets of the line packets, starting well before the population inversion. This effect is an independent confirmation of the Einstein's prohibition on practical realization of 2-level laser. Multilevel lasers may be approached by employing the idea of thermodynamic activity for the emitting atom...

  10. Inflationary magnetogenesis and non-local actions: The conformal anomaly

    CERN Document Server

    El-Menoufi, Basem Kamal

    2015-01-01

    We discuss the possibility of successful magnetogenesis during inflation by employing the one-loop effective action of massless QED. The action is strictly non-local and results from the long distance fluctuations of massless charged particles present at the inflationary scale. Most importantly, it encodes the conformal anomaly of QED which is crucial to avoid the vacuum preservation in classical electromagnetism. In particular, we find a blue spectrum for the magnetic field with spectral index $n_B \\simeq 2 - \\alpha_{\\text{e}}$ where $\\alpha_{\\text{e}}$ depends on both the number of e-folds during inflation as well as the coefficient of the one-loop beta function. In particular, the sign of the beta function has important bearing on the final result. A low reheating temperature is required for the present day magnetic field to be consistent with the lower bound inferred on the field in the intergalactic medium.

  11. Non-Markovian quantum dynamics: local versus non-local

    CERN Document Server

    Chruscinski, Dariusz

    2009-01-01

    We analyze non-Markovian evolution of open quantum systems. It is shown that any dynamical map representing evolution of such a system may be described either by non-local master equation with memory kernel or equivalently by equation which is local in time. Theses two descriptions are complementary: if one is simple the other is quite involved, or even singular, and vice versa. The price one pays for the local approach is that the corresponding generator keeps the memory about the starting point `t_0'. This is the very essence of non-Markovianity. Interestingly, this generator might be highly singular, nevertheless, the corresponding dynamics is perfectly regular. Remarkably, singularities of generator may lead to interesting physical phenomena like revival of coherence or sudden death and revival of entanglement.

  12. Non-local means filter for trim statics

    KAUST Repository

    Huang, Yunsong

    2014-08-05

    Structures will be mispositioned across prestack migration gathers in the presence of inaccuracies in the velocity model. Stacking these misaligned gathers runs the risk of destroying important structures in the stacked migration image. To mitigate this problem, we propose a trim statics inspired by the non-local means algorithm originally developed for image denoising. This method differs from the conventional one in two fundamental respects. First, the trim statics are computed by comparing image patches instead of individual image traces. Second, no global pilot trace is needed because only two migration images at a time participate in trim statics and are stacked into one image. A multitude of migration images are stacked recursively in this two-to-one fashion. Tests with a Gulf of Mexico dataset show a noticeable improvement in the feature coherency of the stacked migration image.

  13. Multiple solutions for perturbed non-local fractional Laplacian equations

    Directory of Open Access Journals (Sweden)

    Massimiliano Ferrara

    2013-11-01

    Full Text Available In article we consider problems modeled by the non-local fractional Laplacian equation $$\\displaylines{ (-\\Delta^s u=\\lambda f(x,u+\\mu g(x,u \\quad\\text{in } \\Omega\\cr u=0 \\quad\\text{in } \\mathbb{R}^n\\setminus \\Omega, }$$ where $s\\in (0,1$ is fixed, $(-\\Delta ^s$ is the fractional Laplace operator, $\\lambda,\\mu$ are real parameters, $\\Omega$ is an open bounded subset of $\\mathbb{R}^n$ ($n>2s$ with Lipschitz boundary $\\partial \\Omega$ and $f,g:\\Omega\\times\\mathbb{R}\\to\\mathbb{R}$ are two suitable Caratheodory functions. By using variational methods in an appropriate abstract framework developed by Servadei and Valdinoci [17] we prove the existence of at least three weak solutions for certain values of the parameters.

  14. STABLE STATIONARY STATES OF NON-LOCAL INTERACTION EQUATIONS

    KAUST Repository

    FELLNER, KLEMENS

    2010-12-01

    In this paper, we are interested in the large-time behaviour of a solution to a non-local interaction equation, where a density of particles/individuals evolves subject to an interaction potential and an external potential. It is known that for regular interaction potentials, stable stationary states of these equations are generically finite sums of Dirac masses. For a finite sum of Dirac masses, we give (i) a condition to be a stationary state, (ii) two necessary conditions of linear stability w.r.t. shifts and reallocations of individual Dirac masses, and (iii) show that these linear stability conditions imply local non-linear stability. Finally, we show that for regular repulsive interaction potential Wε converging to a singular repulsive interaction potential W, the Dirac-type stationary states ρ̄ ε approximate weakly a unique stationary state ρ̄ ∈ L∞. We illustrate our results with numerical examples. © 2010 World Scientific Publishing Company.

  15. Implementing an Equilibrium Law Teaching Sequence for Secondary School Students to Learn Chemical Equilibrium

    Science.gov (United States)

    Ghirardi, Marco; Marchetti, Fabio; Pettinari, Claudio; Regis, Alberto; Roletto, Ezio

    2015-01-01

    A didactic sequence is proposed for the teaching of chemical equilibrium law. In this approach, we have avoided the kinetic derivation and the thermodynamic justification of the equilibrium constant. The equilibrium constant expression is established empirically by a trial-and-error approach. Additionally, students learn to use the criterion of…

  16. Implementing an Equilibrium Law Teaching Sequence for Secondary School Students to Learn Chemical Equilibrium

    Science.gov (United States)

    Ghirardi, Marco; Marchetti, Fabio; Pettinari, Claudio; Regis, Alberto; Roletto, Ezio

    2015-01-01

    A didactic sequence is proposed for the teaching of chemical equilibrium law. In this approach, we have avoided the kinetic derivation and the thermodynamic justification of the equilibrium constant. The equilibrium constant expression is established empirically by a trial-and-error approach. Additionally, students learn to use the criterion of…

  17. 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...

  18. New Thermodynamic Paradigm of Chemical Equilibria

    CERN Document Server

    Zilbergleyt, B

    2011-01-01

    The paper presents new thermodynamic paradigm of chemical equilibrium, setting forth comprehensive basics of Discrete Thermodynamics of Chemical Equilibria (DTd). Along with previous results by the author during the last decade, this work contains also some new developments of DTd. Based on the Onsager's constitutive equations, reformulated by the author thermodynamic affinity and reaction extent, and Le Chatelier's principle, DTd brings forward a notion of chemical equilibrium as a balance of internal and external thermodynamic forces (TdF), acting against a chemical system. Basic expression of DTd is the chemical system logistic map of thermodynamic states that ties together energetic characteristics of chemical reaction, occurring in the system, the system shift from "true" thermodynamic equilibrium (TdE), and causing that shift external thermodynamic forces. Solutions to the basic map are pitchfork bifurcation diagrams in coordinates "shift from TdE - growth factor (or TdF)"; points, corresponding to the ...

  19. Relativistic perfect fluids in local thermal equilibrium

    CERN Document Server

    Coll, Bartolomé; Sáez, Juan Antonio

    2016-01-01

    The inverse problem for conservative perfect fluid energy tensors provides a striking result. Namely that, in spite of its name, its historic origin or its usual conceptualization, the notion of {\\em local thermal equilibrium} for a perfect fluid is a {\\em purely hydrodynamic}, not thermodynamic, notion. This means that it may be thought, defined and detected using exclusively hydrodynamic quantities, without reference to temperature or any other thermodynamic concept, either of equilibrium or irreversible: a relativistic perfect fluid evolves in local thermal equilibrium if, and only if, its hydrodynamic variables evolve keeping a certain relation among them. This relation fixes, but only fixes, a precise fraction of the thermodynamics of the fluid, namely that relating the speed of its sound waves to the hydrodynamic variables. All thermodynamic schemes (sets of thermodynamic variables and their mutual relations) compatible with such a relation on the sole hydrodynamic variables are obtained. This hydrodyna...

  20. Application of nano-magnesso ferrite (n-MgFe{sub 2}O{sub 4}) for the removal of Co{sup 2+} ions from synthetic wastewater: Kinetic, equilibrium and thermodynamic studies

    Energy Technology Data Exchange (ETDEWEB)

    Srivastava, Varsha, E-mail: varsha06bhu@gmail.com [Laboratory of Green Chemistry, Faculty of Technology, Lappeenranta University of Technology, Sammonkatu 12, FI-50130 Mikkeli (Finland); Sharma, Y.C. [Department of Chemistry, Indian Institute of Technology, Banaras Hindu University, Varanasi 221005 (India); Sillanpää, Mika [Laboratory of Green Chemistry, Faculty of Technology, Lappeenranta University of Technology, Sammonkatu 12, FI-50130 Mikkeli (Finland)

    2015-05-30

    Graphical abstract: - Highlights: • The removal efficiency of n-MgFe{sub 2}O{sub 4} for Co(II) ions was investigated. • Rapid removal efficiency was observed within 60 min of contact time. • The kinetic data of Co(II) followed the pseudo-second-order model. • Thermodynamic studies revealed that the adsorption reaction was spontaneous. • Desorption study demonstrated its reusability upto three adsorption–desorption cycles. - Abstract: The aim of this research is to investigate the adsorption characteristics of nano-magnesso ferrite (n-MgFe{sub 2}O{sub 4}) for the removal of Co(II) ions from aqueous solution. n-MgFe{sub 2}O{sub 4} was synthesized by precipitation method. XRD of synthesized particles reveals the formation of single-phase n-MgFe{sub 2}O{sub 4} nanoparticles. TEM confirms the formation of particle size in the range of 25–35 nm. AFM and SEM analysis also support the TEM result. BET surface area of nanoparticles was determined to be 53.83 m{sup 2}/g. The adsorption of Co(II) onto n-MgFe{sub 2}O{sub 4} was found to be dependent on pH and the removal increased in alkaline medium. Co(II) adsorption followed pseudo-second-order model. Thermodynamic study showed that the adsorption process was endothermic and spontaneous. The equilibrium adsorption data was analyzed by two parameters and three parameters isotherm. Langmuir adsorption capacity was determined to be 67.41 mg/g. Chi-square test, standard deviations and the sum of squares of the errors (SSE) were evaluated to find out the better isotherm model. Desorption and reusability test suggested that n-MgFe{sub 2}O{sub 4} can be efficiently used up to three adsorption–desorption cycles. The findings of the present study suggest that n-MgFe{sub 2}O{sub 4} is very efficient for the adsorption of Co(II) ions. Adsorption efficiency of n-MgFe{sub 2}O{sub 4} for Co(II) has not yet been studied, so this study can be helpful for the treatment of Co(II) rich wastewater in near future.

  1. Thermodynamic Properties and Phase Equilibrium Study of Lennard-Jones Model and Application to Real Molecules%LJ模型的热力学特性、相平衡及用于真实分子的研究

    Institute of Scientific and Technical Information of China (English)

    周世琦

    2005-01-01

    Both a free volume approach for Helmholtz free energy and a theoretically-based fitted formula for radial distribution function (rdf) of hard sphere solid were employed to describe the Helmholtz free energy of Lennard-Jones (LJ) solid in the framework of first order thermodynamic perturbation theory. Dividing the LJ potential follows from a modified WCA prescription, the specification of equivalent hard sphere diameter was determined by a simple iteration procedure devised originally for liquid state, but extended to solid state in the present study. Two hundred shells were used in the rdf to get an accurate perturbation term. Bulk fluid thermodynamic property of the LJ model is from a recently proposed equation of state. The present approach is very accurate for the description of excess Helmholtz free energy and equation of state of LJ solid, but shows some deviation from the simulation for excess Helmholtz free energy of uniform LJ fluid when the reduced temperature is lower than 0.75. The present approach is satisfactory for description of phase equilibrium of the LJ model. By choosing the appropriate LJ potential parameter, the present approach can describe the melting curve of real molecules accurately.%结合描述硬球固体Helmholtz自由能的自由体积方法与描述硬球固体径向分布函数的拟合的分析表达式与一阶热力学摄动理论,用于描述Lennard-Jones(LJ)固体的Helmholtz自由能.按照一个修正的WCA方法将LJ势分为短程排斥部分与长程吸引部分,将文献中一个用于求取液相的等价的硬球直径的简单的迭代法扩展到固相,用于求取固相的等价的硬球直径.在固体Helmholtz自由能的计算中,使用200壳层,以便获得精确的结果.体相LJ液体的热力学特性由一个最近提出的状态方程求取.该方法很好地描述了LJ固体的过量Helmholtz自由能与状态方程,满意地描述了Lennard-Jones模型的相平衡;通过选取合适的LJ势参数,能很

  2. Non-local convergence coupling in a simple stochastic convection model

    Science.gov (United States)

    Brenowitz, N. D.; Frenkel, Y.; Majda, A. J.

    2016-06-01

    Observational studies show a strong correlation between large-scale wind convergence and precipitation. However, using this as a convective closure assumption to determine the total precipitation in a numerical model typically leads to deleterious wave-CISK behavior such as grid-scale noise. The quasi-equilibrium (QE) schemes ameliorate this issue and smooth the precipitation field, but still inadequately represent the intermittent and organized nature of tropical convection. However, recent observational evidence highlights that the large-scale convergence field primarily affects precipitation by increasing the overall convective cloud fraction rather than the energetics of individual convective elements. In this article, the dynamical consequences of this diagnostic observation are studied using a simple one baroclinic mode stochastic model for convectively coupled waves. A version of this model is implemented which couples the stochastic formation of convective elements to the wind convergence. Linearized analysis shows that using the local convergence results in a classic wave-CISK standing instability where the growth rate increases with the wavenumber. However, using a large-scale averaged convergence restricts the instability to physically plausible scales. Convergence coupling is interpreted as a surrogate for the non-local effects of gregarious convection. In nonlinear stochastic simulations with a non-uniform imposed sea surface temperature (SST) field, the non-local convergence coupling introduces desirable intermittent variability on intraseasonal time scales. Convergence coupling leads to a circulation with a similar mean but higher variability than the equivalent parameterization without convergence coupling. Finally, the model is shown to retain these features on fine and coarse mesh sizes.

  3. Chemical thermodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Rock, P.A.

    1983-01-01

    This book, suitable as an introductory text for undergraduates, presents temperature, internal energy, and entropy with a minimum of mathematics. The basic mathematical models of classical chemical thermodynamics are developed later in the text. Includes numerous problems at the end of each chapter, an appendix giving thermodynamic data for common substances, a short list of references, answers to selected problems, and a subject index. Contents, abridged: Energy and the first law of thermodynamics. Thermodynamic functions. The third law of thermodynamics and absolute entropies. Thermodynamics of chemical reactions. Phase equilibria: the activity function. Thermodynamics of ions in solution. Statistical thermodynamics. Appendices. Index.

  4. 乙醚-甲醇-正丁醇多元系汽液平衡的热力学性质%Thermodynamic Properties for Vapor-Liquid Equilibrium of Diethyl Ether Methanol-n-Butanol Multicomponent System

    Institute of Scientific and Technical Information of China (English)

    高大明; 张凌云; 管航敏; 孙虹; 陈红; 朱德春

    2011-01-01

    Under different liquid phase compositions, the isobaric vapor-liquid equilibrium (VLE) data of three binary systems (diethyl ether-methanol, diethyi ether-n-butanol and methanol-n-butanol) and one ternary system (diethyl ether-methanol-n-butanol) were determined at 101.325 kPa by using a novel pump-ebullionmeter.The vapor-phase compositions y of above three binary systems were calculated from T,p,x by the indirect method.The activity coefficients of the three binary systems were correlated separately with Wilson, N-RTL, Margules and van Laar models, and the parameters of liquid phase activity coefficient models were calculated through the least square method, and then the obtained parameters were used to calculate the vapor-phase compositions y. The obtained activity coefficients were used to calculate the excess Gibbs function (GE/RT) of the three binary systems,and the results show that all the systems studied here do not exhibit azeotropes. Using the obtained parameters of Wilson, NRTL, Margules and van Laar models, the experimental VLE data of the ternary system were correlated to construct the thermodynamic model of VLE for the ternary system and to calculate its equilibrating vapor-phase composition y and the bubble point, respectively. The calculated bubble points agree with the experimental data well, and the thermodynamic consistency of the phase equilibrium data of the three binary systems calculated by those model parameters were checked with area test method and got satisfactory results.%用新型泵式沸点仪测定了在101.325 kPa下乙醚-甲醇、乙醚-正丁醇、甲醇-正丁醇3个二元系以及乙醚-甲醇-正丁醇三元系在不同液相组成时的沸点,并用间接法Tpx推算了3个二元系的汽相平衡组成y.3个二元体系活度系数分别用Wilson模型、NRTL模型、Margules模型和van Laar模型进行关联,用最小二乘法求出了它们的液相活度系数模型参数,同时,用这些模型参数来计算它们的

  5. Modeling of Competitive Ultrasonic Assisted Removal of The Crystal Violet and Aura Mineo using Mwcnts Functionalized by N-(3-Nitrobenzylidene-Nˊ-Trimethoxysilylpropyl-Ethane-1,2-Diamine:Equilibrium, Kinetics and Thermodynamic Study

    Directory of Open Access Journals (Sweden)

    Farveh Raoufi

    2016-08-01

    Full Text Available In this study, adsorbent was synthesized by covalently anchoring N-(3-nitro-benzylidene-N-trimethoxysilylpropyl-ethane-1, 2-diamine onto multi-walled carbon nanotubes (NBATSPED-MWCNTs. This novel material was characterized by different techniques such as XRD, SEMand FT-IR.Subsequently, itwasusedfortheultrasound-assisted removalofAura mine O(AO and Crystal violet (CV from aqueous solutions was investigated. The dependency of removal percentages to variables such as pH, initial dyes concentration,adsorbent dosage, sonication time on the removal percentages ofAO and CV were simultaneously investigated by central composite design (CCD under response surface methodology (RSM. It was shown that the adsorption of AO and CV follows the pseudo-second-order rate equation, while the Langmuir model explains equilibrium data. Isotherms had also been used to obtain the thermodynamic parameters such as free energy (ΔG°, enthalpy (ΔH° and entropy (ΔS° of adsorption. The negative value of ΔG° indicates the feasibility and spontaneity of the adsorption process. The positive ΔH° suggests the endothermic nature of the adsorption. The positive values of ΔS0 reflect the affinity of multi-walled carbon nanotubes functionalized towards CV and AO. A small amount of the adsorbent was able to remove more than 99.20% of both dyes rapidly with high adsorption capacity in binary-component system (69.36 mgg-1 and 120.65mg g-1for AO and CV respectively.

  6. Non-equilibrium thermodynamics analysis and its application for polymer composites design in tribological fields%非平衡热力学在摩擦领域聚合物复合材料设计中的应用

    Institute of Scientific and Technical Information of China (English)

    穆立文; 史以俊; 冯新; 陆小华

    2014-01-01

    以自润滑材料和摩擦材料为例,基于非平衡热力学原理从热量产生和传递的根本问题出发,研究摩擦系数和热导率对材料接触面温度的影响,指导聚合物基复合材料的设计。对于自润滑材料来说,将摩擦热量产生和传递过程假设成两个过程的串联,发现摩擦热产生是摩擦系统整体稳定运行的关键控制因素。对于摩擦材料来说,将摩擦热量传递过程假设成传递热量和分配热量两个过程的并联,发现需采用降低刹车片热导率的逆向思维降低接触面温度。%The heat generation and transfer process of self-lubricating materials and friction materials was quantitatively described from the fundamental principle of non-equilibrium thermodynamics. The effect of friction coefficient and thermal conductivity on the contact temperature of materials was studied, and the finding could guide the design of polymer composites. For the self-lubricating materials, the frictional heat generation and transfer process was assumed to be two processes in series. The frictional heat generated was the key controlling factor for stable operation of the friction system. For the friction materials, frictional heat transfer process was assumed to be heat transfer and heat distribution, two processes in parallel, and it was required to reduce thermal conductivity of the brake pads in order to lower contact surface temperature.

  7. Optimization of parameters for cerium(III) biosorption onto biowaste materials of animal and plant origin using 5-level Box-Behnken design:Equilibrium, kinetic, thermodynamic and regeneration studies

    Institute of Scientific and Technical Information of China (English)

    Jaya Sre Varsihini C; Devlina Das; Nilanjana Das

    2014-01-01

    Response surface methodology (RSM) employing 5-level Box-Behnken design was used to optimize the biosorption of ce-rium(III) onto biowaste materials of animal and plant origin viz. prawn carapace (PC) and corn style (CS). Various process parame-ters viz. pH (A:3.0-9.0), biomass dosage (B:0.05-0.35 g/L), initial metal concentration (C:50-350 mg/L), contact time (D:2-6 h) and temperature (E:20-60 °C) were chosen for optimization. A log transformation was suggested by the Box-Cox plot in the present case. A low p-value of<0.0001 validated the significance of the model. Maximum Ce(III) uptake of 218.3 mg/g for PC and 180.2 mg/g for CS was noted under optimum conditions. Among the equilibrium isotherms, Freundlich model was found to be the best fit-ted one suggesting a heterogeneous mode of biosorption on PC whereas Langmuir model showed the best fit suggesting homogene-ous mode of cerium biosorption on CS. This was further confirmed by scanning electron microscopy (SEM). Kinetic studies showed better applicability of pseudo-first order model suggesting physisorption as phenomena underlying the process. Film-diffusion was suggested by the non-linearity of the Boyd plot. Thermodynamic studies showed that the process was endothermic and spontaneous. FTIR analysis confirmed a major involvement of the participation of amide, amines, ketones and primary alcohol groups during Ce(III) biosorption. EDAX analysis confirmed the major participation of carbon group during Ce(III) biosorption. This was the first report on parameter optimization of Ce(III) biosorption onto biowaste materials using 5-level Box-Behnken experimental design which might be helpful for the recovery of Ce(III) from aqueous environment.

  8. Understanding Thermal Equilibrium through Activities

    Science.gov (United States)

    Pathare, Shirish; Huli, Saurabhee; Nachane, Madhura; Ladage, Savita; Pradhan, Hemachandra

    2015-01-01

    Thermal equilibrium is a basic concept in thermodynamics. In India, this concept is generally introduced at the first year of undergraduate education in physics and chemistry. In our earlier studies (Pathare and Pradhan 2011 "Proc. episteme-4 Int. Conf. to Review Research on Science Technology and Mathematics Education" pp 169-72) we…

  9. On holographic entanglement entropy of non-local field theories

    CERN Document Server

    Pang, Da-Wei

    2014-01-01

    We study holographic entanglement entropy of non-local field theories both at extremality and finite temperature. The gravity duals, constructed in arXiv:1208.3469 [hep-th], are characterized by a parameter $w$. Both the zero temperature backgrounds and the finite temperature counterparts are exact solutions of Einstein-Maxwell-dilaton theory. For the extremal case we consider the examples with the entangling regions being a strip and a sphere. We find that the leading order behavior of the entanglement entropy always exhibits a volume law when the size of the entangling region is sufficiently small. We also clarify the condition under which the next-to-leading order result is universal. For the finite temperature case we obtain the analytic expressions both in the high temperature limit and in the low temperature limit. In the former case the leading order result approaches the thermal entropy, while the finite contribution to the entanglement entropy at extremality can be extracted by taking the zero temper...

  10. Non-local deformation effects in shear flows

    Directory of Open Access Journals (Sweden)

    A. V. Popova

    2015-01-01

    Full Text Available The method for detection of clusters on the basis of event space–time dependence is classically applied for foreshock–mainshock–aftershock sequences for which event connectedness is generally accepted. In the paper, this approach is used to investigate the whole event catalogue of foreshock and aftershock sequences filtered from the events with small magnitudes, in which connected events are also determined. The space scale is extended due to the inclusion of the parameter of seismic event connectedness in the direction of dislocation shift that allows us to consider the obtained connected events as clusters in a shear flow. A statistical model of the shear flow was constructed by catalogue decomposition into timescales and space scales defined analytically. A modelling algorithm of the shear flow was developed and its stability to initial condition change was investigated. Shear flow structure and arising non-local deformation characteristics which may be the criteria for dynamic process activity in the considered subduction zone of the Kuril–Kamchatka island arc were analysed.

  11. Cosmological evolution of generalized non-local gravity

    CERN Document Server

    Zhang, Xue; Li, Song; Liu, Yu-Chen; Chen, Bo-Hai; Chai, Yun-Tian; Shu, Shuang

    2015-01-01

    We construct a class of generalized non-local gravity (GNLG) model which is the modified theory of general relativity (GR) obtained by adding a term $m^{2n-2} R\\Box^{-n}R$ to the Einstein-Hilbert action. Concretely, we not only study the gravitational equation for the GNLG model by introducing auxiliary scalar fields, but also analyse the classical stability and examine the cosmological consequences of the model for different exponent $n$. We find that the half of the scalar fields are always ghost-like and the exponent $n$ must be taken even number for a stable GNLG model. Meanwhile, the model spontaneously generates three dominant phases of the evolution of the universe, and the equation of state parameters turn out to be phantom-like. Furthermore, we clarify in another way that exponent $n$ should be even numbers by discuss the spherically symmetric static solutions in Newtonian gauge. It is worth stressing that the results given by us can include ones in refs. [24, 29, 31] as the special case of $n=2$.

  12. Non-local correlations within dynamical mean field theory

    Energy Technology Data Exchange (ETDEWEB)

    Li, Gang

    2009-03-15

    The contributions from the non-local fluctuations to the dynamical mean field theory (DMFT) were studied using the recently proposed dual fermion approach. Straight forward cluster extensions of DMFT need the solution of a small cluster, where all the short-range correlations are fully taken into account. All the correlations beyond the cluster scope are treated in the mean-field level. In the dual fermion method, only a single impurity problem needs to be solved. Both the short and long-range correlations could be considered on equal footing in this method. The weak-coupling nature of the dual fermion ensures the validity of the finite order diagram expansion. The one and two particle Green's functions calculated from the dual fermion approach agree well with the Quantum Monte Carlo solutions, and the computation time is considerably less than with the latter method. The access of the long-range order allows us to investigate the collective behavior of the electron system, e.g. spin wave excitations. (orig.)

  13. Non-local in time perturbations of linear hyperbolic PDEs

    CERN Document Server

    Lechner, Gandalf

    2013-01-01

    Linear Integro-differential equations of the form $(D+\\lambda W)f=0$ are studied, where $D$ is a normal or prenormal hyperbolic differential operator on $\\mathbb{R}^n$, $\\lambda\\in\\mathbb{C}$ is a coupling constant, and $W$ is a regular integral operator with compactly supported kernel. In particular, $W$ can be non-local in time, so that a Hamiltonian formulation is not possible. It is shown that for sufficiently small $|\\lambda|$, the hyperbolic character of $D$ is essentially preserved. Unique advanced/retarded fundamental solutions are constructed by means of a convergent expansion in $\\lambda$, and the solution spaces are analyzed. It is shown that the acausal behavior of the solutions is well-controlled, but the Cauchy problem is ill-posed in general. Nonetheless, a scattering operator can be calculated which describes the effect of $W$ on the space of solutions of $D$. It is also described how these structures occur in the context of wave or Dirac equations on noncommutative deformations of Minkowski s...

  14. Black supernovae and black holes in non-local gravity

    CERN Document Server

    Bambi, Cosimo; Modesto, Leonardo

    2016-01-01

    In a previous paper, we studied the interior solution of a collapsing body in a non-local theory of gravity super-renormalizable at the quantum level. We found that the classical singularity is replaced by a bounce, after which the body starts expanding. A black hole, strictly speaking, never forms. The gravitational collapse does not create an event horizon but only an apparent one for a finite time. In this paper, we solve the equations of motion assuming that the exterior solution is static. With such an assumption, we are able to reconstruct the solution in the whole spacetime, namely in both the exterior and interior regions. Now the gravitational collapse creates an event horizon in a finite comoving time, but the central singularity is approached in an infinite time. We argue that these black holes should be unstable, providing a link between the scenarios with and without black holes. Indeed, we find a non catastrophic ghost-instability of the metric in the exterior region. Interestingly, under certai...

  15. The relation between Hardy's non-locality and violation of Bell inequality

    Science.gov (United States)

    Xiang, Yang

    2011-06-01

    We give an analytic quantitative relation between Hardy's non-locality and Bell operator. We find that Hardy's non-locality is a sufficient condition for the violation of Bell inequality, the upper bound of Hardy's non-locality allowed by information causality just corresponds to Tsirelson bound of Bell inequality and the upper bound of Hardy's non-locality allowed by the principle of no-signaling just corresponds to the algebraic maximum of Bell operator. Then we study the Cabello's argument of Hardy's non-locality (a generalization of Hardy's argument) and find a similar relation between it and violation of Bell inequality. Finally, we give a simple derivation of the bound of Hardy's non-locality under the constraint of information causality with the aid of the above derived relation between Hardy's non-locality and Bell operator.

  16. A non-local, ordinary-state-based viscoelasticity model for peridynamics.

    Energy Technology Data Exchange (ETDEWEB)

    Mitchell, John Anthony

    2011-10-01

    A non-local, ordinary-state-based, peridynamics viscoelasticity model is developed. In this model, viscous effects are added to deviatoric deformations and the bulk response remains elastic. The model uses internal state variables and is conceptually similar to linearized isotropic viscolelasticity in the local theory. The modulus state, which is used to form the Jacobian matrix in Newton-Raphson algorithms, is presented. The model is shown to satisfy the 2nd law of thermodynamics and is applicable to problems in solid continuum mechanics where fracture and rate effects are important; it inherits all the advantages for modeling fracture associated with peridynamics. By combining this work with the previously published ordinary-state-based plasticity model, the model may be amenable to viscoplasticity problems where plasticity and rate effects are simultaneously important. Also, the model may be extended to include viscous effects for spherical deformations as well. The later two extensions are not presented and may be the subject of further work.

  17. Non-local effects of point mutations on the stability of a protein module

    Science.gov (United States)

    Chwastyk, Mateusz; Vera, Andrés M.; Galera-Prat, Albert; Gunnoo, Melissabye; Thompson, Damien; Carrión-Vázquez, Mariano; Cieplak, Marek

    2017-09-01

    We combine experimental and theoretical methods to assess the effect of a set of point mutations on c7A, a highly mechanostable type I cohesin module from scaffoldin CipA from Clostridium thermocellum. We propose a novel robust and computationally expedient theoretical method to determine the effects of point mutations on protein structure and stability. We use all-atom simulations to predict structural shifts with respect to the native protein and then analyze the mutants using a coarse-grained model. We examine transitions in contacts between residues and find that changes in the contact map usually involve a non-local component that can extend up to 50 Å. We have identified mutations that may lead to a substantial increase in mechanical and thermodynamic stabilities by making systematic substitutions into alanine and phenylalanine in c7A. Experimental measurements of the mechanical stability and circular dichroism data agree qualitatively with the predictions provided the thermal stability is calculated using only the contacts within the secondary structures.

  18. Thermodynamic model for equilibrium solubility of gibbsite in concentrated NaOH solutions%三水铝石在氢氧化钠溶液中的平衡溶解度热力学模型

    Institute of Scientific and Technical Information of China (English)

    李小斌; 阎丽; 周秋生; 刘桂华; 彭志宏

    2012-01-01

    针对拜耳法生产氧化铝过程中最为重要的NaAl(OH)4-NaOH-H2O体系,构建三水铝石溶解于氢氧化钠溶液的反应平衡常数的理论模型,并得出电解质NaAl(OH)4新的Pitzer模型参数和NaOH-NaAl(OH)4-H2O体系的热力学混合参数(温度范围298.15~373.15 K).将所得模型和参数对NaAl(OH)4-NaOH-H2O体系进行适用性分析.结果表明:将该理论模型用来计算三水铝石溶解反应的平衡常数是适用且准确的;电解质NaAl(OH)4的Pitzer模型参数β(0)(NaAl(OH)4)、β(1)(NaAl(OH)4)和CΦ(NaAl(OH)4),Al(OH)4与OHˉ的二离子相互作用参数θ(OHˉAl(OH)4ˉ),以及Al(OH)4ˉ与OHˉ和Na+的三离子相互作用参数Ψ(Na+OHˉAl(OH)4-)均与温度相关;当温度在298.15~373.15 K时,预测三水铝石溶解于氢氧化钠溶液的平衡溶解度是可行的.%The thermodynamic properties of the most important NaOH-NaAl(OH)4-H2O system in Bayer process for alumina production were investigated.A theoretical model for calculating the equilibrium constant of gibbsite dissolved in sodium hydroxide solution was proposed.New Pitzer model parameters and mixing parameters for the system NaOH-NaAl(OH)4-H2O were yielded and tested in the temperature range of 298.15-373.15 K.The results show that the proposed model for calculating the equilibrium constant of gibbsite dissolution is applicable and accurate.The obtained Pitzer model parameters of β(0)(NaAl(OH)4),β(1)(NaAl(OH)4),CΦ(NaAl(OH)4) for NaAl(OH)4,the binary mixing parameter of θ(OH-Al(OH)4-) for Al(OH)4- with OH-,and the ternary mixing parameter of Ψ(Na+OH-Al(OH)4 ) for Al(OH)4 with OH and Na+ are temperature-dependent.The prediction of the equilibrium solubility of gibbsite dissolved in sodium hydroxide solution was feasible in the temperature range of 298.15-373.15 K.

  19. Zeroth Law, Entropy, Equilibrium, and All That

    Science.gov (United States)

    Canagaratna, Sebastian G.

    2008-01-01

    The place of the zeroth law in the teaching of thermodynamics is examined in the context of the recent discussion by Gislason and Craig of some problems involving the establishment of thermal equilibrium. The concept of thermal equilibrium is introduced through the zeroth law. The relation between the zeroth law and the second law in the…

  20. Zeroth Law, Entropy, Equilibrium, and All That

    Science.gov (United States)

    Canagaratna, Sebastian G.

    2008-01-01

    The place of the zeroth law in the teaching of thermodynamics is examined in the context of the recent discussion by Gislason and Craig of some problems involving the establishment of thermal equilibrium. The concept of thermal equilibrium is introduced through the zeroth law. The relation between the zeroth law and the second law in the…