A comprehensive comparison of five inorganic aerosol thermodynamic equilibrium modules, MARS-A, SEQUILIB, SCAPE2, EQUISOLV II, and AIM2, was conducted for a variety of atmospheric concentrations of particulate matter (PM) constituents, relative humidities (RHs), and temperatures....
IS THE SIZE DISTRIBUTION OF URBAN AEROSOLS DETERMINED BY THERMODYNAMIC EQUILIBRIUM? (R826371C005)
A size-resolved equilibrium model, SELIQUID, is presented and used to simulate the size–composition distribution of semi-volatile inorganic aerosol in an urban environment. The model uses the efflorescence branch of aerosol behavior to predict the equilibrium partitioni...
The partitioning of total nitrate (TNO3) and total ammonium (TNH4) between gas and aerosol phases is studied with two thermodynamic equilibrium models, ISORROPIA and AIM, and three datasets: high time-resolution measurement data from the 1999 Atlanta SuperSite Experiment and from...
Local non-equilibrium thermodynamics
Jinwoo, Lee; Tanaka, Hajime
2015-01-01
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. PMID:25592077
Local non-equilibrium thermodynamics.
Jinwoo, Lee; Tanaka, Hajime
2015-01-01
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. PMID:25592077
A Computationally Efficient Algorithm for Aerosol Phase Equilibrium
Zaveri, Rahul A.; Easter, Richard C.; Peters, Len K.; Wexler, Anthony S.
2004-10-04
Three-dimensional models of atmospheric inorganic aerosols need an accurate yet computationally efficient thermodynamic module that is repeatedly used to compute internal aerosol phase state equilibrium. In this paper, we describe the development and evaluation of a computationally efficient numerical solver called MESA (Multicomponent Equilibrium Solver for Aerosols). The unique formulation of MESA allows iteration of all the equilibrium equations simultaneously while maintaining overall mass conservation and electroneutrality in both the solid and liquid phases. MESA is unconditionally stable, shows robust convergence, and typically requires only 10 to 20 single-level iterations (where all activity coefficients and aerosol water content are updated) per internal aerosol phase equilibrium calculation. Accuracy of MESA is comparable to that of the highly accurate Aerosol Inorganics Model (AIM), which uses a rigorous Gibbs free energy minimization approach. Performance evaluation will be presented for a number of complex multicomponent mixtures commonly found in urban and marine tropospheric aerosols.
The inorganic species of sulfate, nitrate and ammonium constitute a major fraction of atmospheric aerosols. The behavior of nitrate is one of the most intriguing aspects of inorganic atmospheric aerosols because particulate nitrate concentrations depend not only on the amount of ...
Thermodynamic equilibrium at heterogeneous pressure
NASA Astrophysics Data System (ADS)
Vrijmoed, Johannes C.; Podladchikov, Yuri Y.
2014-05-01
Recent advances in metamorphic petrology point out the importance of grain-scale pressure variations in high-temperature metamorphic rocks. Pressures derived from chemical zonation using unconventional geobarometry based on equal chemical potentials fit mechanically feasible pressure variations. Here a thermodynamic equilibrium method is presented that predicts chemical zoning as a result of pressure variations by Gibbs energy minimization. Equilibrium thermodynamic prediction of the chemical zoning in the case of pressure heterogeneity is done by constraint Gibbs minimization using linear programming techniques. Compositions of phases considered in the calculation are discretized into 'pseudo-compounds' spanning the entire compositional space. Gibbs energies of these discrete compounds are generated for a given range and resolution of pressures for example derived by barometry or from mechanical model predictions. Gibbs energy minimization is subsequently performed considering all compounds of different composition and pressure. In addition to constraining the system composition a certain proportion of the system is constraint at a specified pressure. Input pressure variations need to be discretized and each discrete pressure defines an additional constraint for the minimization. The proportion of the system at each different pressure is equally distributed over the number of input pressures. For example if two input pressures P1 and P2 are specified, two constraints are added: 50 percent of the system is constraint at P1 while the remaining 50 percent is constraint at P2. The method has been tested for a set of 10 input pressures obtained by Tajčmanová et al. (2014) using their unconventional geobarometry method in a plagioclase rim around kyanite. Each input pressure is added as constraint to the minimization (1/10 percent of the system for each discrete pressure). Constraining the system composition to the average composition of the plagioclase rim
Stochastic approach to equilibrium and nonequilibrium thermodynamics
NASA Astrophysics Data System (ADS)
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.
Stochastic approach to equilibrium and nonequilibrium thermodynamics.
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. PMID:25974471
Thermodynamic Characterization of Mexico City Aerosol during MILAGRO 2006
Fountoukis, C.; Nenes, A.; Sullivan, A.; Weber, R.; VanReken, T.; Fischer, M.; Matias, E.; Moya, M.; Farmer, D.; Cohen, R.C.
2008-12-05
Fast measurements of aerosol and gas-phase constituents coupled with the ISORROPIA-II thermodynamic equilibrium model are used to study the partitioning of semivolatile inorganic species and phase state of Mexico City aerosol sampled at the T1 site during the MILAGRO 2006 campaign. Overall, predicted semivolatile partitioning agrees well with measurements. PM{sub 2.5} is insensitive to changes in ammonia but is to acidic semivolatile species. For particle sizes up to 1 {micro}m diameter, semi-volatile partitioning requires 30-60 min to equilibrate; longer time is typically required during the night and early morning hours. When the aerosol sulfate-to-nitrate molar ratio is less than unity, predictions improve substantially if the aerosol is assumed to follow the deliquescent phase diagram. Treating crustal species as 'equivalent sodium' (rather than explicitly) in the thermodynamic equilibrium calculations introduces important biases in predicted aerosol water uptake, nitrate and ammonium; neglecting crustals further increases errors dramatically. This suggests that explicitly considering crustals in the thermodynamic calculations is required to accurately predict the partitioning and phase state of aerosols.
Information thermodynamics of near-equilibrium computation.
Prokopenko, Mikhail; Einav, Itai
2015-06-01
In studying fundamental physical limits and properties of computational processes, one is faced with the challenges of interpreting primitive information-processing functions through well-defined information-theoretic as well as thermodynamic quantities. In particular, transfer entropy, characterizing the function of computational transmission and its predictability, is known to peak near critical regimes. We focus on a thermodynamic interpretation of transfer entropy aiming to explain the underlying critical behavior by associating information flows intrinsic to computational transmission with particular physical fluxes. Specifically, in isothermal systems near thermodynamic equilibrium, the gradient of the average transfer entropy is shown to be dynamically related to Fisher information and the curvature of system's entropy. This relationship explicitly connects the predictability, sensitivity, and uncertainty of computational processes intrinsic to complex systems and allows us to consider thermodynamic interpretations of several important extreme cases and trade-offs. PMID:26172697
Equilibrium thermodynamics in modified gravitational theories
NASA Astrophysics Data System (ADS)
Bamba, Kazuharu; Geng, Chao-Qiang; Tsujikawa, Shinji
2010-04-01
We show that it is possible to obtain a picture of equilibrium thermodynamics on the apparent horizon in the expanding cosmological background for a wide class of modified gravity theories with the Lagrangian density f(R,ϕ,X), where R is the Ricci scalar and X is the kinetic energy of a scalar field ϕ. This comes from a suitable definition of an energy-momentum tensor of the “dark” component that respects to a local energy conservation in the Jordan frame. In this framework the horizon entropy S corresponding to equilibrium thermodynamics is equal to a quarter of the horizon area A in units of gravitational constant G, as in Einstein gravity. For a flat cosmological background with a decreasing Hubble parameter, S globally increases with time, as it happens for viable f(R) inflation and dark energy models. We also show that the equilibrium description in terms of the horizon entropy S is convenient because it takes into account the contribution of both the horizon entropy S' in non-equilibrium thermodynamics and an entropy production term.
Thermodynamic and transport properties of gaseous tetrafluoromethane in chemical equilibrium
NASA Technical Reports Server (NTRS)
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.
Non-equilibrium thermodynamics of gravitational screens
NASA Astrophysics Data System (ADS)
Freidel, Laurent; Yokokura, Yuki
2015-11-01
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 behaves like a viscous bubble with a surface tension and an internal energy, and that the Einstein equations take the same forms as non-equilibrium thermodynamic equations for a viscous bubble. We provide a consistent dictionary between gravitational and thermodynamic variables. In the non-viscous cases there are three thermodynamic equations that characterize 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, this approach shows that the mechanism of entropy production for the viscous bubble is mapped onto the production of gravitational waves. We also review the relationship between surface tension and temperature, and discuss black-hole thermodynamics.
Equilibrium Molecular Thermodynamics from Kirkwood Sampling
2015-01-01
We present two methods for barrierless equilibrium sampling of molecular systems based on the recently proposed Kirkwood method (J. Chem. Phys.2009, 130, 134102). Kirkwood sampling employs low-order correlations among internal coordinates of a molecule for random (or non-Markovian) sampling of the high dimensional conformational space. This is a geometrical sampling method independent of the potential energy surface. The first method is a variant of biased Monte Carlo, 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. PMID:25915525
Temperature of systems out of thermodynamic equilibrium
NASA Astrophysics Data System (ADS)
Garden, J.-L.; Richard, J.; Guillou, H.
2008-07-01
Two phenomenological approaches are currently used in the study of the vitreous state. One is based on the concept of fictive temperature introduced by Tool [J. Res. Natl. Bur. Stand. 34, 199 (1945)] and recently revisited by Nieuwenhuizen [Phys. Rev. Lett. 80, 5580 (1998)]. The other is based on the thermodynamics of irreversible processes initiated by De Donder at the beginning of the last century [L'Affinité (Gauthier-Villars, Paris, 1927)] and recently used by Möller et al. for a thorough study of the glass transition [J. Chem. Phys. 125, 094505 (2006)]. This latter approach leads to the possibility of describing the glass transition by means of the freezing-in of one or more order parameters connected to the internal structural degrees of freedom involved in the vitrification process. In this paper, the equivalence of the two preceding approaches is demonstrated, not only for glasses but in a very general way for any system undergoing an irreversible transformation. This equivalence allows the definition of an effective temperature for all systems departed from equilibrium generating a positive amount of entropy. In fact, the initial fictive temperature concept of Tool leads to the generalization of the notion of temperature for systems out of thermodynamic equilibrium, for which glasses are just particular cases.
Teaching Chemical Equilibrium and Thermodynamics in Undergraduate General Chemistry Classes.
ERIC Educational Resources Information Center
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)
Thermodynamics and Kinetics of Chemical Equilibrium in Solution.
ERIC Educational Resources Information Center
Leenson, I. A.
1986-01-01
Discusses theory of thermodynamics of the equilibrium in solution and dissociation-dimerization kinetics. Describes experimental procedure including determination of molar absorptivity and equilibrium constant, reaction enthalpy, and kinetics of the dissociation-dimerization reaction. (JM)
Global equilibrium and local thermodynamics in stationary spacetimes
NASA Astrophysics Data System (ADS)
Panerai, Rodolfo
2016-05-01
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 Einstein's static universe, characterized by inhomogeneous thermodynamic properties and nonvanishing angular momentum.
Far-from-equilibrium measurements of thermodynamic length
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.
The Equilibrium Thermodynamics of Various Peptide Sequences
NASA Astrophysics Data System (ADS)
Yaşar, Fatih
The equilibrium thermodynamic properties of two peptide sequences of β-casein in the α-helix regions were studied by three-dimensional molecular modeling in vacuum. All the three-dimensional conformations of each peptide sequences were obtained by multicanonical simulations using ECEPP/2 force field and each simulation was started from completely random initial conformation. No a-priori information about ground-state is used in the simulations. In the present study, we calculated the average values of total energy, specific heat, fourth-order cumulant for two peptide sequences of β-casein as a function of temperature. We observed that the specific heat shows two peaks as a function of temperature for both peptides. Because our sequences have highly helical structure and two peaks in the specific heat, we have also studied the helix-coil transitions to determine these peaks. Our data indeed show these peptides have highly helical structure and better agreement with the results of spectroscopic techniques and other prediction methods.
ERIC Educational Resources Information Center
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…
ANISORROPIA: the adjoint of the aerosol thermodynamic model ISORROPIA
NASA Astrophysics Data System (ADS)
Capps, S. L.; Henze, D. K.; Hakami, A.; Russell, A. G.; Nenes, A.
2011-08-01
We present the development of ANISORROPIA, the discrete adjoint of the ISORROPIA thermodynamic equilibrium model that treats the Na+-SO42--HSO4--NH4+-NO3--Cl--H2O aerosol system, and we demonstrate its sensitivity analysis capabilities. ANISORROPIA calculates sensitivities of an inorganic species in aerosol or gas phase with respect to the total concentrations of each species present with only a two-fold increase in computational time over the forward model execution. Due to the highly nonlinear and discontinuous solution surface of ISORROPIA, evaluation of the adjoint required a new, complex-variable version of the the model, which determines first-order sensitivities with machine precision and avoids cancellation errors arising from finite difference calculations. The adjoint is verified over an atmospherically relevant range of concentrations, temperature, and relative humidity. We apply ANISORROPIA to recent field campaign results from Atlanta, GA, USA, and Mexico City, Mexico, to characterize the inorganic aerosol sensitivities of these distinct urban air masses. The variability in the relationship between PM2.5 mass and precursor concentrations shown has important implications for air quality and climate. ANISORROPIA enables efficient elucidation of aerosol concentration dependence on aerosol precursor emissions in the context of atmospheric chemical transport model adjoints.
Electrolytes: transport properties and non-equilibrium thermodynamics
Miller, D.G.
1980-12-01
This paper presents a review on the application of non-equilibrium thermodynamics to transport in electrolyte solutions, and some recent experimental work and results for mutual diffusion in electrolyte solutions.
Methane on Mars: Thermodynamic Equilibrium and Photochemical Calculations
NASA Technical Reports Server (NTRS)
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.
Composition and Thermodynamic Properties of Air in Chemical Equilibrium
NASA Technical Reports Server (NTRS)
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.
Considerations on non equilibrium thermodynamics of interactions
NASA Astrophysics Data System (ADS)
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.
ANISORROPIA: the adjoint of the aerosol thermodynamic model ISORROPIA
NASA Astrophysics Data System (ADS)
Capps, S. L.; Henze, D. K.; Hakami, A.; Russell, A. G.; Nenes, A.
2012-01-01
We present the development of ANISORROPIA, the discrete adjoint of the ISORROPIA thermodynamic equilibrium model that treats the Na+-SO42-- HSO4--NH4+ -NO3--Cl--H2O aerosol system, and we demonstrate its sensitivity analysis capabilities. ANISORROPIA calculates sensitivities of an inorganic species in aerosol or gas phase with respect to the total concentrations of each species present with less than a two-fold increase in computational time over the concentration calculations. Due to the highly nonlinear and discontinuous solution surface of ISORROPIA, evaluation of the adjoint required a new, complex-variable version of the model, which determines first-order sensitivities with machine precision and avoids cancellation errors arising from finite difference calculations. The adjoint is verified over an atmospherically relevant range of concentrations, temperature, and relative humidity. We apply ANISORROPIA to recent field campaign results from Atlanta, GA, USA, and Mexico City, Mexico, to characterize the inorganic aerosol sensitivities of these distinct urban air masses. The variability in the relationship between fine mode inorganic aerosol mass and precursor concentrations shown has important implications for air quality and climate.
Radiative processes and non-equilibrium thermodynamics
NASA Astrophysics Data System (ADS)
Callies, U.; Herbert, F.
1988-03-01
With the assumption of an elementary physical concept meteorologically effective radiative processes (absorption-emission, scattering) can be included consistently in nonequilibrium thermodynamics of irreversible phenomena. Analogously to the usual Gibbs relations a fundamental equation was formulated for monochromatic light rays as the nucleus of the theory. Using the methods of classical irreversible theory, a complete entropy balance equation is derived in which the entropy variations of the mass as well as of the radiation field are explicitly represented. The resulting entropy source strength function σ through its analytical structure reveals the dynamical character of the irreversible variation terms. The σ-expression being positive according to the second law of thermodynamics is found to have a bilinear form as a function of the irreversible fluxes representing the entropy generating radiative processes and their conjugated thermodynamic forces. The mathematical structure and the positive sign of σ, following the usual line of reasoning, motivate the assumption of constitutive relations for the irreversible radiative processes. These equations developed from purely thermodynamical reasoning turn out to be equivalent to the usual radiative transfer equation which is founded on a very different theoretical concept. A very fundamental relationship can be deduced in this context from the entropy production function. It provides a direct thermodynamical proof that in nonscattering media the definition of a local temperature is necessarily accompanied by the validity of the Kirchhoff law.
On line Coupling of Aerosole Thermodynamic Model with RegCM3
NASA Astrophysics Data System (ADS)
Shalaby, Ahmed; Zakey, Ashraf
2010-05-01
Development of RegCM3 to be a comprehensive an On-line climate-chemistry model run through two phase. Phase one include coupling of gas-phase chemistry and Second phase include coupling of Aerosole Thermodynamic model. Here ISOROPPIA is coupled with RegCM3 to calculate the composition and phase state of ammonia, sulfate, nitrate, chloride, sodium, calcium, potassium, magnisium, water inorganic aerosole in thermodynamic equilibrium with gas phase precursor. The coupling include only the direct effect of aerosols. The simulation has been done over Northern Africa and Mediterranean region to study the effect of new aerosoles chemistry on the radiation field and how such aerosoles affect the concentration of surface ozone.
Elucidation of Reaction Mechanisms Far from Thermodynamic Equilibrium.
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. PMID:27308227
Reformulating atmospheric aerosol thermodynamics and hygroscopic growth into fog, haze and clouds
NASA Astrophysics Data System (ADS)
Metzger, S.; Lelieveld, J.
2007-06-01
Modeling atmospheric aerosol and cloud microphysics is rather complex, even if chemical and thermodynamical equilibrium is assumed. We show, however, that the thermodynamics can be considerably simplified by reformulating equilibrium to consistently include water, and transform laboratory-based concepts to atmospheric conditions. We generalize the thermodynamic principles that explain hydration and osmosis - merely based on solute solubilities - to explicitly account for the water mass consumed by hydration. As a result, in chemical and thermodynamical equilibrium the relative humidity (RH) suffices to determine the saturation molality, including solute and solvent activities (and activity coefficients), since the water content is fixed by RH for a given aerosol concentration and type. As a consequence, gas/liquid/solid aerosol equilibrium partitioning can be solved analytically and non-iteratively. Our new concept enables an efficient and accurate calculation of the aerosol water mass and directly links the aerosol hygroscopic growth to fog, haze and cloud formation. We apply our new concept in the 3rd Equilibrium Simplified Aerosol Model (EQSAM3) for use in regional and global chemistry-transport and climate models. Its input is limited to the species' solubilities from which a newly introduced stoichiometric coefficient for water is derived. Analogously, we introduce effective stoichiometric coefficients for the solutes to account for complete or incomplete dissociation. We show that these coefficients can be assumed constant over the entire activity range and calculated for various inorganic, organic and non-electrolyte compounds, including alcohols, sugars and dissolved gases. EQSAM3 calculates the aerosol composition and gas/liquid/solid partitioning of mixed inorganic/organic multicomponent solutions and the associated water uptake for almost 100 major compounds. It explicitly accounts for particle hygroscopic growth by computing aerosol properties such as
Reformulating atmospheric aerosol thermodynamics and hygroscopic growth into haze and clouds
NASA Astrophysics Data System (ADS)
Metzger, S.; Lelieveld, J.
2007-01-01
Modeling atmospheric aerosol and cloud microphysics is rather complex, even if chemical and thermodynamical equilibrium is assumed. We show, however, that the thermodynamics can be considerably simplified by reformulating equilibrium to include water, and transform laboratory-based concepts to atmospheric conditions. We generalize the thermodynamic principles that explain hydration and osmosis - merely based on solute solubilities. In chemical and thermodynamical equilibrium the relative humidity (RH) determines the saturation molality, including solute and solvent activities (and activity coefficients), since the water content is fixed by RH for a given aerosol concentration and type. As a consequence, gas/liquid/solid aerosol equilibrium partitioning can be solved analytically and non-iteratively. Our new concept enables an efficient and accurate calculation of the aerosol water mass and to directly link the aerosol hygroscopic growth to haze and cloud formation. We apply our new concept in the 3rd Equilibrium Simplified Aerosol Model (EQSAM3). Its input is limited to the species' solubilities from which a newly introduced stoichiometric coefficient for water is derived. Analogously, we introduce effective stochiometric coefficients for the solutes to account for complete or incomplete dissociation. We show that these coefficients can be assumed constant over the entire activity range and calculated for various inorganic, organic and non-electrolyte compounds, including alcohols, sugars and dissolved gases. EQSAM3 calculates the aerosol composition and gas/liquid/solid partitioning of mixed inorganic/organic multicomponent solutions and the associated water uptake for almost 100 major compounds. It explicitly accounts for particle hygroscopic growth by computing aerosol properties such as single solute molalities, molal based activities, including activity coefficients for volatile compounds, and deliquescence relative humidities of mixed solutes. Various
Thermodynamics of the Rhodamine B Lactone--Zwitterion Equilibrium.
ERIC Educational Resources Information Center
Hinckley, Daniel A.; Seybold, Paul G.
1987-01-01
Discusses the benefits of thermochromic transformations for studying thermodynamic properties. Describes an experiment that uses a commercially available dye, attains equilibrium rapidly, employs a simple, single-beam spectrophotometer, and is suitable for both physical chemistry and introductory chemistry laboratories. (TW)
Local thermodynamic equilibrium for globally disequilibrium open systems under stress
NASA Astrophysics Data System (ADS)
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.
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.
NASA Astrophysics Data System (ADS)
Glavatskiy, K. S.
2015-10-01
Validity of local equilibrium has been questioned for non-equilibrium systems which are characterized by delayed response. In particular, for systems with non-zero thermodynamic inertia, the assumption of local equilibrium leads to negative values of the entropy production, which is in contradiction with the second law of thermodynamics. In this paper, we address this question by suggesting a variational formulation of irreversible evolution of a system with non-zero thermodynamic inertia. We introduce the Lagrangian, which depends on the properties of the normal and the so-called "mirror-image" systems. We show that the standard evolution equations, in particular, the Maxwell-Cattaneo-Vernotte equation, can be derived from the variational procedure without going beyond the assumption of local equilibrium. We also argue that the second law of thermodynamics in non-equilibrium should be understood as a consequence of the variational procedure and the property of local equilibrium. For systems with instantaneous response this leads to the standard requirement of the local instantaneous entropy production being always positive. However, if a system is characterized by delayed response, the formulation of the second law of thermodynamics should be altered. In particular, the quantity, which is always positive, is not the instantaneous entropy production, but the entropy production averaged over a proper time interval.
Glavatskiy, K S
2015-10-28
Validity of local equilibrium has been questioned for non-equilibrium systems which are characterized by delayed response. In particular, for systems with non-zero thermodynamic inertia, the assumption of local equilibrium leads to negative values of the entropy production, which is in contradiction with the second law of thermodynamics. In this paper, we address this question by suggesting a variational formulation of irreversible evolution of a system with non-zero thermodynamic inertia. We introduce the Lagrangian, which depends on the properties of the normal and the so-called "mirror-image" systems. We show that the standard evolution equations, in particular, the Maxwell-Cattaneo-Vernotte equation, can be derived from the variational procedure without going beyond the assumption of local equilibrium. We also argue that the second law of thermodynamics in non-equilibrium should be understood as a consequence of the variational procedure and the property of local equilibrium. For systems with instantaneous response this leads to the standard requirement of the local instantaneous entropy production being always positive. However, if a system is characterized by delayed response, the formulation of the second law of thermodynamics should be altered. In particular, the quantity, which is always positive, is not the instantaneous entropy production, but the entropy production averaged over a proper time interval. PMID:26520492
Stochastic thermodynamics of reactive systems: An extended local equilibrium approach
NASA Astrophysics Data System (ADS)
De Decker, Yannick; Derivaux, Jean-François; Nicolis, Grégoire
2016-04-01
The recently developed extended local equilibrium approach to stochastic thermodynamics is applied to reactive systems. The properties of the fluctuating entropy and entropy production are analyzed for general linear and for prototypical nonlinear kinetic processes. It is shown that nonlinear kinetics typically induces deviations of the mean entropy production from its value in the deterministic (mean-field) limit. The probability distributions around the mean are derived and shown to qualitatively differ in thermodynamic equilibrium, under nonequilibrium conditions and in the vicinity of criticalities associated to the onset of multistability. In each case large deviation-type properties are shown to hold. The results are compared with those of alternative approaches developed in the literature.
Chemical heterogeneities in the mantle: The equilibrium thermodynamic approach
NASA Astrophysics Data System (ADS)
Tirone, M.; Buhre, S.; Schmück, H.; Faak, K.
2016-02-01
This study attempts to answer a simple and yet fundamental question in relation to our understanding of the chemical evolution of deep Earth and planetary interiors. Given two initially separate assemblages (lithologies) in chemical equilibrium can we predict the chemical and mineralogical compositions of the two assemblages when they are put together to form a new equilibrated system? Perhaps a common perception is that given sufficient time, the two assemblages will homogenize chemically and mineralogically, however from a chemical thermodynamic point of view, this is not the case. Certain petrological differences in terms of bulk composition, mineralogy and mineral abundance remain unless other processes, like melting or mechanical mixing come into play. While there is not a standard procedure to address this problem, in this study it is shown that by applying chemical thermodynamic principles and some reasonable assumptions, it is possible to determine the equilibrium composition of each of the two assemblages. Some examples that consider typical mantle rocks, peridotite, lherzolite, dunite and eclogite described by simplified chemical systems are used to illustrate the general approach. A preliminary application to evaluate the effect of melting a heterogeneous mantle in complete chemical equilibrium using a thermodynamic formulation coupled with a two-phase geodynamic model shows that major element composition of the melt product generated by different peridotites is very similar. This may explain the relative homogeneity of major elements of MORBs which could be the product of melting a relatively uniform mantle, as commonly accepted, or alternatively a peridotitic mantle with different compositions but in chemical equilibrium.
Simplified curve fits for the thermodynamic properties of equilibrium air
NASA Technical Reports Server (NTRS)
Srinivasan, S.; Tannehill, J. C.; Weilmuenster, K. J.
1987-01-01
New, improved curve fits for the thermodynamic properties of equilibrium air have been developed. The curve fits are for pressure, speed of sound, temperature, entropy, enthalpy, density, and internal energy. These curve fits can be readily incorporated into new or existing computational fluid dynamics codes if real gas effects are desired. The curve fits are constructed from Grabau-type transition functions to model the thermodynamic surfaces in a piecewise manner. The accuracies and continuity of these curve fits are substantially improved over those of previous curve fits. These improvements are due to the incorporation of a small number of additional terms in the approximating polynomials and careful choices of the transition functions. The ranges of validity of the new curve fits are temperatures up to 25 000 K and densities from 10 to the -7 to 10 to the 3d power amagats.
NASA Astrophysics Data System (ADS)
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.
Foundations and Application of Non-equilibrium Thermodynamics
NASA Astrophysics Data System (ADS)
Robinson, Gregory
2011-11-01
Non-equilibrium thermodynamics provides a powerful but still unfamiliar way to peer into the properties of systems yet unexplored and holds promise for ready application to important engineered systems. This talk will consider some of the challenges, promises, and progress made toward an intuitive statistical theory of non-equilibrium behavior as well as recent work applying it. We will briefly discuss large deviations and the formalism of Freidlin and Wentzell for perturbed dynamical systems, which recasts certain questions about stochastic processes in the form of Hamiltonian mechanics. The methods and their applicability are illustrated by analyzing transitions between different stable states of a chemical reaction network, supplemented by a fast numerical solution of escape trajectories. We conclude with the prospects for using the ideas and methods in the design of more efficient and reliable grid computing platforms, which are crucial both to modern science and the operation of entire industries.
Non-equilibrium thermodynamics analysis of transcriptional regulation kinetics
NASA Astrophysics Data System (ADS)
Hernández-Lemus, Enrique; Tovar, Hugo; Mejía, Carmen
2014-12-01
Gene expression in eukaryotic cells is an extremely complex and interesting phenomenon whose dynamics are controlled by a large number of subtle physicochemical processes commonly described by means of gene regulatory networks. Such networks consist in a series of coupled chemical reactions, conformational changes, and other biomolecular processes involving the interaction of the DNA molecule itself with a number of proteins usually called transcription factors as well as enzymes and other components. The kinetics behind the functioning of such gene regulatory networks are largely unknown, though its description in terms of non-equilibrium thermodynamics has been discussed recently. In this work we will derive general kinetic equations for a gene regulatory network from a non-equilibrium thermodynamical description and discuss its use in understanding the free energy constrains imposed in the network structure. We also will discuss explicit expressions for the kinetics of a simple model of gene regulation and show that the kinetic role of mRNA decay during the RNA synthesis stage (or transcription) is somehow limited due to the comparatively low values of decay rates. At the level discussed here, this implies a decoupling of the kinetics of mRNA synthesis and degradation a fact that may become quite useful when modeling gene regulatory networks from experimental data on whole genome gene expression.
Non-equilibrium Thermodynamics of Rayleigh-Taylor Instability
NASA Astrophysics Data System (ADS)
Sengupta, Tapan K.; Sengupta, Aditi; Sengupta, Soumyo; Bhole, Ashish; Shruti, K. S.
2016-04-01
Here, the fundamental problem of Rayleigh-Taylor instability (RTI) is studied by direct numerical simulation (DNS), where the two air masses at different temperatures, kept apart initially by a non-conducting horizontal interface in a 2D box, are allowed to mix. Upon removal of the partition, mixing is controlled by RTI, apart from mutual mass, momentum, and energy transfer. To accentuate the instability, the top chamber is filled with the heavier (lower temperature) air, which rests atop the chamber containing lighter air. The partition is positioned initially at mid-height of the box. As the fluid dynamical system considered is completely isolated from outside, the DNS results obtained without using Boussinesq approximation will enable one to study non-equilibrium thermodynamics of a finite reservoir undergoing strong irreversible processes. The barrier is removed impulsively, triggering baroclinic instability by non-alignment of density, and pressure gradient by ambient disturbances via the sharp discontinuity at the interface. Adopted DNS method has dispersion relation preservation properties with neutral stability and does not require any external initial perturbations. The complete inhomogeneous problem with non-periodic, no-slip boundary conditions is studied by solving compressible Navier-Stokes equation, without the Boussinesq approximation. This is important as the temperature difference between the two air masses considered is high enough (Δ T = 70 K) to invalidate Boussinesq approximation. We discuss non-equilibrium thermodynamical aspects of RTI with the help of numerical results for density, vorticity, entropy, energy, and enstrophy.
Dynamical horizon entropy and equilibrium thermodynamics of generalized gravity theories
Wu Shaofeng; Ge Xianhui; Yang Guohong; Zhang Pengming
2010-02-15
We study the relation between the thermodynamics and field equations of generalized gravity theories on the dynamical trapping horizon with sphere symmetry. We assume the entropy of a dynamical horizon as the Noether charge associated with the Kodama vector and point out that it satisfies the second law when a Gibbs equation holds. We generalize two kinds of Gibbs equations to Gauss-Bonnet gravity on any trapping horizon. Based on the quasilocal gravitational energy found recently for f(R) gravity and scalar-tensor gravity in some special cases, we also build up the Gibbs equations, where the nonequilibrium entropy production, which is usually invoked to balance the energy conservation, is just absorbed into the modified Wald entropy in the Friedmann-Robertson-Walker spacetime with slowly varying horizon. Moreover, the equilibrium thermodynamic identity remains valid for f(R) gravity in a static spacetime. Our work provides an alternative treatment to reinterpret the nonequilibrium correction and supports the idea that the horizon thermodynamics is universal for generalized gravity theories.
Computation of thermodynamic equilibrium in systems under stress
NASA Astrophysics Data System (ADS)
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
NASA Technical Reports Server (NTRS)
Grossman, B.; Garrett, J.; Cinnella, P.
1989-01-01
Several versions of flux-vector split and flux-difference split algorithms were compared with regard to general applicability and complexity. Test computations were performed using curve-fit equilibrium air chemistry for an M = 5 high-temperature inviscid flow over a wedge, and an M = 24.5 inviscid flow over a blunt cylinder for test computations; for these cases, little difference in accuracy was found among the versions of the same flux-split algorithm. For flows with nonequilibrium chemistry, the effects of the thermodynamic model on the development of flux-vector split and flux-difference split algorithms were investigated using an equilibrium model, a general nonequilibrium model, and a simplified model based on vibrational relaxation. Several numerical examples are presented, including nonequilibrium air chemistry in a high-temperature shock tube and nonequilibrium hydrogen-air chemistry in a supersonic diffuser.
Local thermodynamic equilibrium in rapidly heated high energy density plasmas
Aslanyan, V.; Tallents, G. J.
2014-06-15
Emission spectra and the dynamics of high energy density plasmas created by optical and Free Electron Lasers (FELs) depend on the populations of atomic levels. Calculations of plasma emission and ionization may be simplified by assuming Local Thermodynamic Equilibrium (LTE), where populations are given by the Saha-Boltzmann equation. LTE can be achieved at high densities when collisional processes are much more significant than radiative processes, but may not be valid if plasma conditions change rapidly. A collisional-radiative model has been used to calculate the times taken by carbon and iron plasmas to reach LTE at varying densities and heating rates. The effect of different energy deposition methods, as well as Ionization Potential Depression are explored. This work shows regimes in rapidly changing plasmas, such as those created by optical lasers and FELs, where the use of LTE is justified, because timescales for plasma changes are significantly longer than the times needed to achieve an LTE ionization balance.
Biosorption of uranium by melanin: kinetic, equilibrium and thermodynamic studies.
Saini, Amardeep Singh; Melo, Jose Savio
2013-12-01
Limitation of conventional techniques for the removal of heavy metals present at low concentrations, has led to the need for developing alternate technologies like biosorption. In the present study we describe the use of melanin pigment synthesized through green technology, for sorption of uranium from aqueous system. Biosynthesized melanin showed good uptake over a broad pH range. Removal of uranium was rapid and equilibrium was reached within 2h of contact. It was observed that the kinetic data fits well into Lagergren's pseudo-second order equation. A maximum loading capacity of 588.24 mg g(-1) was calculated from Langmuir plot. Thermodynamic studies performed revealed that sorption process was favorable. Binding of uranium on the surface of melanin was confirmed by FT-IR and energy dispersive spectroscopy (EDS). Thus, biosynthesized melanin can be efficiently used as a sorbent for removal of uranium from aqueous solution. PMID:24099972
Local thermodynamic equilibrium in rapidly heated high energy density plasmas
NASA Astrophysics Data System (ADS)
Aslanyan, V.; Tallents, G. J.
2014-06-01
Emission spectra and the dynamics of high energy density plasmas created by optical and Free Electron Lasers (FELs) depend on the populations of atomic levels. Calculations of plasma emission and ionization may be simplified by assuming Local Thermodynamic Equilibrium (LTE), where populations are given by the Saha-Boltzmann equation. LTE can be achieved at high densities when collisional processes are much more significant than radiative processes, but may not be valid if plasma conditions change rapidly. A collisional-radiative model has been used to calculate the times taken by carbon and iron plasmas to reach LTE at varying densities and heating rates. The effect of different energy deposition methods, as well as Ionization Potential Depression are explored. This work shows regimes in rapidly changing plasmas, such as those created by optical lasers and FELs, where the use of LTE is justified, because timescales for plasma changes are significantly longer than the times needed to achieve an LTE ionization balance.
SOLGAS refined: A computerized thermodynamic equilibrium calculation tool
Trowbridge, L.D.; Leitnaker, J.M.
1993-11-01
SOLGAS, an early computer program for calculating equilibrium in a chemical system, has been made more user-friendly, and several{open_quote} bells and whistles{close_quotes} have been added. The necessity to include elemental species has been eliminated. The input of large numbers of starting conditions has been automated. A revised format for entering data simplifies and reduces chances for error. Calculated errors by SOLGAS are flagged, and several programming errors are corrected. Auxiliary programs are available to assemble and partially automate plotting of large amounts of data. Thermodynamic input data can be changed {open_quotes}on line.{close_quote} The program can be operated with or without a co-processor. Copies of the program, suitable for the IBM-PC or compatible with at least 384 bytes of low RAM, are available from the authors.
Simplified curve fits for the thermodynamic properties of equilibrium air
NASA Technical Reports Server (NTRS)
Srinivasan, S.; Tannehill, J. C.; Weilmuenster, K. J.
1986-01-01
New improved curve fits for the thermodynamic properties of equilibrium air were developed. The curve fits are for p = p(e,rho), a = a(e,rho), T = T(e,rho), s = s(e,rho), T = T(p,rho), h = h(p,rho), rho = rho(p,s), e = e(p,s) and a = a(p,s). These curve fits can be readily incorporated into new or existing Computational Fluid Dynamics (CFD) codes if real-gas effects are desired. The curve fits were constructed using Grabau-type transition functions to model the thermodynamic surfaces in a piecewise manner. The accuracies and continuity of these curve fits are substantially improved over those of previous curve fits appearing in NASA CR-2470. These improvements were due to the incorporation of a small number of additional terms in the approximating polynomials and careful choices of the transition functions. The ranges of validity of the new curve fits are temperatures up to 25,000 K and densities from 10 to the minus 7th to 100 amagats (rho/rho sub 0).
Equilibrium thermodynamics of multiply substituted isotopologues of molecular gases
NASA Astrophysics Data System (ADS)
Wang, Zhengrong; Schauble, Edwin A.; Eiler, John M.
2004-12-01
Isotopologues of molecular gases containing more than one rare isotope (multiply substituted isotopologues) can be analyzed with high precision (1σ <0.1 ‰), despite their low natural abundances (˜ ppm to ppt in air), and can constrain geochemical budgets of natural systems. We derive a method for calculating abundances of all such species in a thermodynamically equilibrated population of isotopologues, and present results of these calculations for O 2, CO, N 2, NO, CO 2, and N 2O between 1000 and 193 to 77 K. In most cases, multiply substituted isotopologues are predicted to be enriched relative to stochastic (random) distributions by ca. 1 to 2 ‰ at earth-surface temperatures. This deviation, defined as Δ i for isotopologue i, generally increases linearly with 1/T at temperatures ≤ 500 K. An exception is N 2O, which shows complex temperature dependences and 10's of per-mill enrichments or depletions of abundances for some isotopologues. These calculations provide a basis for discriminating between fractionations controlled by equilibrium thermodynamics and other sorts of isotopic fractionations in the budgets of atmospheric gases. Moreover, because abundances of multiply substituted isotopologues in thermodynamically equilibrated populations of molecules vary systematically with temperature, they can be used as geothermometers. Such thermometers are unusual in that they involve homogeneous rather than heterogeneous equilibria (e.g., isotopic distribution in gaseous CO 2 alone, rather than difference in isotopic composition between CO 2 and coexisting water). Also, multiple independent thermometers exist for all molecules having more than one multiply substituted isotopologue (e.g., thermometers based on abundances of 18O 13C 16O and 18O 12C 18O are independent); thus, temperatures estimated by this method can be tested for internal consistency.
A Computationally Efficient Multicomponent Equilibrium Solver for Aerosols (MESA)
Zaveri, Rahul A.; Easter, Richard C.; Peters, Len K.
2005-12-23
This paper describes the development and application of a new multicomponent equilibrium solver for aerosol-phase (MESA) to predict the complex solid-liquid partitioning in atmospheric particles containing H+, NH4+, Na+, Ca2+, SO4=, HSO4-, NO3-, and Cl- ions. The algorithm of MESA involves integrating the set of ordinary differential equations describing the transient precipitation and dissolution reactions for each salt until the system satisfies the equilibrium or mass convergence criteria. Arbitrary values are chosen for the dissolution and precipitation rate constants such that their ratio is equal to the equilibrium constant. Numerically, this approach is equivalent to iterating all the equilibrium reactions simultaneously with a single iteration loop. Because CaSO4 is sparingly soluble, it is assumed to exist as a solid over the entire RH range to simplify the algorithm for calcium containing particles. Temperature-dependent mutual deliquescence relative humidity polynomials (valid from 240 to 310 K) for all the possible salt mixtures were constructed using the comprehensive Pitzer-Simonson-Clegg (PSC) activity coefficient model at 298.15 K and temperature-dependent equilibrium constants in MESA. Performance of MESA is evaluated for 16 representative mixed-electrolyte systems commonly found in tropospheric aerosols using PSC and two other multicomponent activity coefficient methods – Multicomponent Taylor Expansion Method (MTEM) of Zaveri et al. [2004], and the widely-used Kusik and Meissner method (KM), and the results are compared against the predictions of the Web-based AIM Model III or available experimental data. Excellent agreement was found between AIM, MESA-PSC, and MESA-MTEM predictions of the multistage deliquescence growth as a function of RH. On the other hand, MESA-KM displayed up to 20% deviations in the mass growth factors for common salt mixtures in the sulfate-poor cases while significant discrepancies were found in the predicted multistage
NASA Astrophysics Data System (ADS)
Mitra, Saugata; Saha, Subhajit; Chakraborty, Subenoy
2015-04-01
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 is 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 for each gravity theory. Finally, due to complicated expressions, the validity of GSLT and TE are also examined from graphical representation, using three Planck data sets.
The thermodynamic and kinetic impacts of organics on marine aerosols
NASA Astrophysics Data System (ADS)
Crahan, Kathleen
Organics can change the manner in which aerosols scatter radiation directly as hydrated aerosols and indirectly as in-cloud activated aerosols, through changing the solution activity, the surface tension, and the accommodation coefficient of the hydrated aerosol. This work explores the kinetic and thermodynamic impacts of the organic component of marine aerosols through data collected over four field campaigns and through several models used to reproduce observations. The Rough Evaporation Duct (RED) project was conducted in the summer of 2001 off the coast of Oahu using the Twin Otter Aircraft and the Floating Instrument Platform research platform for data collection. The Cloud-Aerosol Research in the Marine Atmosphere (CARMA) campaigns were conducted over three summers (2002, 2004, 2005) off the coast of Monterey, California. During the CARMA campaigns, a thick, moist, stratocumulus deck was present during most days, and the Twin Otter Aircraft was the primary research platform used to collect data. However, the research goals and exact instrumentation onboard the Twin Otter varied from campaign to campaign, and each data set was analyzed individually. Data collected from CARMA I were used to explore the mechanism of oxalic acid production in cloud droplets. Oxalate was observed in the clouds in excess to below cloud concentrations by an average of 0.11 mug m-3, suggesting an in-cloud production. The tentative identification in cloud water of an intermediate species in the aqueous oxalate production mechanism lends further support to an in-cloud oxalate source. The data sets collected during the RED campaign and the CARMA II and CARMA III campaigns were used to investigate the impact of aerosol chemical speciation on aerosol hygroscopic behavior. Several models were used to correlate the observations in the subsaturated regime to theory including an explicit thermodynamic model, simple Kohler theory, and a parameterization of the solution activity. These models
Atmospheric aerosols: Their Optical Properties and Effects
NASA Technical Reports Server (NTRS)
1976-01-01
Measured properties of atmospheric aerosol particles are presented. These include aerosol size frequency distribution and complex retractive index. The optical properties of aerosols are computed based on the presuppositions of thermodynamic equilibrium and of Mie-theory.
Thermodynamic Equilibrium Calculations on Cd Transformation during Sewage Sludge Incineration.
Liu, Jing-yong; Huang, Limao; Sun, Shuiyu; Ning, Xun'an; Kuo, Jiahong; Sun, Jian; Wang, Yujie; Xie, Wuming
2016-06-01
Thermodynamic equilibrium calculations were performed to reveal the distribution of cadmium during the sewage sludge incineration process. During sludge incineration in the presence of major minerals, such as SiO2, Al2O3 and CaO, the strongest effect was exerted by SiO2 on the Cd transformation compared with the effect of others. The stable solid product of CdSiO3 was formed easily with the reaction between Cd and SiO2, which can restrain the emissions of gaseous Cd pollutants. CdCl2 was formed more easily in the presence of chloride during incineration, thus, the volatilization of Cd was advanced by increasing chlorine content. At low temperatures, the volatilization of Cd was restrained due to the formation of the refractory solid metal sulfate. At high temperatures, the speciation of Cd was not affected by the presence of sulfur, but sulfur could affect the formation temperature of gaseous metals. PMID:27225784
ERIC Educational Resources Information Center
Ferreira, Joao Paulo M.
2007-01-01
The problem of the equilibrium state of an isolated composite system with a movable internal adiabatic wall is a recurrent one in the literature. Classical equilibrium thermodynamics is unable to predict the equilibrium state, unless supplemented with information about the process taking place. This conclusion is clearly demonstrated in this…
EquilTheTA: Thermodynamic and transport properties of complex equilibrium plasmas
Colonna, G.; D'Angola, A.
2012-11-27
EquilTheTA (EQUILibrium for plasma THErmodynamics and Transport Applications) is a web-based software which calculates chemical equilibrium product concentrations from any set of reactants and determines thermodynamic and transport properties for the product mixture in wide temperature and pressure ranges. The program calculates chemical equilibrium by using a hierarchical approach, thermodynamic properties and transport coefficients starting from recent and accurate databases of atomic and molecular energy levels and collision integrals. In the calculations, Debye length and cut-off are consistently updated and virial corrections (up to third order) can be considered. Transport coefficients are calculated by using high order approximations of the Chapman-Enskog method.
NASA Astrophysics Data System (ADS)
Peluso, F.; Arienzo, I.
Experimental investigation of the behavior of porous media is a field of interest of modern non-equilibrium thermodynamics. In the frame of a multi-disciplinary re- search project we are performing in our laboratory experimental tests to measure equilibrium and nonequilibrium thermodynamic properties of natural porous media. Aim of our study is to characterize some stone samples and to verify whether a mass transport due to coupled pressure and temperature gradients (thermo-mechanic) is ap- preciable in this kind of porous medium. We have designed an apparatus that allows to measure the volume flux across a porous sample at various, predefined pressures and temperatures, both in isothermal and non isothermal conditions. A mechanical piston compels a liquid to flow through the sample, previously saturated under vacuum with the same fluid. Knowing the geometrical dimensions of the stone, the volume flux is estimated by measuring the time needed to a known amount of liquid to flow across the sample. Measurements have been performed in isothermal conditions at various temperatures and in non-isothermal conditions. Non-isothermal measurements have been performed both in unsteady and steady-state thermal conditions. Before to be undergone to a measurement cycle, samples are dried and weighted. Then they are sat- urated under vacuum with pure distilled water and weighted once again. By difference between the two measurements, porosity is determined. In all examined samples the volume flux has been found linear with respect to the applied pressure at the various temperatures. The values of volume flux in unsteady thermal conditions are consid- erably higher than the one obtained at the same pressure in isothermal conditions at the higher temperature (T=+45rC). This could be the evidence of a thermo-mechanic effect, pushing the water from hot to cold. Once the steady thermal state is reached, however, this effect disappears. Only measurements performed in unsteady thermal
NASA Astrophysics Data System (ADS)
Giordano, D.
1998-09-01
The central theme of this study is the thermodynamic equilibrium of multitemperature gas mixtures. The presented material is meant to complement and, for certain aspects, to complete a previous contribution of the author on the subject matter. The analysis begins with a brief introductory survey of the main theoretical approaches pursued to characterize quantitatively multitemperature equilibria with the intent to emphasize the discordant findings of these approaches and the diverging opinions they have originated in the literature. The equilibrium problem is then confronted within the framework of axiomatic thermodynamics. The general equilibrium principle in its axiomatic form is recalled and the importance of the physical constraints imposed on the gas mixture in connection with the application of the principle is recognized. A rigorous proof is given of the equivalence between energy minimization and entropy maximization for the purpose of determining the equilibrium conditions in multitemperature circumstances and regardless of the active internal constraints. Moreover, the influence of the kind of internal constraints in establishing the mathematical form of the equilibrium equations is pointed out and the divergence among the findings of other approaches is thus explained. The equivalence feature is also considered in relation to the thermodynamic potentials. Evidence is given that not all thermodynamic potentials possess the equivalence property, i.e., attainment of an extremum, in conditions of thermodynamic equilibrium. Consistently, mathematical properties relevant to the search of the extrema of the Legendre transforms are recalled and elaborated upon. A selection rule is formulated that permits the identification of the thermodynamic potentials possessing the equivalence property. The essential role played by the internal constraints in the selection procedure is described and fully evidenced in the subsequent application of the method to two
Studies on the formulation of thermodynamics and stochastic theory for systems far from equilibrium
Ross, J.
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.
On Non-Equilibrium Thermodynamics of Space-Time and Quantum Gravity
NASA Astrophysics Data System (ADS)
Munkhammar, Joakim
Based on recent results from general relativistic statistical mechanics and black hole information transfer limits, a space-time entropy-action equivalence is proposed as a generalization of the holographic principle. With this conjecture, the action principle can be replaced by the second law of thermodynamics, and for the Einstein-Hilbert action the Einstein field equations are conceptually the result of thermodynamic equilibrium. For non-equilibrium situations, Jaynes' information-theoretic approach to maximum entropy production is adopted instead of the second law of thermodynamics. As it turns out for appropriate choices of constants, quantum gravity is obtained. For the special case of a free particle the Bekenstein-Verlinde entropy-to-displacement relation of holographic gravity and thus the traditional holographic principle emerges. Although Jacobson's original thermodynamic equilibrium approach proposed that gravity might not necessarily be quantized, this particular non-equilibrium treatment might require it.
A Unified Graphical Representation of Chemical Thermodynamics and Equilibrium
ERIC Educational Resources Information Center
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…
Thermodynamic modeling of atmospheric aerosols: 0-100% relative humidity
NASA Astrophysics Data System (ADS)
Dutcher, Cari S.; Ge, Xinlei; Asato, Caitlin; Wexler, Anthony S.; Clegg, Simon L.
2013-05-01
Accurate models of water and solute activities in aqueous atmospheric aerosols are central to predicting aerosol size, optical properties and cloud formation. A powerful method has been recently developed (Dutcher et al. JPC 2011, 2012, 2013) for representing the thermodynamic properties of multicomponent aerosols at low and intermediate levels of RH (< 90%RH) by applying the principles of multilayer sorption to ion hydration in solutions. In that work, statistical mechanics was used to model sorption of a solvent (water), onto each solute or ion in solution as n energetically distinct layers. This corresponds to n hydration layers surrounding each solute molecule. Here, we extend the model to the 100% RH limit and reduce the number of adjustable model parameters, allowing for a unified thermodynamic treatment for a wider range of atmospheric systems. The long-range interactions due to electrostatic screening of ions in solution are included as a mole fraction based Pitzer-Debye-Hückel (PDH) term. Equations for the Gibbs free energy, solvent and solute activity, and solute concentration are derived, yielding remarkable agreement between measured and fitted solute concentration and osmotic coefficients for solutions over the entire 0 to 100% RH range. By relating the values of the energy of sorption in each hydration layer to known short-range Coulombic electrostatic relationships governed by the size and dipole moment of the solute and solvent molecules, it may be possible to reduce the number of parameters for each solute. Modified equations for mixtures that take into account the long range PDH term will also be presented; these equations include no additional parameters.
NASA Technical Reports Server (NTRS)
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.
Vapor-liquid equilibrium thermodynamics of N2 + CH4 - Model and Titan applications
NASA Technical Reports Server (NTRS)
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.
Local thermodynamical equilibrium and the frame for a quantum relativistic fluid
NASA Astrophysics Data System (ADS)
Becattini, Francesco; Bucciantini, Leda; Grossi, Eduardo; Tinti, Leonardo
2015-05-01
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 temperature four-vector , 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 frame and Landau frame and present an instance where they differ.
NASA Astrophysics Data System (ADS)
Horowitz, Jordan M.
2015-07-01
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 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.
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.
A thermodynamic model of mixed organic-inorganic aerosols to predict activity coefficients
NASA Astrophysics Data System (ADS)
Zuend, A.; Marcolli, C.; Luo, B. P.; Peter, T.
2008-08-01
Tropospheric aerosols contain mixtures of inorganic salts, acids, water, and a large variety of organic compounds. Interactions between these substances in liquid mixtures lead to discrepancies from ideal thermodynamic behaviour. By means of activity coefficients, non-ideal behaviour can be taken into account. We present here a thermodynamic model named AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) that is able to calculate activity coefficients covering inorganic, organic, and organic-inorganic interactions in aqueous solutions over a wide concentration range. This model is based on the activity coefficient model LIFAC by Yan et al. (1999) that we modified and reparametrised to better describe atmospherically relevant conditions and mixture compositions. Focusing on atmospheric applications we considered H+, Li+, Na+, K+, NH+4, Mg2+, Ca2+, Cl-, Br-, NO-3, HSO-4, and SO2-4 as cations and anions and a wide range of alcohols/polyols composed of the functional groups CHn and OH as organic compounds. With AIOMFAC, the activities of the components within an aqueous electrolyte solution are well represented up to high ionic strength. Most notably, a semi-empirical middle-range parametrisation of direct organic-inorganic interactions in alcohol+water+salt solutions strongly improves the agreement between experimental and modelled activity coefficients. At room temperature, this novel thermodynamic model offers the possibility to compute equilibrium relative humidities, gas/particle partitioning and liquid-liquid phase separations with high accuracy. In further studies, other organic functional groups will be introduced. The model framework is not restricted to specific ions or organic compounds and is therefore also applicable for other research topics.
A thermodynamic model of mixed organic-inorganic aerosols to predict activity coefficients
NASA Astrophysics Data System (ADS)
Zuend, A.; Marcolli, C.; Luo, B. P.; Peter, Th.
2008-03-01
Tropospheric aerosols contain mixtures of inorganic salts, acids, water, and a large variety of organic compounds. Interactions between these substances in liquid mixtures lead to discrepancies from ideal thermodynamic behaviour. By means of activity coefficients, non-ideal behaviour can be taken into account. We present here a thermodynamic model named AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) that is able to calculate activity coefficients covering inorganic, organic, and organic-inorganic interactions in aqueous solutions over a wide concentration range. This model is based on the activity coefficient model LIFAC by Yan et al. (1999) that we modified and reparametrised to better describe atmospherically relevant conditions and mixture compositions. Focusing on atmospheric applications we considered H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl-, Br-, NO3-, HSO4-, and SO42- as cations and anions and a wide range of alcohols/polyols composed of the functional groups CHn and OH as organic compounds. With AIOMFAC, the activities of the components within an aqueous electrolyte solution are well represented up to high ionic strength. Most notably, a semi-empirical middle-range parametrisation of direct organic-inorganic interactions in alcohol + water + salt solutions strongly improves the agreement between experimental and modelled activity coefficients. At room temperature, this novel thermodynamic model offers the possibility to compute equilibrium relative humidities, gas/particle partitioning and liquid-liquid phase separations with high accuracy. In further studies, other organic functional groups will be introduced. The model framework is not restricted to specific ions or organic compounds and is therefore also applicable for other research topics.
NASA Astrophysics Data System (ADS)
Singh, Gurpreet; Sharma, Rohit; Singh, Kuldip
2015-09-01
Thermodynamic properties (compressibility coefficient Z γ , specific heat at constant volume c v , adiabatic coefficient γ a , isentropic coefficient γ i s e n , and sound speed c s ) of non-local thermodynamic equilibrium hydrogen thermal plasma have been investigated for different values of pressure and non-equilibrium parameter θ (=Te/Th) in the electron temperature range from 6000 K to 60 000 K. In order to estimate the influence of pressure derivative of partition function on thermodynamic properties, two cases have been considered: (a) in which pressure derivative of partition function is taken into account in the expressions and (b) without pressure derivative of partition function in their expressions. Here, the case (b) represents expressions already available in literature. It has been observed that the temperature from which pressure derivative of partition function starts influencing a given thermodynamic property increases with increase of pressure and non-equilibrium parameter θ. Thermodynamic property in the case (a) is always greater than its value in the case (b) for compressibility coefficient and specific heat at constant volume, whereas for adiabatic coefficient, isentropic coefficient, and sound speed, its value in the case (a) is always less than its value in the case (b). For a given value of θ, the relationship of compressibility coefficient with degree of ionization depends upon pressure in the case (a), whereas it is independent of pressure in the case (b). Relative deviation between the two cases shows that the influence of pressure derivative of partition function is significantly large and increases with the augmentation of pressure and θ for compressibility coefficient, specific heat at constant volume, and adiabatic coefficient, whereas for isentropic coefficient and sound speed, it is marginal even at high values of pressure and non-equilibrium parameter θ.
A code for line blanketing without local thermodynamic equilibrium
NASA Astrophysics Data System (ADS)
Anderson, L. S.
A numerical code has been written which is designed to calculate radiation transport and atmospheric structure under the constraints of statistical equilibrium in atomic transitions and radiative and hydrostatic equilibrium in the medium. In addition to the complete linearization and variable Eddington factor techniques of Auer and Mihalas, it uses a multi-frequency/multi-gray algorithm which admits the inclusion of many spectral lines in full statistical equilibrium. The program can comfortably accept up to about 300 specific lines arising from about 30 lower states and any number of continua. Cleverly constructed artificial model atoms can extend the number of lines to 3000 or more, where opacity sampling techniques can begin to approximate the blanketing accomplished by Kurucz in LTE. By way of example, a model of a stellar atmosphere is presented with effective temperature 35,000 K and surface gravity 10 to the 4 cm per second squared. The calculation includes 98 bound-free transitions and 93 bound-bound transitions (57 with radiative rates) between 91 states in 36 ions of nine cosmically abundant species.
Non-equilibrium thermodynamics and stochasticity: a phenomenological look on Jarzynski's equality
NASA Astrophysics Data System (ADS)
Muschik, W.
2016-07-01
The theory of phenomenological non-equilibrium thermodynamics is extended by including stochastic processes in order to account for recently derived thermodynamical relations such as the Jarzynski's equality. Four phenomenological axioms are postulated resulting in a phenomenological interpretation of Jarzynski's equality. In particular, considering the class of Jarzynski processes Jarzynski's equality follows from the axiom that the statistical average of the exponential work is protocol independent.
Relativistic distribution function for particles with spin at local thermodynamical equilibrium
Becattini, F.; Chandra, V.; Del Zanna, L.; Grossi, E.
2013-11-15
We present an extension of relativistic single-particle distribution function for weakly interacting particles at local thermodynamical equilibrium including spin degrees of freedom, for massive spin 1/2 particles. We infer, on the basis of the global equilibrium case, that at local thermodynamical equilibrium particles acquire a net polarization proportional to the vorticity of the inverse temperature four-vector field. The obtained formula for polarization also implies that a steady gradient of temperature entails a polarization orthogonal to particle momentum. The single-particle distribution function in momentum space extends the so-called Cooper–Frye formula to particles with spin 1/2 and allows us to predict their polarization in relativistic heavy ion collisions at the freeze-out. -- Highlights: •Single-particle distribution function in local thermodynamical equilibrium with spin. •Polarization of spin 1/2 particles in a fluid at local thermodynamical equilibrium. •Prediction of a new effect: a steady gradient of temperature induces a polarization. •Application to the calculation of polarization in relativistic heavy ion collisions.
Canonical deformations of surfaces of equilibrium states in thermodynamic phase space
Jurkowski
2000-08-01
Deformations of submanifolds of thermodynamic equilibrium states introduced by continuous contact maps on a phase-space manifold are considered in terms of the geometrical formulation of thermodynamics. The notion of a contact Hamiltonian is recalled in order to give some possible physical interpretations of such a function in terms of statistical quantities describing initial and deformed systems. Using contact flows we propose a very efficient method for constructing continuous families of thermodynamic systems. A few examples show the possible advantages of using contact Hamiltonians. PMID:11088641
Equilibrium thermodynamics and stochastic nonlinear acoustic fields. [in crystalline lattices
NASA Technical Reports Server (NTRS)
Cantrell, J. H.
1985-01-01
A crystalline solid is considered to consist of a large number of incoherent nonlinear acoustic radiation sources identified with the vibrating particles of the crystalline lattice. Randomization of the field, together with the assumption of a stochastically independent, fluctuating, radiation field at the absolue zero of temperature, leads to an expression of the temperature-dependent radiation field in terms of the zero-point field. The equation is identified with the Planck distribution formula of quantum mechanics in the linear field limit. The thermodynamic state functions are also obtained in terms of the nonlinear acoustic modal energies per unit mass and reduce to the results of the Debye-Einstein stochastic quantum oscillator model in the linear field limit.
Modeling of electrochemical double layers in thermodynamic non-equilibrium.
Dreyer, Wolfgang; Guhlke, Clemens; Müller, Rüdiger
2015-10-28
We consider the contact between an electrolyte and a solid electrode. At first we formulate a thermodynamic consistent model that resolves boundary layers at interfaces. The model includes charge transport, diffusion, chemical reactions, viscosity, elasticity and polarization under isothermal conditions. There is a coupling between these phenomena that particularly involves the local pressure in the electrolyte. Therefore the momentum balance is of major importance for the correct description of the boundary layers. The width of the boundary layers is typically very small compared to the macroscopic dimensions of the system. In the second step we thus apply the method of asymptotic analysis to derive a simpler reduced bulk model that already incorporates the electrochemical properties of the double layers into a set of new boundary conditions. With the reduced model, we analyze the double layer capacitance for a metal-electrolyte interface. PMID:26415592
Alvarez-Romero, J T
2006-01-01
We present a discussion to show that the absorbed dose D is a time-dependent function. This time dependence is demonstrated based on the concepts of charged particle equilibrium and on radiation equilibrium within the context of thermodynamic non-equilibrium. In the latter, the time dependence is due to changes of the rest mass energy of the nuclei and elementary particles involved in the terms summation operator Q and Q that appear in the definitions of energy imparted epsilon and energy deposit epsilon(i), respectively. In fact, nothing is said about the averaging operation of the non-stochastic quantity mean energy imparted epsilon, which is used in the definition of D according to ICRU 60. It is shown in this research that the averaging operation necessary to define the epsilon employed to get D cannot be performed with an equilibrium statistical operator rho(r) as could be expected. Rather, the operation has to be defined with a time-dependent non-equilibrium statistical operator rho(r, t); therefore, D is a time-dependent function D(r,t). PMID:16731692
Thermodynamics of phase equilibrium of binary alloys containing nanprecipitates
NASA Astrophysics Data System (ADS)
L'vov, P. E.; Svetukhin, V. V.; Obukhov, A. V.
2011-02-01
A model of phase equilibrium in binary alloys has been developed taking into account the formation of phase precipitates of arbitrary (including nanometer) size. It has been shown that the phase composition of alloys substantially depends on the size of phase precipitates and, in the case of the formation of nano-precipitates, the phase composition can differ by a factor of several times from the phase composition of macroscopic precipitates. The proposed model has been used for calculating the dependence of the phase composition of some binary alloys (α-Fe-Cr at the temperature T = 773 K and Zr-Nb at the temperature T = 853-873 K) on the size of precipitates. The results of the calculation agree with experimental data obtained by other authors.
Non-Equilibrium Thermodynamics of Gene Expression and Transcriptional Regulation
NASA Astrophysics Data System (ADS)
Lemus, Enrique Hernández
2009-12-01
In recent times whole-genome gene expression analysis has turned out to be a highly important tool to study the coordinated function of a very large number of genes within their corresponding cellular environment, especially in relation to phenotypic diversity and disease. A wide variety of methods of quantitative analysis has been developed to cope with high throughput data sets generated by gene expression profiling experiments. Due to the complexity associated with
Tested Demonstrations: Thermodynamic Changes, Kinetics, Equilibrium, and LeChatelier's Principle.
ERIC Educational Resources Information Center
Gilbert, George L., Ed.
1984-01-01
Procedures for demonstrating thermodynamic changes, kinetics and reaction mechanisms, equilibrium, and LeChatelier's principle are presented. The only materials needed for these demonstrations are beakers, water, assorted wooden blocks of varying thickness, assorted rubber tubing, and a sponge. The concepts illustrated in each demonstration are…
An Easy and Effective Demonstration of Enzyme Stereospecificity and Equilibrium Thermodynamics
ERIC Educational Resources Information Center
Herdman, Chelsea; Dickman, Michael
2011-01-01
Enzyme stereospecificity and equilibrium thermodynamics can be demonstrated using the coupling of two amino acid derivatives by Thermoase C160. This protease will catalyze peptide bond formation between Z-L-AspOH and L-PheOMe to form the Aspartame precursor Z-L-Asp-L-PheOMe. Reaction completion manifests itself by precipitation of the product. As…
Natural gas at thermodynamic equilibrium Implications for the origin of natural gas
2009-01-01
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 [(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°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. PMID:19531233
Fateen, Seif-Eddeen K.; Bonilla-Petriciolet, Adrian
2014-01-01
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. PMID:24967430
Fateen, Seif-Eddeen K; Bonilla-Petriciolet, Adrian
2014-01-01
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. PMID:24967430
The Principle of Minimal Resistance in Non-equilibrium Thermodynamics
NASA Astrophysics Data System (ADS)
Mauri, Roberto
2016-04-01
Analytical models describing the motion of colloidal particles in given force fields are presented. In addition to local approaches, leading to well known master equations such as the Langevin and the Fokker-Planck equations, a global description based on path integration is reviewed. A new result is presented, showing that under very broad conditions, during its evolution a dissipative system tends to minimize its energy dissipation in such a way to keep constant the Hamiltonian time rate, equal to the difference between the flux-based and the force-based Rayleigh dissipation functions. In fact, the Fokker-Planck equation can be interpreted as the Hamilton-Jacobi equation resulting from such minumum principle. At steady state, the Hamiltonian time rate is maximized, leading to a minimum resistance principle. In the unsteady case, we consider the relaxation to equilibrium of harmonic oscillators and the motion of a Brownian particle in shear flow, obtaining results that coincide with the solution of the Fokker-Planck and the Langevin equations.
Possible evidence of thermodynamic equilibrium in dark matter halos
Davidson, Joshua; Sarker, Sanjoy K.; Stern, Allen E-mail: ssarker@ua.edu
2014-06-10
After deducing the density profiles and gravitational potential functions of eight galaxies from the rotation velocity data from THINGS, we find that the density decreases exponentially with the potential in substantial regions of the halos. This behavior is in agreement with that of a single-component isothermal Boltzmann gas, and it suggests that an effective description in terms of a Boltzmann gas is possible for dark matter in these regions. This could be an indication that dark matter self-interactions are sufficient in strength and number to lead to thermal equilibrium in these regions. We write down the dynamics and boundary conditions for a Boltzmann gas description and examine some of its qualitative and quantitative consequences. Solutions to the dynamical system are determined by three dimensionfull parameters, and they provide reasonable fits to the rotational velocity data in the regions where the Boltzmann-like behavior was found. Unlike in the usual approach to curve fitting, we do not assume a specific form for the dark matter density profile, and we do not require a detailed knowledge of the baryonic content of the galaxy.
NASA Astrophysics Data System (ADS)
Jesudason, Christopher G.
2009-07-01
By viewing reactant species to be in a state of thermodynamical equilibrium with its various members which constitutes a set within a set of topological parameters various states of internal equilibrium within the same species would exist subject to the Gibbs thermodynamical criteria. Some examples from actual ab initio computer simulations show that there exists an empirical relationship between the activity coefficient ratio and the so-called reactivity coefficients, defined as a measure of departure of the rate constant with varying concentration of reactants in a system at equilibrium, where forward and backward rates can still be measured. These ideas are applied to charged reaction dynamics where a generalization of the Brönsted and Bjerrum rate expression is obtained.
Jahnke, Annika; MacLeod, Matthew; Wickström, Håkan; Mayer, Philipp
2014-10-01
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 concentrations in sediments and lipid-normalized concentrations in biota and (II) that bioaccumulation does not induce levels exceeding those expected from equilibrium partitioning. Here, we demonstrate that assumption I can be obviated by equilibrating a silicone sampler with chemicals in sediment, measuring chemical concentrations in the silicone, and applying lipid/silicone partition ratios to yield concentrations in lipid at thermodynamic equilibrium with the sediment (CLip⇌Sed). Furthermore, we evaluated the validity of assumption II by comparing CLip⇌Sed of selected persistent, bioaccumulative and toxic pollutants (polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB)) to lipid-normalized concentrations for a range of biota from a Swedish background lake. PCBs in duck mussels, roach, eel, pikeperch, perch and pike were mostly below the equilibrium partitioning level relative to the sediment, i.e., lipid-normalized concentrations were ≤CLip⇌Sed, whereas HCB was near equilibrium between biota and sediment. Equilibrium sampling allows straightforward, sensitive and precise measurement of CLip⇌Sed. We propose CLip⇌Sed as a metric of the thermodynamic potential for bioaccumulation of persistent organic chemicals from sediment useful to prioritize management actions to remediate contaminated sites. PMID:25184484
Wu, Wei; Wang, Jin
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.
Do persistent organic pollutants reach a thermodynamic equilibrium in the global environment?
Schenker, Sebastian; Scheringer, Martin; Hungerbühler, Konrad
2014-05-01
Equilibrium partitioning between different environmental media is one of the main driving forces that govern the environmental fate of organic chemicals. In the global environment, equilibrium partitioning is in competition with long-range transport, advective phase transfer processes such as wet deposition, and degradation. Here we investigate under what conditions equilibrium partitioning is strong enough to control the global distribution of organic chemicals. We use a global multimedia mass-balance model to calculate the Globally Balanced State (GBS) of organic chemicals. The GBS is the state where equilibrium partitioning is in balance with long-range transport; it represents the maximum influence of thermodynamic driving forces on the global distribution of a chemical. Next, we compare the GBS with the Temporal Remote State, which represents the long-term distribution of a chemical in the global environment when the chemical's distribution is influenced by all transport and degradation processes in combination. This comparison allows us to identify the chemical properties required for a substance to reach the GBS as a stable global distribution. We find that thermodynamically controlled distributions are rare and do not occur for most Persistent Organic Pollutants. They are only found for highly volatile and persistent substances, such as chlorofluorocarbons. Furthermore, we find that the thermodynamic cold-trap effect (i.e., accumulation of pollutants at the poles because of reduced vapor pressure at low temperatures) is often strongly attenuated by atmospheric and oceanic long-range transport. PMID:24654605
Thermodynamic parameters for adsorption equilibrium of heavy metals and dyes from wastewaters.
Liu, Xiang; Lee, Duu-Jong
2014-05-01
This meta-analysis evaluates adsorption studies that report thermodynamic parameters for heavy metals and dyes from wastewaters. The adsorbents were derived from agricultural waste, industrial wastes, inorganic particulates, or some natural products. The adsorption mechanisms, derivation of thermodynamic relationships, and possible flaws made in such evaluation are discussed. This analysis shows that conclusions from the examined standard enthalpy and entropy changes are highly contestable. The reason for this flaw may be the poor physical structure of adsorbents tested, such that pore transport controlled the solute flux, leaving a surface reaction process near equilibrium. PMID:24461254
Non-Equilibrium Thermodynamic Chemistry and the Composition of the Atmosphere of Mars
NASA Technical Reports Server (NTRS)
Levine, J. S.; Summers, M. E.
2003-01-01
A high priority objective of the Mars Exploration Program is to Determine if life exists today (MEPAG Goal I, Objective A). The measurement of gases of biogenic origin may be an approach to detect the presence of microbial life on the surface or subsurface of Mars. Chemical thermodynamic calculations indicate that on both Earth and Mars, certain gases should exist in extremely low concentrations, if at all. Microbial metabolic activity is an important non-equilibrium chemistry process on Earth, and if microbial life exists on Mars, may be an important nonequilibrium chemistry process on Mars. The non-equilibrium chemistry of the atmosphere of Mars is discussed in this paper.
Maevskii, K. K. Kinelovskii, S. A.
2015-10-27
The numerical results of modeling of shock wave loading of mixtures with the SiO{sub 2} component are presented. The TEC (thermodynamic equilibrium component) model is employed to describe the behavior of solid and porous multicomponent mixtures and alloys under shock wave loading. State equations of a Mie–Grüneisen type are used to describe the behavior of condensed phases, taking into account the temperature dependence of the Grüneisen coefficient, gas in pores is one of the components of the environment. The model is based on the assumption that all components of the mixture under shock-wave loading are in thermodynamic equilibrium. The calculation results are compared with the experimental data derived by various authors. The behavior of the mixture containing components with a phase transition under high dynamic loads is described.
NASA Astrophysics Data System (ADS)
Wang, Wei-Zong; Rong, Ming-Zhe; Yang, Fei; Wu, Yi
2014-03-01
The transport coefficients of high temperature sulfur hexafluoride (SF6) plasmas in local thermodynamic equilibrium are calculated using collision integrals derived in a phenomenological approach which could be a valuable tool in the calculation of complete data sets for complex mixtures, including interactions hardly handled in the accurate multipotential methods. A systematic comparison with transport coefficients obtained using an old data set and experimental test is performed to check the reliability of the proposed approach in evaluating transport cross sections.
Helali, H.; Bchir, T.; Araoud, Z.; Charrada, K.
2013-04-15
The aim of this work is to study the local thermodynamic equilibrium (LTE) deviations in arc discharges plasma generated in high-intensity discharge lamps operating under an ac (50 Hz) power supply. To achieve this goal, we elaborate a two-temperature, two-dimensional, and time-depending model. We have found numerical results almost reproducing the experimental data, which allows us to validate this model. After validation, we have discussed different energy term effects on the LTE deviations.
THERMODYNAMIC MODELING OF LIQUID AEROSOLS CONTAINING DISSOLVED ORGANICS AND ELECTROLYTES
Many tropospheric aerosols contain large fractions of soluble organic material, believed to derive from the oxidation of precursors such alpha-pinene. The chemical composition of aerosol organic matter is complex and not yet fully understood.
The key properties of solu...
Rapid computation of spectrally integrated non-local thermodynamic equilibrium limb emission
NASA Technical Reports Server (NTRS)
Mlynczak, Martin G.; Olander, Daphne S.; Lopez-Puertas, Manuel
1994-01-01
The interpretation of infrared radiance measurements made by satellite-borne limb-scanning broadband radiometers requires accurate and computationally fast techniques with which to evaluate the equation of radiative transfer. This requirement is made even more stringent when analyzing measurements of non-local thermodynamic equilibrium (non-LTE) emission from the terrestrial mesosphere and lower thermosphere. In principle, line-by-line calculations which explicitly account for the departure from thermodynamic equilibrium in both the source functions and the transmittances are necessary. In this paper we extend the emissivity growth approximation (EGA) technique developed for local thermodynamic equilibrium (LTE) limb radiance for the molecular oxygen dayglow (1.27 micrometers and 762 nm), ozone and carbon dioxide in the 9- to 11-micrometer spectral interval, carbon monoxide (4.6 micrometers), nitric oxide (5.3 micrometers), and the carbon dioxide bands (15 micrometers) are presented. Using the non-LTE form of the EGA, the spectrally integrated limb emission is calculated for 35 tangent heights in the mesosphere and lower thermosphere (a total of 1200 atmospheric layers) with line-by-line accuracy in approximately 0.35 s of CPU time on readily available desktop computer hardware, while the corresponding line-by-line calculations may require several minutes. The non-LTE EGA technique will allow kinetic temperature and minor constituend retrieval algorithms to readily include non-LTE efects limited only by the a priori knowledge of the departure from LTE in the observed bands.
NASA Technical Reports Server (NTRS)
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.
Towards bulk thermodynamics via non-equilibrium methods: gaseous methane as a case study.
Zerbetto, Mirco; Frezzato, Diego
2015-01-21
We illustrate how the Jarzynski equality (JE), which is the progenitor of non-equilibrium methods aimed at constructing free energy landscapes for molecular-sized fluctuating systems subjected to steered transformations, can be applied to derive equations of state for bulk systems. The key-step consists of physically framing the computational strategy of "total energy morphing", recently presented by us as an efficient implementation of the JE [M. Zerbetto, A. Piserchia, D. Frezzato, J. Comput. Chem., 2014, 35, 1865-1881], in terms of build-up of the real thermodynamic state of a bulk material from the corresponding ideal state, in which the particles are non-interacting. In this context, the JE machinery yields the excess free energy versus suitably chosen controlled state variables, whose thermodynamic derivatives eventually lead to the equation of state. As an explanatory case study, we apply the methodology to derive the equation of state of gaseous methane by constructing the Helmholtz free energy versus the particle density (at fixed temperature) and then evaluating the thermodynamic derivative with respect to the volume. In our intent, this "old-style" work on gaseous methane should open the way for the investigation of thermodynamics of extended systems via non-equilibrium methods. PMID:25475171
Reconciling results of MOCVD of a CNT composite with equilibrium thermodynamics
NASA Astrophysics Data System (ADS)
Dhar, Sukanya; Arod, Pallavi; Shivashankar, S. A.
2016-05-01
Composition and microstructure of the composite films can be tailored by controlling the CVD process parameters if an appropriate model can be suggested for quantitative prediction of growth. This is possible by applying equilibrium thermodynamics. A modification of such standard modeling procedure was required to account for the deposition of a hybrid film comprised of carbon nanotubes (CNTs), metallic iron (Fe0), and magnetite (Fe3O4), a composite useful for energy storage. In contrast with such composite nature of the deposits obtained by inert-ambient CVD using Fe(acac)3 as precursor, equilibrium thermodynamic modeling with standard procedure predicts the deposition of only Fe3C and carbon, without any co-deposition of Fe and Fe3O4. A modification of the procedure comprising chemical reasoning is therefore proposed herein, which predicts simultaneous deposition of FeO1-x, Fe3C, Fe3O4 and C. At high temperatures and in a carbon-rich atmosphere, these convert to Fe3O4, Fe and C, in agreement with experimental CVD. Close quantitative agreement between the modified thermodynamic modeling and experiment validates the reliability of the modified procedure. Understanding of the chemical process through thermodynamic modeling provides potential for control of CVD process parameters to achieve desired hybrid growth.
Hudait, Arpa; Molinero, Valeria
2014-06-01
Atmospheric aerosols have a strong influence on Earth's climate. Elucidating the physical state and internal structure of atmospheric aqueous aerosols is essential to predict their gas and water uptake, and the locus and rate of atmospherically important heterogeneous reactions. Ultrafine aerosols with sizes between 3 and 15 nm have been detected in large numbers in the troposphere and tropopause. Nanoscopic aerosols arising from bubble bursting of natural and artificial seawater have been identified in laboratory and field experiments. The internal structure and phase state of these aerosols, however, cannot yet be determined in experiments. Here we use molecular simulations to investigate the phase behavior and internal structure of liquid, vitrified, and crystallized water-salt ultrafine aerosols with radii from 2.5 to 9.5 nm and with up to 10% moles of ions. We find that both ice crystallization and vitrification of the nanodroplets lead to demixing of pure water from the solutions. Vitrification of aqueous nanodroplets yields nanodomains of pure low-density amorphous ice in coexistence with vitrified solute rich aqueous glass. The melting temperature of ice in the aerosols decreases monotonically with an increase of solute fraction and decrease of radius. The simulations reveal that nucleation of ice occurs homogeneously at the subsurface of the water-salt nanoparticles. Subsequent ice growth yields phase-segregated, internally mixed, aerosols with two phases in equilibrium: a concentrated water-salt amorphous mixture and a spherical cap-like ice nanophase. The surface of the crystallized aerosols is heterogeneous, with ice and solution exposed to the vapor. Free energy calculations indicate that as the concentration of salt in the particles, the advance of the crystallization, or the size of the particles increase, the stability of the spherical cap structure increases with respect to the alternative structure in which a core of ice is fully surrounded by
Non-equilibrium Dynamics in the Quantum Brownian Oscillator and the Second Law of Thermodynamics
NASA Astrophysics Data System (ADS)
Kim, Ilki
2012-01-01
We initially prepare a quantum linear oscillator weakly coupled to a bath in equilibrium at an arbitrary temperature. We disturb this system by varying a Hamiltonian parameter of the coupled oscillator, namely, either its spring constant or mass according to an arbitrary but pre-determined protocol in order to perform external work on it. We then derive a closed expression for the reduced density operator of the coupled oscillator along this non-equilibrium process as well as the exact expression pertaining to the corresponding quasi-static process. This immediately allows us to analytically discuss the second law of thermodynamics for non-equilibrium processes. Then we derive a Clausius inequality and obtain its validity supporting the second law, as a consistent generalization of the Clausius equality valid for the quasi-static counterpart, introduced in (Kim and Mahler in Phys. Rev. E 81:011101, 2010, [1]).
Equilibrium thermodynamics of radiation defect clusters in δ-phase Pu-Ga alloys
NASA Astrophysics Data System (ADS)
Karavaev, A. V.; Dremov, V. V.; Ionov, G. V.
2016-01-01
The paper presents a theoretical investigation into the response of δ-phase Pu-Ga alloys to self-irradiation. Using classical molecular dynamics we investigate the long-term behavior of primary radiation defects (vacancies) in the face-centered cubic lattice of the alloys under ambient conditions. High diffusive migration energy barriers and the corresponding low mobility of vacancies do not allow us to track their dynamics in the lattice by direct molecular dynamics simulations. Instead, we use the Helmholtz free energy to investigate the equilibrium thermodynamics of metastable microconfigurations of Pu-Ga crystals with artificially introduced vacancy clusters in various regular and random configurations. The Helmholtz free energy of the microconfigurations are calculated with the thermodynamic integration method. Based on the free energy evaluation we draw conclusions about the relative thermodynamic stability of various microconfigurations under ambient conditions. The equilibrium parameters of vacancy clusters in the bulk of the lattice and in the presence of edge dislocations are estimated.
The solubility of (Ba,Sr)SO 4 precipitates: Thermodynamic equilibrium and reaction path analysis
NASA Astrophysics Data System (ADS)
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.
Quantum corrections to the stress-energy tensor in thermodynamic equilibrium with acceleration
NASA Astrophysics Data System (ADS)
Becattini, F.; Grossi, E.
2015-08-01
We show that the stress-energy tensor has additional terms with respect to the ideal form in states of global thermodynamic equilibrium in flat spacetime with nonvanishing acceleration and vorticity. These corrections are of quantum origin and their leading terms are second order in the gradients of the thermodynamic fields. Their relevant coefficients can be expressed in terms of correlators of the stress-energy tensor operator and the generators of the Lorentz group. With respect to previous assessments, we find that there are more second-order coefficients and that all thermodynamic functions including energy density receive acceleration and vorticity dependent corrections. Notably, also the relation between ρ and p , that is, the equation of state, is affected by acceleration and vorticity. We have calculated the corrections for a free real scalar field—both massive and massless—and we have found that they increase, particularly for a massive field, at very high acceleration and vorticity and very low temperature. Finally, these nonideal terms depend on the explicit form of the stress-energy operator, implying that different stress-energy tensors of the scalar field—canonical or improved—are thermodynamically inequivalent.
Collisional radiative model for heavy atoms in hot non-local-thermodynamical-equilibrium plasmas
NASA Astrophysics Data System (ADS)
Bar-Shalom, A.; Oreg, J.; Klapisch, M.
1997-07-01
A collisional radiative model for calculating non-local-thermodynamical-equilibrium (non-LTE) spectra of heavy atoms in hot plasmas has been developed, taking into account the numerous excited and autoionizing states. This model uses superconfigurations as effective levels with an iterative procedure which converges to the detailed configuration spectrum. The non-LTE opacities and emissivities may serve as a reliable benchmark for simpler on-line models in hydrodynamic code simulations. The model is tested against detailed configuration calculations of selenium and is applied to non-LTE optically thin plasma of lutetium.
Spontaneous charge transfer at organic-organic homointerfaces to establish thermodynamic equilibrium
Duhm, S.; Glowatzki, H.; Rabe, J. P.; Koch, N.; Johnson, R. L.
2007-03-19
The energy level alignment of {alpha},{omega}-dihexylsexithienyl (DH6T) mono- and multilayers on tetrafluorotetracyanoquinodimethane (F4-TCNQ) precovered Ag(111) and polycrystalline Au substrates was investigated with ultraviolet photoelectron spectroscopy. For certain F4-TCNQ precoverages molecular level pinning at DH6T monolayer-multilayer homointerfaces was observed. The pinning behavior shows that thermodynamic equilibrium can be established across hexyl chains via charge transfer, indicating the limited use of these short alkyl chains for insulation in the field of molecular electronics.
NASA Astrophysics Data System (ADS)
Pawel/ek, A.
1987-09-01
The paper deals with a modification of the classical expression derived by John P. Hirth and J. Lothe [Theory of Dislocations (McGraw-Hill, New York, 1972)] for the density of kinks on a dislocation segment in thermodynamic equilibrium imposed by external stresses. The dislocation kink-kink interaction is discussed in terms of soliton-antisoliton interaction, the analytical results obtained by J. Rubinstein [J. Math. Phys. 11, 258 (1970)] and the ones numerically obtained by M. Peyrard and David K. Campbell [Physica 9D, 33 (1983)] being applied for that purpose.
Elemental transport coefficients in viscous plasma flows near local thermodynamic equilibrium.
Orsini, Alessio; Kustova, Elena V
2009-05-01
We propose a convenient formulation of elemental transport coefficients in chemically reacting and plasma flows locally approaching thermodynamic equilibrium. A set of transport coefficients for elemental diffusion velocities, heat flux, and electric current is introduced. These coefficients relate the transport fluxes with the electric field and with the spatial gradients of elemental fractions, pressure, and temperature. The proposed formalism based on chemical elements and fully symmetric with the classical transport theory based on chemical species, is particularly suitable to model mixing and demixing phenomena due to diffusion of chemical elements. The aim of this work is threefold: to define a simple and rigorous framework suitable for numerical implementation, to allow order of magnitude estimations and qualitative predictions of elemental transport phenomena, and to gain a deeper insight into the physics of chemically reacting flows near local equilibrium. PMID:19518564
NASA Astrophysics Data System (ADS)
Louis-Martinez, Domingo
2011-04-01
A classical (non-quantum-mechanical) relativistic ideal gas in thermodynamic equilibrium in a uniformly accelerated frame of reference is studied using Gibbs's microcanonical and grand canonical formulations of statistical mechanics. Using these methods explicit expressions for the particle, energy and entropy density distributions are obtained, which are found to be in agreement with the well known results of the relativistic formulation of Boltzmann's kinetic theory. Explicit expressions for the total entropy, total energy and rest mass of the gas are obtained. The position of the center of mass of the gas in equilibrium is found. The non-relativistic and ultrarelativistic approximations are also considered. The phase space volume of the system is calculated explicitly in the ultrarelativistic approximation.
NASA Astrophysics Data System (ADS)
Louis-Martinez, Domingo J.
2011-02-01
A classical (non-quantum-mechanical) relativistic ideal gas in thermodynamic equilibrium in a uniformly accelerated frame of reference is studied using Gibbs's microcanonical and grand canonical formulations of statistical mechanics. Using these methods explicit expressions for the particle, energy and entropy density distributions are obtained, which are found to be in agreement with the well-known results of the relativistic formulation of Boltzmann's kinetic theory. Explicit expressions for the total entropy, total energy and rest mass of the gas are obtained. The position of the center of mass of the gas in equilibrium is found. The non-relativistic and ultrarelativistic approximations are also considered. The phase space volume of the system is calculated explicitly in the ultrarelativistic approximation.
NASA Astrophysics Data System (ADS)
Mey, Antonia S. J. S.; Wu, Hao; Noé, Frank
2014-10-01
Computing the equilibrium properties of complex systems, such as free energy differences, is often hampered by rare events in the dynamics. Enhanced sampling methods may be used in order to speed up sampling by, for example, using high temperatures, as in parallel tempering, or simulating with a biasing potential such as in the case of umbrella sampling. The equilibrium properties of the thermodynamic state of interest (e.g., lowest temperature or unbiased potential) can be computed using reweighting estimators such as the weighted histogram analysis method or the multistate Bennett acceptance ratio (MBAR). weighted histogram analysis method and MBAR produce unbiased estimates, the simulation samples from the global equilibria at their respective thermodynamic states—a requirement that can be prohibitively expensive for some simulations such as a large parallel tempering ensemble of an explicitly solvated biomolecule. Here, we introduce the transition-based reweighting analysis method (TRAM)—a class of estimators that exploit ideas from Markov modeling and only require the simulation data to be in local equilibrium within subsets of the configuration space. We formulate the expanded TRAM (xTRAM) estimator that is shown to be asymptotically unbiased and a generalization of MBAR. Using four exemplary systems of varying complexity, we demonstrate the improved convergence (ranging from a twofold improvement to several orders of magnitude) of xTRAM in comparison to a direct counting estimator and MBAR, with respect to the invested simulation effort. Lastly, we introduce a random-swapping simulation protocol that can be used with xTRAM, gaining orders-of-magnitude advantages over simulation protocols that require the constraint of sampling from a global equilibrium.
NASA Technical Reports Server (NTRS)
Talcott, N. A., Jr.
1977-01-01
Equations and computer code are given for the thermodynamic properties of gaseous fluorocarbons in chemical equilibrium. In addition, isentropic equilibrium expansions of two binary mixtures of fluorocarbons and argon are included. The computer code calculates the equilibrium thermodynamic properties and, in some cases, the transport properties for the following fluorocarbons: CCl2F, CCl2F2, CBrF3, CF4, CHCl2F, CHF3, CCL2F-CCl2F, CCLF2-CClF2, CF3-CF3, and C4F8. Equilibrium thermodynamic properties are tabulated for six of the fluorocarbons(CCl3F, CCL2F2, CBrF3, CF4, CF3-CF3, and C4F8) and pressure-enthalpy diagrams are presented for CBrF3.
Impact of Aerosols and Atmospheric Thermodynamics on Cloud Properties within the Climate System
NASA Technical Reports Server (NTRS)
Matsui, Toshihisa; Masunaga, Hirohiko; Pielke, Roger, Sr.; Tao, Wei-Kuo
2003-01-01
A combination of cloud-top and columnar droplet sizes derived from the multi Tropical Rainfall Measurement Mission (TRMM) sensors reveals the sensitivity of the aerosols effect on cloud-precipitation process due to environmental vertical thermodynamic structure. First, the magnitude of aerosol indirect effect could be larger with the analysis of columnar droplet sizes than that derived from the cloud-top droplet sizes, since column-droplet size can account for the broader droplet spectra in the cloud layers. Second, a combination of cloud- top and columnar droplet sizes reveals that the warm rain process is prevented regardless of the aerosols concentration under a high static stability such as when a strong temperature inversion exists, while a high aerosol concentration suppresses the warm rain formulation under a low static stability.
NASA Astrophysics Data System (ADS)
Gao, Tianfu; Chen, Jincan
Based on the general model of thermally-driven Brownian motors, an equivalent cycle system is established and the Onsager coefficients and efficiency at the maximum power output of the system are analytically calculated from non-equilibrium thermodynamics. It is found that the Onsager reciprocity relation holds and the Onsager coefficients are affected by the main irreversibilities existing in practical systems. Only when the heat leak and the kinetic energy change of the particle in the system are negligible, can the determinant of the Onsager matrix vanish. It is also found that in the frame of non-equilibrium thermodynamics, the power output and efficiency of an irreversible Brownian motor can be expressed to be the same form as those of an irreversible Carnot heat engine, so the results obtained here are of general significance. Moreover, these results are used to analyze the performance characteristics of a class of thermally-driven Brownian motors so that some important conclusions in literature may be directly derived from the present paper.
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. PMID:26683820
Absolute determination of the gelling point of gelatin under quasi-thermodynamic equilibrium.
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. PMID:25832543
Hu, Wei; Zhang, Chao; Hu, Wenjin; Fang, Yun; Hou, Wenjie
2012-10-01
Aerosol delivery is a route which is advantageous to the therapy of pulmonary diseases, such as lung cancer. The pharmacokinetics and tissue distribution after aerosol delivery of carboxylate form of hydroxycamptothecin (C-HCPT) were investigated. The concentrations of the three different types (lactone, carboxylate and the total of both forms) of HCPT were measured by HPLC analysis. The initial experiment showed no evident difference between lactone and carboxylate in the lungs during the aerosol treatment, compared with the HCPT content in plasma. The AUC(inf) value of lactone in the lungs was higher than that of carboxylate, which was 138,176.00 min ng g⁻¹ and 128,460.00 min ng g⁻¹, respectively. Meanwhile, AUC(inf) in the plasma during the entire treatment indicated that the lactone content was always at a lower level, and the carboxylate form tended to predominate, as shown by the lactone/carboxylate (L/C) equilibrium. The tissue distribution results showed that the lactone proportion in the liver increased up to the maximum value of 69.69% after aerosol administration, whereas the mean L/C equilibrium index for the liver was 2.07±1.06, and the C(max) and AUC(0-∞) values of the total HCPT were highest in the tissues. Based on these results we speculated that the initial wholly carboxylate form of the HCPT atomized liquid did not influence the transformation to lactone form. Moreover, the deposition of the total HCPT and lactone was higher in the lungs and other tissues than in the plasma after the aerosol treatment. This study will be beneficial to the therapy of pulmonary carcinoma. PMID:22858157
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. PMID:20817346
NASA Astrophysics Data System (ADS)
Accardi, Luigi; Fidaleo, Francesco
2016-04-01
In the setting of the principle of local equilibrium which asserts that the temperature is a function of energy levels of the system, we exhibit plenty of steady states describing condensation of free bosons which are not in thermal equilibrium. The surprising facts are that the condensation can occur both in dimension less than 3 in configuration space, and even in excited energy levels. The investigation relative to nonequilibrium suggests a new approach to the condensation which allows a unified analysis involving also condensation of q-particles, -1 ≤ q ≤ 1, where q = ±1 corresponds to the Bose/Fermi alternative. For such q-particles, it is shown that condensation can occur only if 0 equilibrium thermodynamics involving bosons. The new approach proposed in the present paper for the situation of second quantisation of free particles, is based on the theory of distributions, which might hopefully be extended to more general cases.
Dotov, D G; Kim, S; Frank, T D
2015-02-01
We derive explicit expressions for the non-equilibrium thermodynamical variables of a canonical-dissipative limit cycle oscillator describing rhythmic motion patterns of active systems. These variables are statistical entropy, non-equilibrium internal energy, and non-equilibrium free energy. In particular, the expression for the non-equilibrium free energy is derived as a function of a suitable control parameter. The control parameter determines the Hopf bifurcation point of the deterministic active system and describes the effective pumping of the oscillator. In analogy to the equilibrium free energy of the Landau theory, it is shown that the non-equilibrium free energy decays as a function of the control parameter. In doing so, a similarity between certain equilibrium and non-equilibrium phase transitions is pointed out. Data from an experiment on human rhythmic movements is presented. Estimates for pumping intensity as well as the thermodynamical variables are reported. It is shown that in the experiment the non-equilibrium free energy decayed when pumping intensity was increased, which is consistent with the theory. Moreover, pumping intensities close to zero could be observed at relatively slow intended rhythmic movements. In view of the Hopf bifurcation underlying the limit cycle oscillator model, this observation suggests that the intended limit cycle movements were actually more similar to trajectories of a randomly perturbed stable focus. PMID:25619737
Modeling non-local thermodynamic equilibrium plasma using the Flexible Atomic Code data
NASA Astrophysics Data System (ADS)
Han, Bo; Wang, Feilu; Salzmann, David; Zhao, Gang
2015-04-01
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 a rate equation to interpret the plasmas systematically. The Flexible Atomic Code (FAC) supplies all the atomic data needed for RCF, 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 potential emission spectrum. In a preliminary application, RCF successfully reproduced 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.
NASA Technical Reports Server (NTRS)
Thompson, Richard A.; Lee, Kam-Pui; Gupta, Roop N.
1991-01-01
The computer codes developed here provide self-consistent thermodynamic and transport properties for equilibrium air for temperatures from 500 to 30000 K over a temperature range of 10 (exp -4) to 10 (exp -2) atm. These properties are computed through the use of temperature dependent curve fits for discrete values of pressure. Interpolation is employed for intermediate values of pressure. The curve fits are based on mixture values calculated from an 11-species air model. Individual species properties used in the mixture relations are obtained from a recent study by the present authors. A review and discussion of the sources and accuracy of the curve fitted data used herein are given in NASA RP 1260.
Benchmark Measurements of the Ionization Balance of Non-Local-Thermodynamic-Equilibrium Gold Plasmas
Heeter, R. F.; Hansen, S. B.; Fournier, K. B.; Foord, M. E.; Froula, D. H.; Mackinnon, A. J.; May, M. J.; Schneider, M. B.; Young, B. K. F.
2007-11-09
We present a series of benchmark measurements of the ionization balance of well-characterized gold plasmas with and without external radiation fields at electron densities near 10{sup 21} cm{sup -3} and electron temperatures spanning the range 0.8 to 2.4 keV. We have analyzed time- and space-resolved M-shell gold emission spectra using a sophisticated collisional-radiative model with hybrid level structure, finding average ion charges
Adsorptive removal of heavy metals by magnetic nanoadsorbent: an equilibrium and thermodynamic study
NASA Astrophysics Data System (ADS)
Shirsath, D. S.; Shirivastava, V. S.
2015-11-01
An efficient and new magnetic nanoadsorbent photocatalyst was fabricated by co-precipitation technique. This research focuses on understanding metal removal process and developing a cost-effective technology for treatment of heavy metal-contaminated industrial wastewater. In this investigation, magnetic nanoadsorbent has been employed for the removal of Zn(II) ions from aqueous solutions by a batch adsorption technique. The adsorption equilibrium data fitted very well to Langmuir and Freundlich adsorption isotherm models. The thermodynamics of Zn(II) ions adsorption onto the magnetic nanoadsorbents indicated that the adsorption was spontaneous, endothermic and physical in nature. Surface morphology of magnetic nanoadsorbent by scanning electron microscopy (SEM) and elemental analysis by EDX technique. The structural and photocatalytic properties of magnetic nanoadsorbent were characterized using X-ray diffraction (XRD) and FTIR techniques. Also, the magnetic properties of synthesized magnetic nanoadsorbent were determined by vibrating spinning magnetometer (VSM).
Cloud and Precipitation During GoAmazon: The Influence of Aerosol and Thermodynamics.
NASA Astrophysics Data System (ADS)
Machado, L.; Cecchin, M.; Biscaro, T.; Lima, W.; Calheiros, A. J. P.; Albrecht, R. I.; Comstock, J. M.; Schmid, B.; Mei, F.; Schumacher, C.; Eichholz, C.; Giangrande, S. E.; Fan, J.; Wang, J.; Wendisch, M.; Andreae, M. O.; Martin, S. T.; Artaxo, P.; Thalman, R. M.; Rosenfeld, D.; Poeschl, U.
2015-12-01
The Green Ocean Amazon, GOAmazon, intensive field campaign, hereafter called IOP1 (February-March) and IOP2 (September - October) 2014, was an opportunity for broad and joint campaigns of the CHUVA, IARA and ACRIDICON-CHUVA projects. GOAmazon intends to study how aerosols and surface fluxes influence cloud cycles under clean conditions, as well as how aerosol and cloud life cycles, including cloud-aerosol-precipitation interactions, are influenced by pollutant outflow from a tropical megacity. This study employs the SIPAM S band radar, the X Band dual polarization radar, GOES images, disdrometers, CCN counters, radiosondes and data collected by G1 and HALO airplanes. As ancillary data, we used the Shuttle Radar Topography Mission, the TERRACLASS (INPE) and EVI from MODIS for surface topography, surface type classification and vegetation index, respectively. Cloud and precipitation are studied as function of aerosol concentration as well surface type and thermodynamic properties. Different sensors and space-time scales are employed to compare the life cycle and cloud size distribution using radar and satellite for different atmospheric conditions. For each IOP, the droplet size distribution using the airplanes or the particle size distribution using disdrometers are described discussing the aerosol, thermodynamic, surface type and topography effects on the clouds and precipitation. The typical precipitation behavior, for each IOP, is described using CFADs and reflectivity distributions. For few specific flights, those measuring ice particles, during the wet season (IOP1), some examples and classifications of convective and stratiform clouds are discussed. Finally, the microphysical properties of the clouds are presented using X band dual pol radar hydrometeor classifications and evaluating the effect of aerosol loading on the cloud vertical structure.
Non-local thermodynamic equilibrium 1.5D modeling of red giant stars
Young, Mitchell E.; Short, C. Ian
2014-05-20
Spectra for two-dimensional (2D) stars in the 1.5D approximation are created from synthetic spectra of one-dimensional (1D) non-local thermodynamic equilibrium (NLTE) spherical model atmospheres produced by the PHOENIX code. The 1.5D stars have the spatially averaged Rayleigh-Jeans flux of a K3-4 III star while varying the temperature difference between the two 1D component models (ΔT {sub 1.5D}) and the relative surface area covered. Synthetic observable quantities from the 1.5D stars are fitted with quantities from NLTE and local thermodynamic equilibrium (LTE) 1D models to assess the errors in inferred T {sub eff} values from assuming horizontal homogeneity and LTE. Five different quantities are fit to determine the T {sub eff} of the 1.5D stars: UBVRI photometric colors, absolute surface flux spectral energy distributions (SEDs), relative SEDs, continuum normalized spectra, and TiO band profiles. In all cases except the TiO band profiles, the inferred T {sub eff} value increases with increasing ΔT {sub 1.5D}. In all cases, the inferred T {sub eff} value from fitting 1D LTE quantities is higher than from fitting 1D NLTE quantities and is approximately constant as a function of ΔT {sub 1.5D} within each case. The difference between LTE and NLTE for the TiO bands is caused indirectly by the NLTE temperature structure of the upper atmosphere, as the bands are computed in LTE. We conclude that the difference between T {sub eff} values derived from NLTE and LTE modeling is relatively insensitive to the degree of the horizontal inhomogeneity of the star being modeled and largely depends on the observable quantity being fit.
Applications of non-equilibrium thermodynamics to signaling and metabolic pathways
NASA Astrophysics Data System (ADS)
Hu, Dawei; Liu, Ensheng; Yuan, Jian-Min
2006-03-01
Signaling transduction pathways play important roles in regulating cell functions, such as growth, differentiation, and apoptosis. Metabolic pathways, on the other hand, generate many metabolites utilized by human body. Abnormal regulations of the enzymes and metabolites associated with these pathways may be related to diseases. In view of their importance, we are interested in applying non-equilibrium thermodynamics to investigate the properties and dynamic behaviors of these two types of pathways. The systems of concentration are the MAPK, coupled MAPK-PI3K, and insulin metabolic pathways. In the case of signaling pathways we study the properties of thermodynamic variables, such as the affinities and fluxes of individual reaction steps, as affected by the perturbations of rate constants, protein-protein interactions, and cross talks. In the case of metabolic pathways, we study the system dynamics, the stability of steady states, and the flux-affinity relations as functions of constant inputs and outputs as well as the parameters of feedback loops. Our goals are to shed light on the design principles of the biological pathways and to rank the most vulnerable nodes of these pathways.
A spreadsheet-coupled SOLGAS: A computerized thermodynamic equilibrium calculation tool. Revision 1
Trowbridge, L.D.; Leitnaker, J.M.
1995-07-01
SOLGAS, an early computer program for calculating equilibrium in a chemical system, has been made more user-friendly, and several ``bells and whistles`` have been added. The necessity to include elemental species has been eliminated. The input of large numbers of starting conditions has been automated. A revised spreadsheet-based format for entering data, including non-ideal binary and ternary mixtures, simplifies and reduces chances for error. Calculational errors by SOLGAS are flagged, and several programming errors are corrected. Auxiliary programs are available to assemble and partially automate plotting of large amounts of data. Thermodynamic input data can be changed on line. The program can be operated with or without a co-processor. Copies of the program, suitable for the IBM-PC or compatibles with at least 384 bytes of low RAM, are available from the authors. This user manual contains appendices with examples of the use of SOLGAS. These range from elementary examples, such as, the relationships among water, ice, and water vapor, to more complex systems: phase diagram calculation of UF{sub 4} and UF{sub 6} system; burning UF{sub 4} in fluorine; thermodynamic calculation of the Cl-F-O-H system; equilibria calculations in the CCl{sub 4}--CH{sub 3}OH system; and limitations applicable to aqueous solutions. An appendix also contains the source code.
Wang, Chen; Goss, Kai-Uwe; Lei, Ying Duan; Abbatt, Jonathan P D; Wania, Frank
2015-07-21
Challenges in the parametrization of compound distribution between the gas and particle phase contribute significantly to the uncertainty in the prediction of secondary organic aerosol (SOA) formation and are rooted in the complexity and variability of atmospheric condensed matter, which includes water, salts, and a multitude of organic oxidation products, often in two separated phases. Here, we explore the use of the commercial quantum-chemistry-based software COSMOtherm to predict equilibrium partitioning and Setchenow coefficients of a suite of oxidation products of α-pinene ozonolysis in an aerosol that is assumed to separate into an organic-enriched phase and an electrolyte-enriched aqueous phase. The predicted coefficients are used to estimate the phase distribution of the organic compounds, water and ammonium sulfate, the resulting phase composition, and the SOA yield. Four scenarios that differ in terms of organic loading, liquid water content, and chemical aging are compared. The organic compounds partition preferentially to the organic phase rather than the aqueous phase for the studied aerosol scenarios, partially due to the salting-out effect. Extremely low volatile organic compounds are predicted to be the dominant species in the organic aerosols at low loadings and an important component at higher loadings. The highest concentration of oxidation products in the condensed phase is predicted for a scenario assuming the presence of non-phase-separated cloud droplets. Partitioning into an organic aerosol phase composed of the oxidation products is predicted to be similar to partitioning into a phase composed of a single organic surrogate molecule, suggesting that the calculation procedure can be simplified without major loss of accuracy. COSMOtherm is shown to produce results that are comparable to those obtained using group contribution methods. COSMOtherm is likely to have a much larger application domain than those group contribution methods because
Characterization of local thermodynamic equilibrium in a laser-induced aluminum alloy plasma.
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. PMID:27139680
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. PMID:27253197
Calculations and curve fits of thermodynamic and transport properties for equilibrium air to 30000 K
NASA Technical Reports Server (NTRS)
Gupta, Roop N.; Lee, Kam-Pui; Thompson, Richard A.; Yos, Jerrold M.
1991-01-01
A self-consistent set of equilibrium air values were computed for enthalpy, total specific heat at constant pressure, compressibility factor, viscosity, total thermal conductivity, and total Prandtl number from 500 to 30,000 K over a range of 10(exp -4) atm to 10(exp 2) atm. The mixture values are calculated from the transport and thermodynamic properties of the individual species provided in a recent study by the authors. The concentrations of the individual species, required in the mixture relations, are obtained from a free energy minimization calculation procedure. Present calculations are based on an 11-species air model. For pressures less than 10(exp -2) atm and temperatures of about 15,000 K and greater, the concentrations of N(++) and O(++) become important, and consequently, they are included in the calculations determining the various properties. The computed properties are curve fitted as a function of temperature at a constant value of pressure. These curve fits reproduce the computed values within 5 percent for the entire temperature range considered here at specific pressures and provide an efficient means for computing the flowfield properties of equilibrium air, provided the elemental composition remains constant at 0.24 for oxygen and 0.76 for nitrogen by mass.
Trinh, T T; van Erp, T S; Bedeaux, D; Kjelstrup, S; Grande, C A
2015-03-28
Thermodynamic equilibrium for adsorption means that the chemical potential of gas and adsorbed phase are equal. A precise knowledge of the chemical potential is, however, often lacking, because the activity coefficient of the adsorbate is not known. Adsorption isotherms are therefore commonly fitted to ideal models such as the Langmuir, Sips or Henry models. We propose here a new procedure to find the activity coefficient and the equilibrium constant for adsorption which uses the thermodynamic factor. Instead of fitting the data to a model, we calculate the thermodynamic factor and use this to find first the activity coefficient. We show, using published molecular simulation data, how this procedure gives the thermodynamic equilibrium constant and enthalpies of adsorption for CO2(g) on graphite. We also use published experimental data to find similar thermodynamic properties of CO2(g) and of CH4(g) adsorbed on activated carbon. The procedure gives a higher accuracy in the determination of enthalpies of adsorption than ideal models do. PMID:25732332
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
NASA Technical Reports Server (NTRS)
Thompson, R. A.
1994-01-01
Accurate numerical prediction of high-temperature, chemically reacting flowfields requires a knowledge of the physical properties and reaction kinetics for the species involved in the reacting gas mixture. Assuming an 11-species air model at temperatures below 30,000 degrees Kelvin, SPECIES (Computer Codes for the Evaluation of Thermodynamic Properties, Transport Properties, and Equilibrium Constants of an 11-Species Air Model) computes values for the species thermodynamic and transport properties, diffusion coefficients and collision cross sections for any combination of the eleven species, and reaction rates for the twenty reactions normally occurring. The species represented in the model are diatomic nitrogen, diatomic oxygen, atomic nitrogen, atomic oxygen, nitric oxide, ionized nitric oxide, the free electron, ionized atomic nitrogen, ionized atomic oxygen, ionized diatomic nitrogen, and ionized diatomic oxygen. Sixteen subroutines compute the following properties for both a single species, interaction pair, or reaction, and an array of all species, pairs, or reactions: species specific heat and static enthalpy, species viscosity, species frozen thermal conductivity, diffusion coefficient, collision cross section (OMEGA 1,1), collision cross section (OMEGA 2,2), collision cross section ratio, and equilibrium constant. The program uses least squares polynomial curve-fits of the most accurate data believed available to provide the requested values more quickly than is possible with table look-up methods. The subroutines for computing transport coefficients and collision cross sections use additional code to correct for any electron pressure when working with ionic species. SPECIES was developed on a SUN 3/280 computer running the SunOS 3.5 operating system. It is written in standard FORTRAN 77 for use on any machine, and requires roughly 92K memory. The standard distribution medium for SPECIES is a 5.25 inch 360K MS-DOS format diskette. The contents of the
Massucci, M.; Clegg, S.L.; Brimblecombe, P.
1999-05-27
Equilibrium total pressures have been measured above aqueous HNO{sub 3} and aqueous HCl using a capacitance manometer. Equilibrium partial pressures of the acids have also been determined, by mass spectrometry, from 274.8 to 234.6 K for both HCl solutions, and from 265.0 to 240.1 K for 15.73 mol kg{sup {minus}1} HNO{sub 3}. Results are generally consistent with model predictions, though with small systematic deviations for the total pressure measurements over aqueous HCl at about 220 K. Mixtures of HCl{minus}HNO{sub 3}{minus}H{sub 2}O composition yielded measured total pressures orders of magnitude greater than predicted for the gases H{sub 2}O, HNO{sub 3}, and HCl. Mass spectrometric determinations and equilibrium thermodynamic calculations suggest that Cl{sub 2} and NOCl were produced by the reaction: 4H{sup +}{sub aq} + NO{sub 3}{sup {minus}}{sub aq} + 3Cl{sup {minus}}{sub aq} {r_equilibrium} NOCl{sub aq} + Cl{sub 2(aq)} + 2H{sub 2}O{sub (1)}, which is known to occur in aqua regia. Calculations for aqueous solutions of stratospheric aerosol composition suggest, purely on equilibrium grounds, that the reaction could be a source of active chlorine in the stratosphere. The correlation of Clegg and Brimblecombe of the thermodynamic properties of aqueous HNO{sub 3} activities has been revised, and vapor pressure products assessed from literature studies. The activity product for the reaction HNO{sub 3}{center_dot}2H{sub 2}O{sub (cr)} {r_equilibrium} H{sup +}{sub (aq)} + NO{sub 3}{sup {minus}}{sub (aq)} + 2H{sub 2}O{sub (1)} has also been determined. The model of Carslaw et al. has been revised for the solubility of HBr in aqueous H{sub 2}SO{sub 4} to stratospheric temperatures.
NASA Astrophysics Data System (ADS)
Dyke, J. G.; Gans, F.; Kleidon, A.
2010-09-01
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. We estimate that the
Non-equilibrium thermodynamics theory of econometric source discovery for large data analysis
NASA Astrophysics Data System (ADS)
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
NASA Astrophysics Data System (ADS)
Lebon, G.; Jou, D.
2015-03-01
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.
A thermodynamic study of silica-saturated iron silicate slags in equilibrium with liquid copper
NASA Astrophysics Data System (ADS)
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.
Numerical solution of 2D wet steam flow with non-equilibrium condensation and real thermodynamics
Hric, V.; Halama, J.
2015-03-10
An approach to modeling of wet steam flow with non-equilibrium condensation phenomenon is presented. The first part of our flow model is homogeneous Euler system of transport equations for mass, momentum and total energy of wet steam (mixture). The additional second part describes liquid phase via non-homogeneous system of transport equations for moments of droplets number distribution function and relies on corrected classical nucleation theory. Moment equations are closed by linearization of droplet growth rate model. All necessary relations for thermodynamic properties of steam are provided by IAPWS set of equations. However, properties of condensate are simply modeled by liquid saturation data. Two real equations of state are implemented. Recently developed CFD formulation for entropy (does not require iteration process) and so-called IAPWS special gas equation for Helmholtz energy (one iteration loop is necessary). Flow model is validated on converging-diverging supersonic nozzle with Barschdorff geometry. Simulations were performed by in-house CFD code based on finite volume method and stiff character of equations was solved by symmetrical time operator splitting. Achieved results satisfactorily agreed with experimental data.
Equilibrium, kinetic and thermodynamic studies on the adsorption of phenol onto graphene
Li, Yanhui; Du, Qiuju; Liu, Tonghao; Sun, Jiankun; Jiao, Yuqin; Xia, Yanzhi; Xia, Linhua; Wang, Zonghua; Zhang, Wei; Wang, Kunlin; Zhu, Hongwei; Wu, Dehai
2012-08-15
Graphical abstract: The effect of temperature on phenol adsorbed by graphene shows that the equilibrium adsorption capacity of phenol increases with the increase in temperature from 285 to 333 K. Increasing adsorption capacities with temperature indicates that the adsorption of phenol is controlled by an endothermic reaction. Highlights: ► The graphene has high phenol adsorption capacity. ► The graphene has a high specific surface area of 305 m{sup 2}/g. ► The adsorption capacity is high at acidic pH range. ► The graphene has rapid phenol adsorption rate. ► Phenol adsorption is a spontaneous and endothermic process. -- Abstract: Graphene, a new member of carbon family, has been prepared, characterized and used as adsorbent to remove phenol from aqueous solution. The effect parameters including pH, dosage, contact time, and temperature on the adsorption properties of phenol onto graphene were investigated. The results showed that the maximum adsorption capacity can reach 28.26 mg/g at the conditions of initial phenol concentration of 50 mg/L, pH 6.3 and 285 K. Adsorption data were well described by both Freundlich and Langmuir models. The kinetic study illustrated that the adsorption of phenol onto graphene fit the pseudo second-order model. The thermodynamic parameters indicated that the adsorption of phenol onto graphene was endothermic and spontaneous.
NASA Astrophysics Data System (ADS)
Dyke, J. G.; Gans, F.; Kleidon, A.
2011-06-01
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.
Guler, Ulker Asli; Sarioglu, Meltem
2014-01-01
In this study, pumice stone was used for the removal of tetracyline (TC) from aqueous solutions. It was characterized by XRD, FT-IR, SEM and BET analyses. Cation exchange capacity of pumice stone was found to be 9.9 meq/100 g. Effect of various parameters such as solution pH (2-11), adsorbent dosage (0.5-10 g/L), contact time (2.5-120 min), initial TC concentration (5-300 mg/L) and temperature (20-50°C) on TC adsorption onto pumice was investigated. Also the adsorption of TC on pumice stone was studied as a function of Na(+) and Cu(2+) cations changing pH from 2 to 11 using batch experiments. The best removal efficiency performance was exhibited at adsorbent dosage 10 g/L, pH 3, contact time 120 min. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models were applied to the equilibrium data. The result has shown that the adsorption was favorable, physicochemical in nature and agrees well with Langmuir and Freundlich models. The maximum Langmuir adsorption capacity was found to be 20.02 mg/g. The adsorption behavior of TC on pumices stone was fitted well in the pseudo-second order kinetics model. Thermodynamic parameters calculated from the adsorption data at different temperature showed that the adsorption reaction was feasible, spontaneous and exothermic. PMID:24936305
Model uncertainties of local-thermodynamic-equilibrium K-shell spectroscopy
NASA Astrophysics Data System (ADS)
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.
2014-01-01
In this study, pumice stone was used for the removal of tetracyline (TC) from aqueous solutions. It was characterized by XRD, FT-IR, SEM and BET analyses. Cation exchange capacity of pumice stone was found to be 9.9 meq/100 g. Effect of various parameters such as solution pH (2–11), adsorbent dosage (0.5-10 g/L), contact time (2.5-120 min), initial TC concentration (5–300 mg/L) and temperature (20–50°C) on TC adsorption onto pumice was investigated. Also the adsorption of TC on pumice stone was studied as a function of Na+ and Cu2+ cations changing pH from 2 to 11 using batch experiments. The best removal efficiency performance was exhibited at adsorbent dosage 10 g/L, pH 3, contact time 120 min. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models were applied to the equilibrium data. The result has shown that the adsorption was favorable, physicochemical in nature and agrees well with Langmuir and Freundlich models. The maximum Langmuir adsorption capacity was found to be 20.02 mg/g. The adsorption behavior of TC on pumices stone was fitted well in the pseudo-second order kinetics model. Thermodynamic parameters calculated from the adsorption data at different temperature showed that the adsorption reaction was feasible, spontaneous and exothermic. PMID:24936305
NASA Astrophysics Data System (ADS)
Stolz, Douglas C.; Rutledge, Steven A.; Pierce, Jeffrey R.
2015-06-01
Convective features (CFs) observed by the Tropical Rainfall Measuring Mission satellite between 2004 and 2011 are analyzed to determine the relative roles of thermodynamics and aerosols as they modulate radar reflectivity and lightning. We studied the simultaneous impacts of normalized convective available potential energy (NCAPE) and warm cloud depth (WCD) as well as cloud condensation nuclei concentrations (D ≥ 40 nm; N40) on total lightning density (TLD), average height of 30 dBZ echoes (AVGHT30), and vertical profiles of radar reflectivity (VPRR) within individual CFs. The results show that TLD increases by up to 600% and AVGHT30 increases by up to 2-3 km with increasing NCAPE and N40 for fixed WCD. The partial sensitivities of TLD/AVGHT30 to NCAPE and N40 separately were comparable in magnitude but account for a fraction of the total range of variability (i.e., when the influences of NCAPE and N40 are considered simultaneously). Both TLD and AVGHT30 vary inversely with WCD such that maxima of TLD and AVGHT30 are found for the combination of high NCAPE, high N40, and shallower WCD. The relationship between lightning and radar reflectivity was shown to vary as a function of N40 for a fixed thermodynamic environment. Analysis of VPRRs shows that reflectivity in the mixed phase region is up to 5.0-5.6 dB greater for CFs in polluted environments compared to CFs in pristine environments (holding thermodynamics fixed). This analysis favors a merged hypothesis for the simultaneous roles of thermodynamics and aerosols as they influence deep convective clouds in the Tropics.
With the aid of three atmospheric aerosol equilibrium models, we quantify the effect of metastable equilibrium states (efflorescence branch) in comparison to stable (deliquescence branch) on the partitioning of total nitrate between the gas and aerosol phases. On average, effl...
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. PMID:27091667
Ghadim, Ehsan Ezzatpour; Manouchehri, Firouzeh; Soleimani, Gholamreza; Hosseini, Hadi; Kimiagar, Salimeh; Nafisi, Shohreh
2013-01-01
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. PMID:24302989
NASA Astrophysics Data System (ADS)
Sivarajasekar, N.; Baskar, R.; Ragu, T.; Sarika, K.; Preethi, N.; Radhika, T.
2016-01-01
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 ΔH 0, ΔS 0 and ΔG 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.
Thermodynamics and equilibrium structure of Ne38 cluster: quantum mechanics versus classical.
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. PMID:15945633
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
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
Measurements and non-local thermodynamic equilibrium modeling of mid-Z plasma emission
NASA Astrophysics Data System (ADS)
Jacquet, L.; Primout, M.; Kaiser, P.; Clouët, J. F.; Girard, F.; Villette, B.; Reverdin, C.; Oudot, G.
2015-12-01
The x-ray yields from laser-irradiated thin foils of iron, copper, zinc, and germanium have been measured in the soft and multi-keV x-ray ranges at the OMEGA laser at the Laboratory for Laser Energetics. The incident laser power had a pre-pulse to enhance the x-ray emission of a 1 ns flat-top main pulse. The experimental results have been compared with post-shot simulations performed with the two-dimensional radiation-hydrodynamics code FCI2. A new non-local thermodynamic equilibrium model, NOO-RAD, have been incorporated into FCI2. In this approach, the plasma ionization state is in-line calculated by the atomic physics NOHEL package. In the soft x-ray bands, both simulations using RADIOM [M. Busquet, Phys. Fluids B 5, 4191 (1993)] and NOO-RAD clearly over-predict the powers and energies measured by a broad-band spectrometer. In one case (the iron foil), the discrepancy between the measured and simulated x-ray output is nevertheless significantly reduced when NOO-RAD is used in the simulations. In the multi-keV x-ray bands, the simulations display a strong sensitivity to the coupling between the electron thermal conductivity and the NLTE models, and for some particular combinations of these, provide a close match to the measured emission. The comparison between the measured and simulated H-like to He-like line-intensity ratios deduced from high-resolution spectra indicates higher experimental electron temperatures were achieved, compared to the simulated ones. Measurements of the plasma conditions have been achieved using the Thomson-scattering diagnostic. The electron temperatures are found to range from 3 to 5 keV at the end of the laser pulse and are greater than predicted by the simulations. The measured flow velocities are in reasonable agreement with the calculated ones. This last finding gives us confidence in our numerical predictions for the plasma parameters, which are over that time mainly determined by hydrodynamics, such as the mass densities and the
Measurements and non-local thermodynamic equilibrium modeling of mid-Z plasma emission
Jacquet, L. Primout, M.; Kaiser, P.; Clouët, J. F.; Girard, F.; Villette, B.; Reverdin, C.; Oudot, G.
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
NASA Astrophysics Data System (ADS)
Steimer, S. S.; Krieger, U. K.; Te, Y.-F.; Lienhard, D. M.; Huisman, A. J.; Luo, B. P.; Ammann, M.; Peter, T.
2015-06-01
Measurements of a single, levitated particle in an electrodynamic balance are an established tool for deriving thermodynamic and material data such as density, refractive index and activities of components of an aqueous solution under supersaturated conditions, where bulk measurements are not possible. The retrieval relies on combining mass-to-charge data and size data from light scattering. Here, we use a combination of low- and high-resolution Mie resonance spectroscopy to obtain radius data, enabling an accurate size determination not only when the particle is in equilibrium, but also when it is out of equilibrium due to kinetic limitation of mass transport. With the data measured under non-equilibrium conditions, it is possible to retrieve the water diffusivity. A challenge is that the radius retrieval by comparing measured light scattering with Mie theory requires the knowledge of refractive index as a function of concentration. Here, we show an iterative retrieval of refractive index and size for compounds for which data cannot be obtained in the bulk either due to lack of sufficient amounts of sample or limited solubility. We demonstrate the measurement strategy and the retrieval of water activity, density, refractive index and water diffusivity for aqueous shikimic acid. Water diffusivity in concentrated shikimic acid decreases by 6 orders of magnitude at 250 K compared to that at room temperature.
NASA Astrophysics Data System (ADS)
Steimer, S. S.; Krieger, U. K.; Te, Y.-F.; Lienhard, D. M.; Huisman, A. J.; Ammann, M.; Peter, T.
2015-01-01
Measurements of a single, levitated particle in an electrodynamic balance are an established tool for deriving thermodynamic and material data such as density, refractive index and activities of components of an aqueous solution under supersaturated conditions, where bulk measurements are not possible. The retrieval relies on combining mass-to-charge data and size data from light scattering. Here, we use a combination of low- and high-resolution Mie resonance spectroscopy to obtain radius data, enabling an accurate size determination not only when the particle is in equilibrium, but also when it is out of equilibrium due to kinetic limitation of mass transport. With the data measured under non-equilibrium conditions, it is possible to retrieve the water diffusivity. A challenge is that the radius retrieval by comparing measured light scattering with Mie theory requires the knowledge of refractive index as a function of concentration. Here, we show an iterative retrieval of refractive index and size for compounds for which data cannot be obtained in the bulk either due to lack of sufficient amounts of sample or limited solubility. We demonstrate the measurement strategy and the retrieval of water activity, density, refractive index and water diffusivity for aqueous shikimic acid. Water diffusivity in concentrated shikimic acid decreases by 6 orders of magnitude at 250 K compared to that at room temperature.
NASA Astrophysics Data System (ADS)
Karimaian, Kamal Aldin; Amrane, Abdeltif; Kazemian, Hossein; Panahi, Reza; Zarrabi, Mansur
2013-11-01
Natural and Mg2+ 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.
NASA Technical Reports Server (NTRS)
Simmonds, A. L.; Miller, C. G., III; Nealy, J. E.
1976-01-01
Equilibrium thermodynamic properties for pure ammonia were generated for a range of temperature from 500 to 50,000 K and pressure from 0.01 to 40 MN/sq m and are presented in tabulated and graphical form. Properties include pressure, temperature, density, enthalpy, speed of sound, entropy, molecular-weight ratio, specific heat at constant pressure, specific heat at constant volume, isentropic exponent, and species mole fractions. These properties were calculated by the method which is based on minimization of the Gibbs free energy. The data presented herein are for an 18-species ammonia model. Heats of formation and spectroscopic constants used as input data are presented. Comparison of several thermodynamic properties calculated with the present program and a second computer code is performed for a range of pressure and for temperatures up to 30,000 K.
NASA Astrophysics Data System (ADS)
Björnbom, Pehr
2016-03-01
In the first part of this work equilibrium temperature profiles in fluid columns with ideal gas or ideal liquid were obtained by numerically minimizing the column energy at constant entropy, equivalent to maximizing column entropy at constant energy. A minimum in internal plus potential energy for an isothermal temperature profile was obtained in line with Gibbs' classical equilibrium criterion. However, a minimum in internal energy alone for adiabatic temperature profiles was also obtained. This led to a hypothesis that the adiabatic lapse rate corresponds to a restricted equilibrium state, a type of state in fact discussed already by Gibbs. In this paper similar numerical results for a fluid column with saturated air suggest that also the saturated adiabatic lapse rate corresponds to a restricted equilibrium state. The proposed hypothesis is further discussed and amended based on the previous and the present numerical results and a theoretical analysis based on Gibbs' equilibrium theory.
NASA Technical Reports Server (NTRS)
Thompson, Richard A.; Lee, Kam-Pui; Gupta, Roop N.
1990-01-01
The computer codes developed provide data to 30000 K for the thermodynamic and transport properties of individual species and reaction rates for the prominent reactions occurring in an 11-species nonequilibrium air model. These properties and the reaction-rate data are computed through the use of curve-fit relations which are functions of temperature (and number density for the equilibrium constant). The curve fits were made using the most accurate data believed available. A detailed review and discussion of the sources and accuracy of the curve-fitted data used herein are given in NASA RP 1232.
NASA Astrophysics Data System (ADS)
Bruno, D.; Colonna, G.; Laricchiuta, A.; Capitelli, M.
2012-12-01
Internal and reactive contributions to the thermal conductivity of a local thermodynamic equilibrium nitrogen plasma have been calculated using the Chapman-Enskog method. Low-lying (LL) electronically excited states (i.e., states with the same principal quantum number of the ground state) and high-lying (HL) ones (i.e., states with principal quantum number n > 2) have been considered. Several models have been developed, the most accurate being a model that treats the LL states as separate species while disregarding the presence of HL states, on account of their enormous transport cross sections.
NASA Astrophysics Data System (ADS)
Khazri, Hassen; Ghorbel-Abid, Ibtissem; Kalfat, Rafik; Trabelsi-Ayadi, Malika
2016-04-01
This study aimed to describe the adsorption of three pharmaceuticals compounds (ibuprofen, naproxen and carbamazepine) onto natural clay on the basis of equilibrium parameters such as a function of time, effect of pH, varying of the concentration and the temperature. Adsorption kinetic data were modeled using the Lagergren's first-order and the pseudo-second-order kinetic equations. The kinetic results of adsorption are described better using the pseudo-second order model. The isotherm results were tested in the Langmuir, Freundlich and Dubinin-Radushkevich models. The thermodynamic parameters obtained indicate that the adsorption of pharmaceuticals on the clay is a spontaneous and endothermic process.
Bruno, D.; Colonna, G.; Laricchiuta, A.; Capitelli, M.
2012-12-15
Internal and reactive contributions to the thermal conductivity of a local thermodynamic equilibrium nitrogen plasma have been calculated using the Chapman-Enskog method. Low-lying (LL) electronically excited states (i.e., states with the same principal quantum number of the ground state) and high-lying (HL) ones (i.e., states with principal quantum number n> 2) have been considered. Several models have been developed, the most accurate being a model that treats the LL states as separate species while disregarding the presence of HL states, on account of their enormous transport cross sections.
NASA Astrophysics Data System (ADS)
Cvejić, M.; DzierŻega, K.; Pieta, T.
2015-07-01
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 Hα, 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 Hα 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.
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). PMID:26638140
Sharma, Rohit; Singh, Kuldip
2014-03-15
In the present work, two cases of thermal plasma have been considered; the ground state plasma in which all the atoms and ions are assumed to be in the ground state and the excited state plasma in which atoms and ions are distributed over various possible excited states. The variation of Zγ, frozen isentropic coefficient and the isentropic coefficient with degree of ionization and non-equilibrium parameter θ(= T{sub e}/T{sub h}) has been investigated for the ground and excited state helium and argon plasmas at pressures 1 atm, 10 atm, and 100 atm in the temperature range from 6000 K to 60 000 K. For a given value of non-equilibrium parameter, the relationship of Zγ with degree of ionization does not show any dependence on electronically excited states in helium plasma whereas in case of argon plasma this dependence is not appreciable till degree of ionization approaches 2. The minima of frozen isentropic coefficient shifts toward lower temperature with increase of non-equilibrium parameter for both the helium and argon plasmas. The lowering of non-equilibrium parameter decreases the frozen isentropic coefficient more emphatically in helium plasma at high pressures in comparison to argon plasma. The increase of pressure slightly reduces the ionization range over which isentropic coefficient almost remains constant and it does not affect appreciably the dependence of isentropic coefficient on non-equilibrium parameter.
Chun, Paul W.
2003-01-01
Applying the Planck-Benzinger methodology, the sequence-specific hydrophobic interactions of 35 dipeptide pairs were examined over a temperature range of 273–333 K, based on data reported by Nemethy and Scheraga in 1962. The hydrophobic interaction in these sequence-specific dipeptide pairs is highly similar in its thermodynamic behavior to that of other biological systems. The results imply that the negative Gibbs free energy change minimum at a well-defined stable temperature, 〈Ts〉, where the bound unavailable energy, TΔSo = 0, has its origin in the sequence-specific hydrophobic interactions, are highly dependent on details of molecular structure. Each case confirms the existence of a thermodynamic molecular switch wherein a change of sign in ΔCpo(T)reaction (change in specific heat capacity of reaction at constant pressure) leads to true negative minimum in the Gibbs free energy change of reaction, ΔGo(T)reaction, and hence a maximum in the related equilibrium constant, Keq. Indeed, all interacting biological systems examined to date by Chun using the Planck-Benzinger methodology have shown such a thermodynamic switch at the molecular level, suggesting its existence may be universal. PMID:12547816
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. PMID:27028744
NASA Astrophysics Data System (ADS)
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).
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. PMID:26945551
Feng, Y.; Kotamarthi, V. R.; Coulter, R.; Zhao, C.; Cadeddu, M.
2016-01-18
In this study, aerosol radiative effects and thermodynamic responses over South Asia are examined with the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) for March 2012. Model results of aerosol optical depths (AODs) and extinction profiles are analyzed and compared to satellite retrievals and two ground-based lidars located in northern India. The WRF-Chem model is found to heavily underestimate the AOD during the simulated pre-monsoon month and about 83 % of the model's low bias is due to aerosol extinctions below ~2km. Doubling the calculated aerosol extinctions below 850 hPa generates much better agreement with the observed AOD andmore » extinction profiles averaged over South Asia. To separate the effect of absorption and scattering properties, two runs were conducted: in one run (Case I), the calculated scattering and absorption coefficients were increased proportionally, while in the second run (Case II) only the calculated aerosol scattering coefficient was increased. With the same AOD and extinction profiles, the two runs produce significantly different radiative effects over land and oceans. On the regional mean basis, Case I generates 48 % more heating in the atmosphere and 21 % more dimming at the surface than Case II. Case I also produces stronger cooling responses over the land from the longwave radiation adjustment and boundary layer mixing. These rapid adjustments offset the stronger radiative heating in Case I and lead to an overall lower-troposphere cooling up to –0.7 K day−1, which is smaller than that in Case II. Over the ocean, direct radiative effects dominate the heating rate changes in the lower atmosphere lacking such surface and lower atmosphere adjustments due to fixed sea surface temperature, and the strongest atmospheric warming is obtained in Case I. Consequently, atmospheric dynamics (boundary layer heights and meridional circulation) and thermodynamic processes (water vapor and cloudiness) are
NASA Astrophysics Data System (ADS)
Feng, Y.; Kotamarthi, V. R.; Coulter, R.; Zhao, C.; Cadeddu, M.
2016-01-01
Aerosol radiative effects and thermodynamic responses over South Asia are examined with the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) for March 2012. Model results of aerosol optical depths (AODs) and extinction profiles are analyzed and compared to satellite retrievals and two ground-based lidars located in northern India. The WRF-Chem model is found to heavily underestimate the AOD during the simulated pre-monsoon month and about 83 % of the model's low bias is due to aerosol extinctions below ˜ 2 km. Doubling the calculated aerosol extinctions below 850 hPa generates much better agreement with the observed AOD and extinction profiles averaged over South Asia. To separate the effect of absorption and scattering properties, two runs were conducted: in one run (Case I), the calculated scattering and absorption coefficients were increased proportionally, while in the second run (Case II) only the calculated aerosol scattering coefficient was increased. With the same AOD and extinction profiles, the two runs produce significantly different radiative effects over land and oceans. On the regional mean basis, Case I generates 48 % more heating in the atmosphere and 21 % more dimming at the surface than Case II. Case I also produces stronger cooling responses over the land from the longwave radiation adjustment and boundary layer mixing. These rapid adjustments offset the stronger radiative heating in Case I and lead to an overall lower-troposphere cooling up to -0.7 K day-1, which is smaller than that in Case II. Over the ocean, direct radiative effects dominate the heating rate changes in the lower atmosphere lacking such surface and lower atmosphere adjustments due to fixed sea surface temperature, and the strongest atmospheric warming is obtained in Case I. Consequently, atmospheric dynamics (boundary layer heights and meridional circulation) and thermodynamic processes (water vapor and cloudiness) are shown to respond differently
Feng, Y.; Kotamarthi, V. R.; Coulter, R.; Zhao, C.; Cadeddu, M.
2015-06-19
Aerosol radiative effects and thermodynamic responses over South Asia are examined with a version of the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) for March 2012. Model results of Aerosol Optical Depth (AOD) and extinction profiles are analyzed and compared to satellite retrievals and two ground-based lidars located in the northern India. The WRF-Chem model is found to underestimate the AOD during the simulated pre-monsoon month and about 83 % of the model low-bias is due to aerosol extinctions below ~2 km. Doubling the calculated aerosol extinctions below 850 hPa generates much better agreement with the observed AOD and extinction profiles averaged over South Asia. To separate the effect of absorption and scattering properties, two runs were conducted: in one run (Case I), the calculated scattering and absorption coefficients were increased proportionally, while in the second run (Case II) only the calculated aerosol scattering coefficient was increased. With the same AOD and extinction profiles, the two runs produce significantly different radiative effects over land and oceans. On the regional mean basis, Case I generates 48 % more heating in the atmosphere and 21 % more dimming at the surface than Case II. Case I also produces stronger cooling responses over the land from the longwave radiation adjustment and boundary layer mixing. These rapid adjustments offset the stronger radiative heating in Case I and lead to an overall lower-troposphere cooling up to -0.7 K day^{−1}, which is smaller than that in Case II. Over the ocean, direct radiative effects dominate the heating rate changes in the lower atmosphere lacking such surface and lower atmosphere adjustments due to fixed sea surface temperature, and the strongest atmospheric warming is obtained in Case I. Consequently, atmospheric dynamics (boundary layer heights and meridional circulation) and thermodynamic processes (water vapor and cloudiness) are shown to respond
Feng, Y.; Kotamarthi, V. R.; Coulter, R.; Zhao, C.; Cadeddu, M.
2016-01-18
Aerosol radiative effects and thermodynamic responses over South Asia are examined with the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) for March 2012. Model results of aerosol optical depths (AODs) and extinction profiles are analyzed and compared to satellite retrievals and two ground-based lidars located in northern India. The WRF-Chem model is found to heavily underestimate the AOD during the simulated pre-monsoon month and about 83 % of the model's low bias is due to aerosol extinctions below ∼ 2 km. Doubling the calculated aerosol extinctions below 850 hPa generates much better agreement with the observed AOD and extinction profiles averaged over Southmore » Asia. To separate the effect of absorption and scattering properties, two runs were conducted: in one run (Case I), the calculated scattering and absorption coefficients were increased proportionally, while in the second run (Case II) only the calculated aerosol scattering coefficient was increased. With the same AOD and extinction profiles, the two runs produce significantly different radiative effects over land and oceans. On the regional mean basis, Case I generates 48 % more heating in the atmosphere and 21 % more dimming at the surface than Case II. Case I also produces stronger cooling responses over the land from the longwave radiation adjustment and boundary layer mixing. These rapid adjustments offset the stronger radiative heating in Case I and lead to an overall lower-troposphere cooling up to −0.7 K day−1, which is smaller than that in Case II. Over the ocean, direct radiative effects dominate the heating rate changes in the lower atmosphere lacking such surface and lower atmosphere adjustments due to fixed sea surface temperature, and the strongest atmospheric warming is obtained in Case I. Consequently, atmospheric dynamics (boundary layer heights and meridional circulation) and thermodynamic processes (water vapor and
Feng, Y.; Kotamarthi, V. R.; Coulter, R.; Zhao, C.; Cadeddu, M.
2015-06-19
Aerosol radiative effects and thermodynamic responses over South Asia are examined with a version of the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) for March 2012. Model results of Aerosol Optical Depth (AOD) and extinction profiles are analyzed and compared to satellite retrievals and two ground-based lidars located in the northern India. The WRF-Chem model is found to underestimate the AOD during the simulated pre-monsoon month and about 83 % of the model low-bias is due to aerosol extinctions below ~2 km. Doubling the calculated aerosol extinctions below 850 hPa generates much better agreement with the observed AODmore » and extinction profiles averaged over South Asia. To separate the effect of absorption and scattering properties, two runs were conducted: in one run (Case I), the calculated scattering and absorption coefficients were increased proportionally, while in the second run (Case II) only the calculated aerosol scattering coefficient was increased. With the same AOD and extinction profiles, the two runs produce significantly different radiative effects over land and oceans. On the regional mean basis, Case I generates 48 % more heating in the atmosphere and 21 % more dimming at the surface than Case II. Case I also produces stronger cooling responses over the land from the longwave radiation adjustment and boundary layer mixing. These rapid adjustments offset the stronger radiative heating in Case I and lead to an overall lower-troposphere cooling up to -0.7 K day−1, which is smaller than that in Case II. Over the ocean, direct radiative effects dominate the heating rate changes in the lower atmosphere lacking such surface and lower atmosphere adjustments due to fixed sea surface temperature, and the strongest atmospheric warming is obtained in Case I. Consequently, atmospheric dynamics (boundary layer heights and meridional circulation) and thermodynamic processes (water vapor and cloudiness) are shown to respond
Feng, Y.; Kotamarthi, V. R.; Coulter, R.; Zhao, C.; Cadeddu, M.
2016-01-01
Aerosol radiative effects and thermodynamic responses over South Asia are examined with the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) for March 2012. Model results of aerosol optical depths (AODs) and extinction profiles are analyzed and compared to satellite retrievals and two ground-based lidars located in northern India. The WRF-Chem model is found to heavily underestimate the AOD during the simulated pre-monsoon month and about 83 % of the model's low bias is due to aerosol extinctions below ~2 km. Doubling the calculated aerosol extinctions below 850 hPa generates much better agreement with the observed AOD and extinction profiles averaged over South Asia. To separate the effect of absorption and scattering properties, two runs were conducted: in one run (Case I), the calculated scattering and absorption coefficients were increased proportionally, while in the second run (Case II) only the calculated aerosol scattering coefficient was increased. With the same AOD and extinction profiles, the two runs produce significantly different radiative effects over land and oceans. On the regional mean basis, Case I generates 48 % more heating in the atmosphere and 21 % more dimming at the surface than Case II. Case I also produces stronger cooling responses over the land from the longwave radiation adjustment and boundary layer mixing. These rapid adjustments offset the stronger radiative heating in Case I and lead to an overall lower-troposphere cooling up to -0.7 K day^{−1}, which is smaller than that in Case II. Over the ocean, direct radiative effects dominate the heating rate changes in the lower atmosphere lacking such surface and lower atmosphere adjustments due to fixed sea surface temperature, and the strongest atmospheric warming is obtained in Case I. Consequently, atmospheric dynamics (boundary layer heights and meridional circulation) and thermodynamic processes (water vapor and cloudiness) are shown to
NASA Astrophysics Data System (ADS)
Poisson, Alexandre
2011-12-01
In the early 1970s, mathematician and economist Nicolas Georgescu-Roegen developed an alternative framework to macro-economics (his hourglass model) based on two principles of classical thermodynamics applied to the earth-system as a whole. The new model led him to the radical conclusion that "not only growth, but also a zero-growth state, nay, even a declining state which does not converge toward annihilation, cannot exist forever in a finite environment" (Georgescu-Roegen 1976, p.23). Georgescu-Roegen's novel approach long served as a devastating critique of standard neoclassical growth theories. It also helped establish the foundations for the new trans-disciplinary field of ecological economics. In recent decades however, it has remained unclear whether revolutionary developments in "modern non-equilibrium thermodynamics" (Kondepudi and Prigogine 1998) refute some of Georgescu-Roegen's initial conclusions and provide fundamentally new lessons for very long-term macro-economic analysis. Based on a broad historical review of literature from many fields (thermodynamics, cosmology, ecosystems ecology and economics), I argue that Georgescu-Roegen's hourglass model is largely based on old misconceptions and assumptions from 19th century thermodynamics (including an out-dated cosmology) which make it very misleading. Ironically, these assumptions (path independence and linearity of the entropy function in particular) replicate the non-evolutionary thinking he seemed to despise in his colleagues. In light of modern NET, I propose a different model. Contrary to Georgescu-Roegen's hourglass, I do not assume the path independence of the entropy function. In the new model, achieving critical free energy rate density thresholds can abruptly increase the level of complexity and maximum remaining lifespan of stock-based civilizations.
Thermodynamics of open nonlinear systems far from equilibrium: The continuously stirred tank reactor
NASA Astrophysics Data System (ADS)
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.
NASA Astrophysics Data System (ADS)
Ghafuri, Mohazabeh; Nosrati, Mohsen; Hosseinkhani, Saman
2015-03-01
Adenosine triphosphate (ATP) production in living cells is very important. Different researches have shown that in terms of mathematical modeling, the domain of these investigations is essentially restricted. Recently the thermodynamic models have been suggested for calculation of the efficiency of oxidative phosphorylation process and rate of energy loss in animal cells using chemiosmotic theory and non-equilibrium thermodynamics equations. In our previous work, we developed a mathematical model for mitochondria of animal cells. In this research, according to similarities between oxidative phosphorylation process in microorganisms and animal cells, Golfar's model was developed to predict the non-equilibrium thermodynamic behavior of the oxidative phosphorylation process for bacteria in aerobic condition. With this model the rate of energy loss, P/O ratio, and efficiency of oxidative phosphorylation were calculated for Escherichia coli in aerobic condition. The results then were compared with experimental data given by other authors. The thermodynamic model had an acceptable agreement with the experimental data.
NASA Astrophysics Data System (ADS)
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).
Ordering in granular-rod monolayers driven far from thermodynamic equilibrium.
Müller, Thomas; de las Heras, Daniel; Rehberg, Ingo; Huang, Kai
2015-06-01
The orientational order in vertically agitated granular-rod monolayers is investigated experimentally and compared quantitatively with equilibrium Monte Carlo simulations and density functional theory. At sufficiently high number density, short rods form a tetratic state and long rods form a uniaxial nematic state. The length-to-width ratio at which the order changes from tetratic to uniaxial is around 7.3 in both experiments and simulations. This agreement illustrates the universal aspects of the ordering of rod-shaped particles across equilibrium and nonequilibrium systems. Moreover, the assembly of granular rods into ordered states is found to be independent of the agitation frequency and strength, suggesting that the detailed nature of energy injection into such a nonequilibrium system does not play a crucial role. PMID:26172705
The Phosphorus Reaction in Oxygen Steelmaking: Thermodynamic Equilibrium and Metal Droplet Behavior
NASA Astrophysics Data System (ADS)
Assis, Andre N.
Phosphorus equilibrium between liquid metal and slag has been extensively studied since the 1940's. It is well known that CaO and FeO are the main slag constituents that help promote dephosphorization. On the other hand, dephosphorization decreases with temperature due to the endothermic nature of the reaction. Many correlations have been developed to predict the phosphorus partition ratio as a function of metal and slag composition as well as temperature. Nevertheless, there are still disagreements in the laboratory data and the equilibrium phosphorus partition can be predicted with an uncertainty of a factor of up to 5. The first part of the present work focuses on generating more reliable equilibrium data for BOF-type slags by approaching equilibrium from both sides of the reaction. The experimental results were combined with two other sets of data from different authors to produce a new correlation that includes the effect of SiO2 on the phosphorus partition coefficient, LP . Although the quantification of phosphorus equilibrium is extremely important, most industrial furnaces do not operate at equilibrium, usually due to liquid slag formation, kinetics and time constraints. Thus, it is important to know how close to equilibrium different furnaces operate in order to suggest optimal slag compositions to promote dephosphorization. The present work analyzed four large sets of data containing the chemical compositions of both slag and metal phase as well as the tapping temperature of each heat. Each set of data corresponded to different furnaces: one AOD (Argon Oxygen Decarburization), two top-blown BOFs and one Q-BOP or OBM. It was found that the bulk slag composition can greatly "mask" the data due to solid phases coexisting with the liquid slag. The author used the software package FactSage to estimate the amount of solids in the slag and liquid slag composition. It was found that the AOD is the reactor closest to equilibrium, followed by the Q-BOP (OBM) and
Chen, Gang; Rockhold, Mark L.; Strevett, Keith A.
2003-05-15
Equilibrium and kinetic adsorption of Escherichia coli HB 101, E. coli JM 109, Pseudomonas fluorescens, Pseudomonas putida and Pseudomonas sp. on alluvial sand from the Canadian River alluvium (Norman, OK) was investigated through column experiments. Equilibrium adsorption of these five bacterial strains followed the Freundlich expression and was a function of zero energy points, an indication of the zero energy buffer zone. Among the microorganisms studied, P. putida had the greatest equilibrium adsorption (162.4 x 108 cell/g sediment with a microbial injectate concentration of 108 cell/mL), followed by Pseudomonas sp. (127.9 x 108 cell/g sediment), E. coli HB 101 (62.8 x 108 cell/g sediment), E. coli JM 109 (58.4 x 108 cell/g sediment), and P. fluorescens (42.6 x 108 cell/g sediment). The first-order kinetic adsorption rate coefficient was an exponential function of the total interaction free energy between bacteria and sediment evaluated at the primary minimum, (PM). E. coli HB 101 had the greatest kinetic adsorption rate coefficient on the sediment (5.10 h-1), followed by E. coli JM 109 (4.52 h-1), P. fluorescens (2.12 h-1), P. putida (2.04 h-1), and Pseudomonas sp. (1.34 h-1).
Equilibrium thermodynamic properties of interacting two-component bosons in one dimension
Klauser, Antoine; Caux, Jean-Sebastien
2011-09-15
The interplay of quantum statistics, interactions, and temperature is studied within the framework of the bosonic two-component theory with repulsive delta-function interaction in one dimension. We numerically solve the thermodynamic Bethe ansatz and obtain the equation of state as a function of temperature and of the interaction strength, the relative chemical potential, and either the total chemical potential or a fixed number of particles, allowing quantification of the full crossover behavior of the system between its low-temperature ferromagnetic and high-temperature unpolarized regime, and from the low coupling decoherent regime to the fermionization regime at high interaction.
NASA Astrophysics Data System (ADS)
Wang, Sheng; Wang, Shudong
Methanol autothermal reforming was thermodynamically analyzed using FLUENT software. The calculation methodology using this software is simple and convenient, and its validity was confirmed by comparing the obtained data with previous studies. As a function of the effects of temperature, pressure, molar steam-to-carbon ratio (S/C), and molar oxygen-to-carbon ratio (O/C) on the objective products, favorable operational parameters were evaluated, under which H 2 yield maximizes, the CO molar fraction minimizes and carbon deposition can be eliminated. The equilibrium constants of the possible reactions involved in oxidative methanol steam reforming, coupled with the reaction mechanism for the entire investigated temperature range, were elucidated and discussed. On the basis of the concluded possible mechanisms, three areas are inferred. In each individual area, H 2 or CO yield reached a maximum, or solid C was efficiently suppressed. Therein, a favorable operational range is proposed to assure the most optimized product yield.
NASA Astrophysics Data System (ADS)
Malvoisin, Benjamin; Podladchikov, Yury Yu.; Vrijmoed, Johannes C.
2015-12-01
Mineralogical reactions which generate or consume fluids play a key role during fluid flow in porous media. Such reactions are linked to changes in density, porosity, permeability, and fluid pressure which influence fluid flow and rock deformation. To understand such a coupled system, equations were derived from mass conservation and local thermodynamic equilibrium. The presented mass conservative modeling approach describes the relationships among evolving fluid pressure, porosity, fluid and solid density, and devolatilization reactions in multicomponent systems with solid solutions. This first step serves as a framework for future models including aqueous speciation and transport. The complexity of univariant and multivariant reactions is treated by calculating lookup tables from thermodynamic equilibrium calculations. Simplified cases were also investigated to understand previously studied formulations. For nondeforming systems or systems divided into phases of constant density, the equations can be reduced to porosity wave equations with addition of a reactive term taking the volume change of reaction into account. For closed systems, an expression for the volume change of reaction and the associated pressure increase can be obtained. The key equations were solved numerically for the case of devolatilization of three different rock types that may enter a subduction zone. Reactions with positive Clapeyron slope lead to an increase in porosity and permeability with decreasing fluid pressure resulting in sharp fluid pressure gradients around a negative pressure anomaly. The opposite trend is obtained for reactions having a negative Clapeyron slope during which sharp fluid pressure gradients were only generated around a positive pressure anomaly. Coupling of reaction with elastic deformation induces a more efficient fluid flow for reactions with negative Clapeyron slope than for reactions with positive Clapeyron slope.
Sasselli, Ivan Ramos; Halling, Peter J; Ulijn, Rein V; Tuttle, Tell
2016-02-23
Low molecular weight gelators are able to form nanostructures, typically fibers, which entangle to form gel-phase materials. These materials have wide-ranging applications in biomedicine and nanotechnology. While it is known that supramolecular gels often represent metastable structures due to the restricted molecular dynamics in the gel state, the thermodynamic nature of the nanofibrous structure is not well understood. Clearly, 3D extended structures will be able to form more interactions than 1D structures. However, self-assembling molecules are typically amphiphilic, thus giving rise to a combination of solvophobic and solvophilic moieties where a level of solvent exposure at the nanostructure surface is favorable. In this study, we introduce a simple packing model, based on prisms with faces of different nature (solvophobic and solvophilic) and variable interaction parameters, to represent amphiphile self-assembly. This model demonstrates that by tuning shape and "self" or "solvent" interaction parameters either the 1D fiber or 3D crystal may represent the thermodynamic minimum. The model depends on parameters that relate to features of experimentally known systems: the number of faces exposed to the solvent or buried in the fiber; the overall shape of the prism; and the free energy penalties associated with the interactions can be adjusted to match their chemical nature. The model is applied to describe the pH-dependent gelation/precipitation of well-known gelator Fmoc-FF. We conclude that, despite the fact that most experimentally produced gels probably represent metastable states, one-dimensional fibers can represent thermodynamic equilibrium. This conclusion has critical implications for the theoretical treatment of gels. PMID:26812130
NASA Astrophysics Data System (ADS)
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.
NASA Technical Reports Server (NTRS)
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.
Leonard, T.; Lander, B.; Seifert, U.; Speck, T.
2013-11-28
We discuss the stochastic thermodynamics of systems that are described by a time-dependent density field, for example, simple liquids and colloidal suspensions. For a time-dependent change of external parameters, we show that the Jarzynski relation connecting work with the change of free energy holds if the time evolution of the density follows the Kawasaki-Dean equation. Specifically, we study the work distributions for the compression and expansion of a two-dimensional colloidal model suspension implementing a practical coarse-graining scheme of the microscopic particle positions. We demonstrate that even if coarse-grained dynamics and density functional do not match, the fluctuation relations for the work still hold albeit for a different, apparent, change of free energy.
NASA Astrophysics Data System (ADS)
Leonard, T.; Lander, B.; Seifert, U.; Speck, T.
2013-11-01
We discuss the stochastic thermodynamics of systems that are described by a time-dependent density field, for example, simple liquids and colloidal suspensions. For a time-dependent change of external parameters, we show that the Jarzynski relation connecting work with the change of free energy holds if the time evolution of the density follows the Kawasaki-Dean equation. Specifically, we study the work distributions for the compression and expansion of a two-dimensional colloidal model suspension implementing a practical coarse-graining scheme of the microscopic particle positions. We demonstrate that even if coarse-grained dynamics and density functional do not match, the fluctuation relations for the work still hold albeit for a different, apparent, change of free energy.
NASA Astrophysics Data System (ADS)
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.
NASA Astrophysics Data System (ADS)
Vial, J. C.
1982-03-01
The two-dimensional transfer code of Mihalas, Auer and Mihalas (1978) is used to compute emergent profiles of resonance lines of H I, Mg II, and Ca II. The model (a uniform slab limited in two directions) and the radiative and thermodynamic quantities are described. The metallic line profiles are sensitive to the ionization degree, which is fixed at a certain value. Some modifications are implemented in the code, in particular, the true incident profiles of chromospheric lines. A comparison is made between two-dimensional and one-dimensional profiles. Good agreement between computed and observed profiles is found for Ly-alpha and Ca II but not for Mg II lines.
Using equilibrium thermodynamics to estimate pressure and porosity changes during reactive transport
NASA Astrophysics Data System (ADS)
Malvoisin, Benjamin; Podladchikov, Yury; Vrijmoed, Johannes
2015-04-01
Mineralogical reactions play a key role during transport in porous media by generating or consuming fluids and modifying the fluid pathways through volume changes. Here, we used a theoretical and numerical approach to determine the interplays between reaction, transport and deformation during metamorphic reactions. Mass conservations equations were written for a reacting system and a system of equations was obtained to describe the relationships between fluid pressure, porosity and three thermodynamic parameters (the density of the fluid, the density of the non-volatile solid and a function of the volume change). Thermodynamic parameters were calculated by energy minimization with PerpleX for three lithologies found in subduction zones: sedimentary, mafic and ultramafic rocks. The evolution of porosity and fluid pressure was predicted in several cases. First, the maximum pressure changes associated with volume change during reaction was estimated for univariant reactions. Then, multi-variant reactions were considered and the system of equations was solved with several assumptions. Typical equations for porosity waves were obtained by simplifying the system with a solid density as a simple function of pressure or with the assumption of a constant amount of non-volatile species. Numerical models were finally used to solve these equations for three cases: the dehydration of chlorite in mafic rocks (positive Clapeyron slope), the dehydration of serpentine in ultramafic rocks (negative Clapeyron slope) and the decarbonation of calcite (positive Clapeyron slope with a H2O-CO2 fluid). Such kind of models take into account the complexity of mineralogical reactions and allow to better understand the generation of fluid pathways in metamorphic rocks.
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. PMID:26544889
Lapenna, E.; Mucciarelli, A.; Lanzoni, B.; Ferraro, F. R.; Dalessandro, E.; Massari, D.
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.
NASA Astrophysics Data System (ADS)
Travaillé, G.; Peyrusse, O.; Bousquet, B.; Canioni, L.; Pierres, K. Michel-Le; Roy, S.
2009-10-01
We present a collisional-radiative approach of the theoretical analysis of laser-induced breakdown spectroscopy (LIBS) plasmas. This model, which relies on an optimized effective potential atomic structure code, was used to simulate a pure aluminum plasma. The description of aluminum involved a set of 220 atomic levels representative of three different stages of ionization (Al 0, Al + and Al ++). The calculations were carried for stationary plasmas, with input parameters ( ne and Te) ranging respectively between 10 13-18 cm - 3 and 0.3-2 eV. A comparison of our atomic data with some existing databases is made. The code was mainly developed to address the validity of the local thermodynamic equilibrium (LTE) assumption. For usual LIBS plasma parameters, we did not reveal a sizeable discrepancy of the radiative equilibrium of the plasma towards LTE. For cases where LTE was firmly believed to stand, the Boltzmann plot outputs of this code were used to check the physical accuracy of the Boltzmann temperature, as it is currently exploited in several calibration-free laser-induced breakdown spectroscopy (CF-LIBS) studies. In this paper, a deviation ranging between 10 and 30% of the measured Boltzmann temperature to the real excitation temperature is reported. This may be due to the huge dispersion induced on the line emissivities, on which the Boltzmann plots are based to extract this parameter. Consequences of this fact on the CF-LIBS procedure are discussed and further insights to be considered for the future are introduced.
Ayedh, H. M.; Svensson, B. G.; Hallén, A.
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.
NASA Astrophysics Data System (ADS)
Zhu, Xun
2003-07-01
The classic two-level or equivalent two-level model that includes only the statistical equilibrium of radiative and thermal processes of excitation and quenching between two vibrational energy levels is extended by adding chemical production to the rate equations. The modifications to the non-local thermodynamic equilibrium source function and cooling rate are parameterized by ϕc, which characterizes the ratio of chemical production to collisional quenching. For applications of broadband emission of O3 at 9.6 μm, the non-LTE effect of chemical production on the cooling rate and limb emission is proportional to the ratio of O to O3. For a typical [O]/[O3], the maximum enhancements of limb radiance and cooling rate 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 sensitive to the direct cooling rate along the line-of-sight, which makes O3 retrieval feasible but the direct cooling rate retrieval difficult by using the O3 9.6 μm band limb emission.
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. PMID:26802563
Inorganic Components of Atmospheric Aerosols
NASA Astrophysics Data System (ADS)
Wexler, Anthony Stein
The inorganic components comprise 15% to 50% of the mass of atmospheric aerosols. For about the past 10 years the mass of these components was predicted assuming thermodynamic equilibrium between the volatile aerosol -phase inorganic species NH_4NO _3 and NH_4Cl and their gas-phase counterparts NH_3, HNO_3, and HCl. In this thesis I examine this assumption and prove that (1) the time scales for equilibration between the gas and aerosol phases are often too long for equilibrium to hold, and (2) even when equilibrium holds, transport considerations often govern the size distribution of these aerosol components. Water can comprise a significant portion of atmospheric aerosols under conditions of high relative humidity, whereas under conditions of sufficiently low relative humidity atmospheric aerosols tend to be dry. The deliquescence point is the relative humidity where the aerosol goes from a solid dry phase to an aqueous or mixed solid-aqueous phase. In this thesis I derive the temperature dependence of the deliquescence point and prove that in multicomponent solutions the deliquescence point is lower than for corresponding single component solutions. These theories of the transport, thermodynamic, and deliquescent properties of atmospheric aerosols are integrated into an aerosol inorganics model, AIM. The predictions of AIM compare well to fundamental thermodynamic measurements. Comparison of the prediction of AIM to those of other aerosol equilibrium models shows substantial disagreement in the predicted water content at lower relative humidities. The disagreement is due the improved treatment in AIM of the deliquescence properties of multicomponent solutions. In the summer and fall of 1987 the California Air Resources Board conducted the Southern California Air Quality Study, SCAQS, during which atmospheric aerosols were measured in Los Angeles. The size and composition of the aerosol and the concentrations of their gas phase counterparts were measured. When the
Evaluation of anthropogenic influence on thermodynamics, gas and aerosol composition of city air
NASA Astrophysics Data System (ADS)
Uzhegova, Nina; Belan, Boris; Antokhin, Pavel; Zhidovkhin, Evgenii; Ivlev, Georgii; Kozlov, Artem; Fofonov, Aleksandr
2010-05-01
In the last 40-50 years there is a global tendency of urbanisation, which is a consequence of most countries' economical development. Concurrently, the issue of environment's ecological state has become critical. Urban air pollution is among the most important ecological problems nowadays. World Health Organization (WHO) points out certain "classical" polluting agents: carbon monoxide (CO), nitric oxide (NO), nitrogen dioxide (NO2), sulphur dioxide (SO2), troposphere ozone (O3) (studied here), as well as lead, carbon dioxide (CO2), aldehydes, soot, benzpyrene and dredges (including dust, haze and smoke) [1]. An evaluation of antropogenic component's weight in the thermodynamical conditions and gas and aerosol composition of a city's atmosphere (by the example of Tomsk) is given in this paper. Tomsk is located at the South of West Siberia and is the administrative center of Tomsk region. The city's area is equal to 294,6 km2. Its population is 512.6 thousands of people. The overall number of registered motor vehicles in the city in 2008 was 131 700. That is, every fourth city inhabitant has a personal car. From 2002 to 2008 the number of motor vehicles in Tomsk has increased by 25 thousands units [2]. This increase consists mostly of passenger cars. There is also a positive trend in fuel consumtion by the city's industries and motor vehicles - from 2004 to 2007 it has increased by 10%. Such a quick rate of transport quantity's increase in the city provides reason to suggest an unfavorable ecological situation in Tomsk. For this study we have used the AKV-2 mobile station designed by the SB RAS Institute of Atmospheric Optics. The station's equipment provides the following measurements [3]: air temperature and humidity; aerosol disperse composition in 15 channels with a particle size range of 0.3-20 µm by use of the Grimm-1.108 aerosol spectrometer; NO, NO2, O3, SO2, CO, CO2 concentration. This paper describes a single experiment conducted in Tomsk. Date of
NASA Astrophysics Data System (ADS)
Morel, Vincent; Bultel, Arnaud
2014-11-01
The Collisional-Radiative model CoRaM-Al is elaborated and implemented in a 0D numerical approach in the purpose of describing the formation of the plasma resulting from the interaction between a τ = 4 ns Nd:YAG laser pulse and an aluminium sample in vacuum. The influence of the four harmonics at 266, 355, 532 and 1064 nm on the behavior of the nascent plasma is studied. In each case, the fluence is set equal to the threshold above which a phase explosion takes place (fluence of 7.7, 7.4, 6.8, 5.1 J cm-2 in order of increasing wavelength). The model takes into account free electrons and excited states of Al, Al+, Al2+ and Al3+. Both groups of particles are characterized by their translation temperature in thermal non-equilibrium. Besides, each population density is assumed to be in chemical non-equilibrium and to behave freely through the involved seven elementary processes (electron impact induced excitation and ionization, elastic collisions, multiphoton ionization, inverse laser Bremsstrahlung, direct thermal Bremsstrahlung and spontaneous emission). Atoms passing from the sample to the gas are described by considering classical vaporization phenomena (governed by the Hertz-Knudsen law) so that the surface temperature is limited to values less than the critical point (Tc = 6700 K). The relative role of the elementary processes is discussed and the time-evolution of the excitation of the species is analyzed for the four considered wavelengths. This study allows to determine the different excitation temperatures as well as their evolution in time. Thus the conditions required for the achievement of the Local Thermodynamic Equilibrium can be precisely described.
NASA Astrophysics Data System (ADS)
Qian, H.
2015-07-01
Unbalanced probability circulation, which yields cyclic motions in phase space, is the defining characteristics of a stationary diffusion process without detailed balance. In over-damped soft matter systems, such behavior is a hallmark of the presence of a sustained external driving force accompanied with dissipations. In an under-damped and strongly correlated system, however, cyclic motions are often the consequences of a conservative dynamics. In the present paper, we give a novel interpretation of a class of diffusion processes with stationary circulation in terms of a Maxwell-Boltzmann equilibrium in which cyclic motions are on the level set of stationary probability density function thus non-dissipative, e.g., a supercurrent. This implies an orthogonality between stationary circulation J ss ( x) and the gradient of stationary probability density f ss ( x) > 0. A sufficient and necessary condition for the orthogonality is a decomposition of the drift b( x) = j( x) + D( x)∇φ( x) where ∇ṡ j( x) = 0 and j( x) ṡ∇φ( x) = 0. Stationary processes with such Maxwell-Boltzmann equilibrium has an underlying conservative dynamics , and a first integral ϕ( x) ≡ -ln f ss (x) = const, akin to a Hamiltonian system. At all time, an instantaneous free energy balance equation exists for a given diffusion system; and an extended energy conservation law among an entire family of diffusion processes with different parameter α can be established via a Helmholtz theorem. For the general diffusion process without the orthogonality, a nonequilibrium cycle emerges, which consists of external driven φ-ascending steps and spontaneous φ-descending movements, alternated with iso-φ motions. The theory presented here provides a rich mathematical narrative for complex mesoscopic dynamics, with contradistinction to an earlier one [H. Qian et al., J. Stat. Phys. 107, 1129 (2002)]. This article is supplemented with comments by H. Ouerdane and a final reply by the author.
2013-01-01
The adsorption potential of iron acetate coated activated alumina (IACAA) for removal of arsenic [As (III)] as arsenite by batch sorption technique is described. IACAA was characterized by XRD, FTIR, EDAX and SEM instruments. Percentage adsorption on IACAA was determined as a function of pH, contact time and adsorbent dose. The study revealed that the removal of As (III) was best achieved at pH =7.4. The initial As (III) concentration (0.45 mg/L) came down to less than 0.01 mg/L at contact time 90 min with adsorbent dose of 1 g/100 mL. The sorption was reasonably explained with Langmuir and Freundlich isotherms. The thermodynamic parameters such as ΔG 0 , ΔH 0 , ΔS 0 and E a were calculated in order to understand the nature of sorption process. The sorption process was found to be controlled by pseudo-second order and intraparticle diffusion models. PMID:24359995
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.
Contribution of the entropy on the thermodynamic equilibrium of vacancies in nickel.
Metsue, Arnaud; Oudriss, Abdelali; Bouhattate, Jamaa; Feaugas, Xavier
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. PMID:24628194
Modeling of methane and ethane hydrate formation kinetics based on non-equilibrium thermodynamics
NASA Astrophysics Data System (ADS)
Mottahedin, Mona; Varaminian, Farshad; Mafakheri, Kaveh
2011-05-01
In this study, experimental data of the kinetics of methane and ethane hydrate formation at constant volume were collected. The experiments were carried out in a batch reactor at different temperatures and pressures. The property of chemical affinity was used in the modeling of hydrate formation rate in a constant volume process. In this model a macroscopic driving force was defined which only needed the initial (experimental condition, temperature, and pressure) and final conditions (equilibrium conditions); thus, this model did not have the limitations of microscopic models, such as heat and mass transfer coefficients or population of particles, which may differ for each experiment. The experiments were carried out at temperatures 273, 274, 275.5, and 276 K for methane and 272, 273, 274, and 275 K for ethane with different initial pressures. The parameters of the model,
Comments on the compatibility of thermodynamic equilibrium conditions with lattice propagators
NASA Astrophysics Data System (ADS)
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.
Nunes, Diego L; Oliveira, Leandro S; Franca, Adriana S
2015-01-01
Melanoidins are colored products that can be found in food and drinks, formed by Maillard reactions. Sometimes these compounds are considered undesirable in certain food products, because they impart a brownish color and must be removed. An overview of recent patents related to melanoidin removal indicates that it can be performed by chemical/biological degradation or by adsorption processes. Therefore, in the present study, the adsorption mechanism for synthetic melanoidin removal from aqueous solutions was studied using different Raphanus sativus press-cake sorbents, with the precursor material being carbonized in a microwave oven, either with direct heating or after a chemical activation process with phosphoric acid, nitric acid or potassium hydroxide. Physical and chemical modifications were evaluated by FTIR, pHPZC, thermogravimetry and BET. The adsorption kinetics was better described by a pseudo-second order model for all activated carbons (ACs). Evaluation of the diffusion process showed dependence on the initial melanoidin concentration due to the wide range of sizes of the adsorbed molecules. The equilibrium data were best fitted by the Langmuir model for the acid-treated AC and by the Freundlich model for the base-treated and non-chemically treated ACs. Melanoidin adsorption was characterized as a spontaneous, favorable and endothermic process involving hydrogen bonds and π-π interactions between the adsorbents surfaces and the adsorbed molecules. PMID:26013772
Contribution of the entropy on the thermodynamic equilibrium of vacancies in nickel
Metsue, Arnaud Oudriss, Abdelali; Bouhattate, Jamaa; Feaugas, Xavier
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.
Kemp, Melissa; Go, Young-Mi; Jones, Dean P.
2008-01-01
Understanding the dynamics of redox elements in biologic systems remains a major challenge for redox signaling and oxidative stress research. Central redox elements include evolutionarily conserved subsets of cysteines and methionines of proteins which function as sulfur switches and labile reactive oxygen species (ROS) and reactive nitrogen species (RNS) which function in redox signaling. The sulfur switches depend upon redox environments in which rates of oxidation are balanced with rates of reduction through the thioredoxins, glutathione/glutathione disulfide and cysteine/cystine redox couples. These central couples, which we term redox control nodes, are maintained at stable but non-equilibrium steady states, are largely independently regulated in different subcellular compartments and are quasi-independent from each other within compartments. Disruption of the redox control nodes can differentially affect sulfur switches, thereby creating a diversity of oxidative stress responses. Systems biology provides approaches to address the complexity of these responses. In the present review, we summarize thiol/disulfide pathway, redox potential and rate information as a basis for kinetic modeling of sulfur switches. The summary identifies gaps in knowledge especially related to redox communication between compartments, definition of redox pathways and discrimination between types of sulfur switches. A formulation for kinetic modeling of GSH/GSSG redox control indicates that systems biology could encourage novel therapeutic approaches to protect against oxidative stress by identifying specific redox-sensitive sites which could be targeted for intervention. PMID:18155672
Othman, Zeid A Al; Hashem, Ali; Habila, Mohamed A
2011-01-01
Agricultural wastes have great potential for the removal of heavy metal ions from aqueous solution. The contamination of water by toxic heavy metals is a worldwide environmental problem. Unlike organic pollutants, the majority of which are susceptible to biological degradation, heavy metals do not degrade into harmless end products. Discharges containing cadmium, in particular, are strictly controlled because of the highly toxic nature of this element and its tendency to accumulate in the tissues of living organisms. This work aims to develop inexpensive, highly available, effective metal ion adsorbents from natural wastes as alternatives to existing commercial adsorbents. In particular, Tamrix articulata wastes were modified chemically by esterification with maleic acid to yield a carboxyl-rich adsorbent. The adsorption behavior of treated Tamrix articulata wastes toward cadmium ions in aqueous solutions in a batch system has been studied as a function of equilibration time, adsorbent dose, temperature and pH. Results showed that the maximum adsorption capacity was 195.5 mg/g in a pH 4 solution at 30 °C with a contact time of 120 min, an initial concentration of 400 mg/L and an adsorbent dose of 0.3 g/L. The kinetic data were analyzed using pseudo-first-order and pseudo-second-order kinetic models. It was shown that the adsorption of cadmium could be described by a pseudo-second-order equation. The experimental data were also analyzed using the Langmuir and Freundlich models of adsorption. Thermodynamic parameters such as ΔG°, ΔH° and ΔS° have been evaluated and it has been found that the sorption process was spontaneous and exothermic in nature. From all of our data, we conclude that the treated Tamrix articulata wastes investigated in this study showed good potential for cadmium removal from aqueous solutions. PMID:22173337
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. PMID:20194017
NASA Technical Reports Server (NTRS)
Thompson, R. A.
1994-01-01
EQAIRS is a set of FORTRAN 77 routines for computing the thermodynamic and transport properties of equilibrium air for temperatures from 100 to 30000 K. EQAIRS computes these properties over a pressure range of 1.0e-4 to 1.0e2 atm. The properties computed include enthalpy, total specific heat, compressibility factor, viscosity, and the total values of thermal conductivity and Prandtl number. The various properties are calculated through the use of temperature dependent curve-fits for the pressure range given above. The curve fits are based on mixture values calculated from an 11-species air model. Individual species properties used in the mixture relations were obtained from a recent study by the program authors. It is desirable to have these equilibrium air properties computed by curve-fits as opposed to tabulated values because curve-fits generally permit more efficient computation for flow-field analyses. In addition, for accurate calculations, it is preferable that the thermodynamic and transport properties be computed in a self-consistent manner from the same set of data as in the present case. The EQAIRS routines were written in the form of FORTRAN subroutines for easy adaptation to existing programs. The subroutines are commented and can be easily modified to suit the user's needs. In an attempt to maintain generality, a total of six separate subroutines are available for use: 1) ENTHLPY (specific enthalpy); 2) SPECIFC (total specific heat at constant pressure); 3) COMPRES (compressibility factor); 4) VISCSTY (viscosity); 5) CONDUCT (total thermal conductivity; and 6) PRANDTL (total Prandtl number). EQAIRS has been successfully implemented on a DEC VAX series computer running VMS, a Sun4 series computer running SunOS, and an IBM PC compatible computer running MS-DOS. Sample input/output and a sample driver program are provided. The standard distribution medium for EQAIRS is one 5.25 inch 360K MS-DOS format diskette. This program is also available on a .25
Equilibrium size of atmospheric aerosol sulfates as a function of the relative humidity
NASA Astrophysics Data System (ADS)
Koutrakis, Petros; Wolfson, Jack M.; Spengler, John D.; Stern, Bonnie; Franklin, Claire A.
1989-05-01
Size-fractionated acid aerosols were collected, using a microorifice cascade impactor, during the summer of 1986 in Dunnville, Ontario, as part of the Canadian Children Acute Respiratory Effects Study (CARES), sponsored by the Department of National Health and Welfare, Canada. Sulfate and hydrogen ions showed similar size distributions. The molar ratio of H+/SO42- varied little with particle size, but there was a considerable time-dependent variation in aerosol acid content. It was also found that there is a distinct relationship between the geometric mean aerodynamic diameter of sulfate, da, and ambient relative humidity (RH). Atmospheric sulfate particle sizes observed in this study were slightly higher than those found in laboratory experiments at corresponding humidities. However, considering the uncertainties involved, the agreement between the field and laboratory data was remarkable.
NASA Astrophysics Data System (ADS)
Topping, D. O.; Murphy, B.; Riipinen, I.; Percival, C.; Booth, A.
2014-12-01
The growth, composition, and evolution of secondary organic aerosol (SOA) are governed by properties of individual compounds and ensemble mixtures that affect partitioning between the vapor and condensed phase. There has been considerable recent interest in the idea that SOA can form highly viscous particles where the diff usion of either water or semivolatile organics within the particle is suffi ciently hindered to aff ect evaporation and growth. Despite numerous indirect inferences of viscous behavior from SOA evaporation or " bounce" within aerosol instruments, there have been no bulk measurements of the viscosity of well-constrained model aerosol systems of atmospheric signifi cance. Here the viscous behavior of a well-defi ned model system of 9 dicarboxylic acids is investigated directly with complementary measurements and model predictions used to infer phase state. Results not only allow us to discuss the atmospheric implications for SOA formation through this representative mixture, but also the potential impact of current methodologies used for probing this aff ect in both the laboratory and from a modeling perspective. We show, quantitatively, that the physical state transformation from liquid-like to amorphous semisolid can substantially increase the importance of mass transfer limitations within particles by 7 orders of magnitude for 100 nm diameter particles. Recommendations for future research directions are given.
Lee, Hongkyun; Shim, Eunjung; Yun, Hyun-Shik; Park, Young-Tae; Kim, Dohyeong; Ji, Min-Kyu; Kim, Chi-Kyung; Shin, Won-Sik; Choi, Jaeyoung
2016-01-01
Immobilized microalgae using silica (IMS) from Micractinium reisseri KGE33 was synthesized through a sol-gel reaction. Green algal waste biomass, the residue of M. reisseri KGE33 after oil extraction, was used as the biomaterial. The adsorption of Cu(II) on IMS was tested in batch experiments with varying algal doses, pH, contact times, initial Cu(II) concentrations, and temperatures. Three types of IMSs (IMS 14, 70, and 100) were synthesized according to different algal doses. The removal efficiency of Cu(II) in the aqueous phase was in the following order: IMS 14 (77.0%) < IMS 70 (83.3%) < IMS 100 (87.1%) at pH 5. The point of zero charge (PZC) value of IMS100 was 4.5, and the optimum pH for Cu(II) adsorption was 5. Equilibrium data were described using a Langmuir isotherm model. The Langmuir model maximum Cu(II) adsorption capacity (q m) increased with the algal dose in the following order: IMS 100 (1.710 mg g(-1)) > IMS 70 (1.548 mg g(-1)) > IMS 14 (1.282 mg g(-1)). The pseudo-second-order equation fitted the kinetics data well, and the value of the second-order rate constant increased with increasing algal dose. Gibbs free energies (ΔG°) were negative within the temperature range studied, which indicates that the adsorption process was spontaneous. The negative value of enthalpy (ΔH°) again indicates the exothermic nature of the adsorption process. In addition, SEM-energy-dispersive X-ray spectroscopy (EDS), Fourier transform infrared (FT-IR), and X-ray photoelectron spectroscopy (XPS) analyses of the IMS surface reveal that the algal biomass on IMS is the main site for Cu(II) binding. This study shows that immobilized microalgae using silica, a synthesized biosorbent, can be used as a cost-effective sorbent for Cu(II) removal from the aqueous phase. PMID:25953610
The lofting of Western Pacific regional aerosol by island thermodynamics as observed around Borneo
NASA Astrophysics Data System (ADS)
Robinson, N. H.; Allan, J. D.; Trembath, J. A.; Rosenberg, P. D.; Allen, G.; Coe, H.
2012-07-01
Vertical profiles of aerosol chemical composition, number concentration and size were measured throughout the lower troposphere of Borneo, a large tropical island in the western Pacific Ocean. Aerosol composition, size and number concentration measurements (using an Aerodyne Aerosol Mass Spectrometer, Passive Cavity Aerosol Spectrometer Probe and Condensation Particle Counter, respectively) were made both upwind and downwind of Borneo, as well as over the island itself, on board the UK BAe-146 research aircraft as part of the OP3 project. Two meteorological regimes were identified - one dominated by isolated terrestrial convection (ITC) which peaked in the afternoon, and the other characterised by more regionally active mesoscale convective systems (MCS). Upwind profiles show aerosol to be confined to a shallow marine boundary layer below 930 ± 10 hPa (~760 m above sea level, a.s.l.). As this air mass advects over the island with the mean free troposphere synoptic flow during the ITC-dominated regime, it is convectively lofted above the terrestrial surface mixed layer to heights of between 945 ± 22 (~630 m a.s.l.) and 740 ± 44 hPa (~2740 m a.s.l.), consistent with a coupling between the synoptic steering level flow and island sea breeze circulations. Terrestrial aerosol was observed to be lofted into this higher layer through both moist convective uplift and transport through turbulent diurnal sea-breeze cells. At the peak of convective activity in the mid-afternoons, organic aerosol loadings in the lofted layer were observed to be substantially higher than in the morning (by a mean factor of three). This organic matter is dominated by secondary aerosol from processing of biogenic gas phase precursors. Aerosol number concentration profiles suggest formation of new particles aloft in the atmosphere. By the time the air mass reaches the west coast of the island, terrestrial aerosol is enhanced in the lofted layer. Such uplift of aerosol in Borneo is expected to
Behera, Sailesh N; Betha, Raghu; Liu, Ping; Balasubramanian, Rajasekhar
2013-05-01
Aerosol acidity is one of the most important parameters that can influence atmospheric visibility, climate change and human health. Based on continuous field measurements of inorganic aerosol species and their thermodynamic modeling on a time resolution of 1h, this study has investigated the acidic properties of PM2.5 and their relation with the formation of secondary inorganic aerosols (SIA). The study was conducted by taking into account the prevailing ambient temperature (T) and relative humidity (RH) in a tropical urban atmosphere. The in-situ aerosol pH (pH(IS)) on a 12h basis ranged from -0.20 to 1.46 during daytime with an average value of 0.48 and 0.23 to 1.53 during nighttime with an average value of 0.72. These diurnal variations suggest that the daytime aerosol was more acidic than that caused by the nighttime aerosol. The hourly values of pH(IS) showed a reverse trend as compared to that of in-situ aerosol acidity ([H(+)]Ins). The pH(IS) had its maximum values at 3:00 and at 20:00 and its minimum during 11:00 to 12:00. Correlation analyses revealed that the molar concentration ratio of ammonium to sulfate (R(N/S)), equivalent concentration ratio of cations to anions (RC/A), T and RH can be used as independent variables for prediction of pH(IS). A multi-linear regression model consisting of RN/S, RC/A, T and RH was developed to estimate aerosol pH(IS). PMID:23523726
NASA Astrophysics Data System (ADS)
Ogino, Yousuke; Nagano, Atsushi; Ishihara, Tomoaki; Ohnishi, Naofumi
2013-08-01
A fitting formula for radiative cooling with collisional-radiative population for air plasma flowfield has been developed. Population number densities are calculated from rate equations in order to evaluate the effects of nonequilibrium atomic and molecular processes. Many elementary processes are integrated to be applied to optically-thin plasmas in the number density range of 1012/cm3 <= N <= 1019/cm3 and the temperature range of 300 K <= T <= 40,000 K. Our results of the total radiative emissivity calculated from the collisional-radiative population are fitted in terms of temperature and total number density. To validate the analytic fitting formula, numerical simulation of a laser-induced blast wave propagation with the nonequilibrium radiative cooling is conducted and successfully reproduces the shock and plasma wave front time history observed by experiments. In addition, from the comparison between numerical simulations with the radiation cooling effect based on the fitting formula and those with a gray gas radiation model that assumes local thermodynamic equilibrium, we find that the displacement of the plasma front is slightly different due to the deviation of population probabilities. By using the fitting formula, we can easily and more accurately evaluate the radiative cooling effect without solving detailed collisional-radiative rate equations.
Liu, Jingyong; Fu, Jiewen; Ning, Xun'an; Sun, Shuiyu; Wang, Yujie; Xie, Wuming; Huang, Shaosong; Zhong, Sheng
2015-09-01
The effects of different chlorides and operational conditions on the distribution and speciation of six heavy metals (Pb, Zn, Cr, Cu, Mn and Ni) during sludge incineration were investigated using a simulated laboratory tubular-furnace reactor. A thermodynamic equilibrium investigation using the FactSage software was performed to compare the experimental results. The results indicate that the volatility of the target metals was enhanced as the chlorine concentration increased. Inorganic-Cl influenced the volatilization of heavy metals in the order of Pb>Zn>Cr>Cu>Mn>Ni. However, the effects of organic-Cl on the volatility of Mn, Pb and Cu were greater than the effects on Zn, Cr and Ni. With increasing combustion temperature, the presence of organic-Cl (PVC) and inorganic-Cl (NaCl) improved the transfer of Pb and Zn from bottom ash to fly ash or fuse gas. However, the presence of chloride had no obvious influence on Mn, Cu and Ni. Increased retention time could increase the volatilization rate of heavy metals; however, this effect was insignificant. During the incineration process, Pb readily formed PbSiO4 and remained in the bottom ash. Different Pb compounds, primarily the volatile PbCl2, were found in the gas phase after the addition of NaCl; the dominant Pb compounds in the gas phase after the addition of PVC were PbCl2, Pb(ClO4)2 and PbCl2O4. PMID:26354691
De la Luz, Victor; Lara, Alejandro; Raulin, Jean-Pierre
2011-08-10
We use a numerical code called PAKALMPI to compute synthetic spectra of the solar emission in quiet conditions at millimeter, sub-millimeter, and infrared wavelengths. PAKALMPI solves the radiative transfer equation, with non-local thermodynamic equilibrium (NLTE), in a three-dimensional geometry using a multiprocessor environment. The code is able to use three opacity functions: classical bremsstrahlung, H{sup -}, and inverse bremsstrahlung. In this work, we have computed and compared two synthetic spectra, one in the common way: using bremsstrahlung opacity function and considering a fully ionized atmosphere; and a new one considering bremsstrahlung, inverse bremsstrahlung, and H{sup -} opacity functions in NLTE. We analyzed in detail the local behavior of the low atmospheric emission at 17, 212, and 405 GHz (frequencies used by the Nobeyama Radio Heliograph and the Solar Submillimeter Telescope). We found that the H{sup -} is the major emission mechanism at low altitudes (below 500 km) and that at higher altitudes the classical bremsstrahlung becomes the major mechanism of emission. However, the brightness temperature remains unalterable. Finally, we found that the inverse bremsstrahlung process is not important for radio emission at these heights.
NASA Astrophysics Data System (ADS)
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.
NASA Astrophysics Data System (ADS)
Göhring, Holger; Leineweber, Andreas; Mittemeijer, Eric Jan
2016-09-01
The present work is dedicated to investigating the occurrence of the α +ɛ equilibrium at temperatures typically applied for nitrocarburizing treatments. To this end, pearlitic Fe-C specimens were treated between 823 K and 863 K (550 °C and 590 °C) in gaseous nitriding and gaseous nitrocarburizing atmospheres, allowing control of the chemical potentials of N and C. Subsequently, the resulting compound-layer microstructures were investigated using light microscopy and X-ray diffraction. Thermodynamic calculations, adopting several models for the Fe-N-C system from the literature, were performed, showing significantly different predictions for both the sequence of the invariant reactions and their temperatures. Comparison of the experimental data and the theoretical calculations led to the conclusion that none of the models from the literature is able to realistically describe the experimentally observed constitution in the Fe-N-C system in the considered temperature range. Values/value ranges for the temperatures of the invariant reactions were obtained.
Aly, Zaynab; Graulet, Adrien; Scales, Nicholas; Hanley, Tracey
2014-03-01
Economic adsorbents in bead form were fabricated and utilised for the adsorption of Al(3+) from aqueous solutions. Polyacrylonitrile (PAN) beads, PAN powder and the thermally treated PAN beads (250 °C/48 h/Ar and 600 °C/48 h/Ar-H2) were characterised using different techniques including Fourier transform infrared spectroscopy, X-ray diffraction, specific surface analysis (Brunauer-Emmett-Teller), thermogravimetric analysis as well as scanning electron microscopy. Effects of pH, contact time, kinetics and adsorption isotherms at different temperatures were investigated in batch mode experiments. Aluminium kinetic data best fit the Lagergren pseudo-second-order adsorption model indicating a one-step, surface-only, adsorption process with chemisorption being the rate limiting step. Equilibrium adsorption data followed a Langmuir adsorption model with fairly low monolayer adsorption capacities suitable for freshwater clean-up only. Various constants including thermodynamic constants were evaluated from the experimental results obtained at 20, 40 and 60 °C. Positive values of ΔH° indicated that the adsorption of Al(3+) onto all three adsorbents was endothermic with less energy input required for PAN powder compared to PAN beads and low-temperature thermally treated PAN. Negative ΔG° values indicated that the aluminium adsorption process was spontaneous for all adsorbents examined. PMID:24297464
NASA Astrophysics Data System (ADS)
Qu, Lingling; Han, Tingting; Luo, Zhijun; Liu, Cancan; Mei, Yan; Zhu, Ting
2015-03-01
B-Fe3O4@C core-shell composites were synthesized via one-pot hydrothermal carbonization (HTC) process and used as an adsorbent for the removal of methylene blue (MB) from aqueous solution. By using sodium borate as the catalyst, the hydrothermal carbonization process of B-Fe3O4@C core-shell composites was optimized and a higher surface area was obtained. The adsorbent was characterized by XRD, Raman spectra, SEM, TEM and N2 adsorption/desorption isotherms. We studied the dye adsorption process at different conditions and analyzed the data by employing the Langmuir and Freundlich models, and the equilibrium data fitted well with both models. Kinetic analyses were conducted by using the Lagergren pseudo-first-order and pseudo-second-order model and the results showed that the adsorption process was more consistent with the pseudo-second-order kinetics. To better understand the dye adsorption process from the thermodynamics perspective, we also calculated ΔHο, ΔSο, ΔGο and Ea, the results suggesting that the MB adsorption process was physisorption endothermic process, and spontaneous at room temperature. The as-synthesized B-Fe3O4@C showing high magnetic sensitivity provides a facile and efficient way to recycle from aqueous solution.
Gao, Jun-jie; Qin, Ye-bo; Zhou, Tao; Cao, Dong-dong; Xu, Ping; Hochstetter, Danielle; Wang, Yue-fei
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 ZnCl2 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 pseudo-second-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. PMID:23825151
Kausar, Abida; Bhatti, Haq Nawaz; MacKinnon, Gillian
2013-11-01
In this research, biosorption efficiency of different agro-wastes was evaluated with rice husk showing maximum biosorption capacity among the selected biosorbents. Optimization of native, SDS-treated and immobilized rice husk adsorption parameters including pH, biosorbent amount, contact time, initial U(VI) concentration and temperature for maximum U(VI) removal was investigated. Maximum biosorption capacity for native (29.56 mg g(-1)) and immobilized biomass (17.59 mg g(-1)) was observed at pH 4 while SDS-treated biomass showed maximum removal (28.08 mg g(-1)) at pH 5. The Langmuir sorption isotherm model correlated best with the U(IV) biosorption equilibrium data for the 10-100 mg L(-1) concentration range. The kinetics of the reaction followed pseudo-second order kinetic model. Thermodynamic parameters like free energy (ΔG(0)) and enthalpy (ΔH°) confirmed the spontaneous and exothermic nature of the process. Experiments to determine the regeneration capacity of the selected biosorbents and the effect of competing metal ions on biosorption capacity were also conducted. The biomass was characterized using scanning electron microscopy, surface area analysis, Fourier transformed infra-red spectroscopy and thermal gravimetric analysis. The study proved that rice husk has potential to treat uranium in wastewater. PMID:23787279
Ghosh, Somdatta; Xie, Xiangjin; Dey, Abhishek; Sun, Yan; Scholes, Charles P.; Solomon, Edward I.
2009-01-01
A combination of spectroscopies and density functional theory calculations indicate that there are large temperature-dependent absorption spectral changes present in green nitrite reductases (NiRs) due to a thermodynamic equilibrium between a green and a blue type 1 (T1) copper site. The axial methionine (Met) ligand is unconstrained in the oxidized NiRs, which results in an enthalpically favored (ΔH ≈4.6 kcal/mol) Met-bound green copper site at low temperatures, and an entropically favored (TΔS ≈4.5 kcal/mol, at room temperature) Met-elongated blue copper site at elevated temperatures. In contrast to the NiRs, the classic blue copper sites in plastocyanin and azurin show no temperature-dependent behavior, indicating that a single species is present at all temperatures. For these blue copper proteins, the polypeptide matrix opposes the gain in entropy that would be associated with the loss of the weak axial Met ligand at physiological temperatures by constraining its coordination to copper. The potential energy surfaces of Met binding indicate that it stabilizes the oxidized state more than the reduced state. This provides a mechanism to tune down the reduction potential of blue copper sites by >200 mV. PMID:19282479
Chen, Yao; Jiang, Wenju; Jiang, Li; Ji, Xiujuan
2011-01-01
Activated carbon was developed from sewage sludge using pyrolusite as an additive. It was demonstrated that the removal efficiency of two synthetic dyes (Tracid orange GS and Direct fast turquoise blue GL) by the produced adsorbent was up to 97.6%. The activated carbon with pyrolusite addition had 38.2% higher surface area, 43.8% larger micropore and 54.4% larger mesopore production than ordinary sludge-based activated carbons. Equilibrium adsorption isotherms and kinetics were also investigated based on dyes adsorption tests. The experimental data were analyzed by the Langmuir and Freundlich models of adsorption, and the results fitted well to the Langmuir isotherm. The kinetic data have been analyzed using pseudo-first-order, pseudo-second-order and intraparticle diffusion equation. The experimental data fitted very well with pseudo-second-order kinetic model. Activation energies for the adsorption processes ranged between 8.7 and 19.1 kJ mol 1. Thermodynamic parameters such as standard free energy (deltaG0), standard enthalpy (deltaH0) and standard entropy (deltaS0) were evaluated. The adsorption of these two dyes on the activated carbon was found to be a spontaneous and endothermic process in nature. PMID:22097045
Adsorption of Zn2+ ions onto NaA and NaX zeolites: kinetic, equilibrium and thermodynamic studies.
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. PMID:19773115
NASA Astrophysics Data System (ADS)
Xu, Li; Zhang, Feng; Wang, Erkang; Wang, Jin
2013-02-01
In this review, we summarize our recent efforts in exploring the non-equilibrium potential and flux landscape for dynamical systems and networks. The driving force of non-equilibrium dynamics can be decomposed into the gradient of the non-equilibrium potential and the divergent free probability flux divided by the steady-state probability distribution. The potential landscape is linked to the probability distribution of the steady state. We found that the intrinsic potential landscape in the zero noise limit is a Lyapunov function. We have defined and quantified the entropy, energy and free energy of the non-equilibrium systems. These can be used for formulating the first law of non-equilibrium thermodynamics. The free energy of the non-equilibrium system is also a Lyapunov function. Therefore, we can use both the intrinsic potential landscape and the free energy to quantify the robustness and global stability of the system. The Lyapunov property provides the formulation for the second law of non-equilibrium thermodynamics. The non-zero probability flux breaks the detailed balance. The two driving forces from the gradient of intrinsic potential landscape and the probability flux are perpendicular to each other under the zero noise limit. We investigate the dynamics of a new biological example of signal-induced Ca2+ oscillation. We explored the underlying potential landscape which shows a Mexican hat shape attracting the system down to the oscillation ring and the flux which provides the driving force on the ring for coherent and stable oscillation. We explored how the landscape and flux topography change with respect to the system parameters and the relationship to the period of oscillations and how the non-equilibrium free energy changes with respect to different dynamic phases and phase transitions when the system parameters vary. These explain how the system becomes robust and stable under different conditions and can help guide the experiment.
NASA Astrophysics Data System (ADS)
Morel, Vincent; Bultel, Arnaud; Annaloro, Julien; Chambrelan, Cédric; Edouard, Guillaume; Grisolia, Christian
2015-01-01
Beyond the experimental studies, the assessment of the ability of ultra-short (femto or picosecond) laser pulses to provide correct estimates of the elemental composition of unknown samples using laser-induced breakdown spectroscopy requires the modeling of a typical situation. The present article deals with this modeling for aluminum in nitrogen. A spherical layer model is developed. The central aluminum plasma is produced by the ultra-short pulse. This plasma is described using our collisional-radiative model CoRaM-Al in an upgraded version involving 250 levels. Its expansion and relaxation take place in nitrogen, where the formation and the propagation of a shock wave are taken into account. In this shocked nitrogen layer, the equilibrium conditions are assumed. Mass, momentum and energy conservation equations written under an Eulerian form are used to correctly model the global dynamics. Energy losses are due to radiative recombination, thermal Bremsstrahlung and spontaneous emission. These elementary processes are implemented. The only input parameters are the pulse energy E0, the ablated mass M of the sample and the pressure p0 of the surrounding gas. The equilibrium composition involving N2, N, N2+, N+ and free electrons of the shocked nitrogen layer is calculated from the thermodynamic database of our collisional-radiative model CoRaM-N2. The conditions E0 = 10 mJ and M ≃ 10- 10 kg corresponding to a 532 nm laser pulse are chosen. The model assumes the initial equilibrium of the aluminum plasma produced by the laser pulse absorbed by the sample. Then, owing to the significant overpressure with respect to the background gas (p0 is assumed atmospheric), the surrounding gas starts to be compressed while the propagation of a shock wave takes place. The shock layer maximum pressure is obtained at approximately 20 ns. At this characteristic time, the nitrogen pressure is around 400 times the atmospheric pressure. A shock velocity of 7 km s- 1 is predicted. The
Hemingway, B.S.; Bohlen, S.R.; Hankins, W.B.; Westrum, E.F., Jr.; Kuskov, O.L.
1998-01-01
The heat capacities of synthetic coesite and jadeite were measured between about 15 and 850 K by adiabatic and differential scanning calorimetry. The experimental data were smoothed and estimates were made of heat capacities to 1800 K. The following equations represent our estimate of the heat capacities of coesite and jadeite between 298.15 and 1800 K: [see original article for formula]. Tables of thermodynamic values for coesite and jadeite to 1800 K are presented. The entropies of coesite and jadeite are 40.38 ?? 0.12 and 136.5 ?? 0.32 J/(mol.K), respectively, at 298.15 K. The entropy for coesite derived here confirms the value published earlier by Holm et al. (1967). We have derived an equation to describe the quartz-coesite boundary over the temperature range of 600 to 1500 K, P(GPa) = 1.76 + 0.001T(K). Our results are in agreement with the enthalpy of transition reported by Akaogi and Navrotsky (1984) and yield -907.6 ?? 1.4 kJ/mol for the enthalpy of formation of coesite from the elements at 298.15 K and 1 bar, in agreement with the value recommended by CODATA (Khodakovsky et al. 1995). Several sources of uncertainty remain unacceptably high, including: the heat capacities of coesite at temperatures above about 1000 K; the heat capacities and volumetric properties of ?? quartz at higher pressures and at temperatures above 844 K; the pressure corrections for the piston cylinder apparatus used to determine the quartz-coesite equilibrium boundary.
NASA Astrophysics Data System (ADS)
Flores, A.; Joseph, E.; Nalli, N. R.; Smirnov, A.; Morris, V. R.; Wolfe, D. E.; Aerose Team
2011-12-01
An estimated three billion metric tons of mineral aerosols are injected into the troposphere annually from the Saharan desert [Prospero et al., 1996]. These windswept aerosols from the African continent are responsible for a variety of climate, health, and environmental impacts on both global and regional scales that span the Western Hemisphere [Morris et al., 2006]. The Aerosol and Ocean Science Expeditions (AEROSE) are a great opportunity to tackle these impacts. The Saharan Air Layer (SAL) appears to retain its Saharan characteristics of warm, stable air near its base, and dryness and dustiness throughout its depth as it is carried as far as the western Caribbean Sea [Dunion & Velden, 2004]. AEROSE provides insitu characterization of the impact of aerosols of African origin on energy balance and microphysical evolution of mineral dust outflow over the tropical Atlantic Ocean. By quantifying the radiative properties of the SAL, aerosol optical depths (AOD) as high as 1.6 was detected over the Atlantic [Nalli et al., 2011], producing a shortwave forcing of 200 W/m2 and therefore a warming just above the marine boundary layer for this particular case. Also in this study, AOD values from AEROSE have been compared with the Moderate Resolution Imaging Spectroradiometer (MODIS), showing variety on each campaign.
NASA Technical Reports Server (NTRS)
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.
NASA Astrophysics Data System (ADS)
Griffith, S. M.; Huang, X. H. H.; Louie, P. K. K.; Yu, J. Z.
2015-12-01
Nitric acid (HNO3), the gas-phase precursor to aerosol nitrate is known to rapidly transfer to aerosols where NH4+ is in excess to SO42- present in the aerosol, but the HNO3 is also subject to the slower uptake onto sea salt and dust laden particles. Understanding the competition between these routes is necessary to predict the NO3- distribution and impact on aerosols. In this study, we investigated the conditions leading to predominant fine or coarse mode aerosol nitrate using an hourly MARGA 2S dataset from an urban site in Hong Kong. The hourly dataset of inorganic ions (SO42-, NH4+, NO3-, Na+, Cl-, Ca2+, K+, Mg2+) in 2 size ranges (fine, < 2.5 μm; fine+coarse, < 10 μm) and water-soluble gases (HNO3, HCl, and NH3) spanning more than 1 year provides a rich trove for analyzing aerosol nitrate chemistry and the underlying mechanisms that ultimately determine the fraction of NO3- in the fine mode. The urban site in this study is initially characterized for seasonal environmental conditions and the aerosol chemical composition. The relationship between excess NH4+ and NO3- in the fine mode is detailed and contrasted with the influence on fine mode NO3- from uptake on sea salt and dust, which is typically relegated as a 'coarse-mode' mechanism. The distribution of NO3- in the fine and coarse modes is compared with the distribution of the other inorganic ions, where sea-salt ion (Na+, Mg2+) distributions yield the highest explained variability for the nitrate distributions. As a complement to that finding, the cation equivalency (excluding NH4+) in the coarse mode proves to be a crucial factor in leveraging the distribution away from fine mode nitrate. The uptake potential of the water-soluble gases is used to drive a mass transfer model and compare with thermodynamic equilibrium results. In the modeling, the partitioning cycles of fine and coarse mode aerosol nitrate highlight the dynamic relationship between NO3- and Cl- in both the fine and coarse modes, where the
Feng Haidong; Wang Jin
2011-12-21
The driving force of the dynamical system can be decomposed into the gradient of a potential landscape and curl flux (current). The fluctuation-dissipation theorem (FDT) is often applied to near equilibrium systems with detailed balance. The response due to a small perturbation can be expressed by a spontaneous fluctuation. For non-equilibrium systems, we derived a generalized FDT that the response function is composed of two parts: (1) a spontaneous correlation representing the relaxation which is present in the near equilibrium systems with detailed balance and (2) a correlation related to the persistence of the curl flux in steady state, which is also in part linked to a internal curvature of a gauge field. The generalized FDT is also related to the fluctuation theorem. In the equal time limit, the generalized FDT naturally leads to non-equilibrium thermodynamics where the entropy production rate can be decomposed into spontaneous relaxation driven by gradient force and house keeping contribution driven by the non-zero flux that sustains the non-equilibrium environment and breaks the detailed balance. On any particular path, the medium heat dissipation due to the non-zero curl flux is analogous to the Wilson lines of an Abelian gauge theory.
NASA Technical Reports Server (NTRS)
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.
NASA Technical Reports Server (NTRS)
Kaye, Jack A.
1989-01-01
A possible nonlocal thermodynamic equilibrium (non-LTE) effect involving stratospheric HF arising from the direct photochemical excitation of vibrationally excited HF by collisional energy transfer from electronically excited O2 is presented. Although this non-LTE effect is smaller that one associated with the direct solar excitation of both HF(nv = 1) and HF(nv = 2), calculations show that inclusion of the mechanism into retrieval algorithms is necessary if correct daytime upper stratosphere HF profiles are to be inferred in future IR thermal emission measurements.