Science.gov

Sample records for addition thermodynamic analysis

  1. Thermodynamically consistent microstructure prediction of additively manufactured materials

    NASA Astrophysics Data System (ADS)

    Smith, Jacob; Xiong, Wei; Cao, Jian; Liu, Wing Kam

    2016-03-01

    Additive manufacturing has risen to the top of research interest in advanced manufacturing in recent years due to process flexibility, achievability of geometric complexity, and the ability to locally modify and optimize materials. The present work is focused on providing an approach for incorporating thermodynamically consistent properties and microstructure evolution for non-equilibrium supercooling, as observed in additive manufacturing processes, into finite element analysis. There are two primary benefits of this work: (1) the resulting prediction is based on the material composition and (2) the nonlinear behavior caused by the thermodynamic properties of the material during the non-equilibrium solution is accounted for with extremely high resolution. The predicted temperature response and microstructure evolution for additively manufactured stainless steel 316L using standard handbook-obtained thermodynamic properties are compared with the thermodynamic properties calculated using the CALculation of PHAse Diagrams (CALPHAD) approach. Data transfer from the CALPHAD approach to finite element analysis is discussed.

  2. Evaluation of five additional enhancements to the building loads analysis and system thermodynamics (BLAST) program. Final report

    SciTech Connect

    Nemeth, R.J.

    1993-04-01

    The Building Loads Analysis and System Thermodynamics (BLAST) energy analysis computer program has undergone a multiyear enhancement program based on feedback and priorities of the BLAST users' group. This project was conducted to evaluate the convenience and applicability of the following BLAST enhancements: Air-to-Air Heat Pump; Expanded Baseboard Heat Options; Report Writer; Thermal Comfort Model. Ice Storage Model; Evaluation responses indicate that the enhancements satisfied users' needs for advanced building energy analysis tools. Although the evaluations revealed program bugs and the lack of documentation in some areas, the programs were easy to install and use. The bugs have been removed and the documentation expanded in the BLAST Users Reference. It is recommended that the enhancements be distributed with future updates and releases of the BLAST program.... BLAST, Enhancements, Energy efficient, Comfort analysis, Technology Transfer Test Bed(T3B).

  3. Thermodynamic analysis of spectra

    SciTech Connect

    Mitchell, G. E.; Shriner, J. F. Jr.

    2008-04-04

    Although random matrix theory had its initial application to neutron resonances, there is a relative scarcity of suitable nuclear data. The primary reason for this is the sensitivity of the standard measures used to evaluate spectra--the spectra must be essential pure (no state with a different symmetry) and complete (no states missing). Additional measures that are less sensitive to these experimental limitations are of significant value. The standard measure for long range order is the {delta}{sub 3} statistic. In the original paper that introduced this statistic, Dyson and Mehta also attempted to evaluate spectra with thermodynamic variables obtained from the circular orthogonal ensemble. We consider the thermodynamic 'internal energy' and evaluate its sensitivity to experimental limitations such as missing and spurious levels. Monte Carlo simulations suggest that the internal energy is less sensitive to mistakes than is {delta}{sub 3}, and thus the internal energy can serve as a addition to the tool kit for evaluating experimental spectra.

  4. Thermodynamic Analysis of Biodegradation Pathways

    PubMed Central

    Finley, Stacey D.; Broadbelt, Linda J.

    2014-01-01

    Microorganisms provide a wealth of biodegradative potential in the reduction and elimination of xenobiotic compounds in the environment. One useful metric to evaluate potential biodegradation pathways is thermodynamic feasibility. However, experimental data for the thermodynamic properties of xenobiotics is scarce. The present work uses a group contribution method to study the thermodynamic properties of the University of Minnesota Biocatalysis/Biodegradation Database. The Gibbs free energies of formation and reaction are estimated for 914 compounds (81%) and 902 reactions (75%), respectively, in the database. The reactions are classified based on the minimum and maximum Gibbs free energy values, which accounts for uncertainty in the free energy estimates and a feasible concentration range relevant to biodegradation. Using the free energy estimates, the cumulative free energy change of 89 biodegradation pathways (51%) in the database could be estimated. A comparison of the likelihood of the biotransformation rules in the Pathway Prediction System and their thermodynamic feasibility was then carried out. This analysis revealed that when evaluating the feasibility of biodegradation pathways, it is important to consider the thermodynamic topology of the reactions in the context of the complete pathway. Group contribution is shown to be a viable tool for estimating, a priori, the thermodynamic feasibility and the relative likelihood of alternative biodegradation reactions. This work offers a useful tool to a broad range of researchers interested in estimating the feasibility of the reactions in existing or novel biodegradation pathways. PMID:19288443

  5. Additivity, density fluctuations, and nonequilibrium thermodynamics for active Brownian particles

    NASA Astrophysics Data System (ADS)

    Chakraborti, Subhadip; Mishra, Shradha; Pradhan, Punyabrata

    2016-05-01

    Using an additivity property, we study particle-number fluctuations in a system of interacting self-propelled particles, called active Brownian particles (ABPs), which consists of repulsive disks with random self-propulsion velocities. From a fluctuation-response relation, a direct consequence of additivity, we formulate a thermodynamic theory which captures the previously observed features of nonequilibrium phase transition in the ABPs from a homogeneous fluid phase to an inhomogeneous phase of coexisting gas and liquid. We substantiate the predictions of additivity by analytically calculating the subsystem particle-number distributions in the homogeneous fluid phase away from criticality where analytically obtained distributions are compatible with simulations in the ABPs.

  6. WATEQ3 geochemical model: thermodynamic data for several additional solids

    SciTech Connect

    Krupka, K.M.; Jenne, E.A.

    1982-09-01

    Geochemical models such as WATEQ3 can be used to model the concentrations of water-soluble pollutants that may result from the disposal of nuclear waste and retorted oil shale. However, for a model to competently deal with these water-soluble pollutants, an adequate thermodynamic data base must be provided that includes elements identified as important in modeling these pollutants. To this end, several minerals and related solid phases were identified that were absent from the thermodynamic data base of WATEQ3. In this study, the thermodynamic data for the identified solids were compiled and selected from several published tabulations of thermodynamic data. For these solids, an accepted Gibbs free energy of formation, ..delta..G/sup 0//sub f,298/, was selected for each solid phase based on the recentness of the tabulated data and on considerations of internal consistency with respect to both the published tabulations and the existing data in WATEQ3. For those solids not included in these published tabulations, Gibbs free energies of formation were calculated from published solubility data (e.g., lepidocrocite), or were estimated (e.g., nontronite) using a free-energy summation method described by Mattigod and Sposito (1978). The accepted or estimated free energies were then combined with internally consistent, ancillary thermodynamic data to calculate equilibrium constants for the hydrolysis reactions of these minerals and related solid phases. Including these values in the WATEQ3 data base increased the competency of this geochemical model in applications associated with the disposal of nuclear waste and retorted oil shale. Additional minerals and related solid phases that need to be added to the solubility submodel will be identified as modeling applications continue in these two programs.

  7. Thermodynamic network model for predicting effects of substrate addition and other perturbations on subsurface microbial communities

    SciTech Connect

    Jack Istok; Melora Park; James McKinley; Chongxuan Liu; Lee Krumholz; Anne Spain; Aaron Peacock; Brett Baldwin

    2007-04-19

    The overall goal of this project is to develop and test a thermodynamic network model for predicting the effects of substrate additions and environmental perturbations on microbial growth, community composition and system geochemistry. The hypothesis is that a thermodynamic analysis of the energy-yielding growth reactions performed by defined groups of microorganisms can be used to make quantitative and testable predictions of the change in microbial community composition that will occur when a substrate is added to the subsurface or when environmental conditions change.

  8. Thermodynamic analysis of conductive filaments

    NASA Astrophysics Data System (ADS)

    Karpov, V.; Niraula, D.; Karpov, I.

    2016-08-01

    We present a thermodynamic theory of the conductive filament growth and dissolution in random access memory describing the observed features of their current-voltage (IV) characteristics. Our theory is based on the self-consisted Fokker-Planck approach reducing the filament kinetics to its thermodynamics. Expressing the observed IV features through material parameters, our results pave a way to device improvements.

  9. Thermodynamic analysis of total energy gas turbines

    NASA Astrophysics Data System (ADS)

    Stecco, S. S.

    For a thermodynamic analysis of gas turbine power plants (GTPP) with exhaust gases recovery, a simple recovery cogeneration plant and a steam-gas combined cogeneration plant are analyzed according to the First and Second Laws of Thermodynamics. Attention is given to the convenience of different GTPP solutions for different ratios of heat to electricity production; methods of analysis of bottoming Rankine cycle power plants with respect to various fluids; and fuel savings.

  10. Sensitivity analysis of thermodynamic calculations

    NASA Astrophysics Data System (ADS)

    Irwin, C. L.; Obrien, T. J.

    Iterative solution methods and sensitivity analysis for mathematical models of chemical equilibrium are formally similar. For models which are a Newton-type iterative solution scheme, such as the NASA-Lewis CEC code or the R-Gibbs unit of ASPEN, it is shown that extensive sensitivity information is available for approximately the cost of one additional Newton iteration. All matrices and vectors required for implementation of first and second order sensitivity analysis in the CEC code are given in an appendix. A simple problem for which an analytical solution is possible is presented to illustrate the calculations and verify the computer calculations.

  11. Thermodynamic Analysis on Lunar Soil Reduced by Hydrogen

    NASA Astrophysics Data System (ADS)

    Lu, Yuhao; Mantha, Divakar; Reddy, Ramana G.

    2010-12-01

    Although many experiments have been performed to reduce the lunar soil by hydrogen, no systematic thermodynamic analysis has been developed to design and optimize these experiments. Applying a thermodynamic model to the system of simulant lunar soil and hydrogen, this study analyzes and discusses the thermodynamic behavior of the system in detail. The calculations demonstrate that iron is the only metal that can be extracted significantly from the lunar soil. The amount of hydrogen in the system drastically affects the processes of iron extraction and water production. However, the effect of system pressure can be neglected in the process. The yields of metallic iron and water from the lunar soil as functions of temperature and hydrogen content are investigated in this study. Additionally, the calculations explain the metallic iron on the surface of the moon from the thermodynamic point of view.

  12. Thermodynamic Analysis of Nanoporous Membrane Separation Processes

    NASA Astrophysics Data System (ADS)

    Rogers, David; Rempe, Susan

    2011-03-01

    We give an analysis of desalination energy requirements in order to quantify the potential for future improvements in desalination membrane technology. Our thermodynamic analysis makes it possible to draw conclusions from the vast array of equilibrium molecular dynamics simulations present in the literature as well as create a standardized comparison for measuring and reporting experimental reverse osmosis material efficiency. Commonly employed methods for estimating minimum desalination energy costs have been revised to include operations at positive input stream recovery ratios using a thermodynamic cycle analogous to the Carnot cycle. Several gaps in the statistical mechanical theory of irreversible processes have also been identified which may in the future lead to improved communication between materials engineering models and statistical mechanical simulation. Simulation results for silica surfaces and nanochannels are also presented. Sandia National Laboratories is a multi-program laboratory operated by Sandia Corporation, a subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  13. Thermodynamic Analysis of the Amin Engine

    NASA Astrophysics Data System (ADS)

    Wheeler, John C.

    2002-11-01

    Extraordinary claims for the The Amin engine, made recently in full-page paid advertisements in Science Magazine and Physics Today are based upon faulty analysis of the proposed cycle. As presented, the engine constitutes a claim to violate the second law of thermodynamics, purporting to produce net useful work while extracting heat from a reservoir at a single temperature. When analyzed correctly, it conforms to the second law and produces at most zero net work when operating under isothermal conditions. The author neglects the torque-angle work needed to change the angular velocity and/or moment of inertia of the working fluid in the cylinder. When this is correctly accounted for, the contradiction with the second law is resolved.

  14. Thermodynamic analysis of syngas conversion chemistry

    SciTech Connect

    Vijayaraghavan, P.; Lee, S.

    1994-12-31

    The liquid phase catalytic conversion of syngas to methanol (LPMeOH{trademark}), and syngas to methanol and dimethyl ether (LPDME process) was investigated in a three-phase mini-pilot plant version of a mechanically agitated slurry reactor system. In this reactor system, the catalyst particles in powder form are slurried in the oil phase and this slurry is agitated by a mechanically driven impeller. Syngas reacts in the presence of the methanol synthesis catalyst (Cu/ZnO/Al{sub 2}O{sub 3})-oil slurry to form the product methanol in the LPMeOH process. The productivity of methanol in this process, is adversely affected by the chemical equilibrium limitation. Hence the dual catalytic approach (LPDME process), where the productivity of methanol is enhanced by the co-production of dimethyl ether with methanol, was developed to alleviate the chemical equilibrium limitation. In this LPDME process, syngas reacts in the presence of the methanol synthesis catalyst and the methanol dehydration catalyst ({gamma}-alumina), which are both slurried in the oil phase. The thermodynamics of the liquid phase methanol synthesis process and the liquid phase dimethyl ether process were investigated. The equilibrium conversions of H{sub 2}, CO, and syngas in both the processes are compared for nominally identical operating conditions. The effect of water and CO{sub 2} addition to the feed syngas, and the effect of temperature and pressure on the LPMeOH process and the LPDME process were also compared.

  15. Partial Derivative Games in Thermodynamics: A Cognitive Task Analysis

    ERIC Educational Resources Information Center

    Kustusch, Mary Bridget; Roundy, David; Dray, Tevian; Manogue, Corinne A.

    2014-01-01

    Several studies in recent years have demonstrated that upper-division students struggle with the mathematics of thermodynamics. This paper presents a task analysis based on several expert attempts to solve a challenging mathematics problem in thermodynamics. The purpose of this paper is twofold. First, we highlight the importance of cognitive task…

  16. Thermodynamic Effect of Platinum Addition to beta-NiAl: An Initial Investigation

    NASA Technical Reports Server (NTRS)

    2005-01-01

    An initial investigation was conducted to determine the effect of platinum addition on the activities of aluminum and nickel in beta-NiAl(Pt) over the temperature range 1354 to 1692 K. These measurements were made with a multiple effusion-cell configured mass spectrometer (multi-cell KEMS). The results of this study show that Pt additions act to decreased alpha(Al) and increased the alpha(Ni) in beta-NiAl(Pt) for constant X(sub Ni)/X(sub Al) approx. = 1.13, while at constant X(sub Al) the affect of Pt on Al is greatly reduced. The measured partial enthalpies of mixing indicate Al-atoms have a strong self interaction while Ni- and Pt-atoms in have similar interactions with Al-atoms. Conversely the binding of Ni-atoms in beta-NiAl decreases with Pt addition independent of Al concentration. These initial results prove the technique can be applied to the Ni-Al-Pt system but more activity measurements are required to fully understand the thermodynamics of this system and how Pt additions improved the scaling behavior of nickel-based superalloys. In addition, with the choice of a suitable oxide material for the effusion-cell, the "closed" isothermal nature of the effusion-cell allows the direct investigation of an alloy-oxide equilibrium which resembles the "local-equilibrium" description of the metal-scale interface observed during high temperature oxidation. It is proposed that with an Al(l) + Al2O3(s) experimental reference state together with the route measurement of the relative partial-pressures of Al(g) and Al2O(g) allows the activities of O and Al2O3 to be determined along with the activities of Ni and Al. These measurements provide a direct method of investigating the thermodynamics of the metal-scale interface of a TGO-scale.

  17. Thermodynamics in rotating systems—analysis of selected examples

    NASA Astrophysics Data System (ADS)

    Güémez, J.; Fiolhais, M.

    2014-01-01

    We solve a set of selected exercises on rotational motion requiring a mechanical and thermodynamical analysis. When non-conservative forces or thermal effects are present, a complete study must use the first law of thermodynamics together with Newton’s second law. The latter is here better expressed in terms of an ‘angular’ impulse-momentum equation (Poinsot-Euler equation), or, equivalently, in terms of a ‘rotational’ pseudo-work-energy equation. Thermodynamical aspects in rotational systems, when e.g. frictional forces are present or when there is a variation of the rotational kinetic energy due to internal sources of energy, are discussed.

  18. Thermodynamic Analysis of the Combustion of Metallic Materials

    NASA Technical Reports Server (NTRS)

    Wilson, D. Bruce; Stoltzfus, Joel M.

    2000-01-01

    Two types of computer codes are available to assist in the thermodynamic analysis of metallic materials combustion. One type of code calculates phase equilibrium data and is represented by CALPHAD. The other type of code calculates chemical reaction by the Gordon-McBride code. The first has seen significant application for alloy-phase diagrams, but only recently has it been considered for oxidation systems. The Gordon-McBride code has been applied to the combustion of metallic materials. Both codes are limited by their treatment of non-ideal solutions and the fact they are limited to treating volatile and gaseous species as ideal. This paper examines the significance of these limitations for combustion of metallic materials. In addition, the applicability of linear-free energy relationships for solid-phase oxidation and their possible extension to liquid-phase systems is examined.

  19. Thermodynamic analysis of Thermophotovoltaic Efficiency and Power Density Tradeoffs

    SciTech Connect

    P.F. Baldasara; J.E. Reynolds; G.W. Charache; D.M. DePoy; C.T. Ballinger; T. Donovan; J.M. Borrego

    2000-02-22

    This report presents an assessment of the efficiency and power density limitations of thermophotovoltaic (TPV) energy conversion systems for both ideal (radiative-limited) and practical (defect-limited) systems. Thermodynamics is integrated into the unique process physics of TPV conversion, and used to define the intrinsic tradeoff between power density and efficiency. The results of the analysis reveal that the selection of diode bandgap sets a limit on achievable efficiency well below the traditional Carnot level. In addition it is shown that filter performance dominates diode performance in any practical TPV system and determines the optimum bandgap for a given radiator temperature. It is demonstrated that for a given radiator temperature, lower bandgap diodes enable both higher efficiency and power density when spectral control limitations are included. The goal of this work is to provide a better understanding of the basic system limitations that will enable successful long-term development of TPV energy conversion technology.

  20. THERMODYNAMIC STUDY OF THE NICKEL ADDITION IN ZINC HOT-DIP GALVANIZING BATHS

    SciTech Connect

    Pistofidis, N.; Vourlias, G.

    2010-01-21

    A usual practice during zinc hot-dip galvanizing is the addition of nickel in the liquid zinc which is used to inhibit the Sandelin effect. Its action is due to the fact that the zeta(zeta) phase of the Fe-Zn system is replaced by the TAU(tau) phase of the Fe-Zn-Ni system. In the present work an attempt is made to explain the formation of the TAU phase with thermodynamics. For this reason the Gibbs free energy changes for TAU and zeta phases were calculated. The excess free energy for the system was calculated with the Redlich-Kister polyonyme. From this calculation it was deduced that the Gibbs energy change for the tau phase is negative. As a result its formation is spontaneous.

  1. Nanobubbles around plasmonic nanoparticles: Thermodynamic analysis.

    PubMed

    Lombard, Julien; Biben, Thierry; Merabia, Samy

    2015-04-01

    We describe the dynamics of vapor nanobubbles in water, on the basis of simulations of a hydrodynamics phase-field model. This situation is relevant to recent experiments, where a water nanobubble is generated around a nanoparticle immersed in water, and heated by an intense laser pulse. We emphasize the importance of nanoscale effects in the dynamics of the nanobubble. We first analyze the evolution of the temperature inside the bubble. We show that the temperature drops by hundredths of kelvins in a few picoseconds, just after nanobubble formation. This is the result of the huge drop of the thermal boundary conductance between the nanoparticle and the fluid accompanying vaporization. Subsequently, the temperature inside the vapor is almost homogeneous and the temperature gradient is concentrated in the liquid, whose thermodynamic state locally follows the saturation line. We discuss also the evolution of the pressure inside the vapor nanobubble. We show that nanobubble generation is accompanied by a pressure wave propagating in the liquid at a velocity close to the liquid speed of sound. The internal pressure inside the vapor just after its formation largely exceeds Laplace pressure and quickly relaxes as a result of the damping generated by the viscous forces. All these considerations shed light on the thermodynamics of the nanobubbles generated experimentally. PMID:25974580

  2. Cantera Integration with the Toolbox for Modeling and Analysis of Thermodynamic Systems (T-MATS)

    NASA Technical Reports Server (NTRS)

    Lavelle, Thomas M.; Chapman, Jeffryes W.; May, Ryan D.; Litt, Jonathan S.; Guo, Ten-Huei

    2014-01-01

    NASA Glenn Research Center (GRC) has recently developed a software package for modeling generic thermodynamic systems called the Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS). T-MATS is a library of building blocks that can be assembled to represent any thermodynamic system in the Simulink(Registered TradeMark) (The MathWorks, Inc.) environment. These elements, along with a Newton Raphson solver (also provided as part of the T-MATS package), enable users to create models of a wide variety of systems. The current version of T-MATS (v1.0.1) uses tabular data for providing information about a specific mixture of air, water (humidity), and hydrocarbon fuel in calculations of thermodynamic properties. The capabilities of T-MATS can be expanded by integrating it with the Cantera thermodynamic package. Cantera is an object-oriented analysis package that calculates thermodynamic solutions for any mixture defined by the user. Integration of Cantera with T-MATS extends the range of systems that may be modeled using the toolbox. In addition, the library of elements released with Cantera were developed using MATLAB native M-files, allowing for quicker prototyping of elements. This paper discusses how the new Cantera-based elements are created and provides examples for using T-MATS integrated with Cantera.

  3. Cantera Integration with the Toolbox for Modeling and Analysis of Thermodynamic Systems (T-MATS)

    NASA Technical Reports Server (NTRS)

    Lavelle, Thomas M.; Chapman, Jeffryes W.; May, Ryan D.; Litt, Jonathan S.; Guo, Ten-Huei

    2014-01-01

    NASA Glenn Research Center (GRC) has recently developed a software package for modeling generic thermodynamic systems called the Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS). T-MATS is a library of building blocks that can be assembled to represent any thermodynamic system in the Simulink (The MathWorks, Inc.) environment. These elements, along with a Newton Raphson solver (also provided as part of the T-MATS package), enable users to create models of a wide variety of systems. The current version of T-MATS (v1.0.1) uses tabular data for providing information about a specific mixture of air, water (humidity), and hydrocarbon fuel in calculations of thermodynamic properties. The capabilities of T-MATS can be expanded by integrating it with the Cantera thermodynamic package. Cantera is an object-oriented analysis package that calculates thermodynamic solutions for any mixture defined by the user. Integration of Cantera with T-MATS extends the range of systems that may be modeled using the toolbox. In addition, the library of elements released with Cantera were developed using MATLAB native M-files, allowing for quicker prototyping of elements. This paper discusses how the new Cantera-based elements are created and provides examples for using T-MATS integrated with Cantera.

  4. Thermodynamic and Mechanical Analysis of a Thermomagnetic Rotary Engine

    NASA Astrophysics Data System (ADS)

    Fajar, D. M.; Khotimah, S. N.; Khairurrijal

    2016-08-01

    A heat engine in magnetic system had three thermodynamic coordinates: magnetic intensity ℋ, total magnetization ℳ, and temperature T, where the first two of them are respectively analogous to that of gaseous system: pressure P and volume V. Consequently, Carnot cycle that constitutes the principle of a heat engine in gaseous system is also valid on that in magnetic system. A thermomagnetic rotary engine is one model of it that was designed in the form of a ferromagnetic wheel that can rotates because of magnetization change at Curie temperature. The study is aimed to describe the thermodynamic and mechanical analysis of a thermomagnetic rotary engine and calculate the efficiencies. In thermodynamic view, the ideal processes are isothermal demagnetization, adiabatic demagnetization, isothermal magnetization, and adiabatic magnetization. The values of thermodynamic efficiency depend on temperature difference between hot and cold reservoir. In mechanical view, a rotational work is determined through calculation of moment of inertia and average angular speed. The value of mechanical efficiency is calculated from ratio between rotational work and heat received by system. The study also obtains exergetic efficiency that states the performance quality of the engine.

  5. Study of stability and thermodynamic properties of water-in-diesel nanoemulsion fuels with nano-Al additive

    NASA Astrophysics Data System (ADS)

    Mehta, Rakhi N.; More, Utkarsh; Malek, Naved; Chakraborty, Mousumi; Parikh, Parimal A.

    2015-11-01

    The present work addresses the formation of water-in-diesel (W/D) nanoemulsion by blending different percentages of water along with nano-Al additive in various propositions to enhance the combustion characteristics. The roles of various surfactants such as Sorbitan monooleate (Span 80), Triton X-100, Tetradecyltrimethylammonium bromide, and newly synthesized and characterized dicationic surfactants were discussed based upon their ability to stabilize the nanoemulsions. Surface active properties of the surfactants were determined by measuring their interfacial tension and subsequently by measuring the critical micelle concentration of the surfactants. Triton X-100 was found to be the most efficient surfactant for the current water-in-diesel nanoemulsion as it stabilized the suspensions for more than 8 h. Particle size analysis proved emulsion size to be in the order of nanometer, and zeta potential values were found to have neutral behavior at water-diesel interface. Experimental studies confirmed that that blends W/D [1 % (vol.) water] and W/DA [1 % (vol.) water, 0.1 % (wt.) nano-Al] were thermodynamically stable.

  6. Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS) User's Guide

    NASA Technical Reports Server (NTRS)

    Chapman, Jeffryes W.; Lavelle, Thomas M.; May, Ryan D.; Litt, Jonathan S.; Guo, Ten-Huei

    2014-01-01

    The Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS) software package is an open source, MATLABSimulink toolbox (plug in) that can be used by industry professionals and academics for the development of thermodynamic and controls simulations.

  7. Thermodynamic Cycle Analysis of Magnetohydrodynamic-Bypass Hypersonic Airbreathing Engines

    NASA Technical Reports Server (NTRS)

    Litchford, R. J.; Cole, J. W.; Bityurin, V. A.; Lineberry, J. T.

    2000-01-01

    The prospects for realizing a magnetohydrodynamic (MHD) bypass hypersonic airbreathing engine are examined from the standpoint of fundamental thermodynamic feasibility. The MHD-bypass engine, first proposed as part of the Russian AJAX vehicle concept, is based on the idea of redistributing energy between various stages of the propulsion system flow train. The system uses an MHD generator to extract a portion of the aerodynamic heating energy from the inlet and an MHD accelerator to reintroduce this power as kinetic energy in the exhaust stream. In this way, the combustor entrance Mach number can be limited to a specified value even as the flight Mach number increases. Thus, the fuel and air can be efficiently mixed and burned within a practical combustor length, and the flight Mach number operating envelope can be extended. In this paper, we quantitatively assess the performance potential and scientific feasibility of MHD-bypass engines using a simplified thermodynamic analysis. This cycle analysis, based on a thermally and calorically perfect gas, incorporates a coupled MHD generator-accelerator system and accounts for aerodynamic losses and thermodynamic process efficiencies in the various engin components. It is found that the flight Mach number range can be significantly extended; however, overall performance is hampered by non-isentropic losses in the MHD devices.

  8. Thermodynamic analysis of intracellular ice recrystallization in mouse oocytes.

    PubMed

    Kang, Jonghoon; Purnell, Crystal B; Fisher, Nathan R

    2010-08-01

    In a recent article published in Cryobiology, Seki and Mazur performed kinetic analysis to investigate the physicochemical mechanism of the intracellular ice formation in mouse oocytes subjected to rapid cooling. Based on their results, the authors calculated the activation energy for the ice recrystallization process to be 27.5 kcal/mol. In this letter, we report our analysis of the result in terms of the transition-state theory to show that the process is unfavorable in terms of enthalpy but favorable in terms of entropy accompanying molecular expansions. This report is expected to evoke interests in applying thermodynamics to the investigation of the intracellular ice formation.

  9. Statistically optimal analysis of state-discretized trajectory data from multiple thermodynamic states.

    PubMed

    Wu, Hao; Mey, Antonia S J S; Rosta, Edina; Noé, Frank

    2014-12-01

    We propose a discrete transition-based reweighting analysis method (dTRAM) for analyzing configuration-space-discretized simulation trajectories produced at different thermodynamic states (temperatures, Hamiltonians, etc.) dTRAM provides maximum-likelihood estimates of stationary quantities (probabilities, free energies, expectation values) at any thermodynamic state. In contrast to the weighted histogram analysis method (WHAM), dTRAM does not require data to be sampled from global equilibrium, and can thus produce superior estimates for enhanced sampling data such as parallel/simulated tempering, replica exchange, umbrella sampling, or metadynamics. In addition, dTRAM provides optimal estimates of Markov state models (MSMs) from the discretized state-space trajectories at all thermodynamic states. Under suitable conditions, these MSMs can be used to calculate kinetic quantities (e.g., rates, timescales). In the limit of a single thermodynamic state, dTRAM estimates a maximum likelihood reversible MSM, while in the limit of uncorrelated sampling data, dTRAM is identical to WHAM. dTRAM is thus a generalization to both estimators.

  10. Statistically optimal analysis of state-discretized trajectory data from multiple thermodynamic states

    SciTech Connect

    Wu, Hao; Mey, Antonia S. J. S.; Noé, Frank; Rosta, Edina

    2014-12-07

    We propose a discrete transition-based reweighting analysis method (dTRAM) for analyzing configuration-space-discretized simulation trajectories produced at different thermodynamic states (temperatures, Hamiltonians, etc.) dTRAM provides maximum-likelihood estimates of stationary quantities (probabilities, free energies, expectation values) at any thermodynamic state. In contrast to the weighted histogram analysis method (WHAM), dTRAM does not require data to be sampled from global equilibrium, and can thus produce superior estimates for enhanced sampling data such as parallel/simulated tempering, replica exchange, umbrella sampling, or metadynamics. In addition, dTRAM provides optimal estimates of Markov state models (MSMs) from the discretized state-space trajectories at all thermodynamic states. Under suitable conditions, these MSMs can be used to calculate kinetic quantities (e.g., rates, timescales). In the limit of a single thermodynamic state, dTRAM estimates a maximum likelihood reversible MSM, while in the limit of uncorrelated sampling data, dTRAM is identical to WHAM. dTRAM is thus a generalization to both estimators.

  11. Bingel-Hirsch addition on endohedral metallofullerenes: kinetic versus thermodynamic control.

    PubMed

    Alegret, Núria; Rodríguez-Fortea, Antonio; Poblet, Josep M

    2013-04-15

    An extensive theoretical study of the Bingel-Hirsch addition of bromomalonate on scandium nitride endohedral fullerenes has been carried out. The prototypical and highly symmetrical Sc3N@I(h)-C80, with a structure that satisfies the isolated pentagon rule (IPR), and the non-IPR Sc3N@D3(6140)-C68 fullerene show analogous reaction paths despite the distinct topology of the carbon networks and different rotation freedom of the internal nitride cluster. For the two metallofullerenes, our results predict that the reaction takes place under kinetic control yielding open-cage fulleroids on [6,6] bonds, which is in good agreement with experimental data. The theoretical studies also show that predicting the reactivity of endohedral metallofullerenes is not straightforward and often an accurate analysis of the potential energy surface is required.

  12. One component metal sintering additive for {beta}-SiC based on thermodynamic calculation and experimental observations

    SciTech Connect

    Noviyanto, Alfian; Yoon, Dang-Hyok

    2011-08-15

    Graphical abstract: . Standard Gibbs formation free energies vs. temperature for various metal carbides. The heavy line represents the standard Gibbs free energy for {beta}-SiC. The hatched area denotes the typical liquid phase hot pressing temperature of {beta}-SiC (1973-2123 K). Highlights: {yields} Various metal elements were examined as a sintering additive for {beta}-SiC. {yields} Al and Mg enhanced the density significantly without decomposing {beta}-SiC, as predicted by thermodynamic simulation. {yields} Cr, Fe, Ta, Ti, V and W additives formed metal carbide and/or silicide compounds by decomposing {beta}-SiC. {yields} This approach would be useful for selecting effective sintering additive for high temperature ceramics. -- Abstract: Various types of metals were examined as sintering additives for {beta}-SiC by considering the standard Gibbs formation free energy and vapor pressure under hot pressing conditions (1973-2123 K), particularly for applications in nuclear reactors. Metallic elements having the low long-term activation under neutron irradiation condition, such as Cr, Fe, Ta, Ti, V and W, as well as widely used elements, Al, Mg and B, were considered. The conclusions drawn from thermodynamic considerations were compared with the experimental observations. Al and Mg were found to be effective sintering additives, whereas the others were not due to the formation of metal carbides or silicides from the decomposition of SiC under hot pressing conditions.

  13. A thermodynamic analysis of alternative approaches to chemical looping combustion

    SciTech Connect

    Chakravarthy, Veerathu K; Daw, C Stuart; Pihl, Josh A

    2011-01-01

    In this article, we review and clarify some of the points made by previous authors regarding chemical looping combustion (CLC). While much of the recent interest in chemical looping combustion has been associated with carbon sequestration, our primary interest here is its potential to increase the thermodynamic efficiency of converting fuel chemical energy into useful work. We expand on several points about the details of CLC that we feel have not previously been sufficiently explored, and suggest alternative (and possibly more practical) approaches that exploit some of the same thermodynamic concepts. We illustrate our key points with {First} and {Second} Law analyses of ideal conceptual processes, which in addition to {CLC} also include isothermal, non-equilibrium, preheated combustion and combustion with thermochemical recuperation. Our results suggest that a significant portion of the potential efficiency benefit of CLC might be achieved without the need to handle and transport large quantities of solid oxygen storage material. Exploitation of this fact may lead to higher efficiency approaches for power generation from hydrocarbon fuels combustion.

  14. Thermodynamics of the interaction of the food additive tartrazine with serum albumins: a microcalorimetric investigation.

    PubMed

    Basu, Anirban; Kumar, Gopinatha Suresh

    2015-05-15

    The thermodynamics of the interaction of the food colourant tartrazine with two homologous serum proteins, HSA and BSA, were investigated, employing microcalorimetric techniques. At T=298.15K the equilibrium constants for the tartrazine-BSA and HSA complexation process were evaluated to be (1.92 ± 0.05) × 10(5)M(-1) and (1.04 ± 0.05) × 10(5)M(-1), respectively. The binding was driven by a large negative standard molar enthalpic contribution. The binding was dominated essentially by non-polyelectrolytic forces which remained largely invariant at all salt concentrations. The polyelectrolytic contribution was weak at all salt concentrations and accounted for only 6-18% of the total standard molar Gibbs energy change in the salt concentration range 10-50mM. The negative standard molar heat capacity values, in conjunction with the enthalpy-entropy compensation phenomenon observed, established the involvement of dominant hydrophobic forces in the complexation process. Tartrazine enhanced the stability of both serum albumins against thermal denaturation. PMID:25577062

  15. Thermodynamics of the interaction of the food additive tartrazine with serum albumins: a microcalorimetric investigation.

    PubMed

    Basu, Anirban; Kumar, Gopinatha Suresh

    2015-05-15

    The thermodynamics of the interaction of the food colourant tartrazine with two homologous serum proteins, HSA and BSA, were investigated, employing microcalorimetric techniques. At T=298.15K the equilibrium constants for the tartrazine-BSA and HSA complexation process were evaluated to be (1.92 ± 0.05) × 10(5)M(-1) and (1.04 ± 0.05) × 10(5)M(-1), respectively. The binding was driven by a large negative standard molar enthalpic contribution. The binding was dominated essentially by non-polyelectrolytic forces which remained largely invariant at all salt concentrations. The polyelectrolytic contribution was weak at all salt concentrations and accounted for only 6-18% of the total standard molar Gibbs energy change in the salt concentration range 10-50mM. The negative standard molar heat capacity values, in conjunction with the enthalpy-entropy compensation phenomenon observed, established the involvement of dominant hydrophobic forces in the complexation process. Tartrazine enhanced the stability of both serum albumins against thermal denaturation.

  16. Thermodynamic analysis of the province of Ravenna (Italy).

    PubMed

    Bastianoni, Simone; Marchettini, Nadia; Panzieri, Margherita; Ridolfi, Roberto

    2002-09-01

    This is a thermodynamic analysis of the Province of Ravenna (Italy) and its districts (Ravenna, Faenza and Lugo) and an evaluation of entropy waste production based on a balance sheet of greenhouse gases. The method used is energy analysis. The results show that the Province and Ravenna are characterized by a heavy exploitation of local non renewable resources, Faenza strikes a good balance between economic development and environment conservation and Lugo is less sustainable than the others. The greenhouse gas balance shows that the Province emits 10.5 times the quantity of greenhouse gases that it adsorbs and that the emissions reduction is required in the energy sector, which is responsible for 92% of the total. PMID:12407901

  17. Cosmic acceleration without dark energy: background tests and thermodynamic analysis

    SciTech Connect

    Lima, J.A.S.; Graef, L.L.; Pavón, D.; Basilakos, Spyros E-mail: leilagraef@usp.br E-mail: svasil@academyofathens.gr

    2014-10-01

    A cosmic scenario with gravitationally induced particle creation is proposed. In this model the Universe evolves from an early to a late time de Sitter era, with the recent accelerating phase driven only by the negative creation pressure associated with the cold dark matter component. The model can be interpreted as an attempt to reduce the so-called cosmic sector (dark matter plus dark energy) and relate the two cosmic accelerating phases (early and late time de Sitter expansions). A detailed thermodynamic analysis including possible quantum corrections is also carried out. For a very wide range of the free parameters, it is found that the model presents the expected behavior of an ordinary macroscopic system in the sense that it approaches thermodynamic equilibrium in the long run (i.e., as it nears the second de Sitter phase). Moreover, an upper bound is found for the Gibbons–Hawking temperature of the primordial de Sitter phase. Finally, when confronted with the recent observational data, the current 'quasi'-de Sitter era, as predicted by the model, is seen to pass very comfortably the cosmic background tests.

  18. Thermodynamic analysis of acetic acid steam reforming for hydrogen production

    NASA Astrophysics Data System (ADS)

    Goicoechea, Saioa; Ehrich, Heike; Arias, Pedro L.; Kockmann, Norbert

    2015-04-01

    A thermodynamic analysis of hydrogen generation by acetic acid steam reforming has been carried out with respect to applications in solid oxide fuel cells. The effect of operating parameters on equilibrium composition has been examined focusing especially on hydrogen and carbon monoxide production, which are the fuels in this type of fuel cell. The temperature, steam to acetic acid ratio, and to a lesser extent pressure affect significantly the equilibrium product distribution due to their influence on steam reforming, thermal decomposition and water-gas shift reaction. The study shows that steam reforming of acetic acid with a steam to acetic acid ratio of 2 to 1 is thermodynamically feasible with hydrogen, carbon monoxide and water as the main products at the equilibrium at temperatures higher than 700 °C, and achieving CO/CO2 ratios higher than 1. Thus, it can be concluded that within the operation temperature range of solid oxide fuel cells - between 700 °C and 1000 °C - the production of a gas rich in hydrogen and carbon monoxide is promoted.

  19. Finite-time thermodynamic analysis of the Stirling engine

    SciTech Connect

    Ibrahim, O.M.; Ladas, H.G.

    1995-12-31

    This paper presents a finite-time thermodynamic analysis of the Stirling engine cycle. A lumped-parameter thermodynamic model is used to describe the dynamic behavior of the Stirling engine. The mathematical formulation of this model is based on mass and energy balances with associated heat transfer rate equations. These governing equations are formulated into a set of ordinary differential equations, which are then solved numerically to obtain the dynamic behavior of the Stirling engine. Close inspection of the governing equations reveals that the time to complete on cycle, {tau} and the engine time constant, {tau}{sub c} always appear together in a dimensionless ratio. This ratio, {tau}/{tau}{sub c}, is defined here as the Finite-Time Parameter, FTP. The effects of FTP upon power output and efficiency, are studied. The results show that there exists an optimum power output for a given engine design, based on engine speed and heat-transfer contact time. The results also provide an engineering evaluation procedure to improve the efficiency and power output of Stirling engines.

  20. Thermodynamic analysis of fuels in gas phase: ethanol, gasoline and ethanol - gasoline predicted by DFT method.

    PubMed

    Neto, A F G; Lopes, F S; Carvalho, E V; Huda, M N; Neto, A M J C; Machado, N T

    2015-10-01

    This paper presents a theoretical study using density functional theory to calculate thermodynamics properties of major molecules compounds at gas phase of fuels like gasoline, ethanol, and gasoline-ethanol mixture in thermal equilibrium on temperature range up to 1500 K. We simulated a composition of gasoline mixture with ethanol for a thorough study of thermal energy, enthalpy, Gibbs free energy, entropy, heat capacity at constant pressure with respect to temperature in order to study the influence caused by ethanol as an additive to gasoline. We used semi-empirical computational methods as well in order to know the efficiency of other methods to simulate fuels through this methodology. In addition, the ethanol influence through the changes in percentage fractions of chemical energy released in combustion reaction and the variations on thermal properties for autoignition temperatures of fuels was analyzed. We verified how ethanol reduces the chemical energy released by gasoline combustion and how at low temperatures the gas phase fuels in thermal equilibrium have similar thermodynamic behavior. Theoretical results were compared with experimental data, when available, and showed agreement. Graphical Abstract Thermodynamic analysis of fuels in gas phase.

  1. Thermodynamic analysis of the advanced zero emission power plant

    NASA Astrophysics Data System (ADS)

    Kotowicz, Janusz; Job, Marcin

    2016-03-01

    The paper presents the structure and parameters of advanced zero emission power plant (AZEP). This concept is based on the replacement of the combustion chamber in a gas turbine by the membrane reactor. The reactor has three basic functions: (i) oxygen separation from the air through the membrane, (ii) combustion of the fuel, and (iii) heat transfer to heat the oxygen-depleted air. In the discussed unit hot depleted air is expanded in a turbine and further feeds a bottoming steam cycle (BSC) through the main heat recovery steam generator (HRSG). Flue gas leaving the membrane reactor feeds the second HRSG. The flue gas consist mainly of CO2 and water vapor, thus, CO2 separation involves only the flue gas drying. Results of the thermodynamic analysis of described power plant are presented.

  2. Fundamental Thermodynamic Model for Analysis of Stream Temperature Data

    NASA Astrophysics Data System (ADS)

    Davis, L.; Reiter, M.; Groom, J.; Dent, L.

    2012-12-01

    Stream temperature is a critical aquatic ecosystem parameter and has been extensively studied for many years. Complex models have been built as a way to understand stream temperature dynamics and estimate the magnitude of anthropogenic influences on temperature. These models have proven very useful in estimating the relative contribution of various thermal energy sources to the stream heat budget and how management can alter the heat budget. However, the large number of measured or estimated input parameters required by such models makes their application to the analysis of specific stream temperature data difficult when the necessary input data is not readily available. To gain insight into the physical processes governing stream temperature behavior in forested streams we analyzed data based on fundamental thermodynamic concepts. The dataset we used is from a recent multi-year study on the effects of timber harvest on stream temperature in the Oregon Coast Range. From the hourly temperature data we extracted time-averaged diurnal heating and cooling rates. Examining the data in this context allowed us to qualitatively assess changes in the relative magnitude of stream temperature (T), stream equilibrium temperature (Teq), and effective heat transfer coefficient (h) across years and treatments. A benefit of analyzing the data in this way is that it separates the influence of timber harvest on stream temperature from that of climate variation. To categorize longitudinal temperature behaviors before and after timber harvest we developed a data-event matrix which specifies qualitative constraints (i.e., what is physically possible for T, Teq and h) for a given set of observed stream temperature responses. We then analyzed data from 18 different streams to categorize the temperature response to management. Understanding stream temperature dynamics using fundamental thermodynamic concepts provides insight into the processes governing stream temperature and the pathways

  3. Thermodynamic Analysis and Reduction of Bismuth Oxide by Ethanol

    NASA Astrophysics Data System (ADS)

    Korkmaz, Fatih; Cetinkaya, Senol; Eroglu, Serafettin

    2016-08-01

    In this study, ethanol (C2H5OH) was used as an alternative reducing agent for Bi2O3 because ethanol is renewable, increasingly available, and low in toxicity. Thermodynamic analysis was performed to predict experimental conditions for Bi formation in the Bi2O3-C2H5OH-Ar system at Ar/C2H5OH molar ratio of 10.5. Ar was used as a carrier gas for ethanol. Bi2O3 reduction kinetics was investigated at 600 K to 800 K (327 °C to 527 °C) at Ar flow rate 85 sccm. Ar flow rate was also varied at 600 K and 800 K (327 °C and 527 °C) in order to clarify the mechanism controlling the process. Mass measurements and XRD analyses were carried out to determine the extent of reduction. Fractional conversion increased with time and temperature. Full reduction time decreased from ~180 minutes at 600 K (327 °C) to ~30 minutes at 700 K and 800 K (427 °C and 527 °C). The reduction process was external mass transfer limited ( Q a = 7.2 kJ/mole) above 700 K (427 °C). It was controlled by intrinsic chemical kinetics ( Q a = 54.7 kJ/mole) below 700 K (427 °C). In the mass-transport-controlled regime, the extent of reduction increased with flow rate as predicted by a mass-transport theory. Possible reaction pathways were discussed using the thermodynamic and experimental results.

  4. Stochastic thermodynamics

    NASA Astrophysics Data System (ADS)

    Eichhorn, Ralf; Aurell, Erik

    2014-04-01

    theory for small deviations from equilibrium, in which a general framework is constructed from the analysis of non-equilibrium states close to equilibrium. In a next step, Prigogine and others developed linear irreversible thermodynamics, which establishes relations between transport coefficients and entropy production on a phenomenological level in terms of thermodynamic forces and fluxes. However, beyond the realm of linear response no general theoretical results were available for quite a long time. This situation has changed drastically over the last 20 years with the development of stochastic thermodynamics, revealing that the range of validity of thermodynamic statements can indeed be extended deep into the non-equilibrium regime. Early developments in that direction trace back to the observations of symmetry relations between the probabilities for entropy production and entropy annihilation in non-equilibrium steady states [5-8] (nowadays categorized in the class of so-called detailed fluctuation theorems), and the derivations of the Bochkov-Kuzovlev [9, 10] and Jarzynski relations [11] (which are now classified as so-called integral fluctuation theorems). Apart from its fundamental theoretical interest, the developments in stochastic thermodynamics have experienced an additional boost from the recent experimental progress in fabricating, manipulating, controlling and observing systems on the micro- and nano-scale. These advances are not only of formidable use for probing and monitoring biological processes on the cellular, sub-cellular and molecular level, but even include the realization of a microscopic thermodynamic heat engine [12] or the experimental verification of Landauer's principle in a colloidal system [13]. The scientific program Stochastic Thermodynamics held between 4 and 15 March 2013, and hosted by The Nordic Institute for Theoretical Physics (Nordita), was attended by more than 50 scientists from the Nordic countries and elsewhere, amongst them

  5. A thermodynamic analysis of charged mixed micelles in water.

    PubMed

    Maeda, Hiroshi

    2005-08-25

    A thermodynamic analysis is presented for electrically charged mixed micelles in water on the basis of the Gibbs-Duhem relation proposed by Hall in combination with the information on the degree of counterion binding. The proposed analyses are shown to work well for both ionic/nonionic mixed micelles and those consisting of ionic surfactants of like charges. Conclusions for ionic/nonionic mixed micelles are as follows. (1) The contribution from counterions is significant. (2) In media of low ionic strengths, the counterion concentration varies with the micellar mole fraction of the ionic species x. The dependency of the activity coefficients and the excess free energy on x is significantly influenced by this effect, but it can be corrected to a large extent in terms of the Corrin-Harkins relation. (3) The regular solution theory (RST) is not always valid even when the excess free energy is described well with the RST expression unless the observed range of the micelle composition is wide enough. (4) The RST overestimates x and underestimates the activity coefficient of the ionic species when applied to the mixed micelles to which it is inapplicable. For the ionic mixed micelles consisting of surfactants of like charges, the Lange-Shinoda approach is shown to be consistent with the present analysis in terms of the Gibbs-Duhem relation, but Motomura's approach is found to be not exact but approximate.

  6. Thermodynamic Cycle Analysis of Magnetohydrodynamic-Bypass Airbreathing Hypersonic Engines

    NASA Technical Reports Server (NTRS)

    Litchford, Ron J.; Bityurin, Valentine A.; Lineberry, John T.

    1999-01-01

    Established analyses of conventional ramjet/scramjet performance characteristics indicate that a considerable decrease in efficiency can be expected at off-design flight conditions. This can be explained, in large part, by the deterioration of intake mass flow and limited inlet compression at low flight speeds and by the onset of thrust degradation effects associated with increased burner entry temperature at high flight speeds. In combination, these effects tend to impose lower and upper Mach number limits for practical flight. It has been noted, however, that Magnetohydrodynamic (MHD) energy management techniques represent a possible means for extending the flight Mach number envelope of conventional engines. By transferring enthalpy between different stages of the engine cycle, it appears that the onset of thrust degradation may be delayed to higher flight speeds. Obviously, the introduction of additional process inefficiencies is inevitable with this approach, but it is believed that these losses are more than compensated through optimization of the combustion process. The fundamental idea is to use MHD energy conversion processes to extract and bypass a portion of the intake kinetic energy around the burner. We refer to this general class of propulsion system as an MHD-bypass engine. In this paper, we quantitatively assess the performance potential and scientific feasibility of MHD-bypass airbreathing hypersonic engines using ideal gasdynamics and fundamental thermodynamic principles.

  7. A thermodynamical analysis of rf current drive with fast electrons

    NASA Astrophysics Data System (ADS)

    Bizarro, João P. S.

    2015-08-01

    The problem of rf current drive (CD) by pushing fast electrons with high-parallel-phase-velocity waves, such as lower-hybrid (LH) or electron-cyclotron (EC) waves, is revisited using the first and second laws, the former to retrieve the well-known one-dimensional (1D) steady-state CD efficiency, and the latter to calculate a lower bound for the rate of entropy production when approaching steady state. The laws of thermodynamics are written in a form that explicitly takes care of frictional dissipation and are thus applied to a population of fast electrons evolving under the influence of a dc electric field, rf waves, and collisions while in contact with a thermal, Maxwellian reservoir with a well-defined temperature. Besides the laws of macroscopic thermodynamics, there is recourse to basic elements of kinetic theory only, being assumed a residual dc electric field and a strong rf drive, capable of sustaining in the resonant region, where waves interact with electrons, a raised fast-electron tail distribution, which becomes an essentially flat plateau in the case of the 1D theory for LHCD. Within the 1D model, particularly suited for LHCD as it solely retains fast-electron dynamics in velocity space parallel to the ambient magnetic field, an H theorem for rf CD is also derived, which is written in different forms, and additional physics is recovered, such as the synergy between the dc and rf power sources, including the rf-induced hot conductivity, as well as the equation for electron-bulk heating. As much as possible 1D results are extended to 2D, to account for ECCD by also considering fast-electron velocity-space dynamics in the direction perpendicular to the magnetic field, which leads to a detailed discussion on how the definition of an rf-induced conductivity may depend on whether one works at constant rf current or power. Moreover, working out the collisional dissipated power and entropy-production rate written in terms of the fast-electron distribution, it

  8. A thermodynamical analysis of rf current drive with fast electrons

    SciTech Connect

    Bizarro, João P. S.

    2015-08-15

    The problem of rf current drive (CD) by pushing fast electrons with high-parallel-phase-velocity waves, such as lower-hybrid (LH) or electron-cyclotron (EC) waves, is revisited using the first and second laws, the former to retrieve the well-known one-dimensional (1D) steady-state CD efficiency, and the latter to calculate a lower bound for the rate of entropy production when approaching steady state. The laws of thermodynamics are written in a form that explicitly takes care of frictional dissipation and are thus applied to a population of fast electrons evolving under the influence of a dc electric field, rf waves, and collisions while in contact with a thermal, Maxwellian reservoir with a well-defined temperature. Besides the laws of macroscopic thermodynamics, there is recourse to basic elements of kinetic theory only, being assumed a residual dc electric field and a strong rf drive, capable of sustaining in the resonant region, where waves interact with electrons, a raised fast-electron tail distribution, which becomes an essentially flat plateau in the case of the 1D theory for LHCD. Within the 1D model, particularly suited for LHCD as it solely retains fast-electron dynamics in velocity space parallel to the ambient magnetic field, an H theorem for rf CD is also derived, which is written in different forms, and additional physics is recovered, such as the synergy between the dc and rf power sources, including the rf-induced hot conductivity, as well as the equation for electron-bulk heating. As much as possible 1D results are extended to 2D, to account for ECCD by also considering fast-electron velocity-space dynamics in the direction perpendicular to the magnetic field, which leads to a detailed discussion on how the definition of an rf-induced conductivity may depend on whether one works at constant rf current or power. Moreover, working out the collisional dissipated power and entropy-production rate written in terms of the fast-electron distribution, it

  9. Thermodynamic analysis of phase equilibria in the iron-zirconium system

    SciTech Connect

    Pelton, A.D.; Leibowitz, L.; Blomquist, R.A.

    1992-09-01

    Continuing interest in development of metallic fuels for nuclear reactors has prompted an examination of the phase relations of many of the relevant binary and ternary systems of interest. We performed a thermodynamic analysis and optimization of the Fe-Zr system. Overall reasonably good agreement was found with published diagrams, but some significant changes were required to ensure thermodynamic consistency.

  10. Thermodynamic analysis of phase equilibria in the iron-zirconium system

    SciTech Connect

    Pelton, A.D. ); Leibowitz, L.; Blomquist, R.A. )

    1992-01-01

    Continuing interest in development of metallic fuels for nuclear reactors has prompted an examination of the phase relations of many of the relevant binary and ternary systems of interest. We performed a thermodynamic analysis and optimization of the Fe-Zr system. Overall reasonably good agreement was found with published diagrams, but some significant changes were required to ensure thermodynamic consistency.

  11. T-MATS Toolbox for the Modeling and Analysis of Thermodynamic Systems

    NASA Technical Reports Server (NTRS)

    Chapman, Jeffryes W.

    2014-01-01

    The Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS) is a MATLABSimulink (The MathWorks Inc.) plug-in for creating and simulating thermodynamic systems and controls. The package contains generic parameterized components that can be combined with a variable input iterative solver and optimization algorithm to create complex system models, such as gas turbines.

  12. Thermodynamic analysis of hydration in human serum heme-albumin

    SciTech Connect

    Baroni, Simona; Pariani, Giorgio; Fanali, Gabriella; Longo, Dario; Ascenzi, Paolo; Aime, Silvio; Fasano, Mauro

    2009-07-31

    Ferric human serum heme-albumin (heme-HSA) shows a peculiar nuclear magnetic relaxation dispersion (NMRD) behavior that allows to investigate structural and functional properties. Here, we report a thermodynamic analysis of NMRD profiles of heme-HSA between 20 and 60 {sup o}C to characterize its hydration. NMRD profiles, all showing two Lorentzian dispersions at 0.3 and 60 MHz, were analyzed in terms of modulation of the zero field splitting tensor for the S = {sup 5}/{sub 2} manifold. Values of correlation times for tensor fluctuation ({tau}{sub v}) and chemical exchange of water molecules ({tau}{sub M}) show the expected temperature dependence, with activation enthalpies of -1.94 and -2.46 {+-} 0.2 kJ mol{sup -1}, respectively. The cluster of water molecules located in the close proximity of the heme is progressively reduced in size by increasing the temperature, with {Delta}H = 68 {+-} 28 kJ mol{sup -1} and {Delta}S = 200 {+-} 80 J mol{sup -1} K{sup -1}. These results highlight the role of the water solvent in heme-HSA structure-function relationships.

  13. The experimental investigation and thermodynamic analysis of vortex tubes

    NASA Astrophysics Data System (ADS)

    Celik, Adem; Yilmaz, Mehmet; Kaya, Mehmet; Karagoz, Sendogan

    2016-05-01

    In the present study, it was aimed to produce a fundamental i nformation and to investigate the effects of various design parameters on tube performance characteristics by setting up vortex tube experimental system in order to study the parameters predetermined for the design of vortex tubes and by conducting thermodynamic analysis. According to the findings of experiments, as the mass flow rate of cold flow increases (yc) temperature of cold flow also increases, while the temperature of warm flow increases approximately to yc = 0.6 and then decreases. Increases in inlet pressure, inlet nozzle surface and diameter of the cold outlet orifice increased temperature differences between cold and warm flows. Tube with L/D = 10 showed better performance than with L/D = 20. The finding that irreversibility parameter is very close to critical threshold of irreversibility proved that process in vortex tube is considerably irreversible. Coefficient of performance (COP) values in vortex tube were much lower than other heating and cooling systems. This situation may show that vortex tubes are convenient in the processes where productivity is at the second rate compared to other factors.

  14. A thermodynamic analysis of propagating subcritical cracks with cohesive zones

    NASA Technical Reports Server (NTRS)

    Allen, David H.

    1993-01-01

    The results of the so-called energetic approach to fracture with particular attention to the issue of energy dissipation due to crack propagation are applied to the case of a crack with cohesive zone. The thermodynamic admissibility of subcritical crack growth (SCG) is discussed together with some hypotheses that lead to the derivation of SCG laws. A two-phase cohesive zone model for discontinuous crack growth is presented and its thermodynamics analyzed, followed by an example of its possible application.

  15. Advances in thermodynamics

    SciTech Connect

    Sieniutycz, S. ); Salamon, P. )

    1990-01-01

    This book covers: nonequilibrium thermodynamics for solar energy applications; finite-time thermodynamics as applied to solar power conversion; thermodynamics and economics; exergy analysis; and an analysis of cumulative exergy consumption and exergy losses.

  16. Thermodynamic Modeling and Analysis of Human Stress Response

    NASA Technical Reports Server (NTRS)

    Boregowda, S. C.; Tiwari, S. N.

    1999-01-01

    A novel approach based on the second law of thermodynamics is developed to investigate the psychophysiology and quantify human stress level. Two types of stresses (thermal and mental) are examined. A Unified Stress Response Theory (USRT) is developed under the new proposed field of study called Engineering Psychophysiology. The USRT is used to investigate both thermal and mental stresses from a holistic (human body as a whole) and thermodynamic viewpoint. The original concepts and definitions are established as postulates which form the basis for thermodynamic approach to quantify human stress level. An Objective Thermal Stress Index (OTSI) is developed by applying the second law of thermodynamics to the human thermal system to quantify thermal stress or dis- comfort in the human body. The human thermal model based on finite element method is implemented. It is utilized as a "Computational Environmental Chamber" to conduct series of simulations to examine the human thermal stress responses under different environmental conditions. An innovative hybrid technique is developed to analyze human thermal behavior based on series of human-environment interaction simulations. Continuous monitoring of thermal stress is demonstrated with the help of OTSI. It is well established that the human thermal system obeys the second law of thermodynamics. Further, the OTSI is validated against the experimental data. Regarding mental stress, an Objective Mental Stress Index (OMSI) is developed by applying the Maxwell relations of thermodynamics to the combined thermal and cardiovascular system in the human body. The OMSI is utilized to demonstrate the technique of monitoring mental stress continuously and is validated with the help of series of experimental studies. Although the OMSI indicates the level of mental stress, it provides a strong thermodynamic and mathematical relationship between activities of thermal and cardiovascular systems of the human body.

  17. Thermodynamic analysis of organic Rankine cycle using dry working fluids

    SciTech Connect

    Wang, S.K.; Hung, T.C.

    1998-12-31

    Utilization of waste heat is not economically incentive to the industry once the temperature of the waste heat drops to a certain level. This is primarily due to a low efficiency when converting the energy of the waste heat to some forms of useful power. A Rankine cycle using organic fluids as working fluids, called organic Rankine cycle (ORC), is potentially feasible in recovering low-enthalpy containing heat sources. Nevertheless, an efficient operation of the ORC depends heavily on two factors: working conditions of the cycle and the thermodynamic properties of the working fluids. The main objective of this study is to investigate the effects of these two factors on the performance of the ORC. The working fluids under investigation are: benzene (C{sub 6}H), toluene (C{sub 7}H{sub 8}), p-xylene (C{sub 8}H{sub 10}), R113 and R123. Irreversibility of a system using various working fluids was studied since it represents the energy balance in recovering the waste heat. The study shows that the system efficiency increases as the inlet pressure of the turbine increases regardless of the working fluid used. Among the working fluids under investigation, p-xylene shows the highest efficiency while benzene the lowest. The study also shows that irreversibility depends on the type of heat source. Generally speaking, p-xylene has the lowest irreversibility in recovering a high temperature waste heat while R113 and R123 have a better performance in recovering a low temperature waste heat. In addition, an economic feasibility of ORC using various working fluids is given for ORC`s with commercial capacities.

  18. Heading in the right direction: thermodynamics-based network analysis and pathway engineering.

    PubMed

    Ataman, Meric; Hatzimanikatis, Vassily

    2015-12-01

    Thermodynamics-based network analysis through the introduction of thermodynamic constraints in metabolic models allows a deeper analysis of metabolism and guides pathway engineering. The number and the areas of applications of thermodynamics-based network analysis methods have been increasing in the last ten years. We review recent applications of these methods and we identify the areas that such analysis can contribute significantly, and the needs for future developments. We find that organisms with multiple compartments and extremophiles present challenges for modeling and thermodynamics-based flux analysis. The evolution of current and new methods must also address the issues of the multiple alternatives in flux directionalities and the uncertainties and partial information from analytical methods.

  19. Additional EIPC Study Analysis. Final Report

    SciTech Connect

    Hadley, Stanton W; Gotham, Douglas J.; Luciani, Ralph L.

    2014-12-01

    Between 2010 and 2012 the Eastern Interconnection Planning Collaborative (EIPC) conducted a major long-term resource and transmission study of the Eastern Interconnection (EI). With guidance from a Stakeholder Steering Committee (SSC) that included representatives from the Eastern Interconnection States Planning Council (EISPC) among others, the project was conducted in two phases. Phase 1 involved a long-term capacity expansion analysis that involved creation of eight major futures plus 72 sensitivities. Three scenarios were selected for more extensive transmission- focused evaluation in Phase 2. Five power flow analyses, nine production cost model runs (including six sensitivities), and three capital cost estimations were developed during this second phase. The results from Phase 1 and 2 provided a wealth of data that could be examined further to address energy-related questions. A list of 14 topics was developed for further analysis. This paper brings together the earlier interim reports of the first 13 topics plus one additional topic into a single final report.

  20. Thermodynamic and kinetic analysis of heterogeneous photocatalysis for semiconductor systems.

    PubMed

    Liu, Baoshun; Zhao, Xiujian; Terashima, Chiaki; Fujishima, Akira; Nakata, Kazuya

    2014-05-21

    Since the report of the Honda-Fujishima effect, heterogeneous photocatalysis has attracted much attention around the world because of its potential energy and environmental applications. Although great progresses have been made in recent years, most were focused on preparing highly-active photocatalysts and investigating visible light utilization. In fact, we are still unclear on the thermodynamic and kinetic nature of photocatalysis to date, which sometimes leads to misunderstandings for experimental results. It is timely to give a review and discussion on the thermodynamics and kinetics of photocatalysis, so as to direct future researches. However, there is an absence of a detailed review on this topic until now. In this article, we tried to review and discuss the thermodynamics and kinetics of photocatalysis. We explained the thermodynamic driving force of photocatalysis, and distinguished the functions of light and heat in photocatalysis. The Langmuir-Hinshelwood kinetic model, the ˙OH oxidation mechanism, and the direct-indirect (D-I) kinetic model were reviewed and compared. Some applications of the D-I model to study photocatalytic kinetics were also discussed. The electron transport mode and its importance in photocatalysis were investigated. Finally, the intrinsic relation between the kinetics and the thermodynamics of photocatalytic reactions was discussed.

  1. Thermodynamic analysis of tar reforming through auto-thermal reforming process

    SciTech Connect

    Nurhadi, N. Diniyati, Dahlia; Efendi, M. Ade Andriansyah; Istadi, I.

    2015-12-29

    Fixed bed gasification is a simple and suitable technology for small scale power generation. One of the disadvantages of this technology is producing tar. So far, tar is not utilized yet and being waste that should be treated into a more useful product. This paper presents a thermodynamic analysis of tar conversion into gas producer through non-catalytic auto-thermal reforming technology. Tar was converted into components, C, H, O, N and S, and then reacted with oxidant such as mixture of air or pure oxygen. Thus, this reaction occurred auto-thermally and reached chemical equilibrium. The sensitivity analysis resulted that the most promising process performance occurred at flow rate of air was reached 43% of stoichiometry while temperature of process is 1100°C, the addition of pure oxygen is 40% and preheating of oxidant flow is 250°C. The yield of the most promising process performance between 11.15-11.17 kmol/h and cold gas efficiency was between 73.8-73.9%.The results of this study indicated that thermodynamically the conversion of tar into producer gas through non-catalytic auto-thermal reformingis more promising.

  2. Step-wise addition of disulfide bridge in firefly luciferase controls color shift through a flexible loop: a thermodynamic perspective.

    PubMed

    Nazari, Mahboobeh; Hosseinkhani, Saman; Hassani, Leila

    2013-02-01

    Multi-color bioluminescence is developed using the introduction of single/double disulfide bridges in firefly luciferase. The bioluminescence reaction, which uses luciferin, Mg(2+)-ATP and molecular oxygen to yield an electronically excited oxyluciferin, is carried out by the luciferase and emits visible light. The bioluminescence color of firefly luciferases is determined by the luciferase sequence and assay conditions. It has been proposed that the stability of a protein may increase through the introduction of a disulfide bridge that decreases the configurational entropy of unfolding. Single and double disulfide bridges are introduced into Photinus pyralis firefly luciferase to make separate mutant enzymes with a single/double bridge (C(81)-A(105)C, L(306)C-L(309)C, P(451)C-V(469)C; C(81)-A(105)C/P(451)C-V(469)C, and A(296)C-A(326)C/P(451)C-V(469)C). By introduction of disulfide bridges using site-directed mutagenesis in Photinus pyralis luciferase the color of emitted light was changed to red or kept in different extents. The bioluminescence color shift occurred with displacement of a critical loop in the luciferase structure without any change in green emitter mutants. Thermodynamic analysis revealed that among mutants, L(306)C-L(309)C shows a remarkable stability against urea denaturation and also a considerable increase in kinetic stability and a clear shift in bioluminescence spectra towards red.

  3. Analytical modeling and thermodynamic analysis of robust superhydrophobic surfaces with inverse-trapezoidal microstructures.

    PubMed

    Im, Maesoon; Im, Hwon; Lee, Joo-Hyung; Yoon, Jun-Bo; Choi, Yang-Kyu

    2010-11-16

    A polydimethylsiloxane (PDMS) elastomer surface with perfectly ordered microstructures having an inverse-trapezoidal cross-sectional profile (simply PDMS trapezoids) showed superhydrophobic and transparent characteristics under visible light as reported in our previous work. The addition of a fluoropolymer (Teflon) coating enhances both features and provides oleophobicity. This paper focuses on the analytical modeling of the fabricated PDMS trapezoids structure and thermodynamic analysis based on the Gibbs free energy analysis. Additionally, the wetting characteristics of the fabricated PDMS trapezoids surface before and after the application of the Teflon coating are analytically explained. The Gibbs free energy analysis reveals that, due to the Teflon coating, the Cassie-Baxter state becomes energetically more favorable than the Wenzel state and the contact angle difference between the Cassie-Baxter state and the Wenzel state decreases. These two findings support the robustness of the superhydrophobicity of the fabricated Teflon-coated PDMS trapezoids. This is then verified via the impinging test of a water droplet at a high speed. The dependencies of the design parameters in the PDMS trapezoids on the hydrophobicity are also comprehensively studied through a thermodynamic analysis. Geometrical dependency on the hydrophobicity shows that overhang microstructures do not have a significant influence on the hydrophobicity. In contrast, the intrinsic contact angle of the structural material is most important in determining the apparent contact angle. On the other hand, the experimental results showed that the side angles of the overhangs are critical not for the hydrophobic but for the oleophobic property with liquids of a low surface tension. Understanding of design parameters in the PDMS trapezoids surface gives more information for implementation of superhydrophobic surfaces. PMID:20879754

  4. Analytical modeling and thermodynamic analysis of robust superhydrophobic surfaces with inverse-trapezoidal microstructures.

    PubMed

    Im, Maesoon; Im, Hwon; Lee, Joo-Hyung; Yoon, Jun-Bo; Choi, Yang-Kyu

    2010-11-16

    A polydimethylsiloxane (PDMS) elastomer surface with perfectly ordered microstructures having an inverse-trapezoidal cross-sectional profile (simply PDMS trapezoids) showed superhydrophobic and transparent characteristics under visible light as reported in our previous work. The addition of a fluoropolymer (Teflon) coating enhances both features and provides oleophobicity. This paper focuses on the analytical modeling of the fabricated PDMS trapezoids structure and thermodynamic analysis based on the Gibbs free energy analysis. Additionally, the wetting characteristics of the fabricated PDMS trapezoids surface before and after the application of the Teflon coating are analytically explained. The Gibbs free energy analysis reveals that, due to the Teflon coating, the Cassie-Baxter state becomes energetically more favorable than the Wenzel state and the contact angle difference between the Cassie-Baxter state and the Wenzel state decreases. These two findings support the robustness of the superhydrophobicity of the fabricated Teflon-coated PDMS trapezoids. This is then verified via the impinging test of a water droplet at a high speed. The dependencies of the design parameters in the PDMS trapezoids on the hydrophobicity are also comprehensively studied through a thermodynamic analysis. Geometrical dependency on the hydrophobicity shows that overhang microstructures do not have a significant influence on the hydrophobicity. In contrast, the intrinsic contact angle of the structural material is most important in determining the apparent contact angle. On the other hand, the experimental results showed that the side angles of the overhangs are critical not for the hydrophobic but for the oleophobic property with liquids of a low surface tension. Understanding of design parameters in the PDMS trapezoids surface gives more information for implementation of superhydrophobic surfaces.

  5. Communication: Thermodynamic analysis of critical conditions of polymer adsorption

    SciTech Connect

    Cimino, R.; Neimark, A. V.; Rasmussen, C. J.

    2013-11-28

    Polymer adsorption to solid surfaces is a ubiquitous phenomenon, which has attracted long-lasting attention. Dependent on the competition between the polymer-solid adsorption and polymer-solvent solvation interactions, a chain may assume either 3d solvated conformation when adsorption is weak or 2d adsorbed conformation when adsorption is strong. The transition between these conformations occurring upon variation of adsorption strength is quite sharp, and in the limit of “infinite” chain length, can be treated as a critical phenomenon. We suggest a novel thermodynamic definition of the critical conditions of polymer adsorption from the equality of incremental chemical potentials of adsorbed and free chains. We show with the example of freely jointed Lennard-Jones chains tethered to an adsorbing surface that this new definition provides a link between thermodynamic and geometrical features of adsorbed chains and is in line with classical scaling relationships for the fraction of adsorbed monomers, chain radii of gyration, and free energy.

  6. Thermodynamics of antibody-antigen interaction revealed by mutation analysis of antibody variable regions.

    PubMed

    Akiba, Hiroki; Tsumoto, Kouhei

    2015-07-01

    Antibodies (immunoglobulins) bind specific molecules (i.e. antigens) with high affinity and specificity. In order to understand their mechanisms of recognition, interaction analysis based on thermodynamic and kinetic parameters, as well as structure determination is crucial. In this review, we focus on mutational analysis which gives information about the role of each amino acid residue in antibody-antigen interaction. Taking anti-hen egg lysozyme antibodies and several anti-small molecule antibodies, the energetic contribution of hot-spot and non-hot-spot residues is discussed in terms of thermodynamics. Here, thermodynamics of the contribution from aromatic, charged and hydrogen bond-forming amino acids are discussed, and their different characteristics have been elucidated. The information gives fundamental understanding of the antibody-antigen interaction. Furthermore, the consequences of antibody engineering are analysed from thermodynamic viewpoints: humanization to reduce immunogenicity and rational design to improve affinity. Amino acid residues outside hot-spots in the interface play important roles in these cases, and thus thermodynamic and kinetic parameters give much information about the antigen recognition. Thermodynamic analysis of mutant antibodies thus should lead to advanced strategies to design and select antibodies with high affinity.

  7. Acid Rain Analysis by Standard Addition Titration.

    ERIC Educational Resources Information Center

    Ophardt, Charles E.

    1985-01-01

    The standard addition titration is a precise and rapid method for the determination of the acidity in rain or snow samples. The method requires use of a standard buret, a pH meter, and Gran's plot to determine the equivalence point. Experimental procedures used and typical results obtained are presented. (JN)

  8. The role of material flexibility on the drying transition of water between hydrophobic objects: A thermodynamic analysis

    SciTech Connect

    Altabet, Y. Elia; Debenedetti, Pablo G.

    2014-11-14

    Liquid water confined between hydrophobic objects of sufficient size becomes metastable with respect to its vapor at separations smaller than a critical drying distance. Macroscopic thermodynamic arguments predicting this distance have been restricted to the limit of perfectly rigid confining materials. However, no material is perfectly rigid and it is of interest to account for this fact in the thermodynamic analysis. We present a theory that combines the current macroscopic theory with the thermodynamics of elasticity to derive an expression for the critical drying distance for liquids confined between flexible materials. The resulting expression is the sum of the well-known drying distance for perfectly rigid confining materials and a new term that accounts for flexibility. Thermodynamic arguments show that this new term is necessarily positive, meaning that flexibility increases the critical drying distance. To study the expected magnitude and scaling behavior of the flexible term, we consider the specific case of water and present an example of drying between thin square elastic plates that are simply supported along two opposite edges and free at the remaining two. We find that the flexible term can be the same order of magnitude or greater than the rigid solution for materials of biological interest at ambient conditions. In addition, we find that when the rigid solution scales with the characteristic size of the immersed objects, the flexible term is independent of size and vice versa. Thus, the scaling behavior of the overall drying distance will depend on the relative weights of the rigid and flexible contributions.

  9. Electrophoretic analysis of Allium alien addition lines.

    PubMed

    Peffley, E B; Corgan, J N; Horak, K E; Tanksley, S D

    1985-12-01

    Meiotic pairing in an interspecific triploid of Allium cepa and A. fistulosum, 'Delta Giant', exhibits preferential pairing between the two A. cepa genomes, leaving the A. fistulosum genome as univalents. Multivalent pairing involving A. fistulosum chromosomes occurs at a low level, allowing for recombination between the genomes. Ten trisomies were recovered from the backcross of 'Delta Giant' x A. cepa cv., 'Temprana', representing a minimum of four of the eight possible alien addition lines. The alien addition lines possessed different A. fistulosum enzyme markers. Those markers, Adh-1, Idh-1 and Pgm-1 reside on different A. fistulosum chromosomes, whereas Pgi-1 and Idh-1 may be linked. Diploid, trisomic and hyperploid progeny were recovered that exhibited putative pink root resistance. The use of interspecific plants as a means to introgress A. fistulosum genes into A. cepa appears to be successful at both the trisomic and the diploid levels. If introgression can be accomplished using an interspecific triploid such as 'Delta Giant' to generate fertile alien addition lines and subsequent fertile diploids, or if introgression can be accomplished directly at the diploid level, this will have accomplished gene flow that has not been possible at the interspecific diploid level.

  10. Additives

    NASA Technical Reports Server (NTRS)

    Smalheer, C. V.

    1973-01-01

    The chemistry of lubricant additives is discussed to show what the additives are chemically and what functions they perform in the lubrication of various kinds of equipment. Current theories regarding the mode of action of lubricant additives are presented. The additive groups discussed include the following: (1) detergents and dispersants, (2) corrosion inhibitors, (3) antioxidants, (4) viscosity index improvers, (5) pour point depressants, and (6) antifouling agents.

  11. Parallel thermodynamic analysis of duplexes on oligodeoxyribonucleotide microchips.

    SciTech Connect

    Fotin, A. V.; Drobyshev, A. L.; Proudnikov, D. Y.; Perov, A. N.; Mirzabekov, A. D.; Center for Mechanistic Biology and Biotechnology; Engelhardt Inst. of Molecular Biology

    1998-03-15

    A microchip method has been developed for massive and parallel thermodynamic analyses of DNA duplexes. Fluorescently labeled oligonucleotides were hybridized with oligonucleotides immobilized in the 100 x 100 x 20 mum gel pads of the microchips. The equilibrium melting curves for all microchip duplexes were measured in real time in parallel for all microchip duplexes. Thermodynamic data for perfect and mismatched duplexes that were obtained using the microchip method directly correlated with data obtained in solution. Fluorescent labels or longer linkers between the gel and the oligonucleotides appeared to have no significant effect on duplex stability. Extending the immobilized oligonucleotides with a four-base mixture from the 3'-end or one or two universal bases (5-nitroindole) from the 3'- and/or 5'- end increased the stabilities of their duplexes. These extensions were applied to increase the stabilities of the duplexes formed with short oligonucleotides in microchips, to significantly lessen the differences in melting curves of the AT- and GC-rich duplexes, and to improve discrimination of perfect duplexes from those containing poorly recognized terminal mismatches. This study explored a way to increase the efficiency of sequencing by hybridization on oligonucleotide microchips.

  12. Thermodynamic analysis of sorption isotherms of cassava (Manihot esculenta).

    PubMed

    Koua, Blaise Kamenan; Koffi, Paul Magloire Ekoun; Gbaha, Prosper; Toure, Siaka

    2014-09-01

    Sorption isotherms of cassava were determined experimentally using a static gravimetric method at 30, 45 and 60 °C and within the range of 0.10-0.90 water activity. At a constant water activity, equilibrium moisture content decreased with increasing temperature. The equilibrium moisture content increased with increasing water activity at a given temperature. The experimental results were modelled using seven sorption models using non-linear regression technique. Results demonstrated that the GAB model adequately predicted equilibrium moisture content of cassava for the range of temperatures and water activities studied. The thermodynamic functions such as net isosteric heat of sorption, differential entropy of sorption, net integral enthalpy and entropy were evaluated to provide an understanding of the properties of water and energy requirements associated with the sorption behaviour. Net isosteric heat and differential entropy decreased with increasing equilibrium moisture content. The net integral enthalpy decreased while net integral entropy increased with increasing equilibrium moisture content. Net integral entropy was negative in value. All thermodynamic functions were adequately characterised by a power law model. The point of maximum stability was found between 0.053 and 0.154 kg water/kg db for cassava. PMID:25190827

  13. 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.

  14. Thermodynamic and structural analysis of microtubule assembly: the role of GTP hydrolysis.

    PubMed

    Vulevic, B; Correia, J J

    1997-03-01

    that assembly with GTP/2 M glycerol and with taxol is consistent with conformational rearrangements in 3-6% of the total amino acids in the heterodimer. In addition, taxol binding contributes to the thermodynamics of the overall process by reducing the delta H degree and delta S degree for microtubule assembly. In the presence of GMPCPP or GMPCP, tubulin subunits associate with extensive conformational rearrangement, corresponding to 10% and 26% of the total amino acids in the heterodimer, respectively, which gives rise to a large loss of configurational entropy. An alternative, and probably preferable, interpretation of these data is that, especially with GMPCP-tubulin, additional isomerization or protonation events are induced by the presence of the methylene moiety and linked to microtubule assembly. Structural analysis shows that GTP hydrolysis is not required for sheet closure into a microtubule cylinder, but only increases the probability of this event occurring. Sheet extensions and sheet polymers appear to have a similar average length under various conditions, suggesting that the minimum cooperative unit for closure of sheets into a microtubule cylinder is approximately 400 nm long. Because of their low level of occurrence, sheets are not expected to significantly affect the thermodynamics of assembly.

  15. Liquid Nitrogen (Oxygen Simulant) Thermodynamic Vent System Test Data Analysis

    NASA Technical Reports Server (NTRS)

    Hedayat, A.; Nelson, S. L.; Hastings, L. J.; Flachbart, R. H.; Tucker, S. P.

    2005-01-01

    In designing systems for the long-term storage of cryogens in low-gravity (space) environments, one must consider the effects of thermal stratification on tank pressure that will occur due to environmental heat leaks. During low-gravity operations, a Thermodynamic Vent System (TVS) concept is expected to maintain tank pressure without propellant resettling. A series of TVS tests was conducted at NASA Marshall Space Flight Center (MSFC) using liquid nitrogen (LN2) as a liquid oxygen (LO2) simulant. The tests were performed at tank til1 levels of 90%, 50%, and 25%, and with a specified tank pressure control band. A transient one-dimensional TVS performance program is used to analyze and correlate the test data for all three fill levels. Predictions and comparisons of ullage pressure and temperature and bulk liquid saturation pressure and temperature with test data are presented.

  16. Liquid Nitrogen (Oxygen Simulant) Thermodynamic Vent System Test Data Analysis

    NASA Astrophysics Data System (ADS)

    Hedayat, A.; Nelson, S. L.; Hastings, L. J.; Flachbart, R. H.; Tucker, S. P.

    2006-04-01

    In designing systems for the long-term storage of cryogens in low-gravity (space) environments, one must consider the effects of thermal stratification on tank pressure that will occur due to environmental heat leaks. During low-gravity operations, a Thermodynamic Vent System (TVS) concept is expected to maintain tank pressure without propellant resettling. A series of TVS tests was conducted at NASA Marshall Space Flight Center (MSFC) using liquid nitrogen (LN2) as a liquid oxygen (LO2) simulant. The tests were performed at tank fill levels of 90%, 50%, and 25%, and with a specified tank pressure control band. A transient one-dimensional TVS performance program is used to analyze and correlate the test data for all three fill levels. Predictions and comparisons of ullage pressure and temperature and bulk liquid saturation pressure and temperature with test data are presented.

  17. Econophysics and bio-chemical engineering thermodynamics: The exergetic analysis of a municipality

    NASA Astrophysics Data System (ADS)

    Lucia, Umberto

    2016-11-01

    Exergy is a fundamental quantity because it allows us to obtain information on the useful work obtainable in a process. The analyses of irreversibility are important not only in the design and development of the industrial devices, but also in fundamental thermodynamics and in the socio-economic analysis of municipality. Consequently, the link between entropy and exergy is discussed in order to link econophysics to the bio-chemical engineering thermodynamics. Last, this link holds to the fundamental role of fluxes and to the exergy exchanged in the interaction between the system and its environment. The result consists in a thermodynamic approach to the analysis of the unavailability of the economic, productive or social systems. The unavailability is what the system cannot use in relation to its internal processes. This quantity result is interesting also as a support to public manager for economic decisions. Here, the Alessandria Municipality is analyzed in order to highlight the application of the theoretical results.

  18. Thermodynamic analysis of lignocellulosic biofuel production via a biochemical process: guiding technology selection and research focus.

    PubMed

    Sohel, M Imroz; Jack, Michael W

    2011-02-01

    The aim of this paper is to present an exergy analysis of bioethanol production process from lignocellulosic feedstock via a biochemical process to asses the overall thermodynamic efficiency and identify the main loss processes. The thermodynamic efficiency of the biochemical process was found to be 35% and the major inefficiencies of this process were identified as: the combustion of lignin for process heat and power production and the simultaneous scarification and co-fermentation process accounting for 67% and 27% of the lost exergy, respectively. These results were also compared with a previous analysis of a thermochemical process for producing biofuel. Despite fundamental differences, the biochemical and thermochemical processes considered here had similar levels of thermodynamic efficiency. Process heat and power production was the major contributor to exergy loss in both of the processes. Unlike the thermochemical process, the overall efficiency of the biochemical process largely depends on how the lignin is utilized. PMID:21036607

  19. Thermodynamic analysis of lignocellulosic biofuel production via a biochemical process: guiding technology selection and research focus.

    PubMed

    Sohel, M Imroz; Jack, Michael W

    2011-02-01

    The aim of this paper is to present an exergy analysis of bioethanol production process from lignocellulosic feedstock via a biochemical process to asses the overall thermodynamic efficiency and identify the main loss processes. The thermodynamic efficiency of the biochemical process was found to be 35% and the major inefficiencies of this process were identified as: the combustion of lignin for process heat and power production and the simultaneous scarification and co-fermentation process accounting for 67% and 27% of the lost exergy, respectively. These results were also compared with a previous analysis of a thermochemical process for producing biofuel. Despite fundamental differences, the biochemical and thermochemical processes considered here had similar levels of thermodynamic efficiency. Process heat and power production was the major contributor to exergy loss in both of the processes. Unlike the thermochemical process, the overall efficiency of the biochemical process largely depends on how the lignin is utilized.

  20. Fragment growing induces conformational changes in acetylcholine-binding protein: a structural and thermodynamic analysis.

    PubMed

    Edink, Ewald; Rucktooa, Prakash; Retra, Kim; Akdemir, Atilla; Nahar, Tariq; Zuiderveld, Obbe; van Elk, René; Janssen, Elwin; van Nierop, Pim; van Muijlwijk-Koezen, Jacqueline; Smit, August B; Sixma, Titia K; Leurs, Rob; de Esch, Iwan J P

    2011-04-13

    Optimization of fragment hits toward high-affinity lead compounds is a crucial aspect of fragment-based drug discovery (FBDD). In the current study, we have successfully optimized a fragment by growing into a ligand-inducible subpocket of the binding site of acetylcholine-binding protein (AChBP). This protein is a soluble homologue of the ligand binding domain (LBD) of Cys-loop receptors. The fragment optimization was monitored with X-ray structures of ligand complexes and systematic thermodynamic analyses using surface plasmon resonance (SPR) biosensor analysis and isothermal titration calorimetry (ITC). Using site-directed mutagenesis and AChBP from different species, we find that specific changes in thermodynamic binding profiles, are indicative of interactions with the ligand-inducible subpocket of AChBP. This study illustrates that thermodynamic analysis provides valuable information on ligand binding modes and is complementary to affinity data when guiding rational structure- and fragment-based discovery approaches. PMID:21322593

  1. Thermodynamic investigations of nitroxoline sublimation by simultaneous DSC-FTIR method and isothermal TG analysis.

    PubMed

    Gao, Gau-Yi; Lin, Shan-Yang

    2010-01-01

    To investigate the physicochemical characteristics, thermodynamics, possible sublimation process and kinetics of nitroxoline, differential scanning calorimetry (DSC), isothermal thermogravimetry (TG), and Fourier transform infrared (FTIR) microspectroscopy equipped with a micro hot-stage of DSC microscopy assembly (simultaneous DSC-FTIR method) were used. The DSC result indicates that nitroxoline exhibited a sharp endothermic peak at 182 degrees C with enthalpy of 103.1 J/g due to the melting point of nitroxoline. A sublimation behavior of nitroxoline was found from 129 degrees C by gradual weight loss in TG curve. However, the nonisothermal DSC-FTIR method reveals that the temperature at 95 degrees C was the onset temperature of nitroxoline sublimation. A significant difference between DSC-FTIR method and TG analysis suggests that the simultaneous DSC-FTIR method was more sensitive than that of the TG analysis to detect the beginning temperature of nitroxoline sublimation. The sublimation kinetics of nitroxoline determined by isothermal TG analysis evidenced that the zero-order kinetics was followed over the sublimation time. The sublimation enthalpy correction was also carried out by a group additivity approach for the estimation of heat capacity. The enthalpy of nitroxoline sublimation estimated was 86.14 KJ/mol at 298.15 K.

  2. Analysis of thermodynamics of two-fuel power unit integrated with a carbon dioxide separation plant

    NASA Astrophysics Data System (ADS)

    Kotowicz, Janusz; Bartela, Łukasz; Mikosz, Dorota

    2014-12-01

    The article presents the results of thermodynamic analysis of the supercritical coal-fired power plant with gross electrical output of 900 MW and a pulverized coal boiler. This unit is integrated with the absorption-based CO2 separation installation. The heat required for carrying out the desorption process, is supplied by the system with the gas turbine. Analyses were performed for two variants of the system. In the first case, in addition to the gas turbine there is an evaporator powered by exhaust gases from the gas turbine expander. The second expanded variant assumes the application of gas turbine combined cycle with heat recovery steam generator and backpressure steam turbine. The way of determining the efficiency of electricity generation and other defined indicators to assess the energy performance of the test block was showed. The size of the gas turbine system was chosen because of the need for heat for the desorption unit, taking the value of the heat demand 4 MJ/kg CO2. The analysis results obtained for the both variants of the installation with integrated CO2 separation plant were compared with the results of the analysis of the block where the separation is not conducted.

  3. Thermodynamic, energy efficiency, and power density analysis of reverse electrodialysis power generation with natural salinity gradients.

    PubMed

    Yip, Ngai Yin; Vermaas, David A; Nijmeijer, Kitty; Elimelech, Menachem

    2014-05-01

    Reverse electrodialysis (RED) can harness the Gibbs free energy of mixing when fresh river water flows into the sea for sustainable power generation. In this study, we carry out a thermodynamic and energy efficiency analysis of RED power generation, and assess the membrane power density. First, we present a reversible thermodynamic model for RED and verify that the theoretical maximum extractable work in a reversible RED process is identical to the Gibbs free energy of mixing. Work extraction in an irreversible process with maximized power density using a constant-resistance load is then examined to assess the energy conversion efficiency and power density. With equal volumes of seawater and river water, energy conversion efficiency of ∼ 33-44% can be obtained in RED, while the rest is lost through dissipation in the internal resistance of the ion-exchange membrane stack. We show that imperfections in the selectivity of typical ion exchange membranes (namely, co-ion transport, osmosis, and electro-osmosis) can detrimentally lower efficiency by up to 26%, with co-ion leakage being the dominant effect. Further inspection of the power density profile during RED revealed inherent ineffectiveness toward the end of the process. By judicious early discontinuation of the controlled mixing process, the overall power density performance can be considerably enhanced by up to 7-fold, without significant compromise to the energy efficiency. Additionally, membrane resistance was found to be an important factor in determining the power densities attainable. Lastly, the performance of an RED stack was examined for different membrane conductivities and intermembrane distances simulating high performance membranes and stack design. By thoughtful selection of the operating parameters, an efficiency of ∼ 37% and an overall gross power density of 3.5 W/m(2) represent the maximum performance that can potentially be achieved in a seawater-river water RED system with low

  4. Theoretical and Experimental Investigation of Thermodynamics and Kinetics of Thiol-Michael Addition Reactions: A Case Study of Reversible Fluorescent Probes for Glutathione Imaging in Single Cells.

    PubMed

    Chen, Jianwei; Jiang, Xiqian; Carroll, Shaina L; Huang, Jia; Wang, Jin

    2015-12-18

    Density functional theory (DFT) was applied to study the thermodynamics and kinetics of reversible thiol-Michael addition reactions. M06-2X/6-31G(d) with the SMD solvation model can reliably predict the Gibbs free energy changes (ΔG) of thiol-Michael addition reactions with an error of less than 1 kcal·mol(-1) compared with the experimental benchmarks. Taking advantage of this computational model, the first reversible reaction-based fluorescent probe was developed that can monitor the changes in glutathione levels in single living cells.

  5. Thermodynamic analysis of cascade microcryocoolers with low pressure ratios

    SciTech Connect

    Radebaugh, Ray

    2014-01-29

    The vapor-compression cycle for refrigeration near ambient temperature achieves high efficiency because the isenthalpic expansion of the condensed liquid is a rather efficient process. However, temperatures are limited to about 200 K with a single-stage system. Temperatures down to 77 K are possible with many stages. In the case of microcryocoolers using microcompressors, pressure ratios are usually limited to about 6 or less. As a result, even more stages are required to reach 77 K. If the microcompressors can be fabricated with low-cost wafer-level techniques, then the use of many stages with separate compressors may become a viable option for achieving temperatures of 77 K with high efficiency. We analyze the ideal thermodynamic efficiency of a cascade Joule-Thomson system for various temperatures down to 77 K and with low pressure ratios. About nine stages are required for 77 K, but fewer stages are also analyzed for operation at higher temperatures. For 77 K, an ideal second-law efficiency of 83 % of Carnot is possible with perfect recuperative heat exchangers and 65 % of Carnot is possible with no recuperative heat exchangers. The results are compared with calculated efficiencies in mixed-refrigerant cryocoolers over the range of 77 K to 200 K. Refrigeration at intermediate temperatures is also available. The use of single-component fluids in each of the stages is expected to eliminate the problem of pulsating flow and temperature oscillations experienced in microcryocoolers using mixed refrigerants.

  6. Cytochrome c Oxidase Inhibition by Anesthetics: Thermodynamic Analysis

    NASA Astrophysics Data System (ADS)

    Vanderkooi, Garret; Chazotte, Brad

    1982-06-01

    The thermodynamic parameters that characterize the inhibition of cytochrome c oxidase activity, in rat liver submitochondrial particles, by n-butanol, tetracaine, and dibucaine were obtained. Three equilibria were assumed in order to account for the data: for the interaction of inhibitor with the native state of the enzyme, for the interaction of inhibitor with the thermally (reversibly) denatured state, and for the change between the native and thermally denatured states. Inhibition results from interaction with both the native and denatured states but, because the interaction is stronger with the denatured than with the native state, the native/denatured equilibrium is shifted to the right by the anesthetics. The enthalpies of interaction are -2.3, -4.7, and 3.7 kcal/mol (1 cal = 4.18 J) for the native state and -10, -6, and -14 kcal/mol for the denatured state, for n-butanol, tetracaine, and dibucaine, respectively. These values are much smaller than the previous estimates obtained by using the assumption that anesthetics interact only with the thermally denatured state of enzymes (e.g., -81 kcal/mol for tetracaine inhibition of luciferase). Our results suggest that local anesthetics inhibit enzyme activity by causing a reversible perturbation of protein conformation. The magnitude of the perturbation is much smaller (in energetic terms) than that which accompanies thermal denaturation.

  7. Liquid Nitrogen (Oxygen Simulent) Thermodynamic Venting System Test Data Analysis

    NASA Technical Reports Server (NTRS)

    Hedayat, A.; Nelson, S. L.; Hastings, L. J.; Flachbart, R. H.; Tucker, S. P.

    2005-01-01

    In designing systems for the long-term storage of cryogens in low gravity space environments, one must consider the effects of thermal stratification on excessive tank pressure that will occur due to environmental heat leakage. During low gravity operations, a Thermodynamic Venting System (TVS) concept is expected to maintain tank pressure without propellant resettling. The TVS consists of a recirculation pump, Joule-Thomson (J-T) expansion valve, and a parallel flow concentric tube heat exchanger combined with a longitudinal spray bar. Using a small amount of liquid extracted by the pump and passing it though the J-T valve, then through the heat exchanger, the bulk liquid and ullage are cooled, resulting in lower tank pressure. A series of TVS tests were conducted at the Marshall Space Flight Center using liquid nitrogen as a liquid oxygen simulant. The tests were performed at fill levels of 90%, 50%, and 25% with gaseous nitrogen and helium pressurants, and with a tank pressure control band of 7 kPa. A transient one-dimensional model of the TVS is used to analyze the data. The code is comprised of four models for the heat exchanger, the spray manifold and injector tubes, the recirculation pump, and the tank. The TVS model predicted ullage pressure and temperature and bulk liquid saturation pressure and temperature are compared with data. Details of predictions and comparisons with test data regarding pressure rise and collapse rates will be presented in the final paper.

  8. Thermodynamic analysis of shark skin texture surfaces for microchannel flow

    NASA Astrophysics Data System (ADS)

    Yu, Hai-Yan; Zhang, Hao-Chun; Guo, Yang-Yu; Tan, He-Ping; Li, Yao; Xie, Gong-Nan

    2016-09-01

    The studies of shark skin textured surfaces in flow drag reduction provide inspiration to researchers overcoming technical challenges from actual production application. In this paper, three kinds of infinite parallel plate flow models with microstructure inspired by shark skin were established, namely blade model, wedge model and the smooth model, according to cross-sectional shape of microstructure. Simulation was carried out by using FLUENT, which simplified the computation process associated with direct numeric simulations. To get the best performance from simulation results, shear-stress transport k-omega turbulence model was chosen during the simulation. Since drag reduction mechanism is generally discussed from kinetics point of view, which cannot interpret the cause of these losses directly, a drag reduction rate was established based on the second law of thermodynamics. Considering abrasion and fabrication precision in practical applications, three kinds of abraded geometry models were constructed and tested, and the ideal microstructure was found to achieve best performance suited to manufacturing production on the basis of drag reduction rate. It was also believed that bionic shark skin surfaces with mechanical abrasion may draw more attention from industrial designers and gain wide applications with drag-reducing characteristics.

  9. Thermodynamics Analysis of Refinery Sludge Gasification in Adiabatic Updraft Gasifier

    PubMed Central

    Ahmed, Reem; Sinnathambi, Chandra M.; Eldmerdash, Usama; Subbarao, Duvvuri

    2014-01-01

    Limited information is available about the thermodynamic evaluation for biomass gasification process using updraft gasifier. Therefore, to minimize errors, the gasification of dry refinery sludge (DRS) is carried out in adiabatic system at atmospheric pressure under ambient air conditions. The objectives of this paper are to investigate the physical and chemical energy and exergy of product gas at different equivalent ratios (ER). It will also be used to determine whether the cold gas, exergy, and energy efficiencies of gases may be maximized by using secondary air injected to gasification zone under various ratios (0, 0.5, 1, and 1.5) at optimum ER of 0.195. From the results obtained, it is indicated that the chemical energy and exergy of producer gas are magnified by 5 and 10 times higher than their corresponding physical values, respectively. The cold gas, energy, and exergy efficiencies of DRS gasification are in the ranges of 22.9–55.5%, 43.7–72.4%, and 42.5–50.4%, respectively. Initially, all 3 efficiencies increase until they reach a maximum at the optimum ER of 0.195; thereafter, they decline with further increase in ER values. The injection of secondary air to gasification zone is also found to increase the cold gas, energy, and exergy efficiencies. A ratio of secondary air to primary air of 0.5 is found to be the optimum ratio for all 3 efficiencies to reach the maximum values. PMID:24672368

  10. Thermodynamic Analysis of Thermal Hysteresis: Mechanistic Insights into Biological Antifreezes.

    PubMed

    Wang, Sen; Amornwittawat, Natapol; Wen, Xin

    2012-10-01

    Antifreeze proteins (AFPs) bind to ice crystal surfaces and thus inhibit the ice growth. The mechanism for how AFPs suppress freezing is commonly modeled as an adsorption-inhibition process by the Gibbs-Thomson effect. Here we develop an improved adsorption-inhibition model for AFP action based on the thermodynamics of impurity adsorption on the crystal surfaces. We demonstrate the derivation of a realistic relationship between surface protein coverage and the protein concentration. We show that the improved model provides a quantitatively better fit to the experimental antifreeze activities of AFPs from distinct structural classes, including fish and insect AFPs, in a wide range of concentrations. Our theoretical results yielded the adsorption coefficients of the AFPs on ice, suggesting that, despite the distinct difference in their antifreeze activities and structures, the affinities of the AFPs to ice are very close and the mechanism of AFP action is a kinetically controlled, reversible process. The applications of the model to more complex systems along with its potential limitations are also discussed.

  11. Thermodynamic Analysis of Thermal Hysteresis: Mechanistic Insights into Biological Antifreezes

    PubMed Central

    Wang, Sen; Amornwittawat, Natapol; Wen, Xin

    2012-01-01

    Antifreeze proteins (AFPs) bind to ice crystal surfaces and thus inhibit the ice growth. The mechanism for how AFPs suppress freezing is commonly modeled as an adsorption-inhibition process by the Gibbs-Thomson effect. Here we develop an improved adsorption-inhibition model for AFP action based on the thermodynamics of impurity adsorption on the crystal surfaces. We demonstrate the derivation of a realistic relationship between surface protein coverage and the protein concentration. We show that the improved model provides a quantitatively better fit to the experimental antifreeze activities of AFPs from distinct structural classes, including fish and insect AFPs, in a wide range of concentrations. Our theoretical results yielded the adsorption coefficients of the AFPs on ice, suggesting that, despite the distinct difference in their antifreeze activities and structures, the affinities of the AFPs to ice are very close and the mechanism of AFP action is a kinetically controlled, reversible process. The applications of the model to more complex systems along with its potential limitations are also discussed. PMID:22822266

  12. Thermodynamics analysis of refinery sludge gasification in adiabatic updraft gasifier.

    PubMed

    Ahmed, Reem; Sinnathambi, Chandra M; Eldmerdash, Usama; Subbarao, Duvvuri

    2014-01-01

    Limited information is available about the thermodynamic evaluation for biomass gasification process using updraft gasifier. Therefore, to minimize errors, the gasification of dry refinery sludge (DRS) is carried out in adiabatic system at atmospheric pressure under ambient air conditions. The objectives of this paper are to investigate the physical and chemical energy and exergy of product gas at different equivalent ratios (ER). It will also be used to determine whether the cold gas, exergy, and energy efficiencies of gases may be maximized by using secondary air injected to gasification zone under various ratios (0, 0.5, 1, and 1.5) at optimum ER of 0.195. From the results obtained, it is indicated that the chemical energy and exergy of producer gas are magnified by 5 and 10 times higher than their corresponding physical values, respectively. The cold gas, energy, and exergy efficiencies of DRS gasification are in the ranges of 22.9-55.5%, 43.7-72.4%, and 42.5-50.4%, respectively. Initially, all 3 efficiencies increase until they reach a maximum at the optimum ER of 0.195; thereafter, they decline with further increase in ER values. The injection of secondary air to gasification zone is also found to increase the cold gas, energy, and exergy efficiencies. A ratio of secondary air to primary air of 0.5 is found to be the optimum ratio for all 3 efficiencies to reach the maximum values.

  13. Thermodynamic Analysis of Allosteric and Chelate Cooperativity in Di- and Trivalent Ammonium/Crown-Ether Pseudorotaxanes.

    PubMed

    Nowosinski, Karol; von Krbek, Larissa K S; Traulsen, Nora L; Schalley, Christoph A

    2015-10-16

    A detailed thermodynamic analysis of the axle-wheel binding in di- and trivalent secondary ammonium/[24]crown-8 pseudorotaxanes is presented. Isothermal titration calorimetry (ITC) data and double mutant cycle analyses reveal an interesting interplay of positive as well as negative allosteric and positive chelate cooperativity thus providing profound insight into the effects governing multivalent binding in these pseudorotaxanes.

  14. Layer-by-layer and intrinsic analysis of molecular and thermodynamic properties across soft interfaces

    SciTech Connect

    Sega, Marcello; Jedlovszky, Pál

    2015-09-21

    Interfaces are ubiquitous objects, whose thermodynamic behavior we only recently started to understand at the microscopic detail. Here, we borrow concepts from the techniques of surface identification and intrinsic analysis, to provide a complementary point of view on the density, stress, energy, and free energy distribution across liquid (“soft”) interfaces by analyzing the respective contributions coming from successive layers.

  15. Thermodynamic analysis of a process for producing high-octane gasoline components from catalytic cracking gas

    NASA Astrophysics Data System (ADS)

    Ismailova, Z. R.; Pirieva, Kh. B.; Kasimov, A. A.; Dzhamalova, S. A.; Gadzhizade, S. M.; Nuriev, Sh. A.; Zeinalova, S. Kh.; Dzhafarov, R. P.

    2016-03-01

    The results from a thermodynamic analysis of high-octane gasoline component production from catalytic cracking gases using zeolite catalyst OMNIKAT-210P modified with Ni, Co, Cr are presented. The equilibrium constants of the reactions assumed to occur in this process are calculated, along with the equilibrium yield of the reactions.

  16. Thermodynamics of greenhouse systems for the northern latitudes: analysis, evaluation and prospects for primary energy saving.

    PubMed

    Bronchart, Filip; De Paepe, Michel; Dewulf, Jo; Schrevens, Eddie; Demeyer, Peter

    2013-04-15

    In Flanders and the Netherlands greenhouse production systems produce economically important quantities of vegetables, fruit and ornamentals. Indoor environmental control has resulted in high primary energy use. Until now, the research on saving primary energy in greenhouse systems has been mainly based on analysis of energy balances. However, according to the thermodynamic theory, an analysis based on the concept of exergy (free energy) and energy can result in new insights and primary energy savings. Therefore in this paper, we analyse the exergy and energy of various processes, inputs and outputs of a general greenhouse system. Also a total system analysis is then performed by linking the exergy analysis with a dynamic greenhouse climate growth simulation model. The exergy analysis indicates that some processes ("Sources") lie at the origin of several other processes, both destroying the exergy of primary energy inputs. The exergy destruction of these Sources is caused primarily by heat and vapour loss. Their impact can be compensated by exergy input from heating, solar radiation, or both. If the exergy destruction of these Sources is reduced, the necessary compensation can also be reduced. This can be accomplished through insulating the greenhouse and making the building more airtight. Other necessary Sources, namely transpiration and loss of CO2, have a low exergy destruction compared to the other Sources. They are therefore the best candidate for "pump" technologies ("vapour heat pump" and "CO2 pump") designed to have a low primary energy use. The combination of these proposed technologies results in an exergy efficient greenhouse with the highest primary energy savings. It can be concluded that exergy analyses add additional information compared to only energy analyses and it supports the development of primary energy efficient greenhouse systems.

  17. Thermodynamics of greenhouse systems for the northern latitudes: analysis, evaluation and prospects for primary energy saving.

    PubMed

    Bronchart, Filip; De Paepe, Michel; Dewulf, Jo; Schrevens, Eddie; Demeyer, Peter

    2013-04-15

    In Flanders and the Netherlands greenhouse production systems produce economically important quantities of vegetables, fruit and ornamentals. Indoor environmental control has resulted in high primary energy use. Until now, the research on saving primary energy in greenhouse systems has been mainly based on analysis of energy balances. However, according to the thermodynamic theory, an analysis based on the concept of exergy (free energy) and energy can result in new insights and primary energy savings. Therefore in this paper, we analyse the exergy and energy of various processes, inputs and outputs of a general greenhouse system. Also a total system analysis is then performed by linking the exergy analysis with a dynamic greenhouse climate growth simulation model. The exergy analysis indicates that some processes ("Sources") lie at the origin of several other processes, both destroying the exergy of primary energy inputs. The exergy destruction of these Sources is caused primarily by heat and vapour loss. Their impact can be compensated by exergy input from heating, solar radiation, or both. If the exergy destruction of these Sources is reduced, the necessary compensation can also be reduced. This can be accomplished through insulating the greenhouse and making the building more airtight. Other necessary Sources, namely transpiration and loss of CO2, have a low exergy destruction compared to the other Sources. They are therefore the best candidate for "pump" technologies ("vapour heat pump" and "CO2 pump") designed to have a low primary energy use. The combination of these proposed technologies results in an exergy efficient greenhouse with the highest primary energy savings. It can be concluded that exergy analyses add additional information compared to only energy analyses and it supports the development of primary energy efficient greenhouse systems. PMID:23474336

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

    NASA Astrophysics Data System (ADS)

    Dutt, Arun K.

    1990-03-01

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

  19. Propulsion System Simulation Using the Toolbox for the Modeling and Analysis of Thermodynamic System (T-MATS)

    NASA Technical Reports Server (NTRS)

    Chapman, Jeffryes W.; Lavelle, Thomas M.; May, Ryan D.; Litt, Jonathan S.; Guo, Ten-Huei (OA)

    2014-01-01

    A simulation toolbox has been developed for the creation of both steady-state and dynamic thermodynamic software models. This presentation describes the Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS), which combines generic thermodynamic and controls modeling libraries with a numerical iterative solver to create a framework for the development of thermodynamic system simulations, such as gas turbine engines. The objective of this presentation is to present an overview of T-MATS, the theory used in the creation of the module sets, and a possible propulsion simulation architecture.

  20. Quasichemical analysis of the cluster-pair approximation for the thermodynamics of proton hydration

    NASA Astrophysics Data System (ADS)

    Pollard, Travis; Beck, Thomas L.

    2014-06-01

    A theoretical analysis of the cluster-pair approximation (CPA) is presented based on the quasichemical theory of solutions. The sought single-ion hydration free energy of the proton includes an interfacial potential contribution by definition. It is shown, however, that the CPA involves an extra-thermodynamic assumption that does not guarantee uniform convergence to a bulk free energy value with increasing cluster size. A numerical test of the CPA is performed using the classical polarizable AMOEBA force field and supporting quantum chemical calculations. The enthalpy and free energy differences are computed for the kosmotropic Na+/F- ion pair in water clusters of size n = 5, 25, 105. Additional calculations are performed for the chaotropic Rb+/I- ion pair. A small shift in the proton hydration free energy and a larger shift in the hydration enthalpy, relative to the CPA values, are predicted based on the n = 105 simulations. The shifts arise from a combination of sequential hydration and interfacial potential effects. The AMOEBA and quantum chemical results suggest an electrochemical surface potential of water in the range -0.4 to -0.5 V. The physical content of single-ion free energies and implications for ion-water force field development are also discussed.

  1. Thermodynamic analysis of hydrocarbon refrigerants-based ethylene BOG re-liquefaction system

    NASA Astrophysics Data System (ADS)

    Beladjine, Boumedienne M.; Ouadha, Ahmed; Addad, Yacine

    2016-07-01

    The present study aims to make a thermodynamic analysis of an ethylene cascade re-liquefaction system that consists of the following two subsystems: a liquefaction cycle using ethylene as the working fluid and a refrigeration cycle operating with a hydrocarbon refrigerant. The hydrocarbon refrigerants considered are propane (R290), butane (R600), isobutane (R600a), and propylene (R1270). A computer program written in FORTRAN is developed to compute parameters for characteristic points of the cycles and the system's performance, which is determined and analyzed using numerical solutions for the refrigerant condensation temperature, temperature in tank, and temperature difference in the cascade condenser. Results show that R600a gives the best performance, followed by (in order) R600, R290, and R1270. Furthermore, it is found that an increase in tank temperature improves system performance but that an increase in refrigerant condensation temperature causes deterioration. In addition, it is found that running the system at a low temperature difference in the cascade condenser is advantageous.

  2. Thermodynamic analysis of the selective chlorination of electric arc furnace dust.

    PubMed

    Pickles, C A

    2009-07-30

    The remelting of automobile scrap in an electric arc furnace (EAF) results in the production of a dust, which contains high concentrations of the oxides of zinc, iron, calcium and other metals. Typically, the lead and zinc are of commercial value, while the other metals are not worth recovering. At the present time, EAF dusts are treated in high temperature Waelz rotary kiln-type processes, where the lead and zinc oxides are selectively reduced and simultaneously reoxidized and a crude zinc oxide is produced. Another alternative processing route is selective chlorination, in which the non-ferrous metals are preferentially chlorinated to their gaseous chlorides and in this manner separated from the iron. In the present research, a detailed thermodynamic analysis of this chlorination process has been performed and the following factors were investigated; temperature, amount of chlorine, lime content, silica content, presence of an inert gas and the oxygen potential. High lead and zinc recoveries as gaseous chlorides could be achieved but some of the iron oxide was also chlorinated. Additionally, the calcium oxide in the dust consumes chlorine, but this can be minimized by adding silica, which results in the formation of stable calcium silicates. The optimum conditions were determined for a typical dust composition. The selectivities achieved with chlorination were lower than those for reduction, as reported in the literature, but there are other advantages such as the potential recovery of copper.

  3. Quasichemical analysis of the cluster-pair approximation for the thermodynamics of proton hydration

    SciTech Connect

    Pollard, Travis; Beck, Thomas L.

    2014-06-14

    A theoretical analysis of the cluster-pair approximation (CPA) is presented based on the quasichemical theory of solutions. The sought single-ion hydration free energy of the proton includes an interfacial potential contribution by definition. It is shown, however, that the CPA involves an extra-thermodynamic assumption that does not guarantee uniform convergence to a bulk free energy value with increasing cluster size. A numerical test of the CPA is performed using the classical polarizable AMOEBA force field and supporting quantum chemical calculations. The enthalpy and free energy differences are computed for the kosmotropic Na{sup +}/F{sup −} ion pair in water clusters of size n = 5, 25, 105. Additional calculations are performed for the chaotropic Rb{sup +}/I{sup −} ion pair. A small shift in the proton hydration free energy and a larger shift in the hydration enthalpy, relative to the CPA values, are predicted based on the n = 105 simulations. The shifts arise from a combination of sequential hydration and interfacial potential effects. The AMOEBA and quantum chemical results suggest an electrochemical surface potential of water in the range −0.4 to −0.5 V. The physical content of single-ion free energies and implications for ion-water force field development are also discussed.

  4. Thermodynamic analysis of hydrocarbon refrigerants-based ethylene BOG re-liquefaction system

    NASA Astrophysics Data System (ADS)

    Beladjine, Boumedienne M.; Ouadha, Ahmed; Addad, Yacine

    2016-09-01

    The present study aims to make a thermodynamic analysis of an ethylene cascade re-liquefaction system that consists of the following two subsystems: a liquefaction cycle using ethylene as the working fluid and a refrigeration cycle operating with a hydrocarbon refrigerant. The hydrocarbon refrigerants considered are propane (R290), butane (R600), isobutane (R600a), and propylene (R1270). A computer program written in FORTRAN is developed to compute parameters for characteristic points of the cycles and the system's performance, which is determined and analyzed using numerical solutions for the refrigerant condensation temperature, temperature in tank, and temperature difference in the cascade condenser. Results show that R600a gives the best performance, followed by (in order) R600, R290, and R1270. Furthermore, it is found that an increase in tank temperature improves system performance but that an increase in refrigerant condensation temperature causes deterioration. In addition, it is found that running the system at a low temperature difference in the cascade condenser is advantageous.

  5. Thermodynamic analysis and experimental study of the effect of atmospheric pressure on the ice point

    SciTech Connect

    Harvey, A. H.; McLinden, M. O.; Tew, W. L.

    2013-09-11

    We present a detailed thermodynamic analysis of the temperature of the ice point as a function of atmospheric pressure. This analysis makes use of accurate international standards for the properties of water and ice, and of available high-accuracy data for the Henry's constants of atmospheric gases in liquid water. The result is an ice point of 273.150 019(5) K at standard atmospheric pressure, with higher ice-point temperatures (varying nearly linearly with pressure) at lower pressures. The effect of varying ambient CO{sub 2} concentration is analyzed and found to be significant in comparison to other uncertainties in the model. The thermodynamic analysis is compared with experimental measurements of the temperature difference between the ice point and the triple point of water performed at elevations ranging from 145 m to 4302 m, with atmospheric pressures from 101 kPa to 60 kPa.

  6. Additive interaction in survival analysis: use of the additive hazards model.

    PubMed

    Rod, Naja Hulvej; Lange, Theis; Andersen, Ingelise; Marott, Jacob Louis; Diderichsen, Finn

    2012-09-01

    It is a widely held belief in public health and clinical decision-making that interventions or preventive strategies should be aimed at patients or population subgroups where most cases could potentially be prevented. To identify such subgroups, deviation from additivity of absolute effects is the relevant measure of interest. Multiplicative survival models, such as the Cox proportional hazards model, are often used to estimate the association between exposure and risk of disease in prospective studies. In Cox models, deviations from additivity have usually been assessed by surrogate measures of additive interaction derived from multiplicative models-an approach that is both counter-intuitive and sometimes invalid. This paper presents a straightforward and intuitive way of assessing deviation from additivity of effects in survival analysis by use of the additive hazards model. The model directly estimates the absolute size of the deviation from additivity and provides confidence intervals. In addition, the model can accommodate both continuous and categorical exposures and models both exposures and potential confounders on the same underlying scale. To illustrate the approach, we present an empirical example of interaction between education and smoking on risk of lung cancer. We argue that deviations from additivity of effects are important for public health interventions and clinical decision-making, and such estimations should be encouraged in prospective studies on health. A detailed implementation guide of the additive hazards model is provided in the appendix.

  7. anNET: a tool for network-embedded thermodynamic analysis of quantitative metabolome data

    PubMed Central

    Zamboni, Nicola; Kümmel, Anne; Heinemann, Matthias

    2008-01-01

    Background Compared to other omics techniques, quantitative metabolomics is still at its infancy. Complex sample preparation and analytical procedures render exact quantification extremely difficult. Furthermore, not only the actual measurement but also the subsequent interpretation of quantitative metabolome data to obtain mechanistic insights is still lacking behind the current expectations. Recently, the method of network-embedded thermodynamic (NET) analysis was introduced to address some of these open issues. Building upon principles of thermodynamics, this method allows for a quality check of measured metabolite concentrations and enables to spot metabolic reactions where active regulation potentially controls metabolic flux. So far, however, widespread application of NET analysis in metabolomics labs was hindered by the absence of suitable software. Results We have developed in Matlab a generalized software called 'anNET' that affords a user-friendly implementation of the NET analysis algorithm. anNET supports the analysis of any metabolic network for which a stoichiometric model can be compiled. The model size can span from a single reaction to a complete genome-wide network reconstruction including compartments. anNET can (i) test quantitative data sets for thermodynamic consistency, (ii) predict metabolite concentrations beyond the actually measured data, (iii) identify putative sites of active regulation in the metabolic reaction network, and (iv) help in localizing errors in data sets that were found to be thermodynamically infeasible. We demonstrate the application of anNET with three published Escherichia coli metabolome data sets. Conclusion Our user-friendly and generalized implementation of the NET analysis method in the software anNET allows users to rapidly integrate quantitative metabolome data obtained from virtually any organism. We envision that use of anNET in labs working on quantitative metabolomics will provide the systems biology and

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

    PubMed Central

    Solozhenko, Vladimir L.; Kurakevych, Oleksandr O.

    2013-01-01

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

  9. Thermodynamic analysis of geothermal heat pump during the cold season

    NASA Astrophysics Data System (ADS)

    Dumitrașcu, G.; Dumencu, A.; Horbaniuc, B.; Atanasiu, M. V.

    2016-08-01

    The paper is analysing the performances (COP, power and, heating heat rate function of time) for a ground-coupled heat pump that is used to heat a space during winter, for a period of 180 days. The analysis purpose is to evaluate the time based changes in values of COP and, energy transfers of a geothermal heat pump, considering a scenario for the variation of the ambient temperature in time and an analytical solution for the time dependence of the soil one. The temperatures and the energy transfer rates were determined on the basis of the irreversible entropy balance equation.

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

    SciTech Connect

    Zhang Yanguo; Li Qinghai; Jia Jinyan; Meng Aihong

    2012-12-15

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

  11. Thermodynamic analysis of multicomponent working fluids for Rankine bottoming cycle applications

    SciTech Connect

    Ash, J.E.

    1984-01-01

    The basic equations underlying a computer code are developed to describe the thermodynamic behavior of multicomponent working fluids in Rankine cycles. The code is to be employed in the performance analysis of Rankine bottoming cycle systems. The performance of such systems depends strongly on the working fluid characteristics. The introduction of multicomponent mixtures makes available a broad spectrum of fluid properties achievable by varying the mixture composition. The code provides a tool to analytically vary the mixture composition to optimize cycle performance.

  12. Group Contribution Method for Thermodynamic Analysis of Complex Metabolic Networks

    PubMed Central

    Jankowski, Matthew D.; Henry, Christopher S.; Broadbelt, Linda J.; Hatzimanikatis, Vassily

    2008-01-01

    A new, to our knowledge, group contribution method based on the group contribution method of Mavrovouniotis is introduced for estimating the standard Gibbs free energy of formation (ΔfG′°) and reaction (ΔrG′°) in biochemical systems. Gibbs free energy contribution values were estimated for 74 distinct molecular substructures and 11 interaction factors using multiple linear regression against a training set of 645 reactions and 224 compounds. The standard error for the fitted values was 1.90 kcal/mol. Cross-validation analysis was utilized to determine the accuracy of the methodology in estimating ΔrG′° and ΔfG′° for reactions and compounds not included in the training set, and based on the results of the cross-validation, the standard error involved in these estimations is 2.22 kcal/mol. This group contribution method is demonstrated to be capable of estimating ΔrG′° and ΔfG′° for the majority of the biochemical compounds and reactions found in the iJR904 and iAF1260 genome-scale metabolic models of Escherichia coli and in the Kyoto Encyclopedia of Genes and Genomes and University of Minnesota Biocatalysis and Biodegradation Database. A web-based implementation of this new group contribution method is available free at http://sparta.chem-eng.northwestern.edu/cgi-bin/GCM/WebGCM.cgi. PMID:18645197

  13. Thermodynamic and Probabilistic Metabolic Control Analysis of Riboflavin (Vitamin B₂) Biosynthesis in Bacteria.

    PubMed

    Birkenmeier, Markus; Mack, Matthias; Röder, Thorsten

    2015-10-01

    In this study, we applied a coupled in silico thermodynamic and probabilistic metabolic control analysis methodology to investigate the control mechanisms of the commercially relevant riboflavin biosynthetic pathway in bacteria. Under the investigated steady-state conditions, we found that several enzyme reactions of the pathway operate far from thermodynamic equilibrium (transformed Gibbs energies of reaction below about -17 kJ mol(-1)). Using the obtained thermodynamic information and applying enzyme elasticity sampling, we calculated the distributions of the scaled concentration control coefficients (CCCs) and scaled flux control coefficients (FCCs). From the statistical analysis of the calculated distributions, we inferred that the control over the riboflavin producing flux is shared among several enzyme activities and mostly resides in the initial reactions of the pathway. More precisely, the guanosine triphosphate (GTP) cyclohydrolase II activity, and therefore the bifunctional RibA protein of Bacillus subtilis because it catalyzes this activity, appears to mainly control the riboflavin producing flux (mean FCCs = 0.45 and 0.55, respectively). The GTP cyclohydrolase II activity and RibA also exert a high positive control over the riboflavin concentration (mean CCCs = 2.43 and 2.91, respectively). This prediction is consistent with previous findings for microbial riboflavin overproducing strains.

  14. Thermodynamic analysis of carbon formation boundary and reforming performance for steam reforming of dimethyl ether

    NASA Astrophysics Data System (ADS)

    Faungnawakij, Kajornsak; Kikuchi, Ryuji; Eguchi, Koichi

    Thermodynamic analysis of dimethyl ether steam reforming (DME SR) was investigated for carbon formation boundary, DME conversion, and hydrogen yield for fuel cell application. The equilibrium calculation employing Gibbs free minimization was performed to figure out the required steam-to-carbon ratio (S/C = 0-5) and reforming temperature (25-1000 °C) where coke formation was thermodynamically unfavorable. S/C, reforming temperature and product species strongly contributed to the coke formation and product composition. When chemical species DME, methanol, CO 2, CO, H 2, H 2O and coke were considered, complete conversion of DME and hydrogen yield above 78% without coke formation were achieved at the normal operating temperatures of molten carbonate fuel cell (600 °C) and solid oxide fuel cell (900 °C), when S/C was at or above 2.5. When CH 4 was favorable, production of coke and that of hydrogen were significantly suppressed.

  15. Thermodynamic and energy efficiency analysis of power generation from natural salinity gradients by pressure retarded osmosis.

    PubMed

    Yip, Ngai Yin; Elimelech, Menachem

    2012-05-01

    The Gibbs free energy of mixing dissipated when fresh river water flows into the sea can be harnessed for sustainable power generation. Pressure retarded osmosis (PRO) is one of the methods proposed to generate power from natural salinity gradients. In this study, we carry out a thermodynamic and energy efficiency analysis of PRO work extraction. First, we present a reversible thermodynamic model for PRO and verify that the theoretical maximum extractable work in a reversible PRO process is identical to the Gibbs free energy of mixing. Work extraction in an irreversible constant-pressure PRO process is then examined. We derive an expression for the maximum extractable work in a constant-pressure PRO process and show that it is less than the ideal work (i.e., Gibbs free energy of mixing) due to inefficiencies intrinsic to the process. These inherent inefficiencies are attributed to (i) frictional losses required to overcome hydraulic resistance and drive water permeation and (ii) unutilized energy due to the discontinuation of water permeation when the osmotic pressure difference becomes equal to the applied hydraulic pressure. The highest extractable work in constant-pressure PRO with a seawater draw solution and river water feed solution is 0.75 kWh/m(3) while the free energy of mixing is 0.81 kWh/m(3)-a thermodynamic extraction efficiency of 91.1%. Our analysis further reveals that the operational objective to achieve high power density in a practical PRO process is inconsistent with the goal of maximum energy extraction. This study demonstrates thermodynamic and energetic approaches for PRO and offers insights on actual energy accessible for utilization in PRO power generation through salinity gradients.

  16. [Phase transition behavior and thermodynamic analysis of hydrotalcite flame-retardant].

    PubMed

    Zhang, Zhi-qing; Liao, Meng-chen; Zeng, Hong-yan; Xu, Sheng; Xu, Li-hua; Zhu, Pei-han; Yang, Yong-jie

    2015-01-01

    The hydrotalcite with the properties of flame-retardant, eliminating smoke, filling and thermostability is a new kind of inorganic flame retardant. In the work, the MgAl hydrotalcite as flame retardant with Mg/Al molar ratio of 4 (MgAl-LDH) was prepared by using urea as the precipitating agent. The thermolysis behavior of the MgAl-LDH flame retardant was investigated by X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR) and thermogravimetry-differential scanning calorimetry (TG-DSC) as well as self deconvolution and curve-fitting analyses. Thermal phase transition of the MgAl-LDH was clarified, especially the characteristics of the hydroxyl groups (-OH) in the brucite-like layers and the changes in coordinate of the carbonate (CO3(2-)) from the interlayers. Based on thermodynamic data, thermal decomposition process was discussed. By.XRD analysis; it was found that the phase change took place when the decomposition temperature increased. The MgAl-LDH was decarbonated basically to MgAl mixed metal oxides (Mg-Al-O) at 500 °C, and impurity MgAl204 phase formed at 600 °C. According to the analyses of FT-IR, TG-DSC and curve-fitting technique, the hydroxyl groups (-OH) in the brucite-like layers possessed three the ligands such as [Al-OH-Al], [Al-OH-Mg] and [Mg-OH-Mg] modes. Dehydroxylation of the brucite-like layers based on the binding forces, where the [Mg-OH-Mg] among the three modes was the most difficult to be re- moved during the pyrolysis process. In the same way, the CO3(2-) ligands also possessed three modes such as H2O-bridged CO3(2-), monodentate and bidentate coordination modes. Based on the thermodynamic analysis, the thermodynamic properties of the hydrotalcite as flame retardant were evaluated, and the expressions of the Gibbs free energy, (ΔrGθT), as a function of temperature, were derived for the Mg8Al2 (OH)20CO3 crystal. Thermodynamic analysis showed that the removal of -OH from the brucite-like layers was spontaneous process

  17. The stability analysis of magnetohydrodynamic equilibria - Comparing the thermodynamic approach with the energy principle

    NASA Technical Reports Server (NTRS)

    Brinkmann, R. P.

    1989-01-01

    This paper is a contribution to the stability analysis of current-carrying plasmas, i.e., plasma systems that are forced by external mchanisms to carry a nonrelaxing electrical current. Under restriction to translationally invariant configurations, the thermodynamic stability criterion for a multicomponent plasma is rederived within the framework of nonideal MHD. The chosen dynamics neglects scalar resistivity, but allows for other types of dissipation effects both in Ohm's law and in the equation of motion. In the second section of the paper, the thermodynamic stability criterion is compared with the ideal MHD based energy principle of Bernstein et al. With the help of Schwarz's inequality, it is shown that the former criterion is always more 'pessimistic' than the latter, i.e., that thermodynamic stability implies stability according to the MHD principle, but not vice versa. This reuslt confirms the physical plausible idea that dissipational effects tend to weaken the stability properties of current-carrying plasma equilibria by breaking the constraints of ideal MHD and allowing for possibly destabilizing effects such as magnetic field line reconfiguration.

  18. Dynamic memory of a single voltage-gated potassium ion channel: A stochastic nonequilibrium thermodynamic analysis

    SciTech Connect

    Banerjee, Kinshuk

    2015-05-14

    In this work, we have studied the stochastic response of a single voltage-gated potassium ion channel to a periodic external voltage that keeps the system out-of-equilibrium. The system exhibits memory, resulting from time-dependent driving, that is reflected in terms of dynamic hysteresis in the current-voltage characteristics. The hysteresis loop area has a maximum at some intermediate voltage frequency and disappears in the limits of low and high frequencies. However, the (average) dissipation at long-time limit increases and finally goes to saturation with rising frequency. This raises the question: how diminishing hysteresis can be associated with growing dissipation? To answer this, we have studied the nonequilibrium thermodynamics of the system and analyzed different thermodynamic functions which also exhibit hysteresis. Interestingly, by applying a temporal symmetry analysis in the high-frequency limit, we have analytically shown that hysteresis in some of the periodic responses of the system does not vanish. On the contrary, the rates of free energy and internal energy change of the system as well as the rate of dissipative work done on the system show growing hysteresis with frequency. Hence, although the current-voltage hysteresis disappears in the high-frequency limit, the memory of the ion channel is manifested through its specific nonequilibrium thermodynamic responses.

  19. Thermodynamic analysis of chemical compatibility of several compounds with Fe-Cr-Al alloys

    NASA Technical Reports Server (NTRS)

    Misra, Ajay K.

    1993-01-01

    Chemical compatibility between Fe-19.8Cr-4.8Al (weight percent), which is the base composition for the commercial superalloy MA956, and several carbides, borides, nitrides, oxides, and silicides was analyzed from thermodynamic considerations. The effect of addition of minor alloying elements, such as Ti, Y, and Y2O3, to the Fe-Cr-Al alloy on chemical compatibility between the alloy and various compounds was also analyzed. Several chemically compatible compounds that can be potential reinforcement materials and/or interface coating materials for Fe-Cr-Al based composites were identified.

  20. Computed Tomography Inspection and Analysis for Additive Manufacturing Components

    NASA Technical Reports Server (NTRS)

    Beshears, Ronald D.

    2016-01-01

    Computed tomography (CT) inspection was performed on test articles additively manufactured from metallic materials. Metallic AM and machined wrought alloy test articles with programmed flaws were inspected using a 2MeV linear accelerator based CT system. Performance of CT inspection on identically configured wrought and AM components and programmed flaws was assessed using standard image analysis techniques to determine the impact of additive manufacturing on inspectability of objects with complex geometries.

  1. Additivity in the Analysis and Design of HIV Protease Inhibitors

    PubMed Central

    Jorissen, Robert N.; Kiran Kumar Reddy, G. S.; Ali, Akbar; Altman, Michael D.; Chellappan, Sripriya; Anjum, Saima G.; Tidor, Bruce; Schiffer, Celia A.; Rana, Tariq M.; Gilson, Michael K.

    2009-01-01

    We explore the applicability of an additive treatment of substituent effects to the analysis and design of HIV protease inhibitors. Affinity data for a set of inhibitors with a common chemical framework were analyzed to provide estimates of the free energy contribution of each chemical substituent. These estimates were then used to design new inhibitors, whose high affinities were confirmed by synthesis and experimental testing. Derivations of additive models by least-squares and ridge-regression methods were found to yield statistically similar results. The additivity approach was also compared with standard molecular descriptor-based QSAR; the latter was not found to provide superior predictions. Crystallographic studies of HIV protease-inhibitor complexes help explain the perhaps surprisingly high degree of substituent additivity in this system, and allow some of the additivity coefficients to be rationalized on a structural basis. PMID:19193159

  2. Natural Bond Orbital (NBO) Population Analysis, First Order Hyperpolarizabilities and Thermodynamic Properties of Cyclohexanone.

    PubMed

    Gangadharan, Rubarani P; Krishnan, S Sampath

    2015-06-01

    The molecular structure of cyclohexanone was calculated by the B3LYP density functional model with 6-31G(d, p) and 6-311++G(d,p) basis set by Gaussian program. The results from natural bond orbital (NBO) analysis have been analyzed in terms of the hybridization of atoms and the electronic structure of the title molecule. The electron density based local reactivity descriptors such as Fukui functions were calculated. The dipole moment (μ) and polarizability (a), anisotropy polarizability (Δα) and first order hyperpolarizability (β(tot)) of the molecule have been reported. Thermodynamic properties of the title compound were calculated at different temperatures.

  3. Thermodynamic analysis on the role of hydrogen in anodic stress corrosion cracking

    SciTech Connect

    Qiao, L.; Mao, X.

    1995-11-01

    A synergistic effect of hydrogen and stress on a corrosion rate was analyzed with thermodynamics. The results showed that an interaction of stress and hydrogen could increase the corrosion rate remarkably. Stress corrosion cracking (SCC) of austenitic stainless steel (ASS) was investigated in boiling chloride solution to confirm the analysis. Hydrogen could be introduced into the specimen concentrated at the crack tip during SCC in boiling LiCl solution (143 C). The concentrating factor is about 3 which is consistent with calculated results according to stress induced diffusion.

  4. Optimal Multicomponent Analysis Using the Generalized Standard Addition Method.

    ERIC Educational Resources Information Center

    Raymond, Margaret; And Others

    1983-01-01

    Describes an experiment on the simultaneous determination of chromium and magnesium by spectophotometry modified to include the Generalized Standard Addition Method computer program, a multivariate calibration method that provides optimal multicomponent analysis in the presence of interference and matrix effects. Provides instructions for…

  5. Thermodynamic analysis of a possible CO{sub 2}-laser plant included in a heat engine cycle

    SciTech Connect

    Bisio, G.; Rubatto, G.

    1998-07-01

    In these last years, several plants have been realized in some industrialized countries to recover pressure exergy from various fluids. That has been done by means of suitable turbines in particular for blast-furnace top gas and natural gas. Various papers have examined the topic, considering pros and cons. High-power CO{sub 2}-lasers are being more and more widely used for welding, drilling and cutting in machine shops. In the near future different kinds of metal surface treatments will probably become routine practice with laser units. The industries benefiting most from high power lasers will be: the automotive industry, shipbuilding, the offshore industry, the aerospace industry, the nuclear and the chemical processing industries. Both degradation and cooling problems may be alleviated by allowing the gas to flow through the laser tube and by reducing its pressure outside this tube. Thus, a thermodynamic analysis on high-power CO{sub 2}-lasers with particular reference to a possible energy recovery is justified. In previous papers the critical examination of the concept of efficiency has led one of the present authors to the definition of an operational domain in which the process can be achieved. This domain is confined by regions of no entropy production (upper limit) and no useful effects (lower limit). On the basis of these concepts and of what has been done for pressure exergy recovery from other fluids, exergy investigations and an analysis of losses are performed for a cyclic process including a high performance CO2 laser. Thermodynamic analysis of flow processes in a CO{sub 2}-laser plant shows that the inclusion of a turbine in this plant allows us to recover the most part of the exergy necessary for the compressor; in addition, the water consumption for the refrigeration in the heat exchanger is reduced.

  6. Propulsion System Simulation Using the Toolbox for the Modeling and Analysis of Thermodynamic System T-MATS

    NASA Technical Reports Server (NTRS)

    Chapman, Jeffryes W.; Lavelle, Thomas M.; May, Ryan D.; Litt, Jonathan S.; Guo, Ten-Huei

    2014-01-01

    A simulation toolbox has been developed for the creation of both steady-state and dynamic thermodynamic software models. This paper describes the Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS), which combines generic thermodynamic and controls modeling libraries with a numerical iterative solver to create a framework for the development of thermodynamic system simulations, such as gas turbine engines. The objective of this paper is to present an overview of T-MATS, the theory used in the creation of the module sets, and a possible propulsion simulation architecture. A model comparison was conducted by matching steady-state performance results from a T-MATS developed gas turbine simulation to a well-documented steady-state simulation. Transient modeling capabilities are then demonstrated when the steady-state T-MATS model is updated to run dynamically.

  7. Propulsion System Simulation Using the Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS)

    NASA Technical Reports Server (NTRS)

    Chapman, Jeffryes W.; Lavelle, Thomas M.; May, Ryan D.; Litt, Jonathan S.; Guo, Ten-Huei

    2014-01-01

    A simulation toolbox has been developed for the creation of both steady-state and dynamic thermodynamic software models. This paper describes the Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS), which combines generic thermodynamic and controls modeling libraries with a numerical iterative solver to create a framework for the development of thermodynamic system simulations, such as gas turbine engines. The objective of this paper is to present an overview of T-MATS, the theory used in the creation of the module sets, and a possible propulsion simulation architecture. A model comparison was conducted by matching steady-state performance results from a T-MATS developed gas turbine simulation to a well-documented steady-state simulation. Transient modeling capabilities are then demonstrated when the steady-state T-MATS model is updated to run dynamically.

  8. In silico analysis of the thermodynamic stability changes of psychrophilic and mesophilic alpha-amylases upon exhaustive single-site mutations.

    PubMed

    Gilis, Dimitri

    2006-01-01

    Identifying sequence modifications that distinguish psychrophilic from mesophilic proteins is important for designing enzymes with different thermodynamic stabilities and to understand the underlying mechanisms. The PoPMuSiC algorithm is used to introduce, in silico, all the single-site mutations in four mesophilic and one psychrophilic chloride-dependent alpha-amylases and to evaluate the changes in thermodynamic stability. The analysis of the distribution of the sequence positions that could be stabilized upon mutation shows a clear difference between the three domains of psychrophilic and mesophilic alpha-amylases. Most of the mutations stabilizing the psychrophilic enzyme are found in domains B and C, contrary to the mesophilic proteins where they are preferentially situated in the catalytic domain A. Moreover, the calculations show that the environment of some residues responsible for the activity of the psychrophilic protein has evolved to reinforce favorable interactions with these residues. In the second part, these results are exploited to propose rationally designed mutations that are predicted to confer to the psychrophilic enzyme mesophilic-like thermodynamic properties. Interestingly, most of the mutations found in domain C strengthen the interactions with domain A, in agreement with suggestions made on the basis of structural analyses. Although this study focuses on single-site mutations, the thermodynamic effects of the recommended mutations should be additive if the mutated residues are not close in space.

  9. THERMODYNAMIC ANALYSIS OF AMMONIA-WATER-CARBON DIOXIDE MIXTURES FOR DESIGNING NEW POWER GENERATION CYCLES

    SciTech Connect

    Ashish Gupta

    2003-01-15

    This project was undertaken with the goal of developing a computational package for the thermodynamic properties of ammonia-water-carbon dioxide mixtures at elevated temperature and pressure conditions. This objective was accomplished by modifying an existing set of empirical equations of state for ammonia-water mixtures. This involved using the Wagner equation of state for the gas phase properties of carbon dioxide. In the liquid phase, Pitzer's ionic model was used. The implementation of this approach in the form of a computation package that can be used for the optimization of power cycles required additional code development. In particular, this thermodynamic model consisted of a large set of non-linear equations. Consequently, in the interest of computational speed and robustness that is required when applied to optimization problems, analytic gradients were incorporated in the Newton solver routines. The equations were then implemented using a stream property predictor to make initial guesses of the composition, temperature, pressure, enthalpy, entropy, etc. near a known state. The predictor's validity is then tested upon the convergence of an iteration. It proved difficult to obtain experimental data from the literature that could be used to test the accuracy of the new thermodynamic property package, and this remains a critical need for future efforts in the area. It was possible, however, to assess the feasibility of using this complicated property prediction package for power cycle design and optimization. Such feasibility was first demonstrated by modification of our Kalina cycle optimization code to use the package with either a deterministic optimizer, MINOS, or a stochastic optimizer using differential evolution, a genetic-algorithm-based technique. Beyond this feasibility demonstration, a new approach to the design and optimization of power cycles was developed using a graph theoretic approach.

  10. A global analysis of soil acidification caused by nitrogen addition

    NASA Astrophysics Data System (ADS)

    Tian, Dashuan; Niu, Shuli

    2015-02-01

    Nitrogen (N) deposition-induced soil acidification has become a global problem. However, the response patterns of soil acidification to N addition and the underlying mechanisms remain far from clear. Here, we conducted a meta-analysis of 106 studies to reveal global patterns of soil acidification in responses to N addition. We found that N addition significantly reduced soil pH by 0.26 on average globally. However, the responses of soil pH varied with ecosystem types, N addition rate, N fertilization forms, and experimental durations. Soil pH decreased most in grassland, whereas boreal forest was not observed a decrease to N addition in soil acidification. Soil pH decreased linearly with N addition rates. Addition of urea and NH4NO3 contributed more to soil acidification than NH4-form fertilizer. When experimental duration was longer than 20 years, N addition effects on soil acidification diminished. Environmental factors such as initial soil pH, soil carbon and nitrogen content, precipitation, and temperature all influenced the responses of soil pH. Base cations of Ca2+, Mg2+ and K+ were critical important in buffering against N-induced soil acidification at the early stage. However, N addition has shifted global soils into the Al3+ buffering phase. Overall, this study indicates that acidification in global soils is very sensitive to N deposition, which is greatly modified by biotic and abiotic factors. Global soils are now at a buffering transition from base cations (Ca2+, Mg2+ and K+) to non-base cations (Mn2+ and Al3+). This calls our attention to care about the limitation of base cations and the toxic impact of non-base cations for terrestrial ecosystems with N deposition.

  11. Thermodynamic analysis of onset characteristics in a miniature thermoacoustic Stirling engine

    NASA Astrophysics Data System (ADS)

    Huang, Xin; Zhou, Gang; Li, Qing

    2013-06-01

    This paper analyzes the onset characteristics of a miniature thermoacoustic Stirling heat engine using the thermodynamic analysis method. The governing equations of components are reduced from the basic thermodynamic relations and the linear thermoacoustic theory. By solving the governing equation group numerically, the oscillation frequencies and onset temperatures are obtained. The dependences of the kinds of working gas, the length of resonator tube, the diameter of resonator tube, on the oscillation frequency are calculated. Meanwhile, the influences of hydraulic radius and mean pressure on the onset temperature for different working gas are also presented. The calculation results indicate that there exists an optimal dimensionless hydraulic radius to obtain the lowest onset temperature, whose value lies in the range of 0.30-0.35 for different working gases. Furthermore, the amplitude and phase relationship of pressures and volume flows are analyzed in the time-domain. Some experiments have been performed to validate the calculations. The calculation results agree well with the experimental values. Finally, an error analysis is made, giving the reasons that cause the errors of theoretical calculations.

  12. Biosorption of food dyes onto Spirulina platensis nanoparticles: equilibrium isotherm and thermodynamic analysis.

    PubMed

    Dotto, G L; Lima, E C; Pinto, L A A

    2012-01-01

    The biosorption of food dyes FD&C red no. 40 and acid blue 9 onto Spirulina platensis nanoparticles was studied at different conditions of pH and temperature. Four isotherm models were used to evaluate the biosorption equilibrium and the thermodynamic parameters were estimated. Infra red analysis (FT-IR) and energy dispersive X-ray spectroscopy (EDS) were used to verify the biosorption behavior. The maximum biosorption capacities of FD&C red no. 40 and acid blue 9 were found at pH 4 and 298 K, and the values were 468.7 mg g(-1) and 1619.4 mg g(-1), respectively. The Sips model was more adequate to fit the equilibrium experimental data (R2>0.99 and ARE<5%). Thermodynamic study showed that the biosorption was exothermic, spontaneous and favorable. FT-IR and EDS analysis suggested that at pH 4 and 298 K, the biosorption of both dyes onto nanoparticles occurred by chemisorption.

  13. [Kinetic analysis of additive effect on desulfurization activity].

    PubMed

    Han, Kui-hua; Zhao, Jian-li; Lu, Chun-mei; Wang, Yong-zheng; Zhao, Gai-ju; Cheng, Shi-qing

    2006-02-01

    The additive effects of A12O3, Fe2O3 and MnCO3 on CaO sulfation kinetics were investigated by thermogravimetic analysis method and modified grain model. The activation energy (Ea) and the pre-exponential factor (k0) of surface reaction, the activation energy (Ep) and the pre-exponential factor (D0) of product layer diffusion reaction were calculated according to the model. Additions of MnCO3 can enhance the initial reaction rate, product layer diffusion and the final CaO conversion of sorbents, the effect mechanism of which is similar to that of Fe2O3. The method based isokinetic temperature Ts and activation energy can not estimate the contribution of additive to the sulfation reactivity, the rate constant of the surface reaction (k), and the effective diffusivity of reactant in the product layer (Ds) under certain experimental conditions can reflect the effect of additives on the activation. Unstoichiometric metal oxide may catalyze the surface reaction and promote the diffusivity of reactant in the product layer by the crystal defect and distinct diffusion of cation and anion. According to the mechanism and effect of additive on the sulfation, the effective temperature and the stoichiometric relation of reaction, it is possible to improve the utilization of sorbent by compounding more additives to the calcium-based sorbent.

  14. Thermodynamic analysis of ligands at cholecystokinin CCK2 receptors in rat cerebral cortex

    PubMed Central

    Harper, E A; Roberts, S P; Kalindjian, S B

    2007-01-01

    Background and purpose: Several studies using radioligand binding assays, have shown that measurement of thermodynamic parameters can allow discrimination of agonists and antagonists (Weiland et al., 1979; Borea et al., 1996a). Here we investigate whether agonists and antagonists can be thermodynamically discriminated at CCK2 receptors in rat cerebral cortex. Experimental approach: The pKL of [3H]-JB93182 in rat cerebral cortex membranes was determined at 4, 12, 21 and 37°C in 50 mM Tris-HCl buffer (buffer B pH 6.96; containing 0.089 mM bacitracin). pKI values of ligands of diverse chemical structure and with differing intrinsic activity (α), as defined by the lumen-perfused rat and mouse stomach bioassays, were determined in buffer B at 4, 12, 21 and 37°C. Key results: [3H]-JB93182 labelled a homogeneous population of receptors in rat cerebral cortex at 4, 12, 21 and 37°C and the pKL and Bmax were not altered by incubation temperature. [3H]-JB93182 binding reached equilibrium after 10, 50, 90 and 220 min at 37, 21, 12 and 4°C, respectively. pKI values for R-L-365,260, R-L-740,093, YM220, PD134,308 and JB95008 were higher at 4°C than at 37°C. There was no effect of temperature on pKI values for pentagastrin, CCK-8S, S-L-365,260, YM022, PD140,376 and JB93242. Conclusions and implications: CCK2 receptor agonists and antagonists at rat CCK2 receptors cannot be discriminated by thermodynamic analysis using [3H]-JB93182 as the radioligand. PMID:17592503

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

    SciTech Connect

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

    2008-07-15

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

  16. Solubility enhancement of simvastatin by arginine: thermodynamics, solute–solvent interactions, and spectral analysis

    PubMed Central

    Meor Mohd Affandi, MMR; Tripathy, Minaketan; Shah, Syed Adnan Ali; Majeed, ABA

    2016-01-01

    We examined the solubility of simvastatin in water in 0.01 mol·dm−3, 0.02 mol·dm−3, 0.04 mol·dm−3, 0.09 mol·dm−3, 0.18 mol·dm−3, 0.36 mol·dm−3, and 0.73 mol·dm−3 arginine (ARG) solutions. The investigated drug is termed the solute, whereas ARG the cosolute. Phase solubility studies illustrated a higher extent of solubility enhancement for simvastatin. The aforementioned system was subjected to conductometric and volumetric measurements at temperatures (T) of 298.15 K, 303.15 K, 308.15 K, and 313.15 K to illustrate the thermodynamics involved and related solute–solvent interactions. The conductance values were used to evaluate the limiting molar conductance and association constants. Thermodynamic parameters (ΔG0, ΔH0, ΔS0, and Es) for the association process of the solute in the aqueous solutions of ARG were calculated. Limiting partial molar volumes and expansibilities were evaluated from the density values. These values are discussed in terms of the solute–solvent and solute–cosolute interactions. Further, these systems were analyzed using ultraviolet–visible analysis, Fourier-transform infrared spectroscopy, and 13C, 1H, and two-dimensional nuclear overhauser effect spectroscopy nuclear magnetic resonance to complement thermophysical explanation. PMID:27041998

  17. Thermodynamic Analysis of Blast Furnace Slag Waste Heat-Recovery System Integrated with Coal Gasification

    NASA Astrophysics Data System (ADS)

    Duan, W. J.; Li, P.; Lei, W.; Chen, W.; Yu, Q. B.; Wang, K.; Qin, Q.

    2015-05-01

    The blast furnace (BF) slag waste heat was recovered by an integrated system stage by stage, which combined a physical and chemical method. The water and coal gasification reactions were used to recover the heat in the system. Based on the first and second law of thermodynamics, the thermodynamic analysis of the system was carried out by the enthalpy-exergy diagram. The results showed that the concept of the "recovery-temperature countercurrent, energy cascade utilization" was realized by this system to recover and use the high-quality BF slag waste heat. In this system, the high-temperature waste heat was recovered by coal gasification and the relatively low-temperature waste heat was used to produce steam. The system's exergy and thermal recycling efficiency were 52.6% and 75.4%, respectively. The exergy loss of the integrated system was only 620.0 MJ/tslag. Compared with the traditional physical recycling method producing steam, the exergy and thermal efficiencies of the integrated system were improved significantly. Meanwhile, approximately 182.0 m3/tslag syngas was produced by coal gasification. The BF slag waste heat will be used integrally and efficiently by the integrated system. The results provide the theoretical reference for recycling and using the BF slag waste heat.

  18. Thermodynamic analysis and effect of crystallinity for silicon monoxide negative electrode for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Yasuda, Kouji; Kashitani, Yusuke; Kizaki, Shingo; Takeshita, Kohki; Fujita, Takehisa; Shimosaki, Shinji

    2016-10-01

    The electrochemical behavior of SiO negative electrodes for lithium ion batteries is thermodynamically and experimentally investigated. The analysis of the reaction pathway and the calculation of the reaction potentials during the Li insertion/extraction reactions are carried out by the construction of the ternary phase diagram for the Li-Si-O system. In the initial reaction of Li insertion, metallic Si and lithium silicates are formed above 0.37 V vs. Li/Li+ as a conversion reaction of the SiO negative electrode. Further Li insertion produces Li-Si alloys as reversible reaction phases. The decomposition of the Li4SiO4 phase begins before the formation of the Li-Si alloy is completed. The measured electrode behavior of the SiO negative electrode basically agrees with the thermodynamic calculations, especially at a low reaction rate; deviations can be ascribed to kinetic factors and electrode resistance. The values of over 1898 mA h g-1 and 71.0% were obtained for the discharge capacity and the coulombic efficiency, respectively. Furthermore, the overvoltage for an amorphous SiO electrode was smaller than that for a disproportionated SiO electrode into Si and SiO2 phases.

  19. Moisture-swing sorption for carbon dioxide capture from ambient air: a thermodynamic analysis.

    PubMed

    Wang, Tao; Lackner, Klaus S; Wright, Allen B

    2013-01-14

    An ideal chemical sorbent for carbon dioxide capture from ambient air (air capture) must have a number of favourable properties, such as environmentally benign behaviour, a high affinity for CO(2) at very low concentration (400 ppm), and a low energy cost for regeneration. The last two properties seem contradictory, especially for sorbents employing thermal swing adsorption. On the other hand, thermodynamic analysis shows that the energy cost of an air capture device need only be slightly larger than that of a flue gas scrubber. The moisture swing separation process studied in this paper provides a novel approach to low cost CO(2) capture from air. The anionic exchange resin sorbent binds CO(2) when dry and releases it when wet. A thermodynamic model with coupled phase and chemical equilibria is developed to study the complex H(2)O-CO(2)-resin system. The moisture swing behaviour is compatible with hydration energies changing with the activity of water on the resin surfaces. This activity is in turn set by the humidity. The rearrangement of hydration water on the resin upon the sorption of a CO(2) molecule is predicted as a function of the humidity and temperature. Using water as fuel to drive the moisture swing enables an economical, large-scale implementation of air capture. By generating CO(2) with low partial pressures, the present technology has implications for in situ CO(2) utilizations which require low pressure CO(2) gas rather than liquid CO(2). PMID:23172123

  20. Characterization of racemic species of chiral drugs using thermal analysis, thermodynamic calculation, and structural studies.

    PubMed

    Li, Z J; Zell, M T; Munson, E J; Grant, D J

    1999-03-01

    The identification of the racemic species, as a racemic compound, a racemic conglomerate, or a racemic solid solution (pseudoracemate), is crucial for rationalizing the potential for resolution of racemates by crystallization. The melting points and enthalpies of fusion of a number of chiral drugs and their salts were measured by differential scanning calorimetry. Based on a thermodynamic cycle involving the solid and liquid phases of the enantiomers and racemic species, the enthalpy, entropy and Gibbs free energy of the racemic species were derived from the thermal data. The Gibbs free energy of formation, is always negative for a racemic compound, if it can exist, and the contribution from the entropy of mixing in the liquid state to the free energy of formation is the driving force for the process. For a racemic conglomerate, the entropy of mixing in the liquid state is close to the ideal value of R ln 2 (1.38 cal.mol-1. K-1). Pseudoracemates behave differently from the other two types of racemic species. When the melting points of the racemic species is about 30 K below that of the homochiral species, is approximately zero, indicating that the racemic compound and racemic conglomerate possess similar relative stabilities. The powder X-ray diffraction patterns and 13C solid-state nuclear magnetic resonance spectra are valuable for revealing structural differences between a racemic compound and a racemic conglomerate. Thermodynamic prediction, thermal analysis, and structural study are in excellent agreement for identifying the nature of the racemic species.

  1. A numerical solution of the Navier-Stokes equations for supercritical fluid thermodynamic analysis

    NASA Technical Reports Server (NTRS)

    Heinmiller, P. J.

    1971-01-01

    An explicit numerical solution of the compressible Navier-Stokes equations is applied to the thermodynamic analysis of supercritical oxygen in the Apollo cryogenic storage system. The wave character is retained in the conservation equations which are written in the basic fluid variables for a two-dimensional Cartesian coordinate system. Control-volume cells are employed to simplify imposition of boundary conditions and to ensure strict observance of local and global conservation principles. Non-linear real-gas thermodynamic properties responsible for the pressure collapse phenomonon in supercritical fluids are represented by tabular and empirical functions relating pressure and temperature to density and internal energy. Wall boundary conditions are adjusted at one cell face to emit a prescribed mass flowrate. Scaling principles are invoked to achieve acceptable computer execution times for very low Mach number convection problems. Detailed simulations of thermal stratification and fluid mixing occurring under low acceleration in the Apollo 12 supercritical oxygen tank are presented which model the pressure decay associated with de-stratification induced by an ordinary vehicle maneuver and heater cycle operation.

  2. Thermodynamic analysis for the controllability of elements in the recycling process of metals.

    PubMed

    Nakajima, Kenichi; Takeda, Osamu; Miki, Takahiro; Matsubae, Kazuyo; Nagasaka, Tetsuya

    2011-06-01

    This study presents the results of chemical thermodynamic analysis on the distribution of elements in the smelting process of metallic materials to examine the controllability of impurities in the pyrometallurgical technique. The results of the present work can give an answer against the frequently given question; "Which impurity element can be removable in metallurgical process?" or "How far can the impurity level be controlled?". The proposed method was applied to estimate the distribution of 29 elements for a copper converter and 26 elements for a steel-making process and shows the distribution tendency of elements among the gas, slag, and metal phases as well as clarifying which metals can be recovered or removed from secondary resources in metallurgical processes. The effects of temperature, oxygen partial pressure, and slag composition on the distribution ratio of elements were also evaluated, and the removal limit or controllability of impurity in these two processes was presented. This study results in thermodynamic features of various elements in the pyrometallurgical process and also shows, even by varying process parameters such as temperature and oxygen partial pressure, no drastic improvement of removal efficiency should be expected, except for lead and tin in copper.

  3. Solubility enhancement of simvastatin by arginine: thermodynamics, solute-solvent interactions, and spectral analysis.

    PubMed

    Meor Mohd Affandi, M M R; Tripathy, Minaketan; Shah, Syed Adnan Ali; Majeed, A B A

    2016-01-01

    We examined the solubility of simvastatin in water in 0.01 mol·dm(-3), 0.02 mol·dm(-3), 0.04 mol·dm(-3), 0.09 mol·dm(-3), 0.18 mol·dm(-3), 0.36 mol·dm(-3), and 0.73 mol·dm(-3) arginine (ARG) solutions. The investigated drug is termed the solute, whereas ARG the cosolute. Phase solubility studies illustrated a higher extent of solubility enhancement for simvastatin. The aforementioned system was subjected to conductometric and volumetric measurements at temperatures (T) of 298.15 K, 303.15 K, 308.15 K, and 313.15 K to illustrate the thermodynamics involved and related solute-solvent interactions. The conductance values were used to evaluate the limiting molar conductance and association constants. Thermodynamic parameters (ΔG (0), ΔH (0), ΔS (0), and E s) for the association process of the solute in the aqueous solutions of ARG were calculated. Limiting partial molar volumes and expansibilities were evaluated from the density values. These values are discussed in terms of the solute-solvent and solute-cosolute interactions. Further, these systems were analyzed using ultraviolet-visible analysis, Fourier-transform infrared spectroscopy, and (13)C, (1)H, and two-dimensional nuclear overhauser effect spectroscopy nuclear magnetic resonance to complement thermophysical explanation.

  4. Thermodynamic analysis of III-V semiconductor alloys grown by metalorganic vapor phase epitaxy

    NASA Astrophysics Data System (ADS)

    Asai, Toshihiro; Dandy, David S.

    2000-10-01

    A thermodynamic analysis has been applied to systematically study III-V semiconductor alloy deposition, including nitrides grown by metalorganic vapor phase epitaxy. The predicted solid compositions of a number of ternary and quaternary alloys, including AlxGa1-xPyAs1-y, are compared with experimental data. For phosphorus-containing alloys, introduction of a parameter f representing incomplete PH3 pyrolysis yields good agreement with experimental data. It is shown that the input mole fraction of the group III metalorganic sources influences the incorporation of P into the solid for these alloys. Solid composition is also calculated for nitride alloys as a function of inlet gas concentration. To date, thermodynamic models have been applied solely to predict N solubility limits for nitride alloys where mixing occurs on the group V sublattice. The present model is used to predict N solid compositions in ternary and quaternary alloys, and it is demonstrated that these values are below the theoretical solubility limits for In-containing nitrides. The role of H2 in the carrier gas is investigated for III-N-V, III-III-N-V, and III-N-V-V systems.

  5. ANALYSIS OF MPC ACCESS REQUIREMENTS FOR ADDITION OF FILLER MATERIALS

    SciTech Connect

    W. Wallin

    1996-09-03

    This analysis is prepared by the Mined Geologic Disposal System (MGDS) Waste Package Development Department (WPDD) in response to a request received via a QAP-3-12 Design Input Data Request (Ref. 5.1) from WAST Design (formerly MRSMPC Design). The request is to provide: Specific MPC access requirements for the addition of filler materials at the MGDS (i.e., location and size of access required). The objective of this analysis is to provide a response to the foregoing request. The purpose of this analysis is to provide a documented record of the basis for the response. The response is stated in Section 8 herein. The response is based upon requirements from an MGDS perspective.

  6. Thermodynamic analysis of the solidification processes for cryopreservation of biological tissues.

    PubMed

    Costa, Blas Melissari

    2005-01-01

    Nucleation of a cooling liquid occurs when atomic aggregates reach critical size that assures decreasing free energy as the crystal grows. Thermodynamic analysis allows to understand the ways to control the process. Evaluation of crystallized fraction in a freezing process is described as an example of biomedical application. For that purpose, 4 cm3 samples with different mixtures of RPMI 1640 and DMSO cryopreservant, were frozen in a programmed cooling chamber at a cooling rate of 1 degrees C/min. The temperatures of the chamber and the probe were plotted against time. Characteristic curves with different crystallization zones were obtained. The area of that zone beyond the base line determines the Relative Crystallisation Index (RCI) of the solution. The results were compared with usual methods of the National Organs and Tissues Bank of Uruguay. With 10% DMSO and VALPA 799 Program, the BNOT has obtained good quality cryopreserved cardiac valves and elastic arteries.

  7. Thermodynamic analysis of the concentration profiles of epitaxial layers of nonideal solid solutions

    SciTech Connect

    Kazakov, A.I.; Kishmar, I.N.; Mokritskii, V.A.; Yakubovskii, M.V.

    1988-03-01

    Based on thermodynamic analysis employing the quasiregular approach a mathematical model of the process of equilibrium crystallization of nonideal three-component solid solutions of compounds of the type A/sup III/B/sup V/ from a restricted volume of a solution in a melt was constructed. This model enables calculation of the distribution of the components over the thickness of the epitaxial layer for low rates of cooling of the solution in a melt. The computer calculations of the concentration profiles of the epitaxial layers of Ga/sub 1-x/Al/sub x/ agreed well with the experimental data for thicknesses of the epitaxial layers up to 20 ..mu..m. For high rates of cooling the mass transfer in the volume of the solution in a melt must be taken into account.

  8. Thermodynamic analysis of Direct Urea Solid Oxide Fuel Cell in combined heat and power applications

    NASA Astrophysics Data System (ADS)

    Abraham, F.; Dincer, I.

    2015-12-01

    This paper presents a comprehensive steady state modelling and thermodynamic analysis of Direct Urea Solid Oxide Fuel Cell integrated with Gas Turbine power cycle (DU-SOFC/GT). The use of urea as direct fuel mitigates public health and safety risks associated with the use of hydrogen and ammonia. The integration scheme in this study covers both oxygen ion-conducting solid oxide fuel cells (SOFC-O) and hydrogen proton-conducting solid oxide fuel cells (SOFC-H). Parametric case studies are carried out to investigate the effects of design and operating parameters on the overall performance of the system. The results reveal that the fuel cell exhibited the highest level of exergy destruction among other system components. Furthermore, the SOFC-O based system offers better overall performance than that with the SOFC-H option mainly due to the detrimental reverse water-gas shift reaction at the SOFC anode as well as the unique configuration of the system.

  9. Thermodynamic analysis of cesium and iodine behavior in severe light water reactor accidents

    NASA Astrophysics Data System (ADS)

    Minato, Kazuo

    1991-11-01

    In order to understand the release and transport behavior of cesium (Cs) and iodine (I) in severe light water reactor accidents, chemical forms of Cs and I in steam-hydrogen mixtures were analyzed thermodynamically. In the calculations reactions of boron (B) with Cs were taken into consideration. The analysis showed that B plays an important role in determining chemical forms of Cs. The main Cs-containing species are CsBO 2(g) and CsBO 2(l), depending on temperature. The contribution of CsOH(g) is minor. The main I-containing species are HI(g) and CsI(g) over the wide ranges of the parameters considered. Calculations were also carried out under the conditions of the Three Mile Island Unit 2 accident.

  10. Toward Improved Force-Field Accuracy through Sensitivity Analysis of Host-Guest Binding Thermodynamics.

    PubMed

    Yin, Jian; Fenley, Andrew T; Henriksen, Niel M; Gilson, Michael K

    2015-08-13

    Improving the capability of atomistic computer models to predict the thermodynamics of noncovalent binding is critical for successful structure-based drug design, and the accuracy of such calculations remains limited by nonoptimal force field parameters. Ideally, one would incorporate protein-ligand affinity data into force field parametrization, but this would be inefficient and costly. We now demonstrate that sensitivity analysis can be used to efficiently tune Lennard-Jones parameters of aqueous host-guest systems for increasingly accurate calculations of binding enthalpy. These results highlight the promise of a comprehensive use of calorimetric host-guest binding data, along with existing validation data sets, to improve force field parameters for the simulation of noncovalent binding, with the ultimate goal of making protein-ligand modeling more accurate and hence speeding drug discovery.

  11. Thermodynamic analysis questions claims of improved cardiac efficiency by dietary fish oil.

    PubMed

    Loiselle, Denis S; Han, June-Chiew; Goo, Eden; Chapman, Brian; Barclay, Christopher J; Hickey, Anthony J R; Taberner, Andrew J

    2016-09-01

    Studies in the literature describe the ability of dietary supplementation by omega-3 fish oil to increase the pumping efficiency of the left ventricle. Here we attempt to reconcile such studies with our own null results. We undertake a quantitative analysis of the improvement that could be expected theoretically, subject to physiological constraints, by posing the following question: By how much could efficiency be expected to increase if inefficiencies could be eliminated? Our approach utilizes thermodynamic analyses to investigate the contributions, both singly and collectively, of the major components of cardiac energetics to total cardiac efficiency. We conclude that it is unlikely that fish oils could achieve the required diminution of inefficiencies without greatly compromising cardiac performance. PMID:27574288

  12. Distinct role of hydration water in protein misfolding and aggregation revealed by fluctuating thermodynamics analysis.

    PubMed

    Chong, Song-Ho; Ham, Sihyun

    2015-04-21

    decrease in solvation free energy, harnessing the monomer solvation free energy earned during the misfolding. The second step, where a compact dimer structure is formed, is driven by direct protein-protein interactions, but again it is accompanied by an increase in solvation free energy. The increased solvation free energy of the dimer will function as the driving force to recruit another Aβ protein in the approach stage of subsequent oligomerizations. The fluctuating thermodynamics analysis of the misfolding and dimerization of the Aβ protein indicates that the interaction of the protein with surrounding water plays a critical role in protein aggregation. Such a water-centric perspective is further corroborated by demonstrating that, for a large number of Aβ mutants and mutants of other protein systems, the change in the experimental aggregation propensity upon mutation has a significant correlation with the protein solvation free energy change. We also find striking discrimination between the positively and negatively charged residues on the protein surface by surrounding water molecules, which is shown to play a crucial role in determining the protein aggregation propensity. We argue that the protein total charge dictates such striking behavior of the surrounding water molecules. Our results provide new insights for understanding and predicting the protein aggregation propensity, thereby offering novel design principles for producing aggregation-resistant proteins for biotherapeutics.

  13. Thermodynamics and Kinetics of Boron Removal from Metallurgical Grade Silicon by Addition of High Basic Potassium Carbonate to Calcium Silicate Slag

    NASA Astrophysics Data System (ADS)

    Wu, Jijun; Wang, Fanmao; Ma, Wenhui; Lei, Yun; Yang, Bin

    2016-06-01

    In this study, we investigated the thermodynamics and kinetics of boron removal from metallurgical grade silicon (MG-Si) using a calcium silicate slag containing a high basic potassium carbonate. The distribution of boron between slag and silicon was theoretically derived and the distribution coefficients ( L B) of boron with different compositions of CaO, SiO2, and K2CO3 in slag reagents were determined. The maximal value of L B reached 2.08 with a high basicity slag of 40 pctCaO-40 pctSiO2-20 pctK2CO3 (Λ = 0.73). The boron removal rates from MG-Si using CaO-SiO2 and CaO-SiO2-K2CO3 slags at 1823 K (1550 °C) were investigated in an electromagnetic induction furnace. The results showed that the boron concentration in MG-Si can be reduced from 22 to 1.8 ppmw at 1823 K (1550 °C) with 20 pct K2CO3 addition to calcium silicate slag, where the removal efficiency of boron reached 91.8 pct. The mass transfer coefficient ( β S) of boron in binary 50 pctCaO-50 pctSiO2 slag was 3.16 × 10-6 m s-1 at 1823 K (1550 °C) and was 2.43 × 10-5 m s-1 in ternary 40 pctCaO-40 pctSiO2-20 pctK2CO3 slag.

  14. PolyA-Mediated DNA Assembly on Gold Nanoparticles for Thermodynamically Favorable and Rapid Hybridization Analysis.

    PubMed

    Zhu, Dan; Song, Ping; Shen, Juwen; Su, Shao; Chao, Jie; Aldalbahi, Ali; Zhou, Ziang; Song, Shiping; Fan, Chunhai; Zuo, Xiaolei; Tian, Yang; Wang, Lianhui; Pei, Hao

    2016-05-01

    Understanding the behavior of biomolecules on nanointerface is critical in bioanalysis, which is great challenge due to the instability and the difficulty to control the orientation and loading density of biomolecules. Here, we investigated the thermodynamics and kinetics of DNA hybridization on gold nanoparticle, with the aim to improve the efficiency and speed of DNA analysis. We achieved precise and quantitative surface control by applying a recently developed poly adenines (polyA)-based assembly strategy on gold nanoparticles (DNA-AuNPs). PolyA served as an effective anchoring block based on the preferential binding with the AuNP surface and the appended recognition block adopted an upright conformation that favors DNA hybridization. The lateral spacing and surface density of DNA on AuNPs can be systematically modulated by adjusting the length of polyA block. We found the stability of duplex on AuNP was enhanced with the increasing length of polyA block. When the length of polyA block reached to 40 bases, the thermodynamic properties were more similar to that of duplex in solution. Fast hybridization rate was observed on the diblock DNA-AuNPs and was increased along with the length of polyA block. We consider the high stability and excellent hybridization performance come from the minimization of the DNA-DNA and DNA-AuNP interactions with the use of polyA block. This study provides better understanding of the behavior of biomolecules on the nanointerface and opens new opportunities to construct high-efficiency and high-speed biosensors for DNA analysis. PMID:27058116

  15. Thermodynamic analysis of the interaction of the antibiotic teicoplanin and its aglycone with cell-wall peptides.

    PubMed Central

    Arriaga, P; Laynez, J; Menendez, M; Cañada, J; Garcia-Blanco, F

    1990-01-01

    The thermodynamics of the interaction of the glycopeptidic antibiotic teicoplanin and its peptidic moiety with analogues of bacterial cell-wall peptides were studied by means of calorimetric and spectrophotometric techniques. The analysis of the thermodynamic data has allowed us to evaluate the contributions of the different peptide groups to the binding process. The nature of the primary binding forces is also discussed for each interacting group, on the basis of their enthalpic and entropic contribution and in connection with the detailed structural information available for these antibiotics from n.m.r. data. Similar analyses for the case of vancomycin and ristocetin are also reported. PMID:2137332

  16. Thermodynamic analysis of the heterogeneous binding sites of molecularly imprinted polymers

    SciTech Connect

    Kim, Hyunjung; Kaczmarski, Krzysztof; Guiochon, Georges A

    2005-11-01

    The thermodynamic interactions of two polymers, one Fmoc-L-Trp-imprinted (MIP), the other one an unimprinted reference (NIP), with the two Fmoc-tryptophan enantiomers were studied by frontal analysis, which allows accurate measurements of the adsorption isotherms. These isotherms were acquired at temperatures of 40, 50, 60, and 70 C, for sample concentrations ranging between 0.005 and 40 mM. The mobile phase used was acetonitrile with one percent acetic acid as an organic modifier. Within the measured concentration ranges, the tri-Langmuir isotherm model accounts best for the isotherm data of both enantiomers on the MIP, the bi-Langmuir model for the isotherm data of Fmoc-L-Trp on the NIP. These isotherm models were selected using three independent processes: statistical tests on the results from regression of the isotherm data to different isotherm models; calculation of the affinity energy distribution from the raw isotherm data; comparison of the experimental and the calculated band profiles. The isotherm parameters obtained from these best selected isotherm models showed that the enantiomeric selectivity does not change significantly with temperature, while the affinity of the substrates for both the MIP and the NIP decrease considerably with increasing temperatures. These temperature effects on the binding performance of the MIP were clarified by considering the thermodynamic functions (i.e., the standard molar Gibbs free energy, the standard molar entropy of adsorption, and the standard molar enthalpy of adsorption) for each identified type of adsorption sites, derived from the Van't Hoff equation. This showed that the entropy of transfer of Fmoc-L-Trp from the mobile to the MIP stationary phase is the dominant driving force for the selective adsorption of Fmoc-L-Trp onto the enantioselective binding sites. This entropy does not change significantly with increasing temperatures from 40 to 70 C.

  17. A detailed analysis of entropy production and improvement of the thermodynamic cycle of an adsorption refrigerating plant

    NASA Astrophysics Data System (ADS)

    Okunev, B. N.; Safonov, M. S.

    2006-07-01

    A thermodynamic analysis of an adsorption refrigerating plant with closed loops for a working substance and auxiliary liquid heat carrier has been carried out in application to the adsorption pair “water-CaCl2 impregnated into the pores of a silica gel.” Using the obtained periodic solutions of the system of energy-balance equations for the heat carrier and the sorbent layer, the most thermodynamically effective modes of operation of the refrigerating plant have been determined as functions of governing parameters. The entropy production in various modules of the plant is calculated, and the main sources of entropy generation are revealed. This made it possible to suggest an improved scheme of an adsorption refrigerating cycle with regenerative heat exchangers connected at the inlet and outlet from the adsorbers. The possibility of a considerable increase in the coefficient of thermodynamic efficiency in such a system has been justified.

  18. Spectroscopic analysis and DFT calculations of a food additive Carmoisine

    NASA Astrophysics Data System (ADS)

    Snehalatha, M.; Ravikumar, C.; Hubert Joe, I.; Sekar, N.; Jayakumar, V. S.

    2009-04-01

    FT-IR and Raman techniques were employed for the vibrational characterization of the food additive Carmoisine (E122). The equilibrium geometry, various bonding features, and harmonic vibrational wavenumbers have been investigated with the help of density functional theory (DFT) calculations. A good correlation was found between the computed and experimental wavenumbers. Azo stretching wavenumbers have been lowered due to conjugation and π-electron delocalization. Predicted electronic absorption spectra from TD-DFT calculation have been analysed comparing with the UV-vis spectrum. The first hyperpolarizability of the molecule is calculated. Intramolecular charge transfer (ICT) responsible for the optical nonlinearity of the dye molecule has been discussed theoretically and experimentally. Stability of the molecule arising from hyperconjugative interactions, charge delocalization and C-H⋯O, improper, blue shifted hydrogen bonds have been analysed using natural bond orbital (NBO) analysis.

  19. [Analysis of constituents in urushi wax, a natural food additive].

    PubMed

    Jin, Zhe-Long; Tada, Atsuko; Sugimoto, Naoki; Sato, Kyoko; Masuda, Aino; Yamagata, Kazuo; Yamazaki, Takeshi; Tanamoto, Kenichi

    2006-08-01

    Urushi wax is a natural gum base used as a food additive. In order to evaluate the quality of urushi wax as a food additive and to obtain information useful for setting official standards, we investigated the constituents and their concentrations in urushi wax, using the same sample as scheduled for toxicity testing. After methanolysis of urushi wax, the composition of fatty acids was analyzed by GC/MS. The results indicated that the main fatty acids were palmitic acid, oleic acid and stearic acid. LC/MS analysis of urushi wax provided molecular-related ions of the main constituents. The main constituents were identified as triglycerides, namely glyceryl tripalmitate (30.7%), glyceryl dipalmitate monooleate (21.2%), glyceryl dioleate monopalmitate (2.1%), glyceryl monooleate monopalmitate monostearate (2.6%), glyceryl dipalmitate monostearate (5.6%), glyceryl distearate monopalmitate (1.4%). Glyceryl dipalmitate monooleate isomers differing in the binding sites of each constituent fatty acid could be separately determined by LC/MS/MS. PMID:16984037

  20. Decreasing Cloudiness Over China: An Updated Analysis Examining Additional Variables

    SciTech Connect

    Kaiser, D.P.

    2000-01-14

    As preparation of the IPCC's Third Assessment Report takes place, one of the many observed climate variables of key interest is cloud amount. For several nations of the world, there exist records of surface-observed cloud amount dating back to the middle of the 20th Century or earlier, offering valuable information on variations and trends. Studies using such databases include Sun and Groisman (1999) and Kaiser and Razuvaev (1995) for the former Soviet Union, Angel1 et al. (1984) for the United States, Henderson-Sellers (1986) for Europe, Jones and Henderson-Sellers (1992) for Australia, and Kaiser (1998) for China. The findings of Kaiser (1998) differ from the other studies in that much of China appears to have experienced decreased cloudiness over recent decades (1954-1994), whereas the other land regions for the most part show evidence of increasing cloud cover. This paper expands on Kaiser (1998) by analyzing trends in additional meteorological variables for Chi na [station pressure (p), water vapor pressure (e), and relative humidity (rh)] and extending the total cloud amount (N) analysis an additional two years (through 1996).

  1. Analysis of thermodynamic losses in ground source heat pumps and their influence on overall system performance

    NASA Astrophysics Data System (ADS)

    Casarosa, C.; Conti, P.; Franco, A.; Grassi, W.; Testi, D.

    2014-11-01

    The present work aims at identifying the relative influence of GSHP subsystems (viz. ground source, earth heat exchangers, heat pump unit, pumping devices) on the overall efficiency and the limits to which technological improvements should be pushed (because, beyond these limits, only minor benefits may be achieved). To this end, an analysis of thermodynamic losses is conducted for a case study, followed by a sensitivity analysis on the heat pump unit thermal performance. Primary energy consumptions of nine configurations with different combinations of ideal and real subsystems are compared. The completely ideal system is used as the reference to normalize energy consumptions and obtain a dimensionless efficiency parameter. The results show that - when a proper design methodology is employed - the performance of the borehole heat exchangers slightly affects the overall efficiency. On the contrary, the thermal response of the ground and the thermal and hydraulic performances of the heat pump unit are key factors. Finally, a sensitivity analysis is conducted by increasing the heating and cooling efficiencies of the heat pump device.

  2. Thermodynamic and heat transfer analysis of LNG energy recovery for power production

    NASA Astrophysics Data System (ADS)

    Franco, A.; Casarosa, C.

    2014-11-01

    An important option to transport the gas is to convert it into liquid natural gas (LNG) and convey it using insulated LNG tankers. At receiving terminals, the LNG is offloaded into storage tanks and then pumped at the required pressure and vaporized for final transmission to the pipeline. The LNG production process consumes a considerable amount of energy, while the cold availability, as also known as cold energy, has been stored in LNG. At a receiving terminal, LNG needs to be evaporated into gas at environmental temperature before fed into the gas distribution system. Seawater is commonly used for the regasification process of the LNG. In the present paper, after a general analysis of the perspectives of the various thermodynamic schemes proposed for power production from the regasification, a detailed analysis of enhanced direct expansion system is carried out in order to identify the upper level of the energy that can be recovered. The analysis outlines that power production typical of optimized ORC plant configurations (120 kJ/kg) can be obtained with direct expansion solutions.

  3. Sensitivity analysis of geometric errors in additive manufacturing medical models.

    PubMed

    Pinto, Jose Miguel; Arrieta, Cristobal; Andia, Marcelo E; Uribe, Sergio; Ramos-Grez, Jorge; Vargas, Alex; Irarrazaval, Pablo; Tejos, Cristian

    2015-03-01

    Additive manufacturing (AM) models are used in medical applications for surgical planning, prosthesis design and teaching. For these applications, the accuracy of the AM models is essential. Unfortunately, this accuracy is compromised due to errors introduced by each of the building steps: image acquisition, segmentation, triangulation, printing and infiltration. However, the contribution of each step to the final error remains unclear. We performed a sensitivity analysis comparing errors obtained from a reference with those obtained modifying parameters of each building step. Our analysis considered global indexes to evaluate the overall error, and local indexes to show how this error is distributed along the surface of the AM models. Our results show that the standard building process tends to overestimate the AM models, i.e. models are larger than the original structures. They also show that the triangulation resolution and the segmentation threshold are critical factors, and that the errors are concentrated at regions with high curvatures. Errors could be reduced choosing better triangulation and printing resolutions, but there is an important need for modifying some of the standard building processes, particularly the segmentation algorithms.

  4. Nonparametric survival analysis using Bayesian Additive Regression Trees (BART).

    PubMed

    Sparapani, Rodney A; Logan, Brent R; McCulloch, Robert E; Laud, Purushottam W

    2016-07-20

    Bayesian additive regression trees (BART) provide a framework for flexible nonparametric modeling of relationships of covariates to outcomes. Recently, BART models have been shown to provide excellent predictive performance, for both continuous and binary outcomes, and exceeding that of its competitors. Software is also readily available for such outcomes. In this article, we introduce modeling that extends the usefulness of BART in medical applications by addressing needs arising in survival analysis. Simulation studies of one-sample and two-sample scenarios, in comparison with long-standing traditional methods, establish face validity of the new approach. We then demonstrate the model's ability to accommodate data from complex regression models with a simulation study of a nonproportional hazards scenario with crossing survival functions and survival function estimation in a scenario where hazards are multiplicatively modified by a highly nonlinear function of the covariates. Using data from a recently published study of patients undergoing hematopoietic stem cell transplantation, we illustrate the use and some advantages of the proposed method in medical investigations. Copyright © 2016 John Wiley & Sons, Ltd. PMID:26854022

  5. Model-based analysis of coupled equilibrium-kinetic processes: indirect kinetic studies of thermodynamic parameters using the dynamic data.

    PubMed

    Emami, Fereshteh; Maeder, Marcel; Abdollahi, Hamid

    2015-05-01

    Thermodynamic studies of equilibrium chemical reactions linked with kinetic procedures are mostly impossible by traditional approaches. In this work, the new concept of generalized kinetic study of thermodynamic parameters is introduced for dynamic data. The examples of equilibria intertwined with kinetic chemical mechanisms include molecular charge transfer complex formation reactions, pH-dependent degradation of chemical compounds and tautomerization kinetics in micellar solutions. Model-based global analysis with the possibility of calculating and embedding the equilibrium and kinetic parameters into the fitting algorithm has allowed the complete analysis of the complex reaction mechanisms. After the fitting process, the optimal equilibrium and kinetic parameters together with an estimate of their standard deviations have been obtained. This work opens up a promising new avenue for obtaining equilibrium constants through the kinetic data analysis for the kinetic reactions that involve equilibrium processes.

  6. ZnO:HCl single crystals: Thermodynamic analysis of CVT system, feature of growth and characterization

    NASA Astrophysics Data System (ADS)

    Colibaba, G. V.

    2016-06-01

    The full thermodynamic analysis of using HCl as a chemical vapor transport (CVT) agent (TA) for ZnO single crystals growth in closed growth chambers, including 16 chemical species, is carried out for wide temperature and loaded TA pressure ranges. The influence of the growth temperature, of the TA density and of the undercooling on the rate of ZnO mass transport was investigated theoretically and experimentally. It is shown that the mass transport is diffusion-limited at about 1050 °C, and it is limited by kinetics of the CVT reaction at lower temperatures. It is experimentally shown that using HCl favors obtaining void-free n-ZnO crystals with controllable electrical parameters, it reduces the effect of adhesiveness to the walls of the growth chamber. The characterization by the photoluminescence spectra, the transmission spectra and the electrical properties in the wide temperature range allowed analyzing energy spectra of Cl-containing stable defects in ZnO and electrical activity of Cl donors. Some methods of activation energy correction for Cl-containing centers are discussed.

  7. Thermodynamic analysis and performance of a 1 kW bioethanol processor for a PEMFC operation

    NASA Astrophysics Data System (ADS)

    Benito, M.; Padilla, R.; Sanz, J. L.; Daza, L.

    A thermodynamic analysis of a bioethanol steam reforming processor for CO-free hydrogen production was performed. The stages selected to perform CO purification were water gas shift and CO preferential oxidation. In order to optimize the processor efficiency, several configurations were studied. A processor efficiency of 69% for a steam/carbon ratio (S/C) of 4.8 was achieved taking advantage of the heat released during the exothermic stages. An efficiency close to 28% at the same S/C ratio for a bioethanol processor-PEMFC system, which includes a heat recovery system for off-gas from the fuel cell anode, was obtained. To produce a CO-free hydrogen rich stream, a 1 kW bioethanol processor was designed, built and operated, based on previous simulation studies. A new catalyst developed in the Institute of Catalysis and Petro-chemistry (ICP-CSIC) and tested for more than 500 h, that demonstrated excellent results at laboratory scale, was selected for the steam reforming stage. From bioethanol processor operation, a hydrogen rich stream, with CO composition as low as 3 ppmV was obtained, which is able to supply a PEMFC.

  8. Theoretical Analysis of Thermodynamic Measurements near a Liquid-Gas Critical Point

    NASA Technical Reports Server (NTRS)

    Barmatz, M.; Zhong, Fang; Hahn, Inseob

    2003-01-01

    Over the years, many ground-based studies have been performed near liquid-gas critical points to elucidate the expected divergences in thermodynamic quantities. The unambiguous interpretation of these studies very near the critical point is hindered by a gravity-induced density stratification. However, these ground-based measurements can give insight into the crossover behavior between the asymptotic critical region near the transition and the mean field region farther away. We have completed a detailed analysis of heat capacity, susceptibility and coexistence curve measurements near the He-3 liquid-gas critical point using the minimal-subtraction renormalization (MSR) scheme within the phi(exp 4) model. This MSR scheme, using only two adjustable parameters, provides a reasonable global fit to all of these experimental measurements in the gravity-free region out to a reduced temperature of |t| approx. 2x10(exp -2). Recently this approach has also been applied to the earlier microgravity measurements of Haupt and Straub in SF(sub 6) with surprising results. The conclusions drawn from the MSR analyses will be presented. Measurements in the gravity-affected region closer to the He-3 critical point have also been analyzed using the recent crossover parametric model (CPM) of the equation-of-state. The results of fitting heat capacity measurements to the CPM model along the He-3 critical isochore in the gravity-affected region will also be presented.

  9. Thermodynamic analysis of alternate energy carriers, hydrogen and chemical heat pipes

    NASA Technical Reports Server (NTRS)

    Cox, K. E.; Carty, R. H.; Conger, W. L.; Soliman, M. A.; Funk, J. E.

    1976-01-01

    The paper discusses the production concept and efficiency of two new energy transmission and storage media intended to overcome the disadvantages of electricity as an overall energy carrier. These media are hydrogen produced by water-splitting and the chemical heat pipe. Hydrogen can be transported or stored, and burned as energy is needed, forming only water and thus obviating pollution problems. The chemical heat pipe envisions a system in which heat is stored as the heat of reaction in chemical species. The thermodynamic analysis of these two methods is discussed in terms of first-law and second-law efficiency. It is concluded that chemical heat pipes offer large advantages over thermochemical hydrogen generation schemes on a first-law efficiency basis except for the degradation of thermal energy in temperature thus providing a source of low-temperature (800 K) heat for process heat applications. On a second-law efficiency basis, hydrogen schemes are superior in that the amount of available work is greater as compared to chemical heat pipes.

  10. Thermodynamic Analysis of Isothermal Redox Cycling of Ceria for Solar Fuel Production

    SciTech Connect

    Bader, R; Venstrom, LJ; Davidson, JH; Lipinski, W

    2013-09-01

    A thermodynamic analysis of continuous fuel production by redox cycling of ceria in a single solar reactor under isothermal conditions is presented. Ceria is partially reduced in a sweep gas flow of purified nitrogen and reoxidized with either steam or carbon dioxide to produce hydrogen or carbon monoxide, respectively. The sweep gas and oxidizer flows are preheated by the product gases. The influence of selected process parameters, including operating temperature, pressure, and the effectiveness of heat recovery, on the solar-to-fuel conversion efficiency is determined. For a solar concentration ratio of 3000, typical of state-of-the-art solar dish concentrators, and operating temperature of 1773 K, 95.5% of the available gas-phase heat must be recovered to reach conversion efficiencies of 10% and 18% for hydrogen and carbon monoxide production, respectively, assuming the flow rate of inert sweep gas is equivalent to that in a counter-current flow arrangement of gas and ceria. The efficiency depends strongly on the gas-phase heat recovery effectiveness and the sweep gas flow rate. Introducing a temperature swing of 150 K between reduction and oxidation steps strongly reduces the sweep gas flow rate and increases the efficiency from 10% to 31.6% for hydrogen production.

  11. Thermodynamic Analysis of Dual-Mode Scramjet Engine Operation and Performance

    NASA Technical Reports Server (NTRS)

    Riggins, David; Tacket, Regan; Taylor, Trent; Auslender, Aaron

    2006-01-01

    Recent analytical advances in understanding the performance continuum (the thermodynamic spectrum) for air-breathing engines based on fundamental second-law considerations have clarified scramjet and ramjet operation, performance, and characteristics. Second-law based analysis is extended specifically in this work to clarify and describe the performance characteristics for dual-mode scramjet operation in the mid-speed range of flight Mach 4 to 7. This is done by a fundamental investigation of the complex but predictable interplay between heat release and irreversibilities in such an engine; results demonstrate the flow and performance character of the dual mode regime and of dual mode transition behavior. Both analytical and computational (multi-dimensional CFD) studies of sample dual-mode flow-fields are performed in order to demonstrate the second-law capability and performance and operability issues. The impact of the dual-mode regime is found to be characterized by decreasing overall irreversibility with increasing heat release, within the operability limits of the system.

  12. Hydrophobic ion interactions with membranes. Thermodynamic analysis of tetraphenylphosphonium binding to vesicles.

    PubMed Central

    Flewelling, R F; Hubbell, W L

    1986-01-01

    The thermodynamic properties for the interaction of the hydrophobic ion tetraphenylphosphonium (TPP+) with egg phosphatidylcholine vesicles were studied in detail by equilibrium dialysis and spin label techniques. A partition coefficient of beta = 4.2 + 0.4 x 10(-6) cm (K congruent to 100) was determined. Electrostatic saturation sets in at approximately 600 microM (about one absorbed TPP+ molecule per 100 lipids), and is not screened by salt. The temperature dependence of binding was determined, which reveals that the binding is entropy-driven with a positive (repulsive) enthalpy of binding, a result to be compared with hydrophobic anions in which the binding enthalpy is negative. The membrane dipole potential may be responsible for this binding difference. Activity coefficients are determined and shown to be significantly different from those of most common salts, an important result that should be considered in all hydrophobic ion studies. Comparison of the TPP+ results with those of its anionic structural analogue, tetraphenylboron (TPB-), permits a general analysis of hydrophobic ion interactions with membranes. A theoretical model consistent with the entire set of data is developed in an accompanying article. PMID:3006814

  13. Assessment of the sustainability of technology by means of a thermodynamically based life cycle analysis.

    PubMed

    Dewulf, Jo; van Langenhove, Herman

    2002-01-01

    Life cycle analysis is one of the tools in the assessment of the sustainability of technological options. It takes into account all effects on the ecosystem and the population which may endanger the possibilities of current and future generations. However, the main bottleneck in current LCA methodologies is the balancing of different effects, being all quantified on different scales. In this work, a methodology is proposed, which allows one to quantify different effects of the production, consumption and disposal of goods, and services on a single scale. The basis of the methodology is the second law of thermodynamics. All production, consumption and disposal processes affecting the ecosystem and the population, are quantified in terms of loss of exergy. The exergy content of a material is the maximum amount of energy which can be transformed into work at given environmental conditions. Next to the elaboration of the methodology, the new approach is illustrated by examples of the production of synthetic organic polymers, inorganic building insulation materials and different waste gas treatment options.

  14. Precessing rotating flows with additional shear: Stability analysis

    NASA Astrophysics Data System (ADS)

    Salhi, A.; Cambon, C.

    2009-03-01

    We consider unbounded precessing rotating flows in which vertical or horizontal shear is induced by the interaction between the solid-body rotation (with angular velocity Ω0 ) and the additional “precessing” Coriolis force (with angular velocity -ɛΩ0 ), normal to it. A “weak” shear flow, with rate 2ɛ of the same order of the Poincaré “small” ratio ɛ , is needed for balancing the gyroscopic torque, so that the whole flow satisfies Euler’s equations in the precessing frame (the so-called admissibility conditions). The base flow case with vertical shear (its cross-gradient direction is aligned with the main angular velocity) corresponds to Mahalov’s [Phys. Fluids A 5, 891 (1993)] precessing infinite cylinder base flow (ignoring boundary conditions), while the base flow case with horizontal shear (its cross-gradient direction is normal to both main and precessing angular velocities) corresponds to the unbounded precessing rotating shear flow considered by Kerswell [Geophys. Astrophys. Fluid Dyn. 72, 107 (1993)]. We show that both these base flows satisfy the admissibility conditions and can support disturbances in terms of advected Fourier modes. Because the admissibility conditions cannot select one case with respect to the other, a more physical derivation is sought: Both flows are deduced from Poincaré’s [Bull. Astron. 27, 321 (1910)] basic state of a precessing spheroidal container, in the limit of small ɛ . A Rapid distortion theory (RDT) type of stability analysis is then performed for the previously mentioned disturbances, for both base flows. The stability analysis of the Kerswell base flow, using Floquet’s theory, is recovered, and its counterpart for the Mahalov base flow is presented. Typical growth rates are found to be the same for both flows at very small ɛ , but significant differences are obtained regarding growth rates and widths of instability bands, if larger ɛ values, up to 0.2, are considered. Finally, both flow cases

  15. The thermodynamics of general and local anesthesia.

    PubMed

    Graesbøll, Kaare; Sasse-Middelhoff, Henrike; Heimburg, Thomas

    2014-05-20

    General anesthetics are known to cause depression of the freezing point of transitions in biomembranes. This is a consequence of ideal mixing of the anesthetic drugs in the membrane fluid phase and exclusion from the solid phase. Such a generic law provides physical justification of the famous Meyer-Overton rule. We show here that general anesthetics, barbiturates, and local anesthetics all display the same effect on melting transitions. Their effect is reversed by hydrostatic pressure. Thus, the thermodynamic behavior of local anesthetics is very similar to that of general anesthetics. We present a detailed thermodynamic analysis of heat capacity profiles of membranes in the presence of anesthetics. Using this analysis, we are able to describe experimentally observed calorimetric profiles and predict the anesthetic features of arbitrary molecules. In addition, we discuss the thermodynamic origin of the cutoff effect of long-chain alcohols and the additivity of the effect of general and local anesthetics. PMID:24853743

  16. The Thermodynamics of General and Local Anesthesia

    PubMed Central

    Græsbøll, Kaare; Sasse-Middelhoff, Henrike; Heimburg, Thomas

    2014-01-01

    General anesthetics are known to cause depression of the freezing point of transitions in biomembranes. This is a consequence of ideal mixing of the anesthetic drugs in the membrane fluid phase and exclusion from the solid phase. Such a generic law provides physical justification of the famous Meyer-Overton rule. We show here that general anesthetics, barbiturates, and local anesthetics all display the same effect on melting transitions. Their effect is reversed by hydrostatic pressure. Thus, the thermodynamic behavior of local anesthetics is very similar to that of general anesthetics. We present a detailed thermodynamic analysis of heat capacity profiles of membranes in the presence of anesthetics. Using this analysis, we are able to describe experimentally observed calorimetric profiles and predict the anesthetic features of arbitrary molecules. In addition, we discuss the thermodynamic origin of the cutoff effect of long-chain alcohols and the additivity of the effect of general and local anesthetics. PMID:24853743

  17. The Thermodynamics of General and Local Anesthesia

    NASA Astrophysics Data System (ADS)

    Græsbøll, Kaare; Sasse-Middelhoff, Henrike; Heimburg, Thomas

    2014-05-01

    General anesthetics are known to cause depression of the freezing point of transitions in biomembranes. This is a consequence of ideal mixing of the anesthetic drugs in the membrane fluid phase and exclusion from the solid phase. Such a generic law provides physical justification of the famous Meyer-Overton rule. We show here that general anesthetics, barbiturates and local anesthetics all display the same effect on melting transitions. Their effect is reversed by hydrostatic pressure. Thus, the thermodynamic behavior of local anesthetics is very similar to that of general anesthetics. We present a detailed thermodynamic analysis of heat capacity profiles of membranes in the presence of anesthetics. This analysis is able to describe experimentally observed calorimetric profiles and permits prediction of the anesthetic features of arbitrary molecules. In addition, we discuss the thermodynamic origin of the cutoff-effect of long-chain alcohols and the additivity of the effect of general and local anesthetics.

  18. The thermodynamics of general and local anesthesia.

    PubMed

    Graesbøll, Kaare; Sasse-Middelhoff, Henrike; Heimburg, Thomas

    2014-05-20

    General anesthetics are known to cause depression of the freezing point of transitions in biomembranes. This is a consequence of ideal mixing of the anesthetic drugs in the membrane fluid phase and exclusion from the solid phase. Such a generic law provides physical justification of the famous Meyer-Overton rule. We show here that general anesthetics, barbiturates, and local anesthetics all display the same effect on melting transitions. Their effect is reversed by hydrostatic pressure. Thus, the thermodynamic behavior of local anesthetics is very similar to that of general anesthetics. We present a detailed thermodynamic analysis of heat capacity profiles of membranes in the presence of anesthetics. Using this analysis, we are able to describe experimentally observed calorimetric profiles and predict the anesthetic features of arbitrary molecules. In addition, we discuss the thermodynamic origin of the cutoff effect of long-chain alcohols and the additivity of the effect of general and local anesthetics.

  19. Thermodynamic Diagrams

    NASA Astrophysics Data System (ADS)

    Chaston, Scot

    1999-02-01

    Thermodynamic data such as equilibrium constants, standard cell potentials, molar enthalpies of formation, and standard entropies of substances can be a very useful basis for an organized presentation of knowledge in diverse areas of applied chemistry. Thermodynamic data can become particularly useful when incorporated into thermodynamic diagrams that are designed to be easy to recall, to serve as a basis for reconstructing previous knowledge, and to determine whether reactions can occur exergonically or only with the help of an external energy source. Few students in our chemistry-based courses would want to acquire the depth of knowledge or rigor of professional thermodynamicists. But they should nevertheless learn how to make good use of thermodynamic data in their professional occupations that span the chemical, biological, environmental, and medical laboratory fields. This article discusses examples of three thermodynamic diagrams that have been developed for this purpose. They are the thermodynamic energy account (TEA), the total entropy scale, and the thermodynamic scale diagrams. These diagrams help in the teaching and learning of thermodynamics by bringing the imagination into the process of developing a better understanding of abstract thermodynamic functions, and by allowing the reader to keep track of specialist thermodynamic discourses in the literature.

  20. Life cycle assessment integrated with thermodynamic analysis of bio-fuel options for solid oxide fuel cells.

    PubMed

    Lin, Jiefeng; Babbitt, Callie W; Trabold, Thomas A

    2013-01-01

    A methodology that integrates life cycle assessment (LCA) with thermodynamic analysis is developed and applied to evaluate the environmental impacts of producing biofuels from waste biomass, including biodiesel from waste cooking oil, ethanol from corn stover, and compressed natural gas from municipal solid wastes. Solid oxide fuel cell-based auxiliary power units using bio-fuel as the hydrogen precursor enable generation of auxiliary electricity for idling heavy-duty trucks. Thermodynamic analysis is applied to evaluate the fuel conversion efficiency and determine the amount of fuel feedstock needed to generate a unit of electrical power. These inputs feed into an LCA that compares energy consumption and greenhouse gas emissions of different fuel pathways. Results show that compressed natural gas from municipal solid wastes is an optimal bio-fuel option for SOFC-APU applications in New York State. However, this methodology can be regionalized within the U.S. or internationally to account for different fuel feedstock options. PMID:23201905

  1. Life cycle assessment integrated with thermodynamic analysis of bio-fuel options for solid oxide fuel cells.

    PubMed

    Lin, Jiefeng; Babbitt, Callie W; Trabold, Thomas A

    2013-01-01

    A methodology that integrates life cycle assessment (LCA) with thermodynamic analysis is developed and applied to evaluate the environmental impacts of producing biofuels from waste biomass, including biodiesel from waste cooking oil, ethanol from corn stover, and compressed natural gas from municipal solid wastes. Solid oxide fuel cell-based auxiliary power units using bio-fuel as the hydrogen precursor enable generation of auxiliary electricity for idling heavy-duty trucks. Thermodynamic analysis is applied to evaluate the fuel conversion efficiency and determine the amount of fuel feedstock needed to generate a unit of electrical power. These inputs feed into an LCA that compares energy consumption and greenhouse gas emissions of different fuel pathways. Results show that compressed natural gas from municipal solid wastes is an optimal bio-fuel option for SOFC-APU applications in New York State. However, this methodology can be regionalized within the U.S. or internationally to account for different fuel feedstock options.

  2. Dynamical and thermodynamical analysis of the South China Sea winter cold tongue

    NASA Astrophysics Data System (ADS)

    Thompson, Bijoy; Tkalich, Pavel; Malanotte-Rizzoli, Paola; Fricot, Bastien; Mas, Juliette

    2015-12-01

    Spatial distribution of the South China Sea (SCS) surface temperature shows strong cold anomalies over the Sunda Shelf during the boreal winter season. The band of low sea surface temperature (SST) region located south/southeast of Vietnam is called as the winter cold tongue (CT) in the SCS. Using observational and re-analysis datasets a comprehensive investigation of the dynamical and thermodynamical processes associated with the evolution of SCS CT is performed in this study. The role and relative importance of wind-driven ocean transports, air-sea heat fluxes and oceanic processes are explored. The north-south Sverdrup transport demonstrates strong southward transport during the northeast monsoon period aiding the SST cooling by bringing relatively cold water from the north. The zonal and meridional Ekman transports exhibit relatively weak westward and northward transports to the CT region during this period. The study suggests that wind-driven ocean transports have a significant role in regulating the shape and spatial extent of the CT. The heat budget analysis revealed that net surface heat flux decrease during the northeast monsoon acts as the primary cooling mechanism responsible for the development of the SCS CT, while the horizontal advection of cold water by the western boundary current along the coast of Vietnam plays a secondary role. The wintertime SST anomalies over the CT region are significantly linked to the Nino3 index. Most of the warming/cooling events in the SST anomalies coincide with the El Nino/La Nina phenomena in the Pacific Ocean.

  3. Dynamical and thermodynamical analysis of the South China Sea winter cold tongue

    NASA Astrophysics Data System (ADS)

    Thompson, Bijoy; Tkalich, Pavel; Malanotte-Rizzoli, Paola; Fricot, Bastien; Mas, Juliette

    2016-09-01

    Spatial distribution of the South China Sea (SCS) surface temperature shows strong cold anomalies over the Sunda Shelf during the boreal winter season. The band of low sea surface temperature (SST) region located south/southeast of Vietnam is called as the winter cold tongue (CT) in the SCS. Using observational and re-analysis datasets a comprehensive investigation of the dynamical and thermodynamical processes associated with the evolution of SCS CT is performed in this study. The role and relative importance of wind-driven ocean transports, air-sea heat fluxes and oceanic processes are explored. The north-south Sverdrup transport demonstrates strong southward transport during the northeast monsoon period aiding the SST cooling by bringing relatively cold water from the north. The zonal and meridional Ekman transports exhibit relatively weak westward and northward transports to the CT region during this period. The study suggests that wind-driven ocean transports have a significant role in regulating the shape and spatial extent of the CT. The heat budget analysis revealed that net surface heat flux decrease during the northeast monsoon acts as the primary cooling mechanism responsible for the development of the SCS CT, while the horizontal advection of cold water by the western boundary current along the coast of Vietnam plays a secondary role. The wintertime SST anomalies over the CT region are significantly linked to the Nino3 index. Most of the warming/cooling events in the SST anomalies coincide with the El Nino/La Nina phenomena in the Pacific Ocean.

  4. Substrate preference of a Geobacillus maltogenic amylase: a kinetic and thermodynamic analysis.

    PubMed

    Nasrollahi, Samira; Golalizadeh, Leila; Sajedi, Reza H; Taghdir, Majid; Asghari, S Mohsen; Rassa, Mehdi

    2013-09-01

    The gene encoding a maltogenic amylase (MAase) from a newly isolated strain of thermophilic Geobacillus has been isolated, cloned and expressed. Following purification, biochemical and structural characterization have been performed. The enzyme exhibited maximal activity at a broad temperature range between 55 and 65 °C, clearly higher than that of other dimeric MAses. The optimum pH was 6.0 and catalytic activity increased by of Li(+) and K(+). A noticeable preference was demonstrated for α-, β- and γ-cyclodextrin (CD) compared to polymeric substrates (amylose, amylopectin, glycogen and starch) possibly due to steric interference. The affinity for CD substrates increased in the order of γ-CD>β-CD>α-CD, but k(cat)/K(m) increased as α-CD>β-CD>γ-CD, implying that increased substrate specificities are mainly attribute to kcat. Thermodynamic analysis of the activation process showed that improved activity (decrease in ΔG(#)) is accompanied by increases in activation entropy (ΔS(#)) for aforementioned substrates. Molecular docking on the binding interactions between substrates and active site residues revealed a considerably higher accessible surface area for the active site residues in the presence of α-CD than β-CD, indicating that interactions in the transition state are stronger in the presence of α-CD. This result explains the increased ΔH(#) of the activation process and increased K(m) of the enzyme in the presence of α-CD, compared to that of β-CD. This study, which presents the first detailed comparative analysis on the substrate preference of dimeric MAases for different substrates, may shed some lights into the molecular mechanism of these enzymes.

  5. Hybrid Additive Manufacturing Technologies - An Analysis Regarding Potentials and Applications

    NASA Astrophysics Data System (ADS)

    Merklein, Marion; Junker, Daniel; Schaub, Adam; Neubauer, Franziska

    Imposing the trend of mass customization of lightweight construction in industry, conventional manufacturing processes like forming technology and chipping production are pushed to their limits for economical manufacturing. More flexible processes are needed which were developed by the additive manufacturing technology. This toolless production principle offers a high geometrical freedom and an optimized utilization of the used material. Thus load adjusted lightweight components can be produced in small lot sizes in an economical way. To compensate disadvantages like inadequate accuracy and surface roughness hybrid machines combining additive and subtractive manufacturing are developed. Within this paper the principles of mainly used additive manufacturing processes of metals and their possibility to be integrated into a hybrid production machine are summarized. It is pointed out that in particular the integration of deposition processes into a CNC milling center supposes high potential for manufacturing larger parts with high accuracy. Furthermore the combination of additive and subtractive manufacturing allows the production of ready to use products within one single machine. Additionally actual research for the integration of additive manufacturing processes into the production chain will be analyzed. For the long manufacturing time of additive production processes the combination with conventional manufacturing processes like sheet or bulk metal forming seems an effective solution. Especially large volumes can be produced by conventional processes. In an additional production step active elements can be applied by additive manufacturing. This principle is also investigated for tool production to reduce chipping of the high strength material used for forming tools. The aim is the addition of active elements onto a geometrical simple basis by using Laser Metal Deposition. That process allows the utilization of several powder materials during one process what

  6. GISH analysis of disomic Brassica napus-Crambe abyssinica chromosome addition lines produced by microspore culture from monosomic addition lines.

    PubMed

    Wang, Youping; Sonntag, Karin; Rudloff, Eicke; Wehling, Peter; Snowdon, Rod J

    2006-02-01

    Two Brassica napus-Crambe abyssinica monosomic addition lines (2n=39, AACC plus a single chromosome from C. abyssinca) were obtained from the F(2) progeny of the asymmetric somatic hybrid. The alien chromosome from C. abyssinca in the addition line was clearly distinguished by genomic in situ hybridization (GISH). Twenty-seven microspore-derived plants from the addition lines were obtained. Fourteen seedlings were determined to be diploid plants (2n=38) arising from spontaneous chromosome doubling, while 13 seedlings were confirmed as haploid plants. Doubled haploid plants produced after treatment with colchicine and two disomic chromosome addition lines (2n=40, AACC plus a single pair of homologous chromosomes from C. abyssinca) could again be identified by GISH analysis. The lines are potentially useful for molecular genetic analysis of novel C. abyssinica genes or alleles contributing to traits relevant for oilseed rape (B. napus) breeding.

  7. Thermodynamic analysis of the selective carbothermic reduction of electric arc furnace dust.

    PubMed

    Pickles, C A

    2008-01-31

    Electric arc furnace (EAF) dust, which is produced as a result of the melting of automobile scrap in an electric arc furnace, contains considerable amounts of zinc and lead, which are of significant economic value. Typically, the other major components are iron oxide and calcium oxide with minor amounts of other metal oxides. In this research, a detailed thermodynamic study of the pyrometallurgical processing of the dust, using carbon as a reducing agent was performed. The SOLGASMIX solver of Outokumpu HSC Chemistry((R)) 5.1 was used to calculate the equilibrium composition under reducing conditions. The control input dust composition was as follows (in mass percent): 8.100% CaO, 8.250% 2CaO.SiO(2), 11.200% CaCO(3), 8.830% CaO.Fe(2)O(3), 7.840% Fe(3)O(4), 3.770% PbO, 38.150% ZnFe(2)O(4) and 13.860% ZnO. Selective reduction and separation of both the zinc and the lead as metallic vapours, from the iron, in oxide form, was examined. The separation of the zinc or the lead from the iron, was defined quantitatively in terms of the selectivity factor (logbeta) as follows. Equation [see the text] where the subscript symbols refer to the metal being present in gaseous (g), metallic solid (m), solid oxide (o) or metallic liquid (l) form, respectively. The standard calculations were performed for one hundred grams of dust at atmospheric pressure. The variables investigated were as follows; temperature in the range of 1273-1873K, reactant ratio (i.e. moles of carbon per gram of dust), dust composition, addition of inert gas and reduced total pressure. The calculated values were in reasonable agreement with those from previously published studies and also industrial results.

  8. A fundamental approach to adhesion: Synthesis, surface analysis, thermodynamics and mechanics

    NASA Technical Reports Server (NTRS)

    Chen, W.; Wightman, J. P.

    1979-01-01

    Adherend surfaces and fractography were studied using electron spectroscopy for chemical analysis and scanning electron microscopy/energy dispersive analysis of X-rays. In addition, Auger Electron Spectroscopy with depth profiling capability was used. It is shown that contamination of adhesion systems plays an important role not only in determining initial bond strengths but also in the durability of adhesive bonds. It is concluded that the analytical techniques used to characterize and monitor such contamination.

  9. Thermodynamic estimation: Ionic materials

    SciTech Connect

    Glasser, Leslie

    2013-10-15

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

  10. Thermodynamic analysis of F1-ATPase rotary catalysis using high-speed imaging

    PubMed Central

    Watanabe, Rikiya; Minagawa, Yoshihiro; Noji, Hiroyuki

    2014-01-01

    F1-ATPase (F1) is a rotary motor protein fueled by ATP hydrolysis. Although the mechanism for coupling rotation and catalysis has been well studied, the molecular details of individual reaction steps remain elusive. In this study, we performed high-speed imaging of F1 rotation at various temperatures using the total internal reflection dark-field (TIRDF) illumination system, which allows resolution of the F1 catalytic reaction into elementary reaction steps with a high temporal resolution of 72 µs. At a high concentration of ATP, F1 rotation comprised distinct 80° and 40° substeps. The 80° substep, which exhibited significant temperature dependence, is triggered by the temperature-sensitive reaction, whereas the 40° substep is triggered by ATP hydrolysis and the release of inorganic phosphate (Pi). Then, we conducted Arrhenius analysis of the reaction rates to obtain the thermodynamic parameters for individual reaction steps, that is, ATP binding, ATP hydrolysis, Pi release, and TS reaction. Although all reaction steps exhibited similar activation free energy values, ΔG‡ = 53–56 kJ mol−1, the contributions of the enthalpy (ΔH‡), and entropy (ΔS‡) terms were significantly different; the reaction steps that induce tight subunit packing, for example, ATP binding and TS reaction, showed high positive values of both ΔH‡ and ΔS‡. The results may reflect modulation of the excluded volume as a function of subunit packing tightness at individual reaction steps, leading to a gain or loss in water entropy. PMID:25262814

  11. Thermodynamic analysis of the interaction of partially hydrophobic cationic polyelectrolytes with sodium halide salts in water

    NASA Astrophysics Data System (ADS)

    Bončina, Matjaž; Lukšič, Miha; Seručnik, Mojca; Vlachy, Vojko

    2014-05-01

    Isothermal titration calorimetry was used to determine the temperature and concentration dependence of the enthalpy of mixing of 3,3- and 6,6-ionene fluorides, bromides, and iodides with low molecular weight salts (NaF, NaCl, NaBr, and NaI) in water. The magnitudes of the enthalpies, measured in the temperature range from 273 to 318 K, depended on the number of methylene groups on the ionene polyion (hydrophobicity), and on the anion of the added salt (ion-specificity). All enthalpies of mixing of 3,3- and 6,6-ionene fluorides with low molecular weight salts (NaCl, NaBr, and NaI) were negative, which is in contrast to the predictions of standard theories of polyelectrolyte solutions. This fact was interpreted in the light of the ion-water short-range interactions that are not accounted for in those theories. In contrast, the enthalpies of mixing of 3,3- and 6,6-ionene bromides and iodides with NaF were positive, being in accord with theory. Using the calorimetric data, we performed a model thermodynamic analysis of the polyelectrolyte-salt mixing process to obtain changes in the apparent standard Gibbs free energy, enthalpy, entropy, and heat capacity relative to the pure ionene fluorides in water. The results prove that halide ions replace fluoride counterions with a strength increasing in the order chloride < bromide < iodide. The process is enthalpy governed, accompanied by a positive change in the heat capacity.

  12. Thermodynamic analysis of F1-ATPase rotary catalysis using high-speed imaging.

    PubMed

    Watanabe, Rikiya; Minagawa, Yoshihiro; Noji, Hiroyuki

    2014-12-01

    F1-ATPase (F1) is a rotary motor protein fueled by ATP hydrolysis. Although the mechanism for coupling rotation and catalysis has been well studied, the molecular details of individual reaction steps remain elusive. In this study, we performed high-speed imaging of F1 rotation at various temperatures using the total internal reflection dark-field (TIRDF) illumination system, which allows resolution of the F1 catalytic reaction into elementary reaction steps with a high temporal resolution of 72 µs. At a high concentration of ATP, F1 rotation comprised distinct 80° and 40° substeps. The 80° substep, which exhibited significant temperature dependence, is triggered by the temperature-sensitive reaction, whereas the 40° substep is triggered by ATP hydrolysis and the release of inorganic phosphate (Pi). Then, we conducted Arrhenius analysis of the reaction rates to obtain the thermodynamic parameters for individual reaction steps, that is, ATP binding, ATP hydrolysis, Pi release, and TS reaction. Although all reaction steps exhibited similar activation free energy values, ΔG(‡) = 53-56 kJ mol(-1), the contributions of the enthalpy (ΔH(‡)), and entropy (ΔS(‡)) terms were significantly different; the reaction steps that induce tight subunit packing, for example, ATP binding and TS reaction, showed high positive values of both ΔH(‡) and ΔS(‡). The results may reflect modulation of the excluded volume as a function of subunit packing tightness at individual reaction steps, leading to a gain or loss in water entropy.

  13. Analysis of elevated temperature data for thermodynamic properties of selected radionuclides

    SciTech Connect

    Wruck, D.A.; Palmer, C.E.A.

    1997-08-01

    This report is a review of chemical thermodynamic data for Ni, Zr, Tc, U, Np, Pu and Am in aqueous solutions at elevated temperatures. Thermodynamic data for aqueous reactions over the temperature range 20-150{degrees}C are needed for geochemical modeling studies of the Yucca Mountain Project. The present review is focused on the aqueous complexes relevant to expected conditions in the Yucca Mountain region: primarily the hydroxide, carbonate, sulfate and fluoride complexes with the metal ions. Existing thermodynamic data are evaluated, and means of extrapolating 25{degrees}C data to the temperatures of interest are discussed. There will be a separate review of solubility data for relevant Ni, Zr, Tc, Np, Pu and Am compounds.

  14. 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

  15. Thermodynamic analysis of chemical compatibility of several reinforcement materials with niobium aluminides. Final contractor report

    SciTech Connect

    Misra, A.K.

    1989-03-01

    Chemical compatibility of several reinforcement materials with three niobium aluminides, Nb3Al, Nb2Al, and NbAl3, were examined from thermodynamic considerations. The reinforcement materials considered in this study include carbides, borides, nitrides, oxides, silicides, and Engel-Brewer compounds. Thermodynamics of the Nb-Al system were reviewed and activities of Nb and Al were derived at desired calculation temperatures. Criteria for chemical compatibility between the reinforcement material and Nb-Al compounds have been defined and several chemically compatible reinforcement materials have been identified.

  16. Thermodynamic analysis of compatibility of several reinforcement materials with beta phase NiAl alloys

    NASA Technical Reports Server (NTRS)

    Misra, Ajay K.

    1988-01-01

    Chemical compatibility of several reinforcement materials with beta phase NiAl alloys within the concentration range 40 to 50 at. percent Al have been analyzed from thermodynamic considerations at 1373 and 1573 K. The reinforcement materials considered in this study include carbides, borides, oxides, nitrides, beryllides, and silicides. Thermodynamic data for NiAl alloys have been reviewed and activity of Ni and Al in the beta phase have been derived at 1373 and 1573 K. Criteria for chemical compatibility between the reinforcement material and the matrix have been defined and several chemically compatible reinforcement materials have been defined.

  17. Thermodynamic analysis of chemical compatibility of several reinforcement materials with niobium aluminides

    NASA Technical Reports Server (NTRS)

    Misra, Ajay K.

    1989-01-01

    Chemical compatibility of several reinforcement materials with three niobium aluminides, Nb3Al, Nb2Al, and NbAl3, were examined from thermodynamic considerations. The reinforcement materials considered in this study include carbides, borides, nitrides, oxides, silicides, and Engel-Brewer compounds. Thermodynamics of the Nb-Al system were reviewed and activities of Nb and Al were derived at desired calculation temperatures. Criteria for chemical compatibility between the reinforcement material and Nb-Al compounds have been defined and several chemically compatible reinforcement materials have been identified.

  18. Thermodynamic analysis of chemical compatibility of ceramic reinforcement materials with niobium aluminides

    NASA Technical Reports Server (NTRS)

    Misra, Ajay K.

    1990-01-01

    Chemical compatibility of several reinforcement materials with three niobium aluminides, Nb3Al, Nb2Al, and NbAl3, were examined from thermodynamic considerations. The reinforcement materials considered in this study include carbides, borides, nitrides, oxides, silicides, and Engel-Brewer compounds. Thermodynamics of the Nb-Al system were reviewed and activities of Nb and Al were derived at desired calculation temperatures. Criteria for chemical compatibility between the reinforcement material and Nb-Al compounds have been defined and several chemically compatible reinforcement materials have been identified.

  19. Coverage-dependent thermodynamic analysis of the formation of water and hydrogen peroxide on a platinum model catalyst.

    PubMed

    de Morais, Rodrigo Ferreira; Franco, Alejandro A; Sautet, Philippe; Loffreda, David

    2015-05-01

    Understanding the selectivity of the oxygen reduction reaction, especially the formation of water versus hydrogen peroxide in fuel cells, is an ongoing challenge in electrochemistry, surface science and catalysis. In this study, we propose a comprehensive thermodynamic analysis of the reaction intermediates for the formation of water on Pt(111). Density functional theory calculations of all the elementary steps linking hydroxyl and hydroperoxyl surface species with water and hydrogen peroxide have been performed at low (1/12 ML, ML = monolayer) and high (1/4 ML) coverages. The reaction energy variation for the two competing elementary events (molecular oxygen dissociation and hydroperoxyl formation) is strongly coverage-dependent. For the direct dissociation, an increase is observed at low coverage with respect to the usual high coverage picture. The stability of the reaction intermediates is investigated from thermodynamic diagrams. At 353 K and a total pressure of 1 atm, water and hydroxyl surface species are expected to compete for adsorption on Pt(111).

  20. Effect of temperature on microbial growth rate - thermodynamic analysis, the arrhenius and eyring-polanyi connection

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The objective of this work is to develop a new thermodynamic mathematical model for evaluating the effect of temperature on the rate of microbial growth. The new mathematical model is derived by combining the Arrhenius equation and the Eyring-Polanyi transition theory. The new model, suitable for ...

  1. Thermodynamic analysis of endogeneous fluid systems: The paradigm shift of the 21st century

    NASA Astrophysics Data System (ADS)

    Letnikov, F. A.

    2016-06-01

    At the end of the 20th century, the methods of equilibrium thermodynamics in studying natural fluid systems were replaced by synergetics, a more general paradigm. The main difference of the synergetic approach is its interdisciplinary character, and one of its achievements is understanding the role of governing parameters in particular fluid systems and introducing the concept of endogeneous fluid systems as polystationary systems.

  2. Thermodynamic analysis of the process of formation of sulfur compounds in oxygen gasification of coal

    SciTech Connect

    G.Ya. Gerasimov; T.M. Bogacheva

    2001-05-15

    A thermodynamic approach to the description of the behavior of the system fuel-oxidizer in oxygen gasification of coal is used to reveal the main mechanisms of the process of capture of sulfur by the mineral part of the coal and to determine the fundamental possibility of the process for coals from different coal fields.

  3. Discovering the Thermodynamics of Simultaneous Equilibria: An Entropy Analysis Activity Involving Consecutive Equilibria

    ERIC Educational Resources Information Center

    Bindel, Thomas H.

    2007-01-01

    An activity is presented in which the thermodynamics of simultaneous, consecutive equilibria are explored. The activity is appropriate for second-year high school or AP chemistry. Students discover that a reactant-favored (entropy-diminishing or endergonic) reaction can be caused to happen if it is coupled with a product-favored reaction of…

  4. Thermodynamics of downhill folding: multi-probe analysis of PDD, a protein that folds over a marginal free energy barrier.

    PubMed

    Naganathan, Athi N; Muñoz, Victor

    2014-07-31

    Downhill folding proteins fold in microseconds by crossing a very low or no free energy barrier (<3 RT), and exhibit a complex unfolding behavior in equilibrium. Such unfolding complexity is due to the weak thermodynamic coupling that exists between the various structural segments of these proteins, and it is manifested in unfolding curves that differ depending on the structural probe employed to monitor the process. Probe-dependent unfolding has important practical implications because it permits one to investigate the folding energy landscape in detail using multiprobe thermodynamic experiments. This type of thermodynamic behavior has been investigated in depth on the protein BBL, an example of extreme (one-state) downhill folding in which there is no free energy barrier at any condition, including the denaturation midpoint. However, an open question is, to what extent is such thermodynamic behavior observed on less extreme downhill folders? Here we perform a multiprobe spectroscopic characterization of the microsecond folder PDD, a structural and functional homologue of BBL that folds within the downhill regime, but is not an example of one-state downhill folding; rather at the denaturation midpoint PDD folds by crossing an incipient free energy barrier. Model-free analysis of the unfolding curves from four different spectroscopic probes together with differential scanning calorimetry reveals a dispersion of ∼9 K in the apparent melting temperature and also marked differences in unfolding broadness (from ∼50 to ∼130 kJ mol(-1) when analyzed with a two-state model), confirming that such properties are also observed on less extreme downhill folders. We subsequently perform a global quantitative analysis of the unfolding data of PDD using the same ME statistical mechanical model that was used before for the BBL domain. The analysis shows that this simple model captures all of the features observed on the unfolding of PDD (i.e., the intensity and temperature

  5. Thermodynamics of downhill folding: multi-probe analysis of PDD, a protein that folds over a marginal free energy barrier.

    PubMed

    Naganathan, Athi N; Muñoz, Victor

    2014-07-31

    Downhill folding proteins fold in microseconds by crossing a very low or no free energy barrier (<3 RT), and exhibit a complex unfolding behavior in equilibrium. Such unfolding complexity is due to the weak thermodynamic coupling that exists between the various structural segments of these proteins, and it is manifested in unfolding curves that differ depending on the structural probe employed to monitor the process. Probe-dependent unfolding has important practical implications because it permits one to investigate the folding energy landscape in detail using multiprobe thermodynamic experiments. This type of thermodynamic behavior has been investigated in depth on the protein BBL, an example of extreme (one-state) downhill folding in which there is no free energy barrier at any condition, including the denaturation midpoint. However, an open question is, to what extent is such thermodynamic behavior observed on less extreme downhill folders? Here we perform a multiprobe spectroscopic characterization of the microsecond folder PDD, a structural and functional homologue of BBL that folds within the downhill regime, but is not an example of one-state downhill folding; rather at the denaturation midpoint PDD folds by crossing an incipient free energy barrier. Model-free analysis of the unfolding curves from four different spectroscopic probes together with differential scanning calorimetry reveals a dispersion of ∼9 K in the apparent melting temperature and also marked differences in unfolding broadness (from ∼50 to ∼130 kJ mol(-1) when analyzed with a two-state model), confirming that such properties are also observed on less extreme downhill folders. We subsequently perform a global quantitative analysis of the unfolding data of PDD using the same ME statistical mechanical model that was used before for the BBL domain. The analysis shows that this simple model captures all of the features observed on the unfolding of PDD (i.e., the intensity and temperature

  6. Porosity Measurements and Analysis for Metal Additive Manufacturing Process Control.

    PubMed

    Slotwinski, John A; Garboczi, Edward J; Hebenstreit, Keith M

    2014-01-01

    Additive manufacturing techniques can produce complex, high-value metal parts, with potential applications as critical metal components such as those found in aerospace engines and as customized biomedical implants. Material porosity in these parts is undesirable for aerospace parts - since porosity could lead to premature failure - and desirable for some biomedical implants - since surface-breaking pores allows for better integration with biological tissue. Changes in a part's porosity during an additive manufacturing build may also be an indication of an undesired change in the build process. Here, we present efforts to develop an ultrasonic sensor for monitoring changes in the porosity in metal parts during fabrication on a metal powder bed fusion system. The development of well-characterized reference samples, measurements of the porosity of these samples with multiple techniques, and correlation of ultrasonic measurements with the degree of porosity are presented. A proposed sensor design, measurement strategy, and future experimental plans on a metal powder bed fusion system are also presented.

  7. Porosity Measurements and Analysis for Metal Additive Manufacturing Process Control.

    PubMed

    Slotwinski, John A; Garboczi, Edward J; Hebenstreit, Keith M

    2014-01-01

    Additive manufacturing techniques can produce complex, high-value metal parts, with potential applications as critical metal components such as those found in aerospace engines and as customized biomedical implants. Material porosity in these parts is undesirable for aerospace parts - since porosity could lead to premature failure - and desirable for some biomedical implants - since surface-breaking pores allows for better integration with biological tissue. Changes in a part's porosity during an additive manufacturing build may also be an indication of an undesired change in the build process. Here, we present efforts to develop an ultrasonic sensor for monitoring changes in the porosity in metal parts during fabrication on a metal powder bed fusion system. The development of well-characterized reference samples, measurements of the porosity of these samples with multiple techniques, and correlation of ultrasonic measurements with the degree of porosity are presented. A proposed sensor design, measurement strategy, and future experimental plans on a metal powder bed fusion system are also presented. PMID:26601041

  8. Porosity Measurements and Analysis for Metal Additive Manufacturing Process Control

    PubMed Central

    Slotwinski, John A; Garboczi, Edward J; Hebenstreit, Keith M

    2014-01-01

    Additive manufacturing techniques can produce complex, high-value metal parts, with potential applications as critical metal components such as those found in aerospace engines and as customized biomedical implants. Material porosity in these parts is undesirable for aerospace parts - since porosity could lead to premature failure - and desirable for some biomedical implants - since surface-breaking pores allows for better integration with biological tissue. Changes in a part’s porosity during an additive manufacturing build may also be an indication of an undesired change in the build process. Here, we present efforts to develop an ultrasonic sensor for monitoring changes in the porosity in metal parts during fabrication on a metal powder bed fusion system. The development of well-characterized reference samples, measurements of the porosity of these samples with multiple techniques, and correlation of ultrasonic measurements with the degree of porosity are presented. A proposed sensor design, measurement strategy, and future experimental plans on a metal powder bed fusion system are also presented. PMID:26601041

  9. Additional EIPC Study Analysis: Interim Report on High Priority Topics

    SciTech Connect

    Hadley, Stanton W

    2013-11-01

    Between 2010 and 2012 the Eastern Interconnection Planning Collaborative (EIPC) conducted a major long-term resource and transmission study of the Eastern Interconnection (EI). With guidance from a Stakeholder Steering Committee (SSC) that included representatives from the Eastern Interconnection States Planning Council (EISPC) among others, the project was conducted in two phases. Phase 1 involved a long-term capacity expansion analysis that involved creation of eight major futures plus 72 sensitivities. Three scenarios were selected for more extensive transmission- focused evaluation in Phase 2. Five power flow analyses, nine production cost model runs (including six sensitivities), and three capital cost estimations were developed during this second phase. The results from Phase 1 and 2 provided a wealth of data that could be examined further to address energy-related questions. A list of 13 topics was developed for further analysis; this paper discusses the first five.

  10. Disclosure of hydraulic fracturing fluid chemical additives: analysis of regulations.

    PubMed

    Maule, Alexis L; Makey, Colleen M; Benson, Eugene B; Burrows, Isaac J; Scammell, Madeleine K

    2013-01-01

    Hydraulic fracturing is used to extract natural gas from shale formations. The process involves injecting into the ground fracturing fluids that contain thousands of gallons of chemical additives. Companies are not mandated by federal regulations to disclose the identities or quantities of chemicals used during hydraulic fracturing operations on private or public lands. States have begun to regulate hydraulic fracturing fluids by mandating chemical disclosure. These laws have shortcomings including nondisclosure of proprietary or "trade secret" mixtures, insufficient penalties for reporting inaccurate or incomplete information, and timelines that allow for after-the-fact reporting. These limitations leave lawmakers, regulators, public safety officers, and the public uninformed and ill-prepared to anticipate and respond to possible environmental and human health hazards associated with hydraulic fracturing fluids. We explore hydraulic fracturing exemptions from federal regulations, as well as current and future efforts to mandate chemical disclosure at the federal and state level.

  11. Disclosure of hydraulic fracturing fluid chemical additives: analysis of regulations.

    PubMed

    Maule, Alexis L; Makey, Colleen M; Benson, Eugene B; Burrows, Isaac J; Scammell, Madeleine K

    2013-01-01

    Hydraulic fracturing is used to extract natural gas from shale formations. The process involves injecting into the ground fracturing fluids that contain thousands of gallons of chemical additives. Companies are not mandated by federal regulations to disclose the identities or quantities of chemicals used during hydraulic fracturing operations on private or public lands. States have begun to regulate hydraulic fracturing fluids by mandating chemical disclosure. These laws have shortcomings including nondisclosure of proprietary or "trade secret" mixtures, insufficient penalties for reporting inaccurate or incomplete information, and timelines that allow for after-the-fact reporting. These limitations leave lawmakers, regulators, public safety officers, and the public uninformed and ill-prepared to anticipate and respond to possible environmental and human health hazards associated with hydraulic fracturing fluids. We explore hydraulic fracturing exemptions from federal regulations, as well as current and future efforts to mandate chemical disclosure at the federal and state level. PMID:23552653

  12. Risk analysis of sulfites used as food additives in China.

    PubMed

    Zhang, Jian Bo; Zhang, Hong; Wang, Hua Li; Zhang, Ji Yue; Luo, Peng Jie; Zhu, Lei; Wang, Zhu Tian

    2014-02-01

    This study was to analyze the risk of sulfites in food consumed by the Chinese people and assess the health protection capability of maximum-permitted level (MPL) of sulfites in GB 2760-2011. Sulfites as food additives are overused or abused in many food categories. When the MPL in GB 2760-2011 was used as sulfites content in food, the intake of sulfites in most surveyed populations was lower than the acceptable daily intake (ADI). Excess intake of sulfites was found in all the surveyed groups when a high percentile of sulfites in food was in taken. Moreover, children aged 1-6 years are at a high risk to intake excess sulfites. The primary cause for the excess intake of sulfites in Chinese people is the overuse and abuse of sulfites by the food industry. The current MPL of sulfites in GB 2760-2011 protects the health of most populations.

  13. Bulk crystal growth, characterization and thermodynamic analysis of aluminum nitride and related nitrides

    NASA Astrophysics Data System (ADS)

    Du, Li

    The sublimation recondensation crystal growth of aluminum nitride, titanium nitride, and yttrium nitride were explored experimentally and theoretically. Single crystals of these nitrides are potentially suitable as substrates for AlGaInN epitaxial layers, which are employed in ultraviolet optoelectronics including UV light-emitting diodes and laser diodes, and high power high frequency electronic device applications. A thermodynamic analysis was applied to the sublimation crystal growth of aluminum nitride to predict impurities transport (oxygen, carbon, and hydrogen) and to study the aspects of impurities incorporation for different growth conditions. A source purification procedure was established to minimize the impurity concentration and avoid degradation of the crystal's properties. More than 98% of the oxygen, 99.9% of hydrogen and 90% of carbon originally in the source was removed. The AlN crystal growth process was explored in two ways: self-seeded growth with spontaneous nucleation directly on the crucible lid or foil, and seeded growth on SiC and AlN. The oxygen concentration was 2 ˜ 4 x 1018cm-3, as measured by secondary ion mass spectroscopy in the crystals produced by self-seeded growth. Crystals grown from AlN seeds have visible grain size expansion. The initial AlN growth on SiC at a low temperature range (1400°C ˜1600°C) was examined to understand the factors controlling nucleation. Crystals were obtained from c-plane on-axis and off-axis, Si-face and C-face, as well as m-plane SiC seeds. In all cases, crystal growth was fastest perpendicular to the c-axis. The growth rate dependence on temperature and pressure was determined for TiN and YN crystals, and their activation energies were 775.8+/-29.8kJ/mol and 467.1+/-21.7kJ/mol respectively. The orientation relationship of TiN (001) || W (001) with TiN [100] || W [110], a 45° angle between TiN [100] and W [100], was seen for TiN crystals deposited on both (001) textured tungsten and randomly

  14. Contact symmetries and Hamiltonian thermodynamics

    SciTech Connect

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

    2015-10-15

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

  15. Hydrogenation thermodynamics of melt-spun magnesium rich Mg-Ni nanocrystalline alloys with the addition of multiwalled carbon nanotubes and TiF3

    NASA Astrophysics Data System (ADS)

    Hou, Xiaojiang; Hu, Rui; Zhang, Tiebang; Kou, Hongchao; Li, Jinshan

    2016-02-01

    Based on the complexity of hydrogen absorption/desorption process and from the perspective of overall control, the as-cast Mg-10wt%Ni (Mg10Ni) alloy has been successively optimized by melt-spinning and surface catalyzed to realize the internal refinement as well as surface modification. The isothermal hydrogenation behavior of modified Mg-rich alloys has been investigated in this work. The results indicate that melt-spun Mg10Ni catalyzed by multiwalled carbon nanotubes (MWCNTs) coupling with TiF3 possesses superior activation properties and can absorb 6.23 wt% at 250 °C under 2.5 MPa. It is worth mentioning that the hydrogenation capacities of Mg10Ni-MWCNTs-TiF3 are 5.93 wt% and 5.99 wt% within the initial 1 min and 5 min, respectively. Meanwhile, the catalytic effect of MWCNTs and TiF3 has been discussed. The improved activation performance as well as the thermodynamics properties of Mg10Ni catalyzed by MWCNTs and TiF3 is attributed to the synergistic effect on dissociation of H2 molecules, diffusion of H-atoms and heterogeneous nucleation of hydrides.

  16. Thermodynamic analysis of alternative marine fuels for marine gas turbine power plants

    NASA Astrophysics Data System (ADS)

    El Gohary, Mohamed M.; Ammar, Nader R.

    2016-03-01

    The marine shipping industry faces challenges to reduce engine exhaust emissions and greenhouse gases (GHGs) from ships, and in particular, carbon dioxide. International regulatory bodies such as the International Maritime Organization and National Environmental Agencies of many countries have issued rules and regulations to drastically reduce GHG and emissions emanating from marine sources. This study investigates the possibility of using natural gas and hydrogen as alternative fuels to diesel oil for marine gas turbines and uses a mathematical model to assess the effect of these alternative fuels on gas turbine thermodynamic performance. Results show that since natural gas is categorized as a hydrocarbon fuel, the thermodynamic performance of the gas turbine cycle using natural gas was close to that of the diesel case. However, the gas turbine thermal efficiency was found to be slightly lower for natural gas and hydrogen fuels compared to diesel fuel.

  17. Thermodynamic analysis of chemical stability of ceramic materials in hydrogen-containing atmospheres at high temperatures

    NASA Technical Reports Server (NTRS)

    Misra, Ajay K.

    1990-01-01

    The chemical stability of several ceramic materials in hydrogen-containing environments was analyzed with thermodynamic considerations in mind. Equilibrium calculations were made as a function of temperature, moisture content, and total system pressure. The following ceramic materials were considered in this study: SiC, Si3N4, SiO2, Al2O3, mullite, ZrO2, Y2O3, CaO, MgO, BeO, TiB2, TiC, HfC, and ZrC. On the basis of purely thermodynamic arguments, upper temperature limits are suggested for each material for long-term use in H2-containing atmospheres.

  18. Thermodynamic Analysis and Optimization of a High Temperature Triple Absorption Heat Transformer

    PubMed Central

    Khamooshi, Mehrdad; Yari, Mortaza; Egelioglu, Fuat; Salati, Hana

    2014-01-01

    First law of thermodynamics has been used to analyze and optimize inclusively the performance of a triple absorption heat transformer operating with LiBr/H2O as the working pair. A thermodynamic model was developed in EES (engineering equation solver) to estimate the performance of the system in terms of the most essential parameters. The assumed parameters are the temperature of the main components, weak and strong solutions, economizers' efficiencies, and bypass ratios. The whole cycle is optimized by EES software from the viewpoint of maximizing the COP via applying the direct search method. The optimization results showed that the COP of 0.2491 is reachable by the proposed cycle. PMID:25136702

  19. Thermodynamic analysis of the behavior of microimpurities of toxic metals in coal combustion products

    SciTech Connect

    G.Ya. Gerasimov

    2004-01-15

    The thermodynamic approach to the description of the fuel-oxidizer system is used to elucidate the basic laws of behavior of compounds of the most toxic elements/microimpurities in combustion products of coal (Hg, Pb, Cr, Mn, Ni, Co, and As). It has been shown that the distribution of elements over components of the gas and condensed phases strongly depends on the process temperature and the composition of the mineral part of the coal.

  20. Thermodynamic holography.

    PubMed

    Wei, Bo-Bo; Jiang, Zhan-Feng; Liu, Ren-Bao

    2015-01-01

    The holographic principle states that the information about a volume of a system is encoded on the boundary surface of the volume. Holography appears in many branches of physics, such as optics, electromagnetism, many-body physics, quantum gravity, and string theory. Here we show that holography is also an underlying principle in thermodynamics, a most important foundation of physics. The thermodynamics of a system is fully determined by its partition function. We prove that the partition function of a finite but arbitrarily large system is an analytic function on the complex plane of physical parameters, and therefore the partition function in a region on the complex plane is uniquely determined by its values along the boundary. The thermodynamic holography has applications in studying thermodynamics of nano-scale systems (such as molecule engines, nano-generators and macromolecules) and provides a new approach to many-body physics. PMID:26478214

  1. Thermodynamic holography

    PubMed Central

    Wei, Bo-Bo; Jiang, Zhan-Feng; Liu, Ren-Bao

    2015-01-01

    The holographic principle states that the information about a volume of a system is encoded on the boundary surface of the volume. Holography appears in many branches of physics, such as optics, electromagnetism, many-body physics, quantum gravity, and string theory. Here we show that holography is also an underlying principle in thermodynamics, a most important foundation of physics. The thermodynamics of a system is fully determined by its partition function. We prove that the partition function of a finite but arbitrarily large system is an analytic function on the complex plane of physical parameters, and therefore the partition function in a region on the complex plane is uniquely determined by its values along the boundary. The thermodynamic holography has applications in studying thermodynamics of nano-scale systems (such as molecule engines, nano-generators and macromolecules) and provides a new approach to many-body physics. PMID:26478214

  2. Structure and energetics of graphene oxide isomers: ab initio thermodynamic analysis.

    PubMed

    Chaban, Vitaly V; Prezhdo, Oleg V

    2015-10-28

    Graphene oxide (GO) holds significant promise for electronic devices and nanocomposite materials. A number of models were proposed for the GO structure, combining carboxyl, hydroxyl, carbonyl and epoxide groups at different locations. The complexity and variety of GO isomers, whose thermodynamic stability and formation kinetics depend on the applied conditions, make determination of the GO structure with atomistic precision challenging. We report high level theoretical investigation of multiple molecular configurations, which are anticipated in GO. We conclude that all oxygen containing groups at the GO surface are thermodynamically permitted, whereas the 'edge' positions are systematically more favorable than the 'center' and 'side' positions. We discuss a potentially novel type of chemical bond or bonding reinforcement in GO, which consists of a covalent bond and a strong electrostatic contribution from a polarized graphene plane. We observe and analyze significant modifications of the graphene geometry and electronic structure upon oxidation. The reported thermodynamic data guide experiments aimed at deciphering the GO chemical composition and structure, and form the basis for predicting GO properties required for nano-technological applications. PMID:26420562

  3. Structure and energetics of graphene oxide isomers: ab initio thermodynamic analysis

    NASA Astrophysics Data System (ADS)

    Chaban, Vitaly V.; Prezhdo, Oleg V.

    2015-10-01

    Graphene oxide (GO) holds significant promise for electronic devices and nanocomposite materials. A number of models were proposed for the GO structure, combining carboxyl, hydroxyl, carbonyl and epoxide groups at different locations. The complexity and variety of GO isomers, whose thermodynamic stability and formation kinetics depend on the applied conditions, make determination of the GO structure with atomistic precision challenging. We report high level theoretical investigation of multiple molecular configurations, which are anticipated in GO. We conclude that all oxygen containing groups at the GO surface are thermodynamically permitted, whereas the `edge' positions are systematically more favorable than the `center' and `side' positions. We discuss a potentially novel type of chemical bond or bonding reinforcement in GO, which consists of a covalent bond and a strong electrostatic contribution from a polarized graphene plane. We observe and analyze significant modifications of the graphene geometry and electronic structure upon oxidation. The reported thermodynamic data guide experiments aimed at deciphering the GO chemical composition and structure, and form the basis for predicting GO properties required for nano-technological applications.

  4. Thermodynamic metrics for aggregation of natural resources in life cycle analysis: insight via application to some transportation fuels.

    PubMed

    Baral, Anil; Bakshi, Bhavik R

    2010-01-15

    While methods for aggregating emissions are widely used and standardized in life cycle assessment (LCA), there is little agreement about methods for aggregating natural resources for obtaining interpretable metrics. Thermodynamic methods have been suggested including energy, exergy, and emergy analyses. This work provides insight into the nature of thermodynamic aggregation, including assumptions about substitutability between resources and loss of detailed information about the data being combined. Methods considered include calorific value or energy, industrial cumulative exergy consumption (ICEC) and its variations, and ecological cumulative exergy consumption (ECEC) or emergy. A hierarchy of metrics is proposed that spans the range from detailed data to aggregate metrics. At the fine scale, detailed data can help identify resources to whose depletion the selected product is most vulnerable. At the coarse scale, new insight is provided about thermodynamic aggregation methods. Among these, energy analysis is appropriate only for products that rely primarily on fossil fuels, and it cannot provide a useful indication of renewability. Exergy-based methods can provide results similar to energy analysis by including only nonrenewable fuels but can also account for materials use and provide a renewability index. However, ICEC and its variations do not address substitutability between resources, causing its results to be dominated by dilute and low-quality resources such as sunlight. The use of monetary values to account for substitutability does not consider many ecological resources and may not be appropriate for the analysis of emerging products. ECEC or emergy explicitly considers substitutability and resource quality and provides more intuitive results but is plagued by data gaps and uncertainties. This insight is illustrated via application to the life cycles of gasoline, diesel, corn ethanol, and soybean biodiesel. Here, aggregate metrics reveal the dilemma

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

    NASA Astrophysics Data System (ADS)

    De Giacomo, A.; Dell'Aglio, M.; Gaudiuso, R.; Santagata, A.; Senesi, G. S.; Rossi, M.; Ghiara, M. R.; Capitelli, F.; De Pascale, O.

    2012-04-01

    Laser Induced Breakdown Spectroscopy (LIBS) is an appealing technique to study laser-induced plasmas (LIPs), both from the basic diagnostics point of view and for analytical applications. LIPs are complex dynamic systems, expanding at supersonic velocities and undergoing a transition between different plasma regimes. If the Local Thermodynamic Equilibrium (LTE) condition is valid for such plasmas, several analytical methods can be employed and fast quantitative analyses can be performed on a variety of samples. In the present paper, a discussion about LTE is carried out and an innovative application to the analysis of the alexandrite gemstone is presented. In addition, a study about the influence of plasma parameters on the performance of LTE-based methods is reported for bronze and brass targets.

  6. An enthalpic basis of additivity in biphenyl hydroxamic acid ligands for stromelysin-1

    PubMed Central

    Wilfong, Erin M.; Du, Yu; Toone, Eric J.

    2013-01-01

    Fragment based drug discovery remains a successful tool for pharmaceutical lead discovery. Although based upon the principle of thermodynamic additivity, the underlying thermodynamic basis is poorly understood. A thermodynamic additivity analysis was performed using stromelysin-1 and a series of biphenyl hydroxamate ligands identified through fragment additivity. Our studies suggest that, in this instance, additivity arises from enthalpic effects, while interaction entropies are unfavorable; this thermodynamic behavior is masked by proton transfer. Evaluation of the changes in constant pressure heat capacities during binding suggest that solvent exclusion from the binding site does not account for the dramatic affinity enhancements observed. PMID:22985855

  7. Additional challenges for uncertainty analysis in river engineering

    NASA Astrophysics Data System (ADS)

    Berends, Koen; Warmink, Jord; Hulscher, Suzanne

    2016-04-01

    the proposed intervention. The implicit assumption underlying such analysis is that both models are commensurable. We hypothesize that they are commensurable only to a certain extent. In an idealised study we have demonstrated that prediction performance loss should be expected with increasingly large engineering works. When accounting for parametric uncertainty of floodplain roughness in model identification, we see uncertainty bounds for predicted effects of interventions increase with increasing intervention scale. Calibration of these types of models therefore seems to have a shelf-life, beyond which calibration does not longer improves prediction. Therefore a qualification scheme for model use is required that can be linked to model validity. In this study, we characterize model use along three dimensions: extrapolation (using the model with different external drivers), extension (using the model for different output or indicators) and modification (using modified models). Such use of models is expected to have implications for the applicability of surrogating modelling for efficient uncertainty analysis as well, which is recommended for future research. Warmink, J. J.; Straatsma, M. W.; Huthoff, F.; Booij, M. J. & Hulscher, S. J. M. H. 2013. Uncertainty of design water levels due to combined bed form and vegetation roughness in the Dutch river Waal. Journal of Flood Risk Management 6, 302-318 . DOI: 10.1111/jfr3.12014

  8. Kinetic analysis of microbial respiratory response to substrate addition

    NASA Astrophysics Data System (ADS)

    Blagodatskaya, Evgenia; Blagodatsky, Sergey; Yuyukina, Tatayna; Kuzyakov, Yakov

    2010-05-01

    Heterotrophic component of CO2 emitted from soil is mainly due to the respiratory activity of soil microorganisms. Field measurements of microbial respiration can be used for estimation of C-budget in soil, while laboratory estimation of respiration kinetics allows the elucidation of mechanisms of soil C sequestration. Physiological approaches based on 1) time-dependent or 2) substrate-dependent respiratory response of soil microorganisms decomposing the organic substrates allow to relate the functional properties of soil microbial community with decomposition rates of soil organic matter. We used a novel methodology combining (i) microbial growth kinetics and (ii) enzymes affinity to the substrate to show the shift in functional properties of the soil microbial community after amendments with substrates of contrasting availability. We combined the application of 14C labeled glucose as easily available C source to soil with natural isotope labeling of old and young soil SOM. The possible contribution of two processes: isotopic fractionation and preferential substrate utilization to the shifts in δ13C during SOM decomposition in soil after C3-C4 vegetation change was evaluated. Specific growth rate (µ) of soil microorganisms was estimated by fitting the parameters of the equation v(t) = A + B * exp(µ*t), to the measured CO2 evolution rate (v(t)) after glucose addition, and where A is the initial rate of non-growth respiration, B - initial rate of the growing fraction of total respiration. Maximal mineralization rate (Vmax), substrate affinity of microbial enzymes (Ks) and substrate availability (Sn) were determined by Michaelis-Menten kinetics. To study the effect of plant originated C on δ13C signature of SOM we compared the changes in isotopic composition of different C pools in C3 soil under grassland with C3-C4 soil where C4 plant Miscanthus giganteus was grown for 12 years on the plot after grassland. The shift in 13δ C caused by planting of M. giganteus

  9. Identification of Potential Efficiency Opportunities in Internal Combustion Engines Using a Detailed Thermodynamic Analysis of Engine Simulation Results

    SciTech Connect

    Edwards, Kevin Dean; Wagner, Robert M; Graves, Ronald L

    2008-01-01

    Current political and environmental concerns are driving renewed efforts to develop techniques for improving the efficiency of internal combustion engines. A detailed thermodynamic analysis of an engine and its components from a 1st and 2nd law perspective is necessary to characterize system losses and to identify efficiency opportunities. We have developed a method for performing this analysis using engine-simulation results obtained from WAVE , a commercial engine-modeling software package available from Ricardo, Inc. Results from the engine simulation are post-processed to compute thermodynamic properties such as internal energy, enthalpy, entropy, and availability (or exergy), which are required to perform energy and availability balances of the system. This analysis is performed for all major components (turbocharger, intercooler, EGR cooler, etc.) of the engine as a function of crank angle degree for the entire engine cycle. With this information, we are able to identify potential efficiency opportunities as well as guide engine experiments for exploring new technologies for recovering system losses.

  10. Systems analysis of a closed loop ECLSS using the ASPEN simulation tool. Thermodynamic efficiency analysis of ECLSS components. M.S. Thesis

    NASA Technical Reports Server (NTRS)

    Chatterjee, Sharmista

    1993-01-01

    Our first goal in this project was to perform a systems analysis of a closed loop Environmental Control Life Support System (ECLSS). This pertains to the development of a model of an existing real system from which to assess the state or performance of the existing system. Systems analysis is applied to conceptual models obtained from a system design effort. For our modelling purposes we used a simulator tool called ASPEN (Advanced System for Process Engineering). Our second goal was to evaluate the thermodynamic efficiency of the different components comprising an ECLSS. Use is made of the second law of thermodynamics to determine the amount of irreversibility of energy loss of each component. This will aid design scientists in selecting the components generating the least entropy, as our penultimate goal is to keep the entropy generation of the whole system at a minimum.

  11. Thermodynamic analysis of compatibility of several reinforcement materials with FeAl alloys

    NASA Technical Reports Server (NTRS)

    Misra, Ajay K.

    1988-01-01

    Chemical compatibility of several reinforcement materials with FeAl alloys within the concentration range 40 to 50 at pct Al have been analyzed from thermodynamic considerations at 1173 and 1273 K. The reinforcement materials considered in this study include carbides, borides, oxides, nitrides, and silicides. Although several chemically compatible reinforcement materials are identified, the coefficients of thermal expansion for none of these materials match closely with that of FeAl alloys and this might pose serious problems in the design of composite systems based on FeAl alloys.

  12. Thermodynamical Bethe Ansatz analysis in an SU(2)/×U(1) symmetric /σ-model

    NASA Astrophysics Data System (ADS)

    Balog, János; Forgács, Péter

    2000-03-01

    Four different types of free energies are computed by both thermodynamical Bethe Ansatz (TBA) techniques and by weak coupling perturbation theory in an integrable one-parameter deformation of the O(4) principal chiral σ-model (with SU(2)×U(1) symmetry). The model exhibits both `fermionic' and `bosonic' type free energies and in all cases the perturbative and the TBA results are in perfect agreement, strongly supporting the correctness of the proposed S matrix. The mass gap is also computed in terms of the Λ parameters of the modified minimal subtraction scheme and a lattice regularized version of the model.

  13. Phase Transformations in Electrically Conductive Ferromagnetic Shape-Memory Alloys, Their Thermodynamics and Analysis

    NASA Astrophysics Data System (ADS)

    Roubíček, Tomáš; Tomassetti, Giuseppe

    2013-10-01

    We derive a thermodynamically consistent general continuum-mechanical model describing mutually coupled martensitic and ferro/paramagnetic phase transformations in electrically-conductive magnetostrictive materials such as NiMnGa. We use small-strain and eddy-current approximations, yet large velocities and electric current injected through the boundary are allowed. Fully nonlinear coupling of magneto-mechanical and thermal effects is considered. The existence of energy-preserving weak solutions is proved by showing convergence of time-discrete approximations constructed by a carefully designed semi-implicit regularized scheme.

  14. Thermodynamics of technetium: Reconciling theory and experiment using density functional perturbation analysis

    SciTech Connect

    Weck, Philippe F.; Kim, Eunja

    2015-06-11

    The structure, lattice dynamics and thermodynamic properties of bulk technetium were investigated within the framework of density functional theory. The phonon density of states spectrum computed with density functional perturbation theory closely matches inelastic coherent neutron scattering measurements. The thermal properties of technetium were derived from phonon frequencies calculated within the quasi-harmonic approximation (QHA), which introduces a volume dependence of phonon frequencies as a part of the anharmonic effect. As a result, the predicted thermal expansion and isobaric heat capacity of technetium are in excellent agreement with available experimental data for temperatures up to ~1600 K.

  15. Analysis of the pH-dependent thermodynamic stability, local motions, and microsecond folding kinetics of carbonmonoxycytochrome c.

    PubMed

    Kumar, Rajesh

    2016-09-15

    This paper analyzes the effect of pH on thermodynamic stability, low-frequency local motions and microsecond folding kinetics of carbonmonoxycytochrome c (Cyt-CO) all across the alkaline pH-unfolding transition of protein. Thermodynamic analysis of urea-induced unfolding transitions of Cyt-CO measured between pH 6 and pH 11.9 reveals that Cyt-CO is maximally stable at pH∼9.5. Dilution of unfolded Cyt-CO into refolding medium forms a native-like compact state (NCO-state), where Fe(2+)-CO interaction persists. Kinetic and thermodynamic parameters measured for slow thermally-driven CO dissociation (NCO→N+CO) and association (N+CO→NCO) reactions between pH 6.5 and pH 13 reveal that the thermal-motions of M80-containing Ω-loop are decreased in subdenaturing limit of alkaline pH. Laser photolysis of Fe(2+)-CO bond in NCO-state triggers the microsecond folding (NCO→N). The microsecond kinetics measured all across the alkaline pH-unfolding transition of Cyt-CO produce rate rollover in the refolding limb of chevron plot, which suggests a glass transition of NCO en route to N. Between pH 7 and pH 11.9, the natural logarithm of the microsecond folding rate varies by < 1.5 units while the natural logarithm of apparent equilibrium constant varies by 11.8 units. This finding indicates that the pH-dependent ionic-interactions greatly affect the global stability of protein but have very small effect on folding kinetics. PMID:27424489

  16. Thermodynamic analysis of unusually thermostable CutA1 protein from human brain and its protease susceptibility.

    PubMed

    Bagautdinov, Bagautdin; Matsuura, Yoshinori; Yamamoto, Hitoshi; Sawano, Masahide; Ogasahara, Kyoko; Takehira, Michiyo; Kunishima, Naoki; Katoh, Etsuko; Yutani, Katsuhide

    2015-03-01

    Unusually stable proteins are a disadvantage for the metabolic turnover of proteins in cells. The CutA1 proteins from Pyrococcus horikoshii and from Oryza sativa (OsCutA1) have unusually high denaturation temperatures (Td) of nearly 150 and 100 °C, respectively, at pH 7.0. It seemed that the CutA1 protein from the human brain (HsCutA1) also has a remarkably high stability. Therefore, the thermodynamic stabilities of HsCutA1 and its protease susceptibility were examined. The Td was remarkably high, being over 95 °C at pH 7.0. The unfolding Gibbs energy (ΔG(0)H2O) was 174 kJ/mol at 37 °C from the denaturant denaturation. The thermodynamic analysis showed that the unfolding enthalpy and entropy values of HsCutA1 were considerably lower than those of OsCutA1 with a similar stability to HsCutA1, which should be related to flexibility of the unstructured properties in both N- and C-terminals of HsCutA1. HsCutA1 was almost completely digested after 1-day incubation at 37 °C by subtilisin, although OsCutA1 was hardly digested at the same conditions. These results indicate that easily available fragmentation of HsCutA1 with remarkably high thermodynamic stability at the body temperature should be important for its protein catabolism in the human cells.

  17. Thermodynamical analysis of a quantum heat engine based on harmonic oscillators.

    PubMed

    Insinga, Andrea; Andresen, Bjarne; Salamon, Peter

    2016-07-01

    Many models of heat engines have been studied with the tools of finite-time thermodynamics and an ensemble of independent quantum systems as the working fluid. Because of their convenient analytical properties, harmonic oscillators are the most frequently used example of a quantum system. We analyze different thermodynamical aspects with the final aim of the optimization of the performance of the engine in terms of the mechanical power provided during a finite-time Otto cycle. The heat exchange mechanism between the working fluid and the thermal reservoirs is provided by the Lindblad formalism. We describe an analytical method to find the limit cycle and give conditions for a stable limit cycle to exist. We explore the power production landscape as the duration of the four branches of the cycle are varied for short times, intermediate times, and special frictionless times. For short times we find a periodic structure with atolls of purely dissipative operation surrounding islands of divergent behavior where, rather than tending to a limit cycle, the working fluid accumulates more and more energy. For frictionless times the periodic structure is gone and we come very close to the global optimal operation. The global optimum is found and interestingly comes with a particular value of the cycle time. PMID:27575089

  18. Thermodynamical analysis of a quantum heat engine based on harmonic oscillators

    NASA Astrophysics Data System (ADS)

    Insinga, Andrea; Andresen, Bjarne; Salamon, Peter

    2016-07-01

    Many models of heat engines have been studied with the tools of finite-time thermodynamics and an ensemble of independent quantum systems as the working fluid. Because of their convenient analytical properties, harmonic oscillators are the most frequently used example of a quantum system. We analyze different thermodynamical aspects with the final aim of the optimization of the performance of the engine in terms of the mechanical power provided during a finite-time Otto cycle. The heat exchange mechanism between the working fluid and the thermal reservoirs is provided by the Lindblad formalism. We describe an analytical method to find the limit cycle and give conditions for a stable limit cycle to exist. We explore the power production landscape as the duration of the four branches of the cycle are varied for short times, intermediate times, and special frictionless times. For short times we find a periodic structure with atolls of purely dissipative operation surrounding islands of divergent behavior where, rather than tending to a limit cycle, the working fluid accumulates more and more energy. For frictionless times the periodic structure is gone and we come very close to the global optimal operation. The global optimum is found and interestingly comes with a particular value of the cycle time.

  19. Thermodynamic and morphological analysis of large silicon self-interstitial clusters using atomistic simulations

    SciTech Connect

    Chuang, Claire Y.; Sinno, Talid; Sattler, Andreas

    2015-04-07

    We study computationally the formation of thermodynamics and morphology of silicon self-interstitial clusters using a suite of methods driven by a recent parameterization of the Tersoff empirical potential. Formation free energies and cluster capture zones are computed across a wide range of cluster sizes (2 < N{sub i} < 150) and temperatures (0.65 < T/T{sub m} < 1). Self-interstitial clusters above a critical size (N{sub i} ∼ 25) are found to exhibit complex morphological behavior in which clusters can assume either a variety of disordered, three-dimensional configurations, or one of two macroscopically distinct planar configurations. The latter correspond to the well-known Frank and perfect dislocation loops observed experimentally in ion-implanted silicon. The relative importance of the different cluster morphologies is a function of cluster size and temperature and is dictated by a balance between energetic and entropic forces. The competition between these thermodynamic forces produces a sharp transition between the three-dimensional and planar configurations, and represents a type of order-disorder transition. By contrast, the smaller state space available to smaller clusters restricts the diversity of possible structures and inhibits this morphological transition.

  20. Thermodynamical analysis of a quantum heat engine based on harmonic oscillators.

    PubMed

    Insinga, Andrea; Andresen, Bjarne; Salamon, Peter

    2016-07-01

    Many models of heat engines have been studied with the tools of finite-time thermodynamics and an ensemble of independent quantum systems as the working fluid. Because of their convenient analytical properties, harmonic oscillators are the most frequently used example of a quantum system. We analyze different thermodynamical aspects with the final aim of the optimization of the performance of the engine in terms of the mechanical power provided during a finite-time Otto cycle. The heat exchange mechanism between the working fluid and the thermal reservoirs is provided by the Lindblad formalism. We describe an analytical method to find the limit cycle and give conditions for a stable limit cycle to exist. We explore the power production landscape as the duration of the four branches of the cycle are varied for short times, intermediate times, and special frictionless times. For short times we find a periodic structure with atolls of purely dissipative operation surrounding islands of divergent behavior where, rather than tending to a limit cycle, the working fluid accumulates more and more energy. For frictionless times the periodic structure is gone and we come very close to the global optimal operation. The global optimum is found and interestingly comes with a particular value of the cycle time.

  1. Crystal structure analysis and sublimation thermodynamics of bicyclo derivatives of a neuroprotector family.

    PubMed

    Surov, Artem O; Proshin, Alexey N; Perlovich, German L

    2014-02-01

    The crystal structures of three new structurally related drug-like bicyclo derivatives are correlated with measured thermodynamic quantities for their sublimation and melting processes. The sublimation thermodynamics are determined using the temperature dependencies of the vapour pressure, and the melting processes are examined using differential scanning calorimetry. The three compounds contain a common N-(3-thia-1-azabicyclo[3.3.1]non-2-ylidene)aniline core, with either a CH3, F or CF3 substituent at the 4-position of the aniline ring. Lattice energy calculations are made using both the PIXEL and Coulomb-London-Pauli (CLP) models, and the conformational flexibility of the molecules is examined using gas-phase density functional theory (DFT) calculations. The experimentally measured crystal lattice energies (ΔH(0)sub) decrease in the order: CH3 > F > CF3. The calculated lattice energies using the PIXEL approach are in good agreement with the experimental values, and the partitioned intermolecular interaction energies suggest that dispersion contributions dominate the crystal structures of all three compounds. The sublimation energies and melting points are inversely correlated for the three molecules, with the melting points increasing in the order CF3 < F < CH3.

  2. Thermodynamic and thermoeconomic analysis of combined geothermal space heating and thermal storage using phase change materials

    NASA Astrophysics Data System (ADS)

    Chauhan, V.; Ragnarsson, Á.

    2015-12-01

    The present work discusses the utilization of phase change materials for energy storage in geothermal space heating systems. Thermodynamics and thermoeconomics of the combined heating and thermal storing system were studied to show the scope of energy storage and cost savings. A computational model of the combined space heating and thermal storage system was developed and used to perform thermodynamic studies of the heat storage process and heating system efficiency at different times and ambient temperatures. The basis for these studies is daily variations in heating demand that is higher during the night than during the day. The results show the scope of the utilization of phase change material for low ambient temperature conditions. Under proper conditions a sufficient amount of exergy is stored during the charging period at a low ambient temperature to fulfill the daytime heat load requirement. Under these conditions the cost flow rate of exergy storage is found to be lower than the radiator heating cost flow rate. Thus, the use of exergy storage at low ambient temperatures for heating at higher ambient temperatures makes a significant contribution to cost savings.

  3. From cysteine to longer chain thiols: thermodynamic analysis of cadmium binding by phytochelatins and their fragments.

    PubMed

    Chekmeneva, Elena; Gusmão, Rui; Díaz-Cruz, José Manuel; Ariño, Cristina; Esteban, Miquel

    2011-08-01

    Isothermal Titration Calorimetry (ITC) was used to study the binding of Cd(2+) by phytochelatins ((γGlu-Cys)(n)-Gly, PC(n); n = 1-5) and their selected fragments (Cys, Cys-Gly and γGlu-Cys) in order to understand the influence of the chain length on the complex stabilities and the origin of the enhanced affinities in Tris buffer at pH 7.5 and 8.5 and at 25 °C. Different complexes are formed with glutathione (GSH) and its fragments, Cys, Cys-Gly and γGlu-Cys, and their stabilities depend on the corresponding pK(a) value of the thiol group in the ligands. The stability of Cd-PC(n) complexes increases moving towards higher PC(2-5), as well as the complexing capacity expressed as the number of metal ions that can be bound by one ligand molecule. The affinity of Cd(2+) for the PC(n) can be described by the following GSH < PC(2) < PC(3)≤ PC(4)≤ PC(5) sequence. On the basis of these thermodynamic data it is possible to explain the abundance of certain Cd-PC(n) complexes found in nature. The comprehension of the thermodynamic rules that govern the interactions of Cd(2+) with PC(n) and their constituents is of great service in the research with real plant samples subjected to metal stress and in the development of new strategies of bio/phytoremediation.

  4. Analysis of the statistical thermodynamic model for nonlinear binary protein adsorption equilibria.

    PubMed

    Zhou, Xiao-Peng; Su, Xue-Li; Sun, Yan

    2007-01-01

    The statistical thermodynamic (ST) model was used to study nonlinear binary protein adsorption equilibria on an anion exchanger. Single-component and binary protein adsorption isotherms of bovine hemoglobin (Hb) and bovine serum albumin (BSA) on DEAE Spherodex M were determined by batch adsorption experiments in 10 mM Tris-HCl buffer containing a specific NaCl concentration (0.05, 0.10, and 0.15 M) at pH 7.40. The ST model was found to depict the effect of ionic strength on the single-component equilibria well, with model parameters depending on ionic strength. Moreover, the ST model gave acceptable fitting to the binary adsorption data with the fitted single-component model parameters, leading to the estimation of the binary ST model parameter. The effects of ionic strength on the model parameters are reasonably interpreted by the electrostatic and thermodynamic theories. The effective charge of protein in adsorption phase can be separately calculated from the two categories of the model parameters, and the values obtained from the two methods are consistent. The results demonstrate the utility of the ST model for describing nonlinear binary protein adsorption equilibria.

  5. Thermodynamic and morphological analysis of large silicon self-interstitial clusters using atomistic simulations

    NASA Astrophysics Data System (ADS)

    Chuang, Claire Y.; Sattler, Andreas; Sinno, Talid

    2015-04-01

    We study computationally the formation of thermodynamics and morphology of silicon self-interstitial clusters using a suite of methods driven by a recent parameterization of the Tersoff empirical potential. Formation free energies and cluster capture zones are computed across a wide range of cluster sizes (2 < Ni < 150) and temperatures (0.65 < T/Tm < 1). Self-interstitial clusters above a critical size (Ni ˜ 25) are found to exhibit complex morphological behavior in which clusters can assume either a variety of disordered, three-dimensional configurations, or one of two macroscopically distinct planar configurations. The latter correspond to the well-known Frank and perfect dislocation loops observed experimentally in ion-implanted silicon. The relative importance of the different cluster morphologies is a function of cluster size and temperature and is dictated by a balance between energetic and entropic forces. The competition between these thermodynamic forces produces a sharp transition between the three-dimensional and planar configurations, and represents a type of order-disorder transition. By contrast, the smaller state space available to smaller clusters restricts the diversity of possible structures and inhibits this morphological transition.

  6. Comparative Analysis of Binding Kinetics and Thermodynamics of Dipeptidyl Peptidase-4 Inhibitors and Their Relationship to Structure.

    PubMed

    Schnapp, Gisela; Klein, Thomas; Hoevels, Yvette; Bakker, Remko A; Nar, Herbert

    2016-08-25

    The binding kinetics and thermodynamics of dipeptidyl peptidase (DPP)-4 inhibitors (gliptins) were investigated using surface plasmon resonance and isothermal titration calorimetry. Binding of gliptins to DPP-4 is a rapid electrostatically driven process. Off-rates were generally slow partly because of reversible covalent bond formation by some gliptins, and partly because of strong and extensive interactions. Binding of all gliptins is enthalpy-dominated due to strong ionic interactions and strong solvent-shielded hydrogen bonds. Using a congeneric series of molecules which represented the intermediates in the lead optimization program of linagliptin, the onset of slow binding kinetics and development of the thermodynamic repertoire were analyzed in the context of incremental changes of the chemical structures. All compounds rapidly associated, and therefore the optimization of affinity and residence time is highly correlated. The major contributor to the increasing free energy of binding was a strong increase of binding enthalpy, whereas entropic contributions remained low and constant despite significant addition of lipophilicity. PMID:27438064

  7. Thermodynamics of ABC transporters.

    PubMed

    Zhang, Xuejun C; Han, Lei; Zhao, Yan

    2016-01-01

    ABC transporters form the largest of all transporter families, and their structural study has made tremendous progress over recent years. However, despite such advances, the precise mechanisms that determine the energy-coupling between ATP hydrolysis and the conformational changes following substrate binding remain to be elucidated. Here, we present our thermodynamic analysis for both ABC importers and exporters, and introduce the two new concepts of differential-binding energy and elastic conformational energy into the discussion. We hope that the structural analysis of ABC transporters will henceforth take thermodynamic aspects of transport mechanisms into account as well.

  8. Methodology of Thermodynamics

    ERIC Educational Resources Information Center

    Mohan, Gyan

    1969-01-01

    Presents a systematization of the mathematical formulae in thermodynamics. From the set of thermodynamic variables, four equations are derived which contain the total mathematical jargon of thermodynamics. (LC)

  9. An Introduction to Thermodynamic Performance Analysis of Aircraft Gas Turbine Engine Cycles Using the Numerical Propulsion System Simulation Code

    NASA Technical Reports Server (NTRS)

    Jones, Scott M.

    2007-01-01

    This document is intended as an introduction to the analysis of gas turbine engine cycles using the Numerical Propulsion System Simulation (NPSS) code. It is assumed that the analyst has a firm understanding of fluid flow, gas dynamics, thermodynamics, and turbomachinery theory. The purpose of this paper is to provide for the novice the information necessary to begin cycle analysis using NPSS. This paper and the annotated example serve as a starting point and by no means cover the entire range of information and experience necessary for engine performance simulation. NPSS syntax is presented but for a more detailed explanation of the code the user is referred to the NPSS User Guide and Reference document (ref. 1).

  10. Thermodynamic and fluid mechanic analysis of rapid pressurization in a dead-end tube

    NASA Technical Reports Server (NTRS)

    Leslie, Ian H.

    1989-01-01

    Three models have been applied to very rapid compression of oxygen in a dead-ended tube. Pressures as high as 41 MPa (6000 psi) leading to peak temperatures of 1400 K are predicted. These temperatures are well in excess of the autoignition temperature (750 K) of teflon, a frequently used material for lining hoses employed in oxygen service. These findings are in accord with experiments that have resulted in ignition and combustion of the teflon, leading to the combustion of the stainless steel braiding and catastrophic failure. The system analyzed was representative of a capped off-high-pressure oxygen line, which could be part of a larger system. Pressurization of the larger system would lead to compression in the dead-end line, and possible ignition of the teflon liner. The model consists of a large plenum containing oxygen at the desired pressure (500 to 6000 psi). The plenum is connected via a fast acting valve to a stainless steel tube 2 cm inside diameter. Opening times are on the order of 15 ms. Downstream of the valve is an orifice sized to increase filling times to around 100 ms. The total length from the valve to the dead-end is 150 cm. The distance from the valve to the orifice is 95 cm. The models describe the fluid mechanics and thermodynamics of the flow, and do not include any combustion phenomena. A purely thermodynamic model assumes filling to be complete upstream of the orifice before any gas passes through the orifice. This simplification is reasonable based on experiment and computer modeling. Results show that peak temperatures as high as 4800 K can result from recompression of the gas after expanding through the orifice. An approximate transient model without an orifice was developed assuming an isentropic compression process. An analytical solution was obtained. Results indicated that fill times can be considerably shorter than valve opening times. The third model was a finite difference, 1-D transient compressible flow model. Results from

  11. An analysis of quantum effects on the thermodynamic properties of cryogenic hydrogen using the path integral method.

    PubMed

    Nagashima, H; Tsuda, S; Tsuboi, N; Koshi, M; Hayashi, K A; Tokumasu, T

    2014-04-01

    In this paper, we describe the analysis of the thermodynamic properties of cryogenic hydrogen using classical molecular dynamics (MD) and path integral MD (PIMD) method to understand the effects of the quantum nature of hydrogen molecules. We performed constant NVE MD simulations across a wide density-temperature region to establish an equation of state (EOS). Moreover, the quantum effect on the difference of molecular mechanism of pressure-volume-temperature relationship was addressed. The EOS was derived based on the classical mechanism idea only using the MD simulation results. Simulation results were compared with each MD method and experimental data. As a result, it was confirmed that although the EOS on the basis of classical MD cannot reproduce the experimental data of saturation property of hydrogen in the high-density region, the EOS on the basis of PIMD well reproduces those thermodynamic properties of hydrogen. Moreover, it was clarified that taking quantum effects into account makes the repulsion force larger and the potential well shallower. Because of this mechanism, the intermolecular interaction of hydrogen molecules diminishes and the virial pressure increases.

  12. Thermodynamic analysis of a Rankine cycle powered vapor compression ice maker using solar energy.

    PubMed

    Hu, Bing; Bu, Xianbiao; Ma, Weibin

    2014-01-01

    To develop the organic Rankine-vapor compression ice maker driven by solar energy, a thermodynamic model was developed and the effects of generation temperature, condensation temperature, and working fluid types on the system performance were analyzed. The results show that the cooling power per square meter collector and ice production per square meter collector per day depend largely on generation temperature and condensation temperature and they increase firstly and then decrease with increasing generation temperature. For every working fluid there is an optimal generation temperature at which organic Rankine efficiency achieves the maximum value. The cooling power per square meter collector and ice production per square meter collector per day are, respectively, 126.44 W m(-2) and 7.61 kg m(-2) day(-1) at the generation temperature of 140 °C for working fluid of R245fa, which demonstrates the feasibility of organic Rankine cycle powered vapor compression ice maker. PMID:25202735

  13. Thermodynamic analysis of liquefied natural gas (LNG) production cycle in APCI process

    NASA Astrophysics Data System (ADS)

    Nezhad, Shahrooz Abbasi; Shabani, Bezhan; Soleimani, Majid

    2012-12-01

    The appropriate production of liquefied natural gas (LNG) with least consuming energy and maximum efficiency is quite important. In this paper, LNG production cycle by means of APCI Process has been studied. Energy equilibrium equations and exergy equilibrium equations of each equipment in the APCI cycle were established. The equipments are described using rigorous thermodynamics and no significant simplification is assumed. Taken some operating parameters as key parameters, influences of these parameters on coefficient of performance (COP) and exergy efficiency of the cascading cycle were analyzed. The results indicate that COP and exergy efficiency will be improved with the increasing of the inlet pressure of MR (mixed refrigerant) compressors, the decreasing of the NG and MR after precooling process, outlet pressure of turbine, inlet temperature of MR compressor and NG temperature after cooling in main cryogenic heat exchanger (MCHE). The COP and exergy efficiency of the APCI cycle will be above 2% and 40%, respectively, after optimizing the key parameters.

  14. Mechanistic insight into sono-enzymatic degradation of organic pollutants with kinetic and thermodynamic analysis.

    PubMed

    Malani, Ritesh S; Khanna, Swati; Chakma, Sankar; Moholkar, Vijayanand S

    2014-07-01

    In this paper, we have attempted to get a physical insight into process of sono-enzymatic treatment for degradation of recalcitrant organic pollutants. Decolourization of an azo dye has been used as model reaction with different experimental protocols that alter characteristics of ultrasound and cavitation phenomena in the system. Experimental data is analyzed to determine kinetic and thermodynamic parameters of decolorization process. The trends observed in kinetic and thermodynamic parameters of decolourization are essentially manifestations of the dominating mechanism of the decolorization of the textile dye (or nature of prevalent chemical reaction in the system), viz. either molecular reaction due to enzyme or radical reaction due to transient cavitation. The activation energy for sonochemical protocol is negative, which indicates instantaneity of the radical reactions. The frequency factor is also low, which is attributed to high instability of radicals. For enzymatic and sono-enzymatic protocols, activation energy is positive with higher frequency factor. Enthalpy change for sonochemical protocol is negative, while that for enzymatic and sono-enzymatic protocols is positive. The net entropy change for sonochemical protocol is more negative than enzymatic or sono-enzymatic protocol due to differences in prevalent chemical mechanism of dye decolorization. Due to inverse variations of frequency factor and activation energy, marginal rise in reaction kinetics is seen for sono-enzymatic protocol, as compared to enzymatic treatment alone. Due to inverse variations of enthalpy and entropy change, net Gibbs energy change in all experimental protocols shows little variation indicating synergism of the mechanism of ultrasound and enzyme. PMID:24548544

  15. KINETIC AND THERMODYNAMIC ANALYSIS ON OH ADDITION TO ETHYLENE: ADDUCT FORMATION, ISOMERIZATION, AND ISOMER DISSOCIATIONS. (R824970)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  16. Interfacing computer-assisted drafting and design with the building loads analysis and system thermodynamics (BLAST) program. Final report

    SciTech Connect

    Morton, J.D.; Pyo, C.; Choi, B.

    1992-10-01

    Energy efficient building design requires in-depth thermal analysis. Existing Computer Aided Design and Drafting (CADD) software packages already enhance the productivity and quality of design. Thermal analysis tools use much the same information as that contained in CADD drawings to determine the most energy efficient design configuration during the design process. To use these analysis tools, data already contained in the CADD system must be re-keyed into the analysis packages. This project created an interface to automate the migration of data from CADD to the Building Loads Analysis System and Thermodynamics (BLAST) analysis program, which is an Army-standard system for evaluating building energy performance. Two interfaces were developed, one batch-oriented (IN2BLAS7) and one interactive (the Drawing Navigator). Lessons learned from the development of IN2BLAST were carried into the development of the Drawing Navigator, and the Drawing Navigator was field tested. Feedback indicated that useful automation of the data migration is possible, and that proper application of such automation can increase productivity.... Blast, CADD, Interface, IN2BLAST, Drawing navigator.

  17. Dried blood spot analysis of creatinine with LC-MS/MS in addition to immunosuppressants analysis.

    PubMed

    Koster, Remco A; Greijdanus, Ben; Alffenaar, Jan-Willem C; Touw, Daan J

    2015-02-01

    In order to monitor creatinine levels or to adjust the dosage of renally excreted or nephrotoxic drugs, the analysis of creatinine in dried blood spots (DBS) could be a useful addition to DBS analysis. We developed a LC-MS/MS method for the analysis of creatinine in the same DBS extract that was used for the analysis of tacrolimus, sirolimus, everolimus, and cyclosporine A in transplant patients with the use of Whatman FTA DMPK-C cards. The method was validated using three different strategies: a seven-point calibration curve using the intercept of the calibration to correct for the natural presence of creatinine in reference samples, a one-point calibration curve at an extremely high concentration in order to diminish the contribution of the natural presence of creatinine, and the use of creatinine-[(2)H3] with an eight-point calibration curve. The validated range for creatinine was 120 to 480 μmol/L (seven-point calibration curve), 116 to 7000 μmol/L (1-point calibration curve), and 1.00 to 400.0 μmol/L for creatinine-[(2)H3] (eight-point calibration curve). The precision and accuracy results for all three validations showed a maximum CV of 14.0% and a maximum bias of -5.9%. Creatinine in DBS was found stable at ambient temperature and 32 °C for 1 week and at -20 °C for 29 weeks. Good correlations were observed between patient DBS samples and routine enzymatic plasma analysis and showed the capability of the DBS method to be used as an alternative for creatinine plasma measurement.

  18. Thermodynamic, kinetic and conformational analysis of proteins diffusion-sorption on a solid surface.

    PubMed

    Sanfeld, Albert; Royer, Catherine; Steinchen, Annie

    2015-08-01

    In this paper we examine particularly some of the more fundamental properties of protein conformational changes at a solid surface coupled with diffusion from the bulk of an aqueous solution and with the adsorption-desorption processes. We focus our attention on adsorbed protein monolayers upon a solid surface using a thermodynamic and kinetic analytical development. Account is also taken of the effects on the overall rate of the conformational change on a solid surface of deviation from ideality, of protein flexibility, of surface free energy and of interaction with reactive solid sites. Our theory applied to steady states is illustrated by examples such as folding-misfolding-unfolding of RNase and SNase on a solid surface after diffusion and adsorption from an aqueous solution. For this purpose, we put forward the determining steps which shall lead to the steady state. The existence of three situations is highlighted according to the values of the typical constants relevant for the protein considered: reaction rate determining step, diffusion and sorption determining steps, mixed adsorption diffusion and reaction rate. Finally, we have tried to link the developments of our theories to a large literature based on experimental results encountered during proteins diffusion-sorption-reaction processes, fundamental topics that has been since long investigated by Miller's team in MPKG.

  19. Thermodynamic Analysis of a Rankine Cycle Powered Vapor Compression Ice Maker Using Solar Energy

    PubMed Central

    Hu, Bing; Bu, Xianbiao; Ma, Weibin

    2014-01-01

    To develop the organic Rankine-vapor compression ice maker driven by solar energy, a thermodynamic model was developed and the effects of generation temperature, condensation temperature, and working fluid types on the system performance were analyzed. The results show that the cooling power per square meter collector and ice production per square meter collector per day depend largely on generation temperature and condensation temperature and they increase firstly and then decrease with increasing generation temperature. For every working fluid there is an optimal generation temperature at which organic Rankine efficiency achieves the maximum value. The cooling power per square meter collector and ice production per square meter collector per day are, respectively, 126.44 W m−2 and 7.61 kg m−2 day−1 at the generation temperature of 140°C for working fluid of R245fa, which demonstrates the feasibility of organic Rankine cycle powered vapor compression ice maker. PMID:25202735

  20. Thermodynamic analysis of Bacillus subtilis endospore protonation using isothermal titration calorimetry

    NASA Astrophysics Data System (ADS)

    Harrold, Zoë R.; Gorman-Lewis, Drew

    2013-05-01

    Bacterial proton and metal adsorption reactions have the capacity to affect metal speciation and transport in aqueous environments. We coupled potentiometric titration and isothermal titration calorimetry (ITC) analyses to study Bacillus subtilis spore-proton adsorption. We modeled the potentiometric data using a four and five-site non-electrostatic surface complexation model (NE-SCM). Heats of spore surface protonation from coupled ITC analyses were used to determine site specific enthalpies of protonation based on NE-SCMs. The five-site model resulted in a substantially better model fit for the heats of protonation but did not significantly improve the potentiometric titration model fit. The improvement observed in the five-site protonation heat model suggests the presence of a highly exothermic protonation reaction circa pH 7 that cannot be resolved in the less sensitive potentiometric data. From the log Ks and enthalpies we calculated corresponding site specific entropies. Log Ks and site concentrations describing spore surface protonation are statistically equivalent to B. subtilis cell surface protonation constants. Spore surface protonation enthalpies, however, are more exothermic relative to cell based adsorption suggesting a different bonding environment. The thermodynamic parameters defined in this study provide insight on molecular scale spore-surface protonation reactions. Coupled ITC and potentiometric titrations can reveal highly exothermic, and possibly endothermic, adsorption reactions that are overshadowed in potentiometric models alone. Spore-proton adsorption NE-SCMs derived in this study provide a framework for future metal adsorption studies.

  1. Thermodynamic analysis of the energy recovery from the aerobic bioconversion of solid urban waste organic fraction.

    PubMed

    Di Maria, Francesco; Benavoli, Manuel; Zoppitelli, Mirco

    2008-01-01

    Waste management is of the utmost importance for many countries and especially for highly developed ones due to its implications on society. In particular, proper treatment before disposal of the solid urban waste organic fraction is one of the main issues that is addressed in waste management. In fact, the organic fraction is particularly reactive and if disposed in sanitary landfills without previous adequate treatment, a large amount of dangerous and polluting gaseous, liquid and solid substances can be produced. Some waste treatment processes can also present an opportunity to produce other by-products like energy, recycled materials and other products with both economic and environmental benefits. In this paper, the aerobic treatment of the organic fraction of solid urban waste, performed in a biocell plant with the possibility of recovering heat for civil or industrial needs, was examined from the thermodynamic point of view. A theoretical model was proposed both for the biological process of the organic fraction, as well as for the heat recovery system. The most significant results are represented and discussed. PMID:17512716

  2. Material Based Structure Design: Numerical Analysis Thermodynamic Response of Thermal Pyrolytic Graphite /Al Sandwich Composites

    NASA Astrophysics Data System (ADS)

    Wang, Junxia; Yan, Shilin; Yu, Dingshan

    2016-06-01

    Amine-grafted multiwalled carbon nanotubes (MWCNTs) based thermally conductive adhesive (TCA) was studied in the previous paper and applied here in thermal pyrolytic graphite (TPG)/Al radiator due to its high thermal conductivity, toughness and cohesiveness. In this paper, in an attempt to confirm the application of TCA to TPG/Al sandwich radiator, the thermodynamic response in TPG/Al sandwich composites associated with key material properties and structural design was investigated using finite element simulation with commercial available ANSYS software. The induced thermal stress in TCA layer is substantial due to the thermal expansion mismatch between Al plate and TPG. The maximum thermal stress is located near the edge of TCA layer with the von Mises stress value of 4.02 MPa and the shear stress value of 1.66 MPa. The reasonable adjustment of physical-mechanical properties including thermal conductivity, thermal expansion, Young,s modulus and the thickness of TCA layer, Al plate and TPG are beneficial for reducing the temperature of the top surface of the upper skin and their effects on the reduction of thermal structural response in some ways. These findings will highlight the structural optimization of TPG/Al radiator for future application.

  3. Descriptive thermodynamics

    NASA Astrophysics Data System (ADS)

    Ford, David; Huntsman, Steven

    2006-06-01

    Thermodynamics (in concert with its sister discipline, statistical physics) can be regarded as a data reduction scheme based on partitioning a total system into a subsystem and a bath that weakly interact with each other. Whereas conventionally, the systems investigated require this form of data reduction in order to facilitate prediction, a different problem also occurs, in the context of communication networks, markets, etc. Such “empirically accessible” systems typically overwhelm observers with the sort of information that in the case of (say) a gas is effectively unobtainable. What is required for such complex interacting systems is not prediction (this may be impossible when humans besides the observer are responsible for the interactions) but rather, description as a route to understanding. Still, the need for a thermodynamical data reduction scheme remains. In this paper, we show how an empirical temperature can be computed for finite, empirically accessible systems, and further outline how this construction allows the age-old science of thermodynamics to be fruitfully applied to them.

  4. Thermodynamics of graphene

    NASA Astrophysics Data System (ADS)

    Rusanov, A. I.

    2014-12-01

    The 21st century has brought a lot of new results related to graphene. Apparently, graphene has been characterized from all points of view except surface science and, especially, surface thermodynamics. This report aims to close this gap. Since graphene is the first real two-dimensional solid, a general formulation of the thermodynamics of two-dimensional solid bodies is given. The two-dimensional chemical potential tensor coupled with stress tensor is introduced, and fundamental equations are derived for energy, free energy, grand thermodynamic potential (in the classical and hybrid forms), enthalpy, and Gibbs energy. The fundamentals of linear boundary phenomena are formulated with explaining the concept of a dividing line, the mechanical and thermodynamic line tensions, line energy and other linear properties with necessary thermodynamic equations. The one-dimensional analogs of the Gibbs adsorption equation and Shuttleworth-Herring relation are presented. The general thermodynamic relationships are illustrated with calculations based on molecular theory. To make the reader sensible of the harmony of chemical and van der Waals forces in graphene, the remake of the classical graphite theory is presented with additional variable combinations of graphene sheets. The calculation of the line energy of graphene is exhibited including contributions both from chemical bonds and van der Waals forces (expectedly, the latter are considerably smaller than the former). The problem of graphene holes originating from migrating vacancies is discussed on the basis of the Gibbs-Curie principle. An important aspect of line tension is the planar sheet/nanotube transition where line tension acts as a driving force. Using the bending stiffness of graphene, the possible radius range is estimated for achiral (zigzag and armchair) nanotubes.

  5. Thermodynamic aspects of heat pipe operation

    NASA Technical Reports Server (NTRS)

    Richter, Robert; Gottschlich, Joseph

    1990-01-01

    An expanded heat pipe operating model is described which includes thermodynamic and heat transfer considerations to reconcile disparities between actual and theoretical heat pipe performances. The analysis shows that thermodynamic considerations can explain the observed heat pipe performance limitations. A full understanding of thermodynamic processes could lead to advanced concepts for thermal transport devices.

  6. Thermodynamic Stability Analysis of Tolbutamide Polymorphs and Solubility in Organic Solvents.

    PubMed

    Svärd, Michael; Valavi, Masood; Khamar, Dikshitkumar; Kuhs, Manuel; Rasmuson, Åke C

    2016-06-01

    Melting temperatures and enthalpies of fusion have been determined by differential scanning calorimetry (DSC) for 2 polymorphs of the drug tolbutamide: FI(H) and FV. Heat capacities have been determined by temperature-modulated DSC for 4 polymorphs: FI(L), FI(H), FII, FV, and for the supercooled melt. The enthalpy of fusion of FII at its melting point has been estimated from the enthalpy of transition of FII into FI(H) through a thermodynamic cycle. Calorimetric data have been used to derive a quantitative polymorphic stability relationship between these 4 polymorphs, showing that FII is the stable polymorph below approximately 333 K, above which temperature FI(H) is the stable form up to its melting point. The relative stability of FV is well below the other polymorphs. The previously reported kinetic reversibility of the transformation between FI(L) and FI(H) has been verified using in situ Raman spectroscopy. The solid-liquid solubility of FII has been gravimetrically determined in 5 pure organic solvents (methanol, 1-propanol, ethyl acetate, acetonitrile, and toluene) over the temperature range 278 to 323 K. The ideal solubility has been estimated from calorimetric data, and solution activity coefficients at saturation in the 5 solvents determined. All solutions show positive deviation from Raoult's law, and all van't Hoff plots of solubility data are nonlinear. The solubility in toluene is well below that observed in the other investigated solvents. Solubility data have been correlated and extrapolated to the melting point using a semiempirical regression model. PMID:27238487

  7. Structural and Thermodynamic Analysis of a Conformationally Strained Circular Permutant of Barnase

    SciTech Connect

    Butler, S.; Mitrea, D; Mitrousis, G; Cingolani, G; Loh, S

    2009-01-01

    Circular permutation of a protein covalently links its original termini and creates new ends at another location. To maintain the stability of the permuted structure, the termini are typically bridged by a peptide long enough to span the original distance between them. Here, we take the opposite approach and employ a very short linker to introduce conformational strain into a protein by forcing its termini together. We join the N- and C-termini of the small ribonuclease barnase (normally 27.2 A distant) with a single Cys residue and introduce new termini at a surface loop, to create pBn. Compared to a similar variant permuted with an 18-residue linker, permutation with a single amino acid dramatically destabilizes barnase. Surprisingly, pBn is folded at 10 C and possesses near wild-type ribonuclease activity. The 2.25 A X-ray crystal structure of pBn reveals how the barnase fold is able to adapt to permutation, partially defuse conformational strain, and preserve enzymatic function. We demonstrate that strain in pBn can be relieved by cleaving the linker with a chemical reagent. Catalytic activity of both uncleaved (strained) pBn and cleaved (relaxed) pBn is proportional to their thermodynamic stabilities, i.e., the fraction of folded molecules. The stability and activity of cleaved pBn are dependent on protein concentration. At concentrations above 2 ?M, cleaving pBn is predicted to increase the fraction of folded molecules and thus enhance ribonuclease activity at 37 C. This study suggests that introducing conformational strain by permutation, and releasing strain by cleavage, is a potential mechanism for engineering an artificial zymogen.

  8. Numerical power balance and free energy loss analysis for solar cells including optical, thermodynamic, and electrical aspects

    SciTech Connect

    Greulich, Johannes Höffler, Hannes; Würfel, Uli; Rein, Stefan

    2013-11-28

    A method for analyzing the power losses of solar cells is presented, supplying a complete balance of the incident power, the optical, thermodynamic, and electrical power losses and the electrical output power. The involved quantities have the dimension of a power density (units: W/m{sup 2}), which permits their direct comparison. In order to avoid the over-representation of losses arising from the ultraviolet part of the solar spectrum, a method for the analysis of the electrical free energy losses is extended to include optical losses. This extended analysis does not focus on the incident solar power of, e.g., 1000 W/m{sup 2} and does not explicitly include the thermalization losses and losses due to the generation of entropy. Instead, the usable power, i.e., the free energy or electro-chemical potential of the electron-hole pairs is set as reference value, thereby, overcoming the ambiguities of the power balance. Both methods, the power balance and the free energy loss analysis, are carried out exemplarily for a monocrystalline p-type silicon metal wrap through solar cell with passivated emitter and rear (MWT-PERC) based on optical and electrical measurements and numerical modeling. The methods give interesting insights in photovoltaic (PV) energy conversion, provide quantitative analyses of all loss mechanisms, and supply the basis for the systematic technological improvement of the device.

  9. Numerical power balance and free energy loss analysis for solar cells including optical, thermodynamic, and electrical aspects

    NASA Astrophysics Data System (ADS)

    Greulich, Johannes; Höffler, Hannes; Würfel, Uli; Rein, Stefan

    2013-11-01

    A method for analyzing the power losses of solar cells is presented, supplying a complete balance of the incident power, the optical, thermodynamic, and electrical power losses and the electrical output power. The involved quantities have the dimension of a power density (units: W/m2), which permits their direct comparison. In order to avoid the over-representation of losses arising from the ultraviolet part of the solar spectrum, a method for the analysis of the electrical free energy losses is extended to include optical losses. This extended analysis does not focus on the incident solar power of, e.g., 1000 W/m2 and does not explicitly include the thermalization losses and losses due to the generation of entropy. Instead, the usable power, i.e., the free energy or electro-chemical potential of the electron-hole pairs is set as reference value, thereby, overcoming the ambiguities of the power balance. Both methods, the power balance and the free energy loss analysis, are carried out exemplarily for a monocrystalline p-type silicon metal wrap through solar cell with passivated emitter and rear (MWT-PERC) based on optical and electrical measurements and numerical modeling. The methods give interesting insights in photovoltaic (PV) energy conversion, provide quantitative analyses of all loss mechanisms, and supply the basis for the systematic technological improvement of the device.

  10. An Ontological and Epistemological Analysis of the Presentation of the First Law of Thermodynamics in School and University Textbooks

    ERIC Educational Resources Information Center

    Poblete, Joaquin Castillo; Rojas, Rocio Ogaz; Merino, Cristian; Quiroz, Waldo

    2016-01-01

    Considering the relevance of thermodynamics to the scientific discipline of chemistry and the curriculum of the Western school system, the philosophical system of Mario Bunge, particularly his ontology and epistemology, is used herein to analyze the presentation of the first law of thermodynamics in 15 school and university textbooks. The…

  11. Statistical thermodynamic analysis of peptide and protein insertion into lipid membranes.

    PubMed Central

    Ben-Shaul, A; Ben-Tal, N; Honig, B

    1996-01-01

    A statistical thermodynamic approach is used to analyze the various contributions to the free energy change associated with the insertion of proteins and protein fragments into lipid bilayers. The partition coefficient that determines the equilibrium distribution of proteins between the membrane and the solution is expressed as the ratio between the partition functions of the protein in the two phases. It is shown that when all of the relevant degrees of freedom (i.e., those that change their character upon insertion into the membrane) can be treated classically, the partition coefficient is fully determined by the ratio of the configurational integrals and thus does not involve any mass-dependent factors, a conclusion that is also valid for related processes such as protein adsorption on a membrane surface or substrate binding to proteins. The partition coefficient, and hence the transfer free energy, depend only on the potential energy of the protein in the membrane. Expressing this potential as a sum of a "static" term, corresponding to the equilibrium (minimal free energy) configuration of the protein in the membrane, and a "dynamical" term representing fluctuations around the equilibrium configuration, we show that the static term contains the "solvation" and "lipid perturbation" contributions to the transfer free energy. The dynamical term is responsible for the "immobilization" free energy, reflecting the loss of translational and rotational entropy of the protein upon incorporation into the membrane. Based on a recent molecular theory of lipid-protein interactions, the lipid perturbation and immobilization contributions are then expressed in terms of the elastic deformation free energy resulting from the perturbation of the lipid environment by the foreign (protein) inclusion. The model is formulated for cylindrically shaped proteins, and numerical estimates are given for the insertion of an alpha-helical peptide into a lipid bilayer. The immobilization

  12. Nanoscopic Thermodynamics.

    PubMed

    Qi, Weihong

    2016-09-20

    Conventional thermodynamics for bulk substances encounters challenges when one considers materials on the nanometer scale. Quantities such as entropy, enthalpy, free energy, melting temperature, ordering temperature, Debye temperature, and specific heat no longer remain constant but change with the crystal dimension, size, and morphology. Often, one phenomenon is associated with a variety of theories from different perspectives. Still, a model that can reconcile the size and shape dependence of the thermal properties of the nanoscaled substances remains one of the goals of nanoscience and nanotechnology. This Account highlights the nanoscopic thermodynamics for nanoparticles, nanowires, and nanofilms, with particular emphasis on the bond energy model. The central idea is that the atomic cohesive energy determines the thermodynamic performance of a substance and the cohesive energy varies with the atomic coordination environment. It is the cohesive energy difference between the core and the shell that dictates the nanoscopic thermodynamics. This bond energy model rationalizes the following: (i) how the surface dangling bonds depress the melting temperature, entropy, and enthalpy; (ii) how the order-disorder transition of the nanoparticles depends on particle size and how their stability may vary when they are embedded in an appropriate matrix; (iii) predictions of the existence of face-centered cubic structures of Ti, Zr, and Hf at small size; (iv) how two elements that are immiscible in the bulk can form an alloy on the nanoscale, where the critical size can be predicted. The model has enabled us to reproduce the size and shape dependence of a number of physical properties, such as melting temperature, melting entropy, melting enthalpy, ordering temperature, Gibbs free energy, and formation heat, among others, for materials such as Pd, Au, Ag, Cu, Ni, Sn, Pb, In, Bi, Al, Ti, Zr, Hf, In-Al, Ag-Ni, Co-Pt, Cu-Ag, Cu-Ni, Au-Ni, Ag-Pt, and Au-Pt on the nanometer scale

  13. A fundamental approach to adhesion: Synthesis, surface analysis, thermodynamics and mechanics

    NASA Technical Reports Server (NTRS)

    Beck, B.; Siriwardane, R.; Wightman, J. P.

    1981-01-01

    Pretreated and primed Ti 6-4 surfaces were characterized by scanning electron microscopy/energy dispersive analysis of X-rays (SEM/EDAX) and electron spectroscopy for chemical analysis (ESCA). Fractured lap shear bonded Ti 6-4 specimens were also characterized by SEM/EDAX and ESCA. A number of surface techniques were used to characterize Ti02 powders.

  14. Taming catalysts in quantum thermodynamics

    NASA Astrophysics Data System (ADS)

    Skrzypczyk, Paul

    2015-08-01

    Auxiliary quantum systems which can be borrowed to help facilitate thermodynamic processes but must be returned almost undisturbed—i.e. catalysts—are very powerful objects in quantum thermodynamics. In fact, they appear almost too powerful, since they allow for any state transformation to be carried out while being disturbed by an arbitrarily small amount. In their recent paper Ng et al (2015 New J. Phys. 17 085004) show how to tame catalysts in quantum thermodynamics by placing additional physical constraints on them, in terms of dimension and energy.

  15. Thermodynamic properties of modified gravity theories

    NASA Astrophysics Data System (ADS)

    Bamba, Kazuharu

    2016-06-01

    We review thermodynamic properties of modified gravity theories, such as F(R) gravity and f(T) gravity, where R is the scalar curvature and T is the torsion scalar in teleparallelism. In particular, we explore the equivalence between the equations of motion for modified gravity theories and the Clausius relation in thermodynamics. In addition, thermodynamics of the cosmological apparent horizon is investigated in f(T) gravity. We show both equilibrium and nonequilibrium descriptions of thermodynamics. It is demonstrated that the second law of thermodynamics in the universe can be met, when the temperature of the outside of the apparent horizon is equivalent to that of the inside of it.

  16. Analysis methods for the determination of anthropogenic additions of P to agricultural soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Phosphorus additions and measurement in soil is of concern on lands where biosolids have been applied. Colorimetric analysis for plant-available P may be inadequate for the accurate assessment of soil P. Phosphate additions in a regulatory environment need to be accurately assessed as the reported...

  17. Thermodynamic analysis of the cubic-tetragonal phase equilibria in the system ZrO{sub 2}-YO{sub 1.5}

    SciTech Connect

    Katamura, Junji; Sakuma, Taketo

    1997-10-01

    The cubic-tetragonal (c-t) phase equilibria in the system ZrO{sub 2}-YO{sub 1.5} are thermodynamically analyzed from Landau`s phenomenological theory. The calculated c-t two-phase field is depicted as a miscibility gap with a sharp maximum and the spinodal region as originally predicted by Hillert and Sakuma. However, the observed c-t two-phase field and the spinodal region are better described by the present model. In addition, this model can be used to discuss the nature of the c-t diffusionless transformation from the order parameter in contrast with the original model. The predicted change in the tetragonality of t-ZrO{sub 2} with YO{sub 1.5} content is slightly different from that in the cla axial ratio estimated from X-ray diffraction analysis. The displacement of cations and anions may not take place simultaneously during the c-t transformation.

  18. Molecular structure, spectroscopy (FT-IR, FT-Raman), thermodynamic parameters, molecular electrostatic potential and HOMO-LUMO analysis of 2, 6-dichlorobenzamide

    NASA Astrophysics Data System (ADS)

    Tao, Yaping; Han, Ligang; Li, Xiaofeng; Han, Yunxia; Liu, Zhaojun

    2016-03-01

    2, 6-dichlorobenzamide is the degradation product of 2, 6-dichlorobenzonitrile, which is often used as herbicide and can cause groundwater pollution. The FT-IR and FT-Raman spectra of 2, 6-dichlorobenzamide at room temperature were recorded and analyzed in the range 4000-400 and 3700-100 cm-1, respectively. In order to obtain the most stable structure, a potential energy surface (PES) scan for internal rotations was carried out at the B3LYP/6-31G(d) level. The optimized geometry, structural parameters energies, theoretical IR and Raman spectra for the title compound have been obtained by employing B3LYP exchange-correlation functional with high-quality aug-cc-pVTZ basis-set. Detailed vibrational assignments of vibrational spectra have been made on the basis of the potential energy distributions (PED) analysis. In addition, the HOMO-LUMO gap and molecular electrostatic potential (MEP) were studied theoretically. Finally, the thermodynamic functions (heat capacity, entropy, enthalpy, and Gibbs free energy) of 2, 6-dichlorobenzamide were obtained in the range of 100-1000 K.

  19. [Correlativity analysis based on radiation spectrum of correlated color temperature and thermodynamic temperature of a radiating source].

    PubMed

    Fu, Tai-ran; Cheng, Xiao-fang; Zhong, Mao-hua; Yang, Zang-jian

    2006-11-01

    Correlated color temperature, which describes the chromaticity characteristics of a radiating source, is different from its thermodynamic temperature derived from primary spectrum pyrometry. However, establishing their mathematical relationship is feasible. Therefore, the authors theoretically analyzed the variation rule of the correlativity difference between the correlated color temperature of the source and its thermodynamic temperature with the emissivity parameter. And the authors gave the corresponding numerical simulation results. The above theoretical and numerical discussions will make it possible that a colorimeter used to measure the correlated color temperature serves as a pyrometer to realize the measurement of the thermodynamic temperature.

  20. [Correlativity analysis based on radiation spectrum of correlated color temperature and thermodynamic temperature of a radiating source].

    PubMed

    Fu, Tai-ran; Cheng, Xiao-fang; Zhong, Mao-hua; Yang, Zang-jian

    2006-11-01

    Correlated color temperature, which describes the chromaticity characteristics of a radiating source, is different from its thermodynamic temperature derived from primary spectrum pyrometry. However, establishing their mathematical relationship is feasible. Therefore, the authors theoretically analyzed the variation rule of the correlativity difference between the correlated color temperature of the source and its thermodynamic temperature with the emissivity parameter. And the authors gave the corresponding numerical simulation results. The above theoretical and numerical discussions will make it possible that a colorimeter used to measure the correlated color temperature serves as a pyrometer to realize the measurement of the thermodynamic temperature. PMID:17260737

  1. Quantitative Analysis of Polymer Additives with MALDI-TOF MS Using an Internal Standard Approach

    NASA Astrophysics Data System (ADS)

    Schwarzinger, Clemens; Gabriel, Stefan; Beißmann, Susanne; Buchberger, Wolfgang

    2012-06-01

    MALDI-TOF MS is used for the qualitative analysis of seven different polymer additives directly from the polymer without tedious sample pretreatment. Additionally, by using a solid sample preparation technique, which avoids the concentration gradient problems known to occur with dried droplets and by adding tetraphenylporphyrine as an internal standard to the matrix, it is possible to perform quantitative analysis of additives directly from the polymer sample. Calibration curves for Tinuvin 770, Tinuvin 622, Irganox 1024, Irganox 1010, Irgafos 168, and Chimassorb 944 are presented, showing coefficients of determination between 0.911 and 0.990.

  2. Quantitative analysis of polymer additives with MALDI-TOF MS using an internal standard approach.

    PubMed

    Schwarzinger, Clemens; Gabriel, Stefan; Beißmann, Susanne; Buchberger, Wolfgang

    2012-06-01

    MALDI-TOF MS is used for the qualitative analysis of seven different polymer additives directly from the polymer without tedious sample pretreatment. Additionally, by using a solid sample preparation technique, which avoids the concentration gradient problems known to occur with dried droplets and by adding tetraphenylporphyrine as an internal standard to the matrix, it is possible to perform quantitative analysis of additives directly from the polymer sample. Calibration curves for Tinuvin 770, Tinuvin 622, Irganox 1024, Irganox 1010, Irgafos 168, and Chimassorb 944 are presented, showing coefficients of determination between 0.911 and 0.990.

  3. A fundamental approach to adhesion: Synthesis, surface analysis, thermodynamics and mechanics

    NASA Technical Reports Server (NTRS)

    Beck, B.; Siriwardane, R.; Wightman, J. P.

    1980-01-01

    Several techniques were used to study pretreated Ti 6-4 surfaces including scanning electron microscopy (SEM), electron spectroscopy of chemical analysis (ESCA), and, reflectance visible spectroscopy. Each pretreatment type gave a characteristic surface morphology as seen by SEM. Elemental analysis of the Ti 6-4 surfaces was done using ESCA. Trace residual contaminants from particular chemical pretreatments were identified readily. Results indicate that reflectance visible spectroscopy using indicator dyes placed on Ti 6-4 surfaces appears to be a feasible approach to establish surface acidity. Differences in surface acidity were observed using bromthymol blue on Ti 6-4 surfaces pretreated by two different methods.

  4. Natural thermodynamics

    NASA Astrophysics Data System (ADS)

    Annila, Arto

    2016-02-01

    The principle of increasing entropy is derived from statistical physics of open systems assuming that quanta of actions, as undividable basic build blocks, embody everything. According to this tenet, all systems evolve from one state to another either by acquiring quanta from their surroundings or by discarding quanta to the surroundings in order to attain energetic balance in least time. These natural processes result in ubiquitous scale-free patterns: skewed distributions that accumulate in a sigmoid manner and hence span log-log scales mostly as straight lines. Moreover, the equation for least-time motions reveals that evolution is by nature a non-deterministic process. Although the obtained insight in thermodynamics from the notion of quanta in motion yields nothing new, it accentuates that contemporary comprehension is impaired when modeling evolution as a computable process by imposing conservation of energy and thereby ignoring that quantum of actions are the carriers of energy from the system to its surroundings.

  5. Carbothermic synthesis of 820 μm uranium nitride kernels: Literature review, thermodynamics, analysis, and related experiments

    NASA Astrophysics Data System (ADS)

    Lindemer, T. B.; Voit, S. L.; Silva, C. M.; Besmann, T. M.; Hunt, R. D.

    2014-05-01

    The US Department of Energy is developing a new nuclear fuel that would be less susceptible to ruptures during a loss-of-coolant accident. The fuel would consist of tristructural isotropic coated particles with uranium nitride (UN) kernels with diameters near 825 μm. This effort explores factors involved in the conversion of uranium oxide-carbon microspheres into UN kernels. An analysis of previous studies with sufficient experimental details is provided. Thermodynamic calculations were made to predict pressures of carbon monoxide and other relevant gases for several reactions that can be involved in the conversion of uranium oxides and carbides into UN. Uranium oxide-carbon microspheres were heated in a microbalance with an attached mass spectrometer to determine details of calcining and carbothermic conversion in argon, nitrogen, and vacuum. A model was derived from experiments on the vacuum conversion to uranium oxide-carbide kernels. UN-containing kernels were fabricated using this vacuum conversion as part of the overall process. Carbonitride kernels of ∼89% of theoretical density were produced along with several observations concerning the different stages of the process.

  6. Dynamically tunable transformation thermodynamics

    NASA Astrophysics Data System (ADS)

    García-Meca, Carlos; Barceló, Carlos

    2016-04-01

    Recently, the introduction of transformation thermodynamics has provided a way to design thermal media that alter the flow of heat according to any spatial deformation, enabling the construction of novel devices such as thermal cloaks or concentrators. However, in its current version, this technique only allows static deformations of space. Here, we develop a space–time theory of transformation thermodynamics that incorporates the possibility of performing time-varying deformations. This extra freedom greatly widens the range of achievable effects, providing an additional degree of control for heat management applications. As an example, we design a reconfigurable thermal cloak that can be opened and closed dynamically, therefore being able to gradually adjust the temperature distribution of a given region.

  7. Thermodynamic analysis of energy density in pressure retarded osmosis: The impact of solution volumes and costs

    SciTech Connect

    Reimund, Kevin K.; McCutcheon, Jeffrey R.; Wilson, Aaron D.

    2015-08-01

    A general method was developed for estimating the volumetric energy efficiency of pressure retarded osmosis via pressure-volume analysis of a membrane process. The resulting model requires only the osmotic pressure, π, and mass fraction, w, of water in the concentrated and dilute feed solutions to estimate the maximum achievable specific energy density, uu, as a function of operating pressure. The model is independent of any membrane or module properties. This method utilizes equilibrium analysis to specify the volumetric mixing fraction of concentrated and dilute solution as a function of operating pressure, and provides results for the total volumetric energy density of similar order to more complex models for the mixing of seawater and riverwater. Within the framework of this analysis, the total volumetric energy density is maximized, for an idealized case, when the operating pressure is π/(1+√w⁻¹), which is lower than the maximum power density operating pressure, Δπ/2, derived elsewhere, and is a function of the solute osmotic pressure at a given mass fraction. It was also found that a minimum 1.45 kmol of ideal solute is required to produce 1 kWh of energy while a system operating at “maximum power density operating pressure” requires at least 2.9 kmol. Utilizing this methodology, it is possible to examine the effects of volumetric solution cost, operation of a module at various pressure, and operation of a constant pressure module with various feed.

  8. Spatial analysis and quantification of the thermodynamic driving forces in protein-ligand binding: binding site variability.

    PubMed

    Raman, E Prabhu; MacKerell, Alexander D

    2015-02-25

    The thermodynamic driving forces behind small molecule-protein binding are still not well-understood, including the variability of those forces associated with different types of ligands in different binding pockets. To better understand these phenomena we calculate spatially resolved thermodynamic contributions of the different molecular degrees of freedom for the binding of propane and methanol to multiple pockets on the proteins Factor Xa and p38 MAP kinase. Binding thermodynamics are computed using a statistical thermodynamics based end-point method applied on a canonical ensemble comprising the protein-ligand complexes and the corresponding free states in an explicit solvent environment. Energetic and entropic contributions of water and ligand degrees of freedom computed from the configurational ensemble provide an unprecedented level of detail into the mechanisms of binding. Direct protein-ligand interaction energies play a significant role in both nonpolar and polar binding, which is comparable to water reorganization energy. Loss of interactions with water upon binding strongly compensates these contributions leading to relatively small binding enthalpies. For both solutes, the entropy of water reorganization is found to favor binding in agreement with the classical view of the "hydrophobic effect". Depending on the specifics of the binding pocket, both energy-entropy compensation and reinforcement mechanisms are observed. It is notable to have the ability to visualize the spatial distribution of the thermodynamic contributions to binding at atomic resolution showing significant differences in the thermodynamic contributions of water to the binding of propane versus methanol. PMID:25625202

  9. Structural and Thermodynamic Analysis of a Three-Component Assembly Forming ortho-Iminophenylboronate Esters.

    PubMed

    Chapin, Brette M; Metola, Pedro; Lynch, Vincent M; Stanton, John F; James, Tony D; Anslyn, Eric V

    2016-09-16

    Structural studies of a three-component assembly-a host and two distinct guests-were carried out using a combination of (11)B and (1)H NMR. In aprotic solvent, the imino group that forms ortho to the boronic acid or boronate ester group can form a dative N-B bond. In protic solvent, a molecule of solvent inserts between the nitrogen and boron atoms, partially ionizing the solvent molecule. Additionally, (11)B NMR was used in combination with a seventh-order polynomial to calculate five binding constants for each of the individual steps in protic solvent. Comparison of these binding constants was used to establish positive cooperativity in the binding of the two guests. PMID:27588921

  10. Analysis of oxygen binding by hemoglobin on the basis of mean intrinsic thermodynamic quantities.

    PubMed

    Bordbar, Abdol-Khalegh; Mousavi, Sayed Habib-Allah; Dazhampanah, Hamid

    2006-01-01

    The binding data for oxygenation of human hemoglobin, Hb, at various temperatures and in the absence and presence of 2,3-diphosphoglycerate, DPG, and inositol hexakis phosphate, IHP, were analyzed for extraction of mean intrinsic Gibbs free energy, DeltaGo, enthalpy, DeltaHo, and entropy, DeltaSo, of binding at various partial oxygen pressures. This method of analysis considers all the protein species present such as dimer and tetramer forms which were not considered by Imai et al. (Imai K et al., 1970, Biochim Biophys Acta 200: 189-196), in their analysis which was based on Adair equation. In this regard, the values of Hill equation parameters were estimated with high precision at all points of the binding curve and used for calculation of DeltaGo, DeltaHo and DeltaSo were also calculated by analysis of DeltaGo values at various temperatures using van't Hoff equation. The results represent the enthalpic nature of the cooperativity in Hb oxygenation and the compensation effect of intrinsic entropy. The interpretation of results also to be, into account the decrease of the binding affinity of sites for oxygen in the presence of DPG and IHP without any considerable changes in the site-site interaction (extent of cooperativity). In other words, the interactions between bound ligands, organic phosphates and oxygen, are more due to a decreasing binding affinity and not to the reduction of the cooperative interaction between sites. The results also document the more heterotropic effect of IHP compared to DPG.

  11. Computer program for thermodynamic analysis of open cycle multishaft power system with multiple reheat and intercool

    NASA Technical Reports Server (NTRS)

    Glassman, A. J.

    1974-01-01

    A computer program to analyze power systems having any number of shafts up to a maximum of five is presented. On each shaft there can be as many as five compressors and five turbines, along with any specified number of intervening intercoolers and reheaters. A recuperator can be included. Turbine coolant flow can be accounted for. Any fuel consisting entirely of hydrogen and/or carbon can be used. The program is valid for maximum temperatures up to about 2000 K (3600 R). The system description, the analysis method, a detailed explanation of program input and output including an illustrative example, a dictionary of program variables, and the program listing are explained.

  12. Thermodynamic analysis of alternate energy carriers, hydrogen and chemical heat pipes

    NASA Technical Reports Server (NTRS)

    Cox, K. E.; Carty, R. H.; Conger, W. L.; Soliman, M. A.; Funk, J. E.

    1976-01-01

    Hydrogen and chemical heat pipes were proposed as methods of transporting energy from a primary energy source (nuclear, solar) to the user. In the chemical heat pipe system, primary energy is transformed into the energy of a reversible chemical reaction; the chemical species are then transmitted or stored until the energy is required. Analysis of thermochemical hydrogen schemes and chemical heat pipe systems on a second law efficiency or available work basis show that hydrogen is superior especially if the end use of the chemical heat pipe is electrical power.

  13. Thermodynamic analysis of biofuels as fuels for high temperature fuel cells

    NASA Astrophysics Data System (ADS)

    Milewski, Jarosław; Bujalski, Wojciech; Lewandowski, Janusz

    2013-02-01

    Based on mathematical modeling and numerical simulations, applicativity of various biofuels on high temperature fuel cell performance are presented. Governing equations of high temperature fuel cell modeling are given. Adequate simulators of both solid oxide fuel cell (SOFC) and molten carbonate fuel cell (MCFC) have been done and described. Performance of these fuel cells with different biofuels is shown. Some characteristics are given and described. Advantages and disadvantages of various biofuels from the system performance point of view are pointed out. An analysis of various biofuels as potential fuels for SOFC and MCFC is presented. The results are compared with both methane and hydrogen as the reference fuels. The biofuels are characterized by both lower efficiency and lower fuel utilization factors compared with methane. The presented results are based on a 0D mathematical model in the design point calculation. The governing equations of the model are also presented. Technical and financial analysis of high temperature fuel cells (SOFC and MCFC) are shown. High temperature fuel cells can be fed by biofuels like: biogas, bioethanol, and biomethanol. Operational costs and possible incomes of those installation types were estimated and analyzed. A comparison against classic power generation units is shown. A basic indicator net present value (NPV) for projects was estimated and commented.

  14. Thermodynamic analysis of biofuels as fuels for high temperature fuel cells

    NASA Astrophysics Data System (ADS)

    Milewski, Jarosław; Bujalski, Wojciech; Lewandowski, Janusz

    2011-11-01

    Based on mathematical modeling and numerical simulations, applicativity of various biofuels on high temperature fuel cell performance are presented. Governing equations of high temperature fuel cell modeling are given. Adequate simulators of both solid oxide fuel cell (SOFC) and molten carbonate fuel cell (MCFC) have been done and described. Performance of these fuel cells with different biofuels is shown. Some characteristics are given and described. Advantages and disadvantages of various biofuels from the system performance point of view are pointed out. An analysis of various biofuels as potential fuels for SOFC and MCFC is presented. The results are compared with both methane and hydrogen as the reference fuels. The biofuels are characterized by both lower efficiency and lower fuel utilization factors compared with methane. The presented results are based on a 0D mathematical model in the design point calculation. The governing equations of the model are also presented. Technical and financial analysis of high temperature fuel cells (SOFC and MCFC) are shown. High temperature fuel cells can be fed by biofuels like: biogas, bioethanol, and biomethanol. Operational costs and possible incomes of those installation types were estimated and analyzed. A comparison against classic power generation units is shown. A basic indicator net present value (NPV) for projects was estimated and commented.

  15. Thermodynamic analysis of performance improvement by reheat on the CO2 transcritical power cycle

    NASA Astrophysics Data System (ADS)

    Tuo, Hanfei

    2012-06-01

    The CO2 transcritical rankine power cycle has been widely investigated recently, because of its better temperature glide matching between sensible heat source and working fluid in vapor generator, and its desirable qualities, such as moderate critical point, little environment impact and low cost. A reheat CO2 transcritical power cycle with two stage expansion is presented to improve baseline cycle performance in this paper. Energy and exergy analysis are carried out to investigate effects of important parameters on cycle performance. The main results show that reheat cycle performance is sensitive to the variation of medium pressures and the optimum medium pressures exist for maximizing work output and thermal efficiency, respectively. Reheat cycle is compared to baseline cycle under the same conditions. More significant improvements by reheat are obtained at lower turbine inlet temperatures and larger high cycle pressure. Work output improvement is much higher than thermal efficiency improvement, because extra waste heat is required to reheat CO2. Based on second law analysis, exergy efficiency of reheat cycle is also higher than that of baseline cycle, because more useful work is converted from waste heat. Reheat with two stage expansion has great potential to improve thermal efficiency and especially net work output of a CO2 transcritical power cycle using a low-grade heat source.

  16. A thermodynamics based damage mechanics framework for fatigue analysis of microelectronics solder joints with size effects

    NASA Astrophysics Data System (ADS)

    Gomez, Juan

    Experimental observations of an increase in resistance with decreasing specimen size and under the presence of non-uniform plastic deformation fields have pushed the development for small scale plasticity theories since the early 90's. The observed phenomenon has been explained in terms of an accumulation of a density of geometrically necessary dislocations, which is required in order to accommodate nonuniform plastic deformation fields. This extra density of dislocations, contributes to the additional hardening observed in small scale specimens under imposed non-uniform plastic deformations. The density of geometrically necessary dislocations has been related to the gradients of plastic strain which are imposed either by the loading conditions or the geometry of the specimen. The proposed set of theories has promoted the idea that there is an additional material parameter, namely a plastic length scale. Within these theories when the material is under the presence of a non-uniform plastic deformation field and once typical structural dimensions approaches the material length scale there is an increase in resistance. Such a class of mathematical framework is currently known as strain gradient plasticity (SGP) theory. On the other hand, the current trend towards miniaturization in the microelectronics industry has raised questions about the true behavior of small structural systems. In this dissertation we address such a problem but from the perspective of eutectic solder alloys. Eutectic solder alloys as frequently used in the microelectronics industry exhibit considerable rate dependent response even at room temperature. Moreover for this type of material, the problem of interest is the response under cyclic loadings induced by thermomechanical fatigue leading to the classical case of creep-fatigue interaction. Several experimental and theoretical studies have been developed in order to generate robust constitutive descriptions for this class of applications. For

  17. Interactions of ionic liquids and acetone: thermodynamic properties, quantum-chemical calculations, and NMR analysis.

    PubMed

    Ruiz, Elia; Ferro, Victor R; Palomar, Jose; Ortega, Juan; Rodriguez, Juan Jose

    2013-06-20

    The interactions between ionic liquids (ILs) and acetone have been studied to obtain a further understanding of the behavior of their mixtures, which generally give place to an exothermic process, mutual miscibility, and negative deviation of Raoult's law. COSMO-RS was used as a suitable computational method to systematically analyze the excess enthalpy of IL-acetone systems (>300), in terms of the intermolecular interactions contributing to the mixture behavior. Spectroscopic and COSMO-RS results indicated that acetone, as a polar compound with strong hydrogen bond acceptor character, in most cases, establishes favorable hydrogen bonding with ILs. This interaction is strengthened by the presence of an acidic cation and an anion with dispersed charge and non-HB acceptor character in the IL. COSMO-RS predictions indicated that gas-liquid and vapor-liquid equilibrium data for IL-acetone systems can be finely tuned by the IL selection, that is, acting on the intermolecular interactions between the molecular and ionic species in the liquid phase. NMR measurements for IL-acetone mixtures at different concentrations were also carried out. Quantum-chemical calculations by using molecular clusters of acetone and IL species were finally performed. These results provided additional evidence of the main role played by hydrogen bonding in the behavior of systems containing ILs and HB acceptor compounds, such as acetone. PMID:23688030

  18. Analysis of Aero-Thermodynamic Behavior of EXPERT Capsule in Transitional Regime

    NASA Astrophysics Data System (ADS)

    Zuppardi, Gennaro; Morsa, Luigi; Schettino, Antonio; Votta, Raffaele

    2011-05-01

    The aerodynamic behavior of the EXPERT capsule has been already widely studied at low altitudes. In order to broaden the aerodynamic data base of the capsule, additional computations of the aerodynamic forces and an evaluation of the longitudinal stability and fluctuation of the pressure center have been carried out in the altitude interval 80-105 km. The effect of the rolling angle has been also evaluated. As EXPERT, in the considered altitude interval is in transitional regime, computations have been made by the DSMC code DS3V. Heat flux along the capsule surface has been also evaluated. This is an important topic because the nose and the frustum are made of low and high catalyticity materials, respectively. Computations, already performed in continuum regime by the CFD code H3NS, showed that, at the nose-frustum junction, an abrupt and strong peak of heat flux is present. In this work, this problem has been analyzed also in transitional regime. For this application, the DSMC 2-D code DS2V, requiring smaller computer resources, compared with the ones required by DS3V, has been used for making computations at lower altitudes. Furthermore, using DS2V made possible also to get a more detailed definition of the body surface and therefore to increase the surface resolution. The launch of the capsule is currently scheduled in 2011; flight data should be available to verify the results of the present computations.

  19. Thermodynamic analysis of the oxidation period of making a nickel-based multicomponent superalloy

    NASA Astrophysics Data System (ADS)

    Shil'nikov, E. V.; Alpatov, A. V.; Paderin, S. N.

    2013-11-01

    The oxygen activity is studied by oxygen sensors during the oxidation period in experimental heat of a superalloy in a 5-t electric arc furnace. The results of chemical analysis of metal and slag samples are used to calculate the activities of the metallic and oxide solution components using the energy parameters of the models of a pseudosubregular solution for the melt and a pseudoregular ionic solution for the slag, which were determined and presented in our earlier works. Equations are derived for the activity of oxygen in equilibrium with all melt components simultaneously and with each component individually. The entire oxidation process and the oxidation reaction of each metallic solution component are analyzed by comparing the actual and equilibrium oxygen activities in the metal at the beginning, middle, and end of the oxidation period of heat. The driving forces of the oxidation process are calculated from the difference between the actual and equilibrium chemical potentials of oxygen.

  20. Thermodynamic modeling and performance analysis of the variable-temperature heat reservoir absorption heat pump cycle

    NASA Astrophysics Data System (ADS)

    Qin, Xiaoyong; Chen, Lingen; Ge, Yanlin; Sun, Fengrui

    2015-10-01

    For practical absorption heat pump (AHP) plants, not all external heat reservoir heat capacities are infinite. External heat reservoir heat capacity should be an effect factor in modeling and performance analysis of AHP cycles. A variable-temperature heat reservoir AHP cycle is modeled, in which internal working substance is working in four temperature levels and all irreversibility factors are considered. The irreversibility includes heat transfer irreversibility, internal dissipation irreversibility and heat leakage irreversibility. The general equations among coefficient of performance (COP), heating load and some key characteristic parameters are obtained. The general and optimal characteristics are obtained by using numerical calculations. Besides, the influences of heat capacities of heat reservoirs, internal dissipation irreversibility, and heat leakage irreversibility on cycle performance are analyzed. The conclusions can offer some guidelines for design and operation of AHP plants.

  1. Fluid dynamic and thermodynamic analysis of a model pertaining to cryogenic fluid management in low gravity environments for a system with dynamically induced settling

    NASA Technical Reports Server (NTRS)

    Rios, J.

    1982-01-01

    The settling behavior of the liquid and gaseous phases of a fluid in a propellant and in a zero-g environment, when such settling is induced through the use of a dynamic device, in this particular case, a helical screw was studied. Particular emphasis was given to: (1) the description of a fluid mechanics model which seems applicable to the system under consideration, (2) a First Law of Thermodynamics analysis of the system, and (3) a discussion of applicable scaling rules.

  2. Thermodynamic characterization of pyrazole and azaindole derivatives binding to p38 mitogen-activated protein kinase using Biacore T100 technology and van't Hoff analysis.

    PubMed

    Papalia, Giuseppe A; Giannetti, Anthony M; Arora, Nidhi; Myszka, David G

    2008-12-15

    Biacore T100 technology was used in conjunction with a van't Hoff analysis to characterize the thermodynamic binding parameters of 85 small-molecule inhibitors of adenosine triphosphate (ATP) binding to p38 mitogen-activated protein (MAP) kinase. The compounds were selected from a large panel of azaindole and pyrazole derivatives for which IC(50) data exist. We showed a strong relationship between the K(D) and IC(50) of a compound, but only a modest relationship between k(off) and IC(50) was detected and an apparent relationship between a compound's k(on) and its IC(50) could not be discerned. Similarly, a correlation between a compound's IC(50) and its thermodynamic parameters DeltaH degrees and DeltaS degrees could not be established. The lack of a predominant kinetic or thermodynamic signature associated with the inhibitory potential of these compounds demonstrates that there exists, even within a single well-defined system, a library of kinetic routes or, alternatively, a library of initial and final enthalpic and entropic states from which to effect inhibition. As a complement to these studies, selected double mutant thermodynamic cycles were performed to probe the energetic coupling, if any, between common sites of fluorination in both the azaindole and pyrazole classes and two different substituents. Although both cycles indicated negligible coupling free energies, both revealed significant coupling enthalpies, an observation made in other similarly dissected systems. The possible significance and caveats associated with these findings along with the advantages of using Biacore technology to derive thermodynamic parameters in drug discovery efforts are discussed.

  3. Thermodynamic systems analysis of open-cycle Ocean Thermal Energy Conversion (OTEC)

    NASA Astrophysics Data System (ADS)

    Parsons, B. K.; Bharathan, D.; Althof, J. A.

    1985-09-01

    This report describes an updated thermal-hydraulic systems analysis program called OTECSYS that studies the integrated performance of an open-cycle ocean thermal energy conversion (OTEC) plant, specifically, the effects of component performance, design parameters, and site specific resource data on the total system performance and plant size. OTECSYS can size the various open-cycle power cycle and hydraulic components. Models for the evaporator, mist eliminator, turbine-generator diffuser, direct-contact condenser, exhaust compressors, seawater pumps, and seawater piping are included, as are evaluations of the pressure drops associated with the intercomponent connections. It can also determine the required steam, cold seawater, and warm seawater flow rates. OTECSYS uses an approach similar to earlier work and integrates the most up-to-date developments in component performance and configuration. The program format allows the user to examine subsystem concepts not currently included by creating new component models. It will be useful to the OTEC plant designer who wants to quantify the design point sizing, performance, and power production using site-specific resource data. Detailed design trade-offs are easily evaluated, and several examples of these types of investigations are presented using plant size and power as criteria.

  4. A Thermodynamic, kinematic and microphysical analysis of a jet and gigantic jet-producing Florida thunderstorm

    NASA Astrophysics Data System (ADS)

    Lazarus, S. M.; Splitt, M. E.; Brownlee, James; Spiva, Nicholas; Liu, Ningyu

    2015-08-01

    This paper presents a meteorological analysis of a storm that produced two jets, four gigantic jets (GJ), and a starter, which were observed by two radars as well as the Kennedy Space Center 4-Dimensional Lightning Surveillance System on 3 August 2013 in Central Florida. The work is the first application of dual polarization data to a jet-producing storm and is the fifth case related to a tropical disturbance. The storm environment is consistent with the moist tropical paradigm that characterizes about three quarters of the surface and aircraft observed jet and GJ events. The most unstable (MU) convective available potential energy is not unusual for Florida summer convection and is below the climatological mean for these events. An unusual speed shear layer is located near the storm equilibrium level (EL) and the storm exhibits a tilted structure with CGs displaced upshear. The turbulence, as measured by the eddy dissipation rate, is extreme near the storm top during the event window, consistent with the GJ mixing hypothesis. The individual events are collocated with, and track along, the center axis of the divergent outflow at the EL and occur within the region of the coldest GOES IR temperatures—placing the events within the overshoot. The dual polarization data indicate a deep graupel column, extending above the mixed phase layer, to a 13 km altitude.

  5. [Highly efficient and rapid capillary electrophoretic analysis of seven organic acid additives in beverages using polymeric ionic liquid as additive].

    PubMed

    Han, Haifeng; Wang, Qing; Liu, Xi; Jiang, Shengxiang

    2012-05-01

    A new capillary electrophoretic method for the rapid and direct separation of seven organic acids in beverages was developed, with poly (1-vinyl-3-butylimidazolium bromide) as the reliable background electrolyte modifier to reverse the direction of anode electroosmotic flow (EOF) severely. Several factors that affected the separation efficiency were investigated in detail. The optimal running buffer consisted of 125 mmol/L sodium dihydrogen phosphate (pH 6.5) and 0.01 g/L poly (1-vinyl-3-butylimidazolium bromide). Highly efficient separation (105,000 to 636,000 plates/m) was achieved within 4 min and standard deviations of the migration times (n=3) were lower than 0.0213 min under optimal conditions. The limits of detection (S/N = 3) ranged from 0.001 to 0.05 g/L. The present method was applied to determine a beverage sample (Mirinda) for sodium citrate, benzoic acid and sorbic acid with concentration of 2.64, 0.10 and 0.08 g/L, respectively. The recoveries of the three analytes in the sample were 100.3%, 100.7% and 131.7%, respectively. The method is simple, rapid, inexpensive, and can be applied to determine organic acids as additives in beverages.

  6. New Tendencies in Development of Carbonaceous Additives for Welding Fluxes

    NASA Astrophysics Data System (ADS)

    Kozyrev, N. A.; Kryukov, R. E.; Kozyreva, O. A.

    2015-09-01

    The paper provides results of comparative analysis of the effect of carbonaceous components introduced into welding fluxes on molten metal - slag interaction. Thermodynamical calculations of dehydrogenization are presented for submerged arc welding. A positive influence of carbonaceous additives on gas content and mechanical properties of welds is demonstrated. Carbon and fluorine containing additives are emphasized to be promising for automatic submerged arc welding.

  7. Nonequilibrium thermodynamics of nucleation

    SciTech Connect

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

    2014-12-14

    We present a novel approach to nucleation processes based on the GENERIC framework (general equation for the nonequilibrium reversible-irreversible coupling). Solely based on the GENERIC structure of time-evolution equations and thermodynamic consistency arguments of exchange processes between a metastable phase and a nucleating phase, we derive the fundamental dynamics for this phenomenon, based on continuous Fokker-Planck equations. We are readily able to treat non-isothermal nucleation even when the nucleating cores cannot be attributed intensive thermodynamic properties. In addition, we capture the dynamics of the time-dependent metastable phase being continuously expelled from the nucleating phase, and keep rigorous track of the volume corrections to the dynamics. Within our framework the definition of a thermodynamic nuclei temperature is manifest. For the special case of nucleation of a gas phase towards its vapor-liquid coexistence, we illustrate that our approach is capable of reproducing recent literature results obtained by more microscopic considerations for the suppression of the nucleation rate due to nonisothermal effects.

  8. Thermodynamic black di-rings

    SciTech Connect

    Iguchi, Hideo; Mishima, Takashi

    2010-10-15

    Previously the five dimensional S{sup 1}-rotating black rings have been superposed in a concentric way by some solitonic methods, and regular systems of two S{sup 1}-rotating black rings were constructed by the authors and then Evslin and Krishnan (we called these solutions 'black di-rings'). In this place we show some characteristics of the solutions of five dimensional black di-rings, especially in thermodynamic equilibrium. After the summary of the di-ring expressions and their physical quantities, first we comment on the equivalence of the two different solution sets of the black di-rings. Then the existence of thermodynamic black di-rings is shown, in which both isothermality and isorotation between the inner black ring and the outer black ring are realized. We also give detailed analysis of peculiar properties of the thermodynamic black di-ring including discussion about a certain kind of thermodynamic stability (instability) of the system.

  9. NMR and X-ray analysis of structural additivity in metal binding site-swapped hybrids of rubredoxin

    PubMed Central

    LeMaster, David M; Anderson, Janet S; Wang, Limin; Guo, Yi; Li, Hongmin; Hernández, Griselda

    2007-01-01

    Background Chimeric hybrids derived from the rubredoxins of Pyrococcus furiosus (Pf) and Clostridium pasteurianum (Cp) provide a robust system for the characterization of protein conformational stability and dynamics in a differential mode. Interchange of the seven nonconserved residues of the metal binding site between the Pf and Cp rubredoxins yields a complementary pair of hybrids, for which the sum of the thermodynamic stabilities is equal to the sum for the parental proteins. Furthermore, the increase in amide hydrogen exchange rates for the hyperthermophile-derived metal binding site hybrid is faithfully mirrored by a corresponding decrease for the complementary hybrid that is derived from the less thermostable rubredoxin, indicating a degree of additivity in the conformational fluctuations that underlie these exchange reactions. Results Initial NMR studies indicated that the structures of the two complementary hybrids closely resemble "cut-and-paste" models derived from the parental Pf and Cp rubredoxins. This protein system offers a robust opportunity to characterize differences in solution structure, permitting the quantitative NMR chemical shift and NOE peak intensity data to be analyzed without recourse to the conventional conversion of experimental NOE peak intensities into distance restraints. The intensities for 1573 of the 1652 well-resolved NOE crosspeaks from the hybrid rubredoxins were statistically indistinguishable from the intensities of the corresponding parental crosspeaks, to within the baseplane noise level of these high sensitivity data sets. The differences in intensity for the remaining 79 NOE crosspeaks were directly ascribable to localized dynamical processes. Subsequent X-ray analysis of the metal binding site-swapped hybrids, to resolution limits of 0.79 Å and 1.04 Å, demonstrated that the backbone and sidechain heavy atoms in the NMR-derived structures lie within the range of structural variability exhibited among the individual

  10. Separation and Extraction of Bismuth and Manganese from Roasted Low-Grade Bismuthinite and Pyrolusite: Thermodynamic Analysis and Sulfur Fixing

    NASA Astrophysics Data System (ADS)

    Zhan, Jing; Wang, Zhi-Jian; Zhang, Chuan-Fu; Hwang, Jiann-Yang; Xia, Chu-Ping

    2015-05-01

    A new environmentally friendly technology with higher recovery of bismuth is proposed to extract bismuth from low-grade bismuthinite and co-production MnSO4 from low-grade pyrolusite. The effects of simultaneous roasting process parameters on the sulfur-fixing rate and MnSO4 formation rate are investigated. Based on the Pourbaix diagram of metal-sulfur-oxygen system, the behavior of bismuth, manganese, and associated metal elements such ferrous, copper, lead, and sulfur in the bismuthinite and pyrolusite during roasting process is analyzed. The experimental results show that Bi in the ores can be converted into bismuth oxide or oxygen bismuth sulfate, and most of Mn in the ores can react with SO2 from bismuthinite to form MnSO4, which agree with thermodynamic analysis. A maximum of sulfur-fixing rate of 98.14% and MnSO4 formation rate of 70.2% are obtained under the conditions of 1.4 for the molar ratio of MnO2 to total sulfur in mixing ores of bismuthinite and pyrolusite ( n(MnO2)/ n(S)), 923 K for the roasting temperature, 2 h for roasting time, 140 L/h for air rate, and less than 74 μm for particle size. The ultimate recovery rate of bismuth reaches 96.25% by selective leaching of the roasted product, purification of leaching solution, and hydrolysis, which is higher than the current applied technology for the low-grade bismuthinite.

  11. Thermodynamics of Radiation Modes

    ERIC Educational Resources Information Center

    Pina, Eduardo; de la Selva, Sara Maria Teresa

    2010-01-01

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

  12. Multivariate qualitative analysis of banned additives in food safety using surface enhanced Raman scattering spectroscopy

    NASA Astrophysics Data System (ADS)

    He, Shixuan; Xie, Wanyi; Zhang, Wei; Zhang, Liqun; Wang, Yunxia; Liu, Xiaoling; Liu, Yulong; Du, Chunlei

    2015-02-01

    A novel strategy which combines iteratively cubic spline fitting baseline correction method with discriminant partial least squares qualitative analysis is employed to analyze the surface enhanced Raman scattering (SERS) spectroscopy of banned food additives, such as Sudan I dye and Rhodamine B in food, Malachite green residues in aquaculture fish. Multivariate qualitative analysis methods, using the combination of spectra preprocessing iteratively cubic spline fitting (ICSF) baseline correction with principal component analysis (PCA) and discriminant partial least squares (DPLS) classification respectively, are applied to investigate the effectiveness of SERS spectroscopy for predicting the class assignments of unknown banned food additives. PCA cannot be used to predict the class assignments of unknown samples. However, the DPLS classification can discriminate the class assignment of unknown banned additives using the information of differences in relative intensities. The results demonstrate that SERS spectroscopy combined with ICSF baseline correction method and exploratory analysis methodology DPLS classification can be potentially used for distinguishing the banned food additives in field of food safety.

  13. Multivariate qualitative analysis of banned additives in food safety using surface enhanced Raman scattering spectroscopy.

    PubMed

    He, Shixuan; Xie, Wanyi; Zhang, Wei; Zhang, Liqun; Wang, Yunxia; Liu, Xiaoling; Liu, Yulong; Du, Chunlei

    2015-02-25

    A novel strategy which combines iteratively cubic spline fitting baseline correction method with discriminant partial least squares qualitative analysis is employed to analyze the surface enhanced Raman scattering (SERS) spectroscopy of banned food additives, such as Sudan I dye and Rhodamine B in food, Malachite green residues in aquaculture fish. Multivariate qualitative analysis methods, using the combination of spectra preprocessing iteratively cubic spline fitting (ICSF) baseline correction with principal component analysis (PCA) and discriminant partial least squares (DPLS) classification respectively, are applied to investigate the effectiveness of SERS spectroscopy for predicting the class assignments of unknown banned food additives. PCA cannot be used to predict the class assignments of unknown samples. However, the DPLS classification can discriminate the class assignment of unknown banned additives using the information of differences in relative intensities. The results demonstrate that SERS spectroscopy combined with ICSF baseline correction method and exploratory analysis methodology DPLS classification can be potentially used for distinguishing the banned food additives in field of food safety.

  14. Multivariate qualitative analysis of banned additives in food safety using surface enhanced Raman scattering spectroscopy.

    PubMed

    He, Shixuan; Xie, Wanyi; Zhang, Wei; Zhang, Liqun; Wang, Yunxia; Liu, Xiaoling; Liu, Yulong; Du, Chunlei

    2015-02-25

    A novel strategy which combines iteratively cubic spline fitting baseline correction method with discriminant partial least squares qualitative analysis is employed to analyze the surface enhanced Raman scattering (SERS) spectroscopy of banned food additives, such as Sudan I dye and Rhodamine B in food, Malachite green residues in aquaculture fish. Multivariate qualitative analysis methods, using the combination of spectra preprocessing iteratively cubic spline fitting (ICSF) baseline correction with principal component analysis (PCA) and discriminant partial least squares (DPLS) classification respectively, are applied to investigate the effectiveness of SERS spectroscopy for predicting the class assignments of unknown banned food additives. PCA cannot be used to predict the class assignments of unknown samples. However, the DPLS classification can discriminate the class assignment of unknown banned additives using the information of differences in relative intensities. The results demonstrate that SERS spectroscopy combined with ICSF baseline correction method and exploratory analysis methodology DPLS classification can be potentially used for distinguishing the banned food additives in field of food safety. PMID:25300041

  15. Stimulation of terrestrial ecosystem carbon storage by nitrogen addition: a meta-analysis

    NASA Astrophysics Data System (ADS)

    Yue, Kai; Peng, Yan; Peng, Changhui; Yang, Wanqin; Peng, Xin; Wu, Fuzhong

    2016-01-01

    Elevated nitrogen (N) deposition alters the terrestrial carbon (C) cycle, which is likely to feed back to further climate change. However, how the overall terrestrial ecosystem C pools and fluxes respond to N addition remains unclear. By synthesizing data from multiple terrestrial ecosystems, we quantified the response of C pools and fluxes to experimental N addition using a comprehensive meta-analysis method. Our results showed that N addition significantly stimulated soil total C storage by 5.82% ([2.47%, 9.27%], 95% CI, the same below) and increased the C contents of the above- and below-ground parts of plants by 25.65% [11.07%, 42.12%] and 15.93% [6.80%, 25.85%], respectively. Furthermore, N addition significantly increased aboveground net primary production by 52.38% [40.58%, 65.19%] and litterfall by 14.67% [9.24%, 20.38%] at a global scale. However, the C influx from the plant litter to the soil through litter decomposition and the efflux from the soil due to microbial respiration and soil respiration showed insignificant responses to N addition. Overall, our meta-analysis suggested that N addition will increase soil C storage and plant C in both above- and below-ground parts, indicating that terrestrial ecosystems might act to strengthen as a C sink under increasing N deposition.

  16. Stimulation of terrestrial ecosystem carbon storage by nitrogen addition: a meta-analysis

    PubMed Central

    Yue, Kai; Peng, Yan; Peng, Changhui; Yang, Wanqin; Peng, Xin; Wu, Fuzhong

    2016-01-01

    Elevated nitrogen (N) deposition alters the terrestrial carbon (C) cycle, which is likely to feed back to further climate change. However, how the overall terrestrial ecosystem C pools and fluxes respond to N addition remains unclear. By synthesizing data from multiple terrestrial ecosystems, we quantified the response of C pools and fluxes to experimental N addition using a comprehensive meta-analysis method. Our results showed that N addition significantly stimulated soil total C storage by 5.82% ([2.47%, 9.27%], 95% CI, the same below) and increased the C contents of the above- and below-ground parts of plants by 25.65% [11.07%, 42.12%] and 15.93% [6.80%, 25.85%], respectively. Furthermore, N addition significantly increased aboveground net primary production by 52.38% [40.58%, 65.19%] and litterfall by 14.67% [9.24%, 20.38%] at a global scale. However, the C influx from the plant litter to the soil through litter decomposition and the efflux from the soil due to microbial respiration and soil respiration showed insignificant responses to N addition. Overall, our meta-analysis suggested that N addition will increase soil C storage and plant C in both above- and below-ground parts, indicating that terrestrial ecosystems might act to strengthen as a C sink under increasing N deposition. PMID:26813078

  17. Thermodynamic analysis of compatibility of several reinforcement materials with beta phase NiAl alloys. Final report

    SciTech Connect

    Misra, A.K.

    1988-11-01

    Chemical compatibility of several reinforcement materials with beta phase NiAl alloys within the concentration range 40 to 50 at. percent Al have been analyzed from thermodynamic considerations at 1373 and 1573 K. The reinforcement materials considered in this study include carbides, borides, oxides, nitrides, beryllides, and silicides. Thermodynamic data for NiAl alloys have been reviewed and activity of Ni and Al in the beta phase have been derived at 1373 and 1573 K. Criteria for chemical compatibility between the reinforcement material and the matrix have been defined and several chemically compatible reinforcement materials have been defined.

  18. Procedural analysis of a new method for determining the Gibbs energy and experimental data on thermodynamic properties of liquid-metal coolants based on alkali metal alloys

    SciTech Connect

    Kagan, D. N. Krechetova, G. A.; Shpil'rain, E. E.

    2010-12-15

    A detailed procedural analysis is given and results of implementation of the new version of the effusion method for determining the Gibbs energy (thermodynamic activity) of binary and ternary systems of alkali metals Cs-Na, K-Na, Cs-K, and Cs-K-Na are presented. The activity is determined using partial pressures of the components measured according the effusion method by the intensity of their atomic beams. The pressure range used in the experiment is intermediate between the Knudsen and hydrodynamic effusion modes. A generalized version of the effusion method involves the pressure range beyond the limits of the applicability of the Hertz-Knudsen equation. Employment of this method provides the differential equation of chemical thermodynamics; solution of this equation makes it possible to construct the Gibbs energy in the range of temperatures 400 {<=} T {<=} 1200 K and concentrations 0 {<=} x{sub i} {<=} 1.

  19. On an Additive Semigraphoid Model for Statistical Networks With Application to Pathway Analysis

    PubMed Central

    Li, Bing; Chun, Hyonho; Zhao, Hongyu

    2014-01-01

    We introduce a nonparametric method for estimating non-gaussian graphical models based on a new statistical relation called additive conditional independence, which is a three-way relation among random vectors that resembles the logical structure of conditional independence. Additive conditional independence allows us to use one-dimensional kernel regardless of the dimension of the graph, which not only avoids the curse of dimensionality but also simplifies computation. It also gives rise to a parallel structure to the gaussian graphical model that replaces the precision matrix by an additive precision operator. The estimators derived from additive conditional independence cover the recently introduced nonparanormal graphical model as a special case, but outperform it when the gaussian copula assumption is violated. We compare the new method with existing ones by simulations and in genetic pathway analysis. PMID:26401064

  20. Analysis of occupational accidents: prevention through the use of additional technical safety measures for machinery

    PubMed Central

    Dźwiarek, Marek; Latała, Agata

    2016-01-01

    This article presents an analysis of results of 1035 serious and 341 minor accidents recorded by Poland's National Labour Inspectorate (PIP) in 2005–2011, in view of their prevention by means of additional safety measures applied by machinery users. Since the analysis aimed at formulating principles for the application of technical safety measures, the analysed accidents should bear additional attributes: the type of machine operation, technical safety measures and the type of events causing injuries. The analysis proved that the executed tasks and injury-causing events were closely connected and there was a relation between casualty events and technical safety measures. In the case of tasks consisting of manual feeding and collecting materials, the injuries usually occur because of the rotating motion of tools or crushing due to a closing motion. Numerous accidents also happened in the course of supporting actions, like removing pollutants, correcting material position, cleaning, etc. PMID:26652689

  1. Thermodynamic basis of electron transfer in dihydroorotate dehydrogenase B from Lactococcus lactis: analysis by potentiometry, EPR spectroscopy, and ENDOR spectroscopy.

    PubMed

    Mohsen, Al-Walid A; Rigby, Stephen E J; Jensen, Kaj Frank; Munro, Andrew W; Scrutton, Nigel S

    2004-06-01

    Dihydroorotate dehydrogenase B (DHODB) is a complex iron-sulfur flavoprotein that catalyzes the conversion of dihydroorotate to orotate and the reduction of NAD(+). The enzyme is a dimer of heterodimers containing an FMN, an FAD, and a 2Fe-2S center. UV-visible, EPR, and ENDOR spectroscopies have been used to determine the reduction potentials of the flavins and the 2Fe-2S center and to characterize radicals and their interactions. Reductive titration using dithionite indicates a five-electron capacity for DHODB. The midpoint reduction potential of the 2Fe-2S center (-212 +/- 3 mV) was determined from analysis of absorption data at 540 nm, where absorption contributions from the two flavins are small. The midpoint reduction potentials of the oxidized/semiquinone (E(1)) and semiquinone/hydroquinone (E(2)) couples for the FMN (E(1) = -301 +/- 6 mV; E(2) = -252 +/- 8 mV) and FAD (E(1) = -312 +/- 6 mV; E(2) = -297 +/- 5 mV) were determined from analysis of spectral changes at 630 nm. Corresponding values for the midpoint reduction potentials for FMN (E(1) = -298 +/- 4 mV; E(2) = -259 +/- 5 mV) in the isolated catalytic subunit (subunit D, which lacks the 2Fe-2S center and FAD) are consistent with the values determined for the FMN couples in DHODB. During reductive titration of DHODB, small amounts of the neutral blue semiquinone are observed at approximately 630 nm, consistent with the measured midpoint reduction potentials of the flavins. An ENDOR spectrum of substrate-reduced DHODB identifies hyperfine couplings to proton nuclei similar to those recorded for the blue semiquinone of free flavins in aqueous solution, thus confirming the presence of this species in DHODB. Spectral features observed during EPR spectroscopy of dithionite-reduced DHODB are consistent with the midpoint reduction potentials determined using UV-visible spectroscopy and further identify an unusual EPR signal with very small rhombic anisotropy and g values of 2.02, 1.99, and 1.96. This unusual

  2. Molecular structure, vibrational spectroscopic, hyperpolarizability, natural bond orbital analysis, frontier molecular orbital analysis and thermodynamic properties of 2,3,4,5,6-pentafluorophenylacetic acid.

    PubMed

    Balachandran, V; Karunakaran, V

    2014-06-01

    The FT-IR (4000-400cm(-)(1)) and FT-Raman spectra (3500-100cm(-)(1)) of 2,3,4,5,6-pentafluorophenylacetic acid (PAA) have been recorded. Density functional theory calculation with LSDA/6-31+G(d,p) and B3LYP/6-31+G(d,p) basis sets have been used to determine ground state molecular geometries (bond lengths and bond angles), harmonic vibrational frequencies, infrared intensities, Raman intensities and bonding features of the title compound. The assignments of the vibrational spectra have been carried out with the help of normal coordinate analysis (NCA) following the scaled quantum mechanical force field (SQMFF) methodology. The first order hyperpolarizability (β0) and related properties (β, α0 and Δα) of PAA are calculated using B3LYP/6-31+G(d,p) method on the finite-field approach. The calculated first hyperpolarizability shows that the molecule is an attractive molecule for future applications in non-linear optics. The stability of molecule has been analyzed by using NBO analysis. The calculated HOMO and LUMO energies show that charge transfer occurs within this molecule. Mulliken population analysis on atomic charges is also calculated. Thermodynamic properties (heat capacity, enthalpy, Gibb's free energy and entropy) of the title compound at different temperatures were calculated.

  3. Analysis of zinc in biological samples by flame atomic absorption spectrometry: use of addition calibration technique.

    PubMed

    Dutra, Rosilene L; Cantos, Geny A; Carasek, Eduardo

    2006-01-01

    The quantification of target analytes in complex matrices requires special calibration approaches to compensate for additional capacity or activity in the matrix samples. The standard addition is one of the most important calibration procedures for quantification of analytes in such matrices. However, this technique requires a great number of reagents and material, and it consumes a considerable amount of time throughout the analysis. In this work, a new calibration procedure to analyze biological samples is proposed. The proposed calibration, called the addition calibration technique, was used for the determination of zinc (Zn) in blood serum and erythrocyte samples. The results obtained were compared with those obtained using conventional calibration techniques (standard addition and standard calibration). The proposed addition calibration was validated by recovery tests using blood samples spiked with Zn. The range of recovery for blood serum and erythrocyte samples were 90-132% and 76-112%, respectively. Statistical studies among results obtained by the addition technique and conventional techniques, using a paired two-tailed Student's t-test and linear regression, demonstrated good agreement among them. PMID:16943611

  4. Thermodynamic analysis of ionizable groups involved in the catalytic mechanism of human matrix metalloproteinase 7 (MMP-7).

    PubMed

    Takeharu, Hitoshi; Yasukawa, Kiyoshi; Inouye, Kuniyo

    2011-12-01

    Human matrix metalloproteinase 7 (MMP-7) exhibits a broad bell-shaped pH-dependence with the acidic and alkaline pK(e) (pK(e1) and pK(e2)) values of about 4 and 10. In this study, we estimated the ionizable groups involved in its catalytic mechanism by thermodynamic analysis. pK(a) of side chains of L-Asp, L-Glu, L-His, L-Cys, L-Tyr, L-Lys, and L-Arg at 25-45°C were determined by the pH titration of amino-acid solutions, from which their enthalpy changes, ∆H°, of deprotonation were calculated. pK(e1) and pK(e2) of MMP-7 at 15-45°C were determined in the hydrolysis of (7-methoxycoumarin-4-yl)acetyl-L-Pro-L-Leu-Gly-L-Leu-[N(3)-(2,4-dinitrophenyl)-L-2,3-diaminopropionyl]-L-Ala-L-Arg-NH(2), from which ∆H(o) for pK(e1) and pK(e2) was calculated. The ∆H(o) for pK(e1) (-20.6±6.1kJmol(-1)) was similar to that for L-Glu (-23.6±5.8kJmol(-1)), and the ∆H(o) for pK(e2) (89.9±4.0kJmol(-1)) was similar to those for L-Arg (87.6±5.5kJmol(-1)) and L-Lys (70.4±4.4kJmol(-1)). The mutation of the active-site residue Glu198 into Ala completely abolished the activity, suggesting that Glu198 is the ionizable group for pK(e1). On the other hand, no arginine or lysine residues are found in the active site of MMP-7. We proposed a possibility that a protein-bound water is the ionizable group for pK(e2).

  5. Measuring Thermodynamic Length

    SciTech Connect

    Crooks, Gavin E

    2007-09-07

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

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

    PubMed

    Rupesh, Shanmughom; Muraleedharan, Chandrasekharan; Arun, Palatel

    2014-01-01

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

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

    PubMed Central

    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

  8. Polymorph selection and nanocrystallite rearrangement of calcium carbonate in carboxymethyl chitosan aqueous solution: Thermodynamic and kinetic analysis

    SciTech Connect

    Zhao, Donghui; Zhu, Yingchun; Li, Fang; Ruan, Qichao; Zhang, Shengmao; Zhang, Linlin; Xu, Fangfang

    2010-01-15

    In this article, the polymorph selection of calcium carbonate has been successfully achieved in water-soluble carboxymethyl chitosan aqueous solution at different temperatures (25-95 {sup o}C). Vaterite is formed in carboxymethyl chitosan solution 25 {sup o}C accompanied with trace of calcite, whereas pure aragonite is obtained at 95 {sup o}C. Scanning electron microscopy and transmission electron microscopy analyses show that the products are formed from the recrystallization of nanometer crystallites. Thermodynamic and kinetic analyses reveal that the polymorph of calcium carbonate is controlled and selected by kinetics in various temperatures. As a heterogeneous nucleator and stabilizing agent, carboxymethyl chitosan changes the nucleation and growth of calcium carbonate from thermodynamic into kinetic control. Under kinetic limitation, the reaction rate of aragonite increases along with the elevating of temperature and surpasses the rate of vaterite above 327 K.

  9. Summarizing lecture: factors influencing enzymatic H-transfers, analysis of nuclear tunnelling isotope effects and thermodynamic versus specific effects

    PubMed Central

    Marcus, R.A

    2006-01-01

    In the articles in this Discussion, a wide variety of topics are treated, including reorganization energy, initially introduced for electron transfers (‘environmentally assisted tunnelling’), nuclear tunnelling, H/D and C12/C13 kinetic isotope effects (KIEs), the effect of changes of distal and nearby amino acid residues using site-directed mutagenesis, and dynamics versus statistical effects. A coordinate-free form of semi-classical theory is used to examine topics on data such as tunnelling versus ‘over-the-barrier’ paths and temperature and pressure effects on KIEs. The multidimensional semi-classical theory includes classically allowed and classically forbidden transitions. More generally, we address the question of relating kinetic to thermodynamic factors, as in the electron transfer field, so learning about specific versus thermodynamic effects in enzyme catalysis and KIEs. PMID:16873131

  10. Wetting state on hydrophilic and hydrophobic micro-textured surfaces: Thermodynamic analysis and X-ray visualization

    SciTech Connect

    Yu, Dong In; Kwak, Ho Jae; Doh, Seung Woo; Park, Hyun Sun Kiyofumi, Moriyama; Kang, Hie Chan; Ahn, Ho Seon; Kim, Moo Hwan

    2015-04-27

    In this study, the wetting state on hydrophobic and hydrophilic micro-textured surfaces was investigated. High spatial resolution synchrotron X-ray radiography was used to overcome the limitations in visualization in previous research and clearly visualize the wetting state for each droplet under quantified surface conditions. Based on thermodynamic characteristics, a theoretical model for wetting state depending on the chemical composition (intrinsic contact angle) and geometrical morphology (roughness ratio) of the surfaces was developed.

  11. RNA Thermodynamic Structural Entropy

    PubMed Central

    Garcia-Martin, Juan Antonio; Clote, Peter

    2015-01-01

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

  12. RNA Thermodynamic Structural Entropy.

    PubMed

    Garcia-Martin, Juan Antonio; Clote, Peter

    2015-01-01

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

  13. ANALYSIS OF DISTRIBUTION FEEDER LOSSES DUE TO ADDITION OF DISTRIBUTED PHOTOVOLTAIC GENERATORS

    SciTech Connect

    Tuffner, Francis K.; Singh, Ruchi

    2011-08-09

    Distributed generators (DG) are small scale power supplying sources owned by customers or utilities and scattered throughout the power system distribution network. Distributed generation can be both renewable and non-renewable. Addition of distributed generation is primarily to increase feeder capacity and to provide peak load reduction. However, this addition comes with several impacts on the distribution feeder. Several studies have shown that addition of DG leads to reduction of feeder loss. However, most of these studies have considered lumped load and distributed load models to analyze the effects on system losses, where the dynamic variation of load due to seasonal changes is ignored. It is very important for utilities to minimize the losses under all scenarios to decrease revenue losses, promote efficient asset utilization, and therefore, increase feeder capacity. This paper will investigate an IEEE 13-node feeder populated with photovoltaic generators on detailed residential houses with water heater, Heating Ventilation and Air conditioning (HVAC) units, lights, and other plug and convenience loads. An analysis of losses for different power system components, such as transformers, underground and overhead lines, and triplex lines, will be performed. The analysis will utilize different seasons and different solar penetration levels (15%, 30%).

  14. Analysis of redox additive-based overcharge protection for rechargeable lithium batteries

    NASA Technical Reports Server (NTRS)

    Narayanan, S. R.; Surampudi, S.; Attia, A. I.; Bankston, C. P.

    1991-01-01

    The overcharge condition in secondary lithium batteries employing redox additives for overcharge protection, has been theoretically analyzed in terms of a finite linear diffusion model. The analysis leads to expressions relating the steady-state overcharge current density and cell voltage to the concentration, diffusion coefficient, standard reduction potential of the redox couple, and interelectrode distance. The model permits the estimation of the maximum permissible overcharge rate for any chosen set of system conditions. Digital simulation of the overcharge experiment leads to numerical representation of the potential transients, and estimate of the influence of diffusion coefficient and interelectrode distance on the transient attainment of the steady state during overcharge. The model has been experimentally verified using 1,1-prime-dimethyl ferrocene as a redox additive. The analysis of the experimental results in terms of the theory allows the calculation of the diffusion coefficient and the formal potential of the redox couple. The model and the theoretical results may be exploited in the design and optimization of overcharge protection by the redox additive approach.

  15. Thermodynamics from a scaling Hamiltonian

    NASA Astrophysics Data System (ADS)

    Del Pino, L. A.; Troncoso, P.; Curilef, S.

    2007-11-01

    There are problems with defining the thermodynamic limit of systems with long-range interactions; as a result, the thermodynamic behavior of these types of systems is anomalous. In the present work, we review some concepts from both extensive and nonextensive thermodynamic perspectives. We use a model, whose Hamiltonian takes into account spins ferromagnetically coupled in a chain via a power law that decays at large interparticle distance r as 1/rα for α⩾0 . Here, we review old nonextensive scaling. In addition, we propose a Hamiltonian scaled by 2((N/2)1-α-1)/(1-α) that explicitly includes symmetry of the lattice and dependence on the size N of the system. The approach enabled us to improve upon previous results. A numerical test is conducted through Monte Carlo simulations. In the model, periodic boundary conditions are adopted to eliminate surface effects.

  16. Analysis of the benefits of carbon credits to hydrogen addition to midsize gas turbine feedstocks.

    SciTech Connect

    Miller, J.; Towns, B.; Keller, Jay O.; Schefer, Robert W.; Skolnik, Edward G.

    2006-02-01

    The addition of hydrogen to the natural gas feedstocks of midsize (30-150 MW) gas turbines was analyzed as a method of reducing nitrogen oxides (NO{sub x}) and CO{sub 2} emissions. In particular, the costs of hydrogen addition were evaluated against the combined costs for other current NO{sub x} and CO{sub 2} emissions control technologies for both existing and new systems to determine its benefits and market feasibility. Markets for NO{sub x} emissions credits currently exist in California and the Northeast States and are expected to grow. Although regulations are not currently in place in the United States, several other countries have implemented carbon tax and carbon credit programs. The analysis thus assumes that the United States adopts future legislation similar to these programs. Therefore, potential sale of emissions credits for volunteer retrofits was also included in the study. It was found that hydrogen addition is a competitive alternative to traditional emissions abatement techniques under certain conditions. The existence of carbon credits shifts the system economics in favor of hydrogen addition.

  17. Coherence and measurement in quantum thermodynamics

    NASA Astrophysics Data System (ADS)

    Kammerlander, P.; Anders, J.

    2016-02-01

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

  18. Coherence and measurement in quantum thermodynamics.

    PubMed

    Kammerlander, P; Anders, J

    2016-02-26

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

  19. Coherence and measurement in quantum thermodynamics.

    PubMed

    Kammerlander, P; Anders, J

    2016-01-01

    Thermodynamics is a highly successful macroscopic theory widely used across the natural sciences and for the construction of everyday devices, from car engines to solar cells. With thermodynamics predating quantum theory, research now aims to uncover the thermodynamic laws that govern finite size systems which may in addition host quantum effects. Recent theoretical breakthroughs include the characterisation of the efficiency of quantum thermal engines, the extension of classical non-equilibrium fluctuation theorems to the quantum regime and a new thermodynamic resource theory has led to the discovery of a set of second laws for finite size systems. These results have substantially advanced our understanding of nanoscale thermodynamics, however putting a finger on what is genuinely quantum in quantum thermodynamics has remained a challenge. Here we identify information processing tasks, the so-called projections, that can only be formulated within the framework of quantum mechanics. We show that the physical realisation of such projections can come with a non-trivial thermodynamic work only for quantum states with coherences. This contrasts with information erasure, first investigated by Landauer, for which a thermodynamic work cost applies for classical and quantum erasure alike. Repercussions on quantum work fluctuation relations and thermodynamic single-shot approaches are also discussed. PMID:26916503

  20. Coherence and measurement in quantum thermodynamics

    PubMed Central

    Kammerlander, P.; Anders, J.

    2016-01-01

    Thermodynamics is a highly successful macroscopic theory widely used across the natural sciences and for the construction of everyday devices, from car engines to solar cells. With thermodynamics predating quantum theory, research now aims to uncover the thermodynamic laws that govern finite size systems which may in addition host quantum effects. Recent theoretical breakthroughs include the characterisation of the efficiency of quantum thermal engines, the extension of classical non-equilibrium fluctuation theorems to the quantum regime and a new thermodynamic resource theory has led to the discovery of a set of second laws for finite size systems. These results have substantially advanced our understanding of nanoscale thermodynamics, however putting a finger on what is genuinely quantum in quantum thermodynamics has remained a challenge. Here we identify information processing tasks, the so-called projections, that can only be formulated within the framework of quantum mechanics. We show that the physical realisation of such projections can come with a non-trivial thermodynamic work only for quantum states with coherences. This contrasts with information erasure, first investigated by Landauer, for which a thermodynamic work cost applies for classical and quantum erasure alike. Repercussions on quantum work fluctuation relations and thermodynamic single-shot approaches are also discussed. PMID:26916503

  1. Addition of three-dimensional isoparametric elements to NASA structural analysis program (NASTRAN)

    NASA Technical Reports Server (NTRS)

    Field, E. I.; Johnson, S. E.

    1973-01-01

    Implementation is made of the three-dimensional family of linear, quadratic and cubic isoparametric solid elements into the NASA Structural Analysis program, NASTRAN. This work included program development, installation, testing, and documentation. The addition of these elements to NASTRAN provides a significant increase in modeling capability particularly for structures requiring specification of temperatures, material properties, displacements, and stresses which vary throughout each individual element. Complete program documentation is presented in the form of new sections and updates for direct insertion to the three NASTRAN manuals. The results of demonstration test problems are summarized. Excellent results are obtained with the isoparametric elements for static, normal mode, and buckling analyses.

  2. A near-infrared spectroscopic study of young field ultracool dwarfs: additional analysis

    NASA Astrophysics Data System (ADS)

    Allers, K. N.; Liu, M. C.

    We present additional analysis of the classification system presented in \\citet{allers13}. We refer the reader to \\citet{allers13} for a detailed discussion of our near-IR spectral type and gravity classification system. Here, we address questions and comments from participants of the Brown Dwarfs Come of Age meeting. In particular, we examine the effects of binarity and metallicity on our classification system. We also present our classification of Pleiades brown dwarfs using published spectra. Lastly, we determine SpTs and calculate gravity-sensitive indices for the BT-Settl atmospheric models and compare them to observations.

  3. Re-analysis of survival data of cancer patients utilizing additive homeopathy.

    PubMed

    Gleiss, Andreas; Frass, Michael; Gaertner, Katharina

    2016-08-01

    In this short communication we present a re-analysis of homeopathic patient data in comparison to control patient data from the same Outpatient´s Unit "Homeopathy in malignant diseases" of the Medical University of Vienna. In this analysis we took account of a probable immortal time bias. For patients suffering from advanced stages of cancer and surviving the first 6 or 12 months after diagnosis, respectively, the results show that utilizing homeopathy gives a statistically significant (p<0.001) advantage over control patients regarding survival time. In conclusion, bearing in mind all limitations, the results of this retrospective study suggest that patients with advanced stages of cancer might benefit from additional homeopathic treatment until a survival time of up to 12 months after diagnosis. PMID:27515878

  4. A multiple additive regression tree analysis of three exposure measures during Hurricane Katrina.

    PubMed

    Curtis, Andrew; Li, Bin; Marx, Brian D; Mills, Jacqueline W; Pine, John

    2011-01-01

    This paper analyses structural and personal exposure to Hurricane Katrina. Structural exposure is measured by flood height and building damage; personal exposure is measured by the locations of 911 calls made during the response. Using these variables, this paper characterises the geography of exposure and also demonstrates the utility of a robust analytical approach in understanding health-related challenges to disadvantaged populations during recovery. Analysis is conducted using a contemporary statistical approach, a multiple additive regression tree (MART), which displays considerable improvement over traditional regression analysis. By using MART, the percentage of improvement in R-squares over standard multiple linear regression ranges from about 62 to more than 100 per cent. The most revealing finding is the modelled verification that African Americans experienced disproportionate exposure in both structural and personal contexts. Given the impact of exposure to health outcomes, this finding has implications for understanding the long-term health challenges facing this population.

  5. Towards internationally acceptable standards for food additives and contaminants based on the use of risk analysis.

    PubMed

    Huggett, A; Petersen, B J; Walker, R; Fisher, C E; Notermans, S H; Rombouts, F M; Abbott, P; Debackere, M; Hathaway, S C; Hecker, E F; Knaap, A G; Kuznesof, P M; Meyland, I; Moy, G; Narbonne, J F; Paakkanen, J; Smith, M R; Tennant, D; Wagstaffe, P; Wargo, J; Würtzen, G

    1998-06-01

    Internationally acceptable norms need to incorporate sound science and consistent risk management principles in an open and transparent manner, as set out in the Agreement on the Application of Sanitary and Phytosanitary Measures (the SPS Agreement). The process of risk analysis provides a procedure to reach these goals. The interaction between risk assessors and risk managers is considered vital to this procedure. This paper reports the outcome of a meeting of risk assessors and risk managers on specific aspects of risk analysis and its application to international standard setting for food additives and contaminants. Case studies on aflatoxins and aspartame were used to identify the key steps of the interaction process which ensure scientific justification for risk management decisions. A series of recommendations were proposed in order to enhance the scientific transparency in these critical phases of the standard setting procedure.

  6. A thermodynamic analysis of native point defect and dopant solubilities in zinc-blende III-V semiconductors

    SciTech Connect

    Hurle, D. T. J.

    2010-06-15

    A thermodynamic model is used to analyze available experimental data relevant to point defects in the binary zinc-blende III-V compounds (Ga,In)-(P,As,Sb). The important point defects and their complexes in each of the materials are identified and included in the model. Essentially all of the available experimental data on dopant solubility, crystal density, and lattice parameter of melt and solution grown crystals and epilayers are reproduced by the model. It extends an earlier study [Hurle, J. Appl. Phys. 85, 6957 (1999)] devoted solely to GaAs. Values for the enthalpy and entropy of formation of both native and dopant related point defects are obtained by fitting to experimental data. In undoped material, vacancies, and interstitials on the Group V sublattice dominate in the vicinity of the melting point (MP) in both the phosphides and arsenides, whereas, in the antimonides, vacancies on both sublattices dominate. The calculated concentrations of the native point defects are used to construct the solidus curves of all the compounds. The charged native point defect concentrations at the MP in four of the six materials are significantly higher than their intrinsic carrier concentrations. Thus the usually assumed high temperature 'intrinsic' electroneutrality condition for undoped material (n=p) is not valid for these materials. In GaSb, the Ga{sub Sb} antisite defect appears to be grown-in from the melt. This contrasts with the As{sub Ga} defect in GaAs for which the concentration grown-in at the MP is negligibly small. Compensation of donor-doped material by donor-Group III vacancy complexes is shown to exist in all the compounds except InP where Group VI doped crystals are uncompensated and in InSb where there is a lack of experimental data. The annealing effects in n{sup +} GaAs, including lattice superdilation, which were shown in the earlier paper to be due to Group III vacancy undersaturation during cooling, are found to be present also in GaSb and In

  7. Analyze distillation columns with thermodynamics

    SciTech Connect

    Ognisty, T.P. )

    1995-02-01

    In a distillation column, heat supplies the work for separating the components of a feed stream into products. Distillation columns consume some 95% of the total energy used in separations. This amounts to roughly 3% of the energy consumed in the US. Since distillation is so energy intensive and requires significant capital outlays, an endless quest to improve the economics has continued since the beginning of the industry. By analyzing the thermodynamics of a distillation column, an engineer can quantify the thermodynamic efficiency of the process, identify the regions where energy can be better utilized, and define the minimum targets for energy consumption. This article reviews the principles of distillation column thermodynamics and outlines the analysis of lost work profiles and column heat profiles. It then illustrates these concepts through three examples.

  8. Thermodynamics: Frontiers and Foundations.

    SciTech Connect

    JEFFERY,; LEWINS, D.

    2009-07-27

    Version 00 Dr. J.D. Lewins has now released the following new book for free distribution: Thermodynamics: Frontiers and Foundations, Preface by Sir Alan Cottrell Introduction 1. Four-Square Foundations: The Laws of Thermodynamics 2. Maximum Entropy and Minimum Energy: The Master Functions and Equations 3. Ideal Gases and their Applications 4. Real Fluids and Some Applications 5. Van der Waals: A Model for Real Fluids 6. Surface Tension: Bubbles and Drops 7. Inert and Reactive Mixtures; An introduction to Chemical Thermodynamics 8. Radiation Thermodynamics: Solar Power Potential 9. Outposts of the Empire 10. A Glimpse into Statistical Thermodynamics Envoi

  9. Thermodynamics: Frontiers and Foundations.

    2009-07-27

    Version 00 Dr. J.D. Lewins has now released the following new book for free distribution: Thermodynamics: Frontiers and Foundations, Preface by Sir Alan Cottrell Introduction 1. Four-Square Foundations: The Laws of Thermodynamics 2. Maximum Entropy and Minimum Energy: The Master Functions and Equations 3. Ideal Gases and their Applications 4. Real Fluids and Some Applications 5. Van der Waals: A Model for Real Fluids 6. Surface Tension: Bubbles and Drops 7. Inert and Reactive Mixtures;more » An introduction to Chemical Thermodynamics 8. Radiation Thermodynamics: Solar Power Potential 9. Outposts of the Empire 10. A Glimpse into Statistical Thermodynamics Envoi« less

  10. Prediction of the solubility in lipidic solvent mixture: Investigation of the modeling approach and thermodynamic analysis of solubility.

    PubMed

    Patel, Shruti V; Patel, Sarsvatkumar

    2015-09-18

    Self-micro emulsifying drug delivery system (SMEDDS) is one of the methods to improve solubility and bioavailability of poorly soluble drug(s). The knowledge of the solubility of pharmaceuticals in pure lipidic solvents and solvent mixtures is crucial for designing the SMEDDS of poorly soluble drug substances. Since, experiments are very time consuming, a model, which allows for solubility predictions in solvent mixtures based on less experimental data is desirable for efficiency. Solvents employed were Labrafil® M1944CS and Labrasol® as lipidic solvents; Capryol-90®, Capryol-PGMC® and Tween®-80 as surfactants; Transcutol® and PEG-400 as co-solvents. Solubilities of both drugs were determined in single solvent systems at temperature (T) range of 283-333K. In present study, we investigated the applicability of the thermodynamic model to understand the solubility behavior of drugs in the lipiodic solvents. By using the Van't Hoff and general solubility theory, the thermodynamic functions like Gibbs free energy, enthalpy and entropy of solution, mixing and solvation for drug in single and mixed solvents were understood. The thermodynamic parameters were understood in the framework of drug-solvent interaction based on their chemical similarity and dissimilarity. Clotrimazole and Fluconazole were used as active ingredients whose solubility was measured in single solvent as a function of temperature and the data obtained were used to derive mathematical models which can predict solubility in multi-component solvent mixtures. Model dependent parameters for each drug were calculated at each temperature. The experimental solubility data of solute in mixed solvent system were measured experimentally and further correlated with the calculates values obtained from exponent model and log-linear model of Yalkowsky. The good correlation was observed between experimental solubility and predicted solubility.

  11. Student understanding of entropy and the second law of thermodynamics in an introductory physics course

    NASA Astrophysics Data System (ADS)

    Christensen, Warren M.

    2005-03-01

    We are investigating students' thinking regarding entropy and the second law of thermodynamics in a calculus-based general physics course. Most students enrolled in the class have had previous exposure to thermodynamics in chemistry courses or in high-school physics, and so many of them have specific ideas about these concepts even before instruction begins. To explore these ideas we administered a series of free-response pretest questions during the first week of class, before any instruction on thermodynamics had taken place. The questions probed student conceptions about entropy and its relationship with other thermodynamic properties. We will present an analysis of these data, as well as follow-up interview data that shed additional light on students' thinking.

  12. A Fully Non-Metallic Gas Turbine Engine Enabled by Additive Manufacturing Part I: System Analysis, Component Identification, Additive Manufacturing, and Testing of Polymer Composites

    NASA Technical Reports Server (NTRS)

    Grady, Joseph E.; Haller, William J.; Poinsatte, Philip E.; Halbig, Michael C.; Schnulo, Sydney L.; Singh, Mrityunjay; Weir, Don; Wali, Natalie; Vinup, Michael; Jones, Michael G.; Patterson, Clark; Santelle, Tom; Mehl, Jeremy

    2015-01-01

    The research and development activities reported in this publication were carried out under NASA Aeronautics Research Institute (NARI) funded project entitled "A Fully Nonmetallic Gas Turbine Engine Enabled by Additive Manufacturing." The objective of the project was to conduct evaluation of emerging materials and manufacturing technologies that will enable fully nonmetallic gas turbine engines. The results of the activities are described in three part report. The first part of the report contains the data and analysis of engine system trade studies, which were carried out to estimate reduction in engine emissions and fuel burn enabled due to advanced materials and manufacturing processes. A number of key engine components were identified in which advanced materials and additive manufacturing processes would provide the most significant benefits to engine operation. The technical scope of activities included an assessment of the feasibility of using additive manufacturing technologies to fabricate gas turbine engine components from polymer and ceramic matrix composites, which were accomplished by fabricating prototype engine components and testing them in simulated engine operating conditions. The manufacturing process parameters were developed and optimized for polymer and ceramic composites (described in detail in the second and third part of the report). A number of prototype components (inlet guide vane (IGV), acoustic liners, engine access door) were additively manufactured using high temperature polymer materials. Ceramic matrix composite components included turbine nozzle components. In addition, IGVs and acoustic liners were tested in simulated engine conditions in test rigs. The test results are reported and discussed in detail.

  13. Surface thermodynamic analysis of fluid confined in a cone and comparison with the sphere-plate and plate-plate geometries.

    PubMed

    Zargarzadeh, Leila; Elliott, Janet A W

    2013-10-22

    The behavior of pure fluid confined in a cone is investigated using thermodynamic stability analysis. Four situations are explained on the basis of the initial confined phase (liquid/vapor) and its pressure (above/below the saturation pressure). Thermodynamic stability analysis (a plot of the free energy of the system versus the size of the new potential phase) reveals whether the phase transition is possible and, if so, the number and type (unstable/metastable/stable) of equilibrium states in each of these situations. Moreover we investigated the effect of the equilibrium contact angle and the cone angle (equivalent to the confinement's surface separation distance) on the free energy (potential equilibrium states). The results are then compared to our previous study of pure fluid confined in the gap between a sphere and a flat plate and the gap between two flat plates.1 Confined fluid behavior of the four possible situations (for these three geometries) can be explained in a unified framework under two categories based on only the meniscus shape (concave/convex). For systems with bulk-phase pressure imposed by a reservoir, the stable coexistence of pure liquid and vapor is possible only when the meniscus is concave. PMID:24041429

  14. Kinetic and thermodynamic analysis of the conformational folding process of SS-reduced bovine pancreatic ribonuclease A using a selenoxide reagent with high oxidizing ability.

    PubMed

    Arai, Kenta; Kumakura, Fumio; Iwaoka, Michio

    2012-01-01

    Redox-coupled folding pathways of bovine pancreatic ribonuclease A (RNase A) with four intramolecular disulfide (SS) bonds comprise three phases: (I) SS formation to generate partially oxidized intermediate ensembles with no rigid folded structure; (II) SS rearrangement from the three SS intermediate ensemble (3S) to the des intermediates having three native SS linkages; (III) final oxidation of the last native SS linkage to generate native RNase A. We previously demonstrated that DHS(ox), a water-soluble selenoxide reagent for rapid and quantitative SS formation, allows clear separation of the three folding phases. In this study, the main conformational folding phase (phase II) has been extensively analyzed at pH 8.0 under a wide range of temperatures (5-45 °C), and thermodynamic and kinetic parameters for the four des intermediates were determined. The free-energy differences (ΔG) as a function of temperature suggested that the each SS linkage has different thermodynamic and kinetic roles in stability of the native structure. On the other hand, comparison of the rate constants and the activation energies for 3S → des with those reported for the conformational folding of SS-intact RNase A suggested that unfolded des species (desU) having three native SS linkages but not yet being folded are involved in very small amounts (<1%) in the 3S intermediate ensemble and the desU species would gain the native-like structures via X-Pro isomerization like SS-intact RNase A. It was revealed that DHS(ox) is useful for kinetic and thermodynamic analysis of the conformational folding process on the oxidative folding pathways of SS-reduced proteins.

  15. A thermodynamic analysis of the sequence-specific binding of RNA by bacteriophage MS2 coat protein

    PubMed Central

    Johansson, Hans E.; Dertinger, Dagmar; LeCuyer, Karen A.; Behlen, Linda S.; Greef, Charles H.; Uhlenbeck, Olke C.

    1998-01-01

    Most mutations in the sequence of the RNA hairpin that specifically binds MS2 coat protein either reduce the binding affinity or have no effect. However, one RNA mutation, a uracil to cytosine change in the loop, has the unusual property of increasing the binding affinity to the protein by nearly 100-fold. Guided by the structure of the protein–RNA complex, we used a series of protein mutations and RNA modifications to evaluate the thermodynamic basis for the improved affinity: The tight binding of the cytosine mutation is due to (i) the amino group of the cytosine residue making an intra-RNA hydrogen bond that increases the propensity of the free RNA to adopt the structure seen in the complex and (ii) the increased affinity of hydrogen bonds between the protein and a phosphate two bases away from the cytosine residue. The data are in good agreement with a recent comparison of the cocrystal structures of the two complexes, where small differences in the two structures are seen at the thermodynamically important sites. PMID:9689065

  16. Thermodynamic analysis of the thermal stability of sulphonamides in milk using liquid chromatography tandem mass spectrometry detection.

    PubMed

    Roca, M; Althaus, R L; Molina, M P

    2013-01-15

    The present study investigates the kinetics of the degradation of eight sulphonamides in skimmed milk when heated at 60, 70, 80, 90 and 100°C using an LC-MS/MS methodology. To determine the thermal stability of these compounds, the first-order kinetic model was applied and the activation energies, half-lives and degradation percentages were calculated. Application of kinetic equations to the different heat treatments used in dairy processing indicates that sulphonamides are very stable during pasteurisation (63°C; 30 min and 72°C; 15s) as well as UHT sterilisation (140°C; 4s). In contrast, the calculations performed with the kinetic model estimated losses in concentrations between 6.5% (sulfadimethoxine) and 85.1% (sulfamethazine) for the sterilisation at 120°C for 20 min. The existence of thermodynamic compensation was also tested for sulphonamide degradation. Results show that enthalpy and entropy values displayed a good linear relationship, and thermodynamically we can establish that the thermal degradation of sulphonamides in skimmed milk exhibits enthalpy-entropy compensation.

  17. Extraction, Thermodynamic Analysis, and Precipitation Mechanism of MnS-TiN Complex Inclusions in Low-Sulfur Steels

    NASA Astrophysics Data System (ADS)

    Liu, Yang; Zhang, Lifeng; Duan, Haojian; Zhang, Ying; Luo, Yan; Conejo, Alberto N.

    2016-06-01

    Inclusions in square billets of low-sulfur steels employed in the production of steel springs were fully extracted using an improved non-aqueous solution electrolytic method and were characterized as oxides, MnS, and TiN-MnS complex inclusions. Inclusions were analyzed using SEM for their three-dimensional morphology. The formation mechanism of the complex TiN-MnS was investigated analyzing the equilibrium precipitation conditions during cooling from the liquid through solidification and in the solid state. In this analysis, three microsegregation models were employed. It was found that titanium nitride precipitates first and then manganese sulfide. Electron backscattered diffraction is employed to explore the crystal orientation relationship between TiN and MnS in the complex inclusions, which provided additional elements to fully describe the mechanism of formation of the observed TiN-MnS complex inclusions.

  18. Genetic linkage analysis to identify a gene required for the addition of phosphoethanolamine to meningococcal lipopolysaccharide.

    PubMed

    Tang, Christoph M; Stroud, Dave; Mackinnon, Fiona; Makepeace, Katherine; Plested, Joyce; Moxon, E Richard; Chalmers, Ronald

    2002-02-01

    Lipopolysaccharide (LPS) is important for the virulence of Neisseria meningitidis, and is the target of immune responses. We took advantage of a monoclonal antibody (Mab B5) that recognises phosphoethanolamine (PEtn) attached to the inner core of meningococcal LPS to identify genes required for the addition of PEtn to LPS. Insertional mutants that lost Mab B5 reactivity were isolated and characterised, but failed to yield genes directly responsible for PEtn substitution. Subsequent genetic linkage analysis was used to define a region of DNA containing a single intact open reading frame which is sufficient to confer B5 reactivity to a B5 negative meningococcal isolate. The results provide an initial characterisation of the genetic basis of a key, immunodominant epitope of meningococcal LPS.

  19. Formation Pathways of a Guanine-Quadruplex DNA Revealed by Molecular Dynamics and Thermodynamic Analysis of the Substates

    PubMed Central

    Štefl, Richard; Cheatham, Thomas E.; Špačková, Nad'a; Fadrná, Eva; Berger, Imre; Koča, Jaroslav; Šponer, Jiří

    2003-01-01

    The formation of a cation-stabilized guanine quadruplex (G-DNA) stem is an exceptionally slow process involving complex kinetics that has not yet been characterized at atomic resolution. Here, we investigate the formation of a parallel stranded G-DNA stem consisting of four strands of d(GGGG) using molecular dynamics simulations with explicit inclusion of counterions and solvent. Due to the limitations imposed by the nanosecond timescale of the simulations, rather than watching for the spontaneous formation of G-DNA, our approach probes the stability of possible supramolecular intermediates (including two-, three-, and four-stranded assemblies with out-of-register basepairing between guanines) on the formation pathway. The simulations suggest that “cross-like” two-stranded assemblies may serve as nucleation centers in the initial formation of parallel stranded G-DNA quadruplexes, proceeding through a series of rearrangements involving trapping of cations, association of additional strands, and progressive slippage of strands toward the full stem. To supplement the analysis, approximate free energies of the models are obtained with explicit consideration of the integral cations. The approach applied here serves as a prototype for qualitatively investigating other G-DNA molecules using molecular dynamics simulation and free-energy analysis. PMID:12944293

  20. Thermodynamical stability of the Bardeen black hole

    SciTech Connect

    Bretón, Nora; Perez Bergliaffa, Santiago E.

    2014-01-14

    We analyze the stability of the regular magnetic Bardeen black hole both thermodynamically and dynamically. For the thermodynamical analysis we consider a microcanonical ensemble and apply the turning point method. This method allows to decide a change in stability (or instability) of a system, requiring only the assumption of smoothness of the area functional. The dynamical stability is asserted using criteria based on the signs of the Lagrangian and its derivatives. It turns out from our analysis that the Bardeen black hole is both thermodynamically and dynamically stable.

  1. Thermodynamics of protein-ligand interactions as a reference for computational analysis: how to assess accuracy, reliability and relevance of experimental data.

    PubMed

    Krimmer, Stefan G; Klebe, Gerhard

    2015-09-01

    For a conscientious interpretation of thermodynamic parameters (Gibbs free energy, enthalpy and entropy) obtained by isothermal titration calorimetry (ITC), it is necessary to first evaluate the experimental setup and conditions at which the data were measured. The data quality must be assessed and the precision and accuracy of the measured parameters must be estimated. This information provides the basis at which level discussion of the data is appropriate, and allows insight into the significance of comparisons with other data. The aim of this article is to provide the reader with basic understanding of the ITC technique and the experimental practices commonly applied, in order to foster an appreciation for how much measured thermodynamic parameters can deviate from ideal, error-free values. Particular attention is paid to the shape of the recorded isotherm (c-value), the influence of the applied buffer used for the reaction (protonation reactions, pH), the chosen experimental settings (temperature), impurities of protein and ligand, sources of systematic errors (solution concentration, solution activity, and device calibration) and to the applied analysis software. Furthermore, we comment on enthalpy-entropy compensation, heat capacities and van't Hoff enthalpies. PMID:26376645

  2. Development of a Twin-spool Turbofan Engine Simulation Using the Toolbox for Modeling and Analysis of Thermodynamic Systems (T-MATS)

    NASA Technical Reports Server (NTRS)

    Zinnecker, Alicia M.; Chapman, Jeffryes W.; Lavelle, Thomas M.; Litt, Johathan S.

    2014-01-01

    The Toolbox for Modeling and Analysis of Thermodynamic Systems (T-MATS) is a tool that has been developed to allow a user to build custom models of systems governed by thermodynamic principles using a template to model each basic process. Validation of this tool in an engine model application was performed through reconstruction of the Commercial Modular Aero-Propulsion System Simulation (C-MAPSS) (v2) using the building blocks from the T-MATS (v1) library. In order to match the two engine models, it was necessary to address differences in several assumptions made in the two modeling approaches. After these modifications were made, validation of the engine model continued by integrating both a steady-state and dynamic iterative solver with the engine plant and comparing results from steady-state and transient simulation of the T-MATS and C-MAPSS models. The results show that the T-MATS engine model was accurate within 3 of the C-MAPSS model, with inaccuracy attributed to the increased dimension of the iterative solver solution space required by the engine model constructed using the T-MATS library. This demonstrates that, given an understanding of the modeling assumptions made in T-MATS and a baseline model, the T-MATS tool provides a viable option for constructing a computational model of a twin-spool turbofan engine that may be used in simulation studies.

  3. Development of a Twin-Spool Turbofan Engine Simulation Using the Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS)

    NASA Technical Reports Server (NTRS)

    Zinnecker, Alicia M.; Chapman, Jeffryes W.; Lavelle, Thomas M.; Litt, Jonathan S.

    2014-01-01

    The Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS) is a tool that has been developed to allow a user to build custom models of systems governed by thermodynamic principles using a template to model each basic process. Validation of this tool in an engine model application was performed through reconstruction of the Commercial Modular Aero-Propulsion System Simulation (C-MAPSS) (v2) using the building blocks from the T-MATS (v1) library. In order to match the two engine models, it was necessary to address differences in several assumptions made in the two modeling approaches. After these modifications were made, validation of the engine model continued by integrating both a steady-state and dynamic iterative solver with the engine plant and comparing results from steady-state and transient simulation of the T-MATS and C-MAPSS models. The results show that the T-MATS engine model was accurate within 3% of the C-MAPSS model, with inaccuracy attributed to the increased dimension of the iterative solver solution space required by the engine model constructed using the T-MATS library. This demonstrates that, given an understanding of the modeling assumptions made in T-MATS and a baseline model, the T-MATS tool provides a viable option for constructing a computational model of a twin-spool turbofan engine that may be used in simulation studies.

  4. Thermodynamic analysis of a new combined cooling, heat and power system driven by solid oxide fuel cell based on ammonia-water mixture

    NASA Astrophysics Data System (ADS)

    Ma, Shaolin; Wang, Jiangfeng; Yan, Zhequan; Dai, Yiping; Lu, Bingheng

    2011-10-01

    Although a solid oxide fuel cell combined with a gas turbine (SOFC-GT) has good performance, the temperature of exhaust from gas turbine is still relatively high. In order to recover the waste heat of exhaust from the SOFC-GT to enhance energy conversion efficiency as well as to reduce the emissions of greenhouse gases and pollutants, in this study a new combined cooling, heat and power (CCHP) system driven by the SOFC is proposed to perform the trigeneration by using ammonia-water mixture to recover the waste heat of exhaust from the SOFC-GT. The CCHP system, whose main fuel is methane, can generate electricity, cooling effect and heat effect simultaneously. The overall system performance has been evaluated by mathematical models and thermodynamic laws. A parametric analysis is also conducted to examine the effects of some key thermodynamic parameters on the system performance. Results indicate that the overall energy conversion efficiency exceeds 80% under the given conditions, and it is also found that the increasing the fuel flow rate can improve overall energy conversion efficiency, even though both the SOFC efficiency and electricity efficiency decrease. Moreover, with an increased compressor pressure ratio, the SOFC efficiency, electricity efficiency and overall energy conversion efficiency all increase. Ammonia concentration and pressure entering ammonia-water turbine can also affect the CCHP system performance.

  5. Enantiomeric separation of volatile organics by gas chromatography for the in situ analysis of extraterrestrial materials: kinetics and thermodynamics investigation of various chiral stationary phases.

    PubMed

    Freissinet, C; Buch, A; Szopa, C; Sternberg, R

    2013-09-01

    The performances of several commercial chiral capillary columns have been evaluated with the aim of determining the one most suitable for enantiomeric separation in a gas chromatograph onboard a space probe. We compared the GC-MS response of three capillary columns coated with different chiral stationary phases (CSP) using volatile chiral organic molecules which are potential markers of a prebiotic organic chemistry. The three different chiral capillary columns are Chirasil-Val, with an amino acid derivative CSP, ChiralDex-β-PM, with a CSP composed of dissolved permethylated β-cyclodextrins in polysiloxane, and Chirasil-Dex, with a CSP made of modified cyclodextrins chemically bonded to the polysiloxane backbone. Both kinetics and thermodynamics studies have been carried out to evaluate the chiral recognition potential in these different types of columns. The thermodynamic parameters also allow a better understanding of the driving forces affecting the retention and separation of the enantiomers. The Chirasil-Dex-CSP displays the best characteristics for an optimal resolution of the chiral compounds, without preliminary derivatization. This CSP had been chosen to be the only chiral column in the Sample Analysis at Mars (SAM) experiment onboard the current Mars Science Laboratory (MSL) mission, and is also part of the Mars Organic Molecules Analyzer (MOMA) gas chromatograph onboard the next Martian mission ExoMars. The use of this column could also be extended to all space missions aimed at studying chirality in space. PMID:23921265

  6. Enantiomeric separation of volatile organics by gas chromatography for the in situ analysis of extraterrestrial materials: kinetics and thermodynamics investigation of various chiral stationary phases.

    PubMed

    Freissinet, C; Buch, A; Szopa, C; Sternberg, R

    2013-09-01

    The performances of several commercial chiral capillary columns have been evaluated with the aim of determining the one most suitable for enantiomeric separation in a gas chromatograph onboard a space probe. We compared the GC-MS response of three capillary columns coated with different chiral stationary phases (CSP) using volatile chiral organic molecules which are potential markers of a prebiotic organic chemistry. The three different chiral capillary columns are Chirasil-Val, with an amino acid derivative CSP, ChiralDex-β-PM, with a CSP composed of dissolved permethylated β-cyclodextrins in polysiloxane, and Chirasil-Dex, with a CSP made of modified cyclodextrins chemically bonded to the polysiloxane backbone. Both kinetics and thermodynamics studies have been carried out to evaluate the chiral recognition potential in these different types of columns. The thermodynamic parameters also allow a better understanding of the driving forces affecting the retention and separation of the enantiomers. The Chirasil-Dex-CSP displays the best characteristics for an optimal resolution of the chiral compounds, without preliminary derivatization. This CSP had been chosen to be the only chiral column in the Sample Analysis at Mars (SAM) experiment onboard the current Mars Science Laboratory (MSL) mission, and is also part of the Mars Organic Molecules Analyzer (MOMA) gas chromatograph onboard the next Martian mission ExoMars. The use of this column could also be extended to all space missions aimed at studying chirality in space.

  7. Thermodynamics of protein-ligand interactions as a reference for computational analysis: how to assess accuracy, reliability and relevance of experimental data.

    PubMed

    Krimmer, Stefan G; Klebe, Gerhard

    2015-09-01

    For a conscientious interpretation of thermodynamic parameters (Gibbs free energy, enthalpy and entropy) obtained by isothermal titration calorimetry (ITC), it is necessary to first evaluate the experimental setup and conditions at which the data were measured. The data quality must be assessed and the precision and accuracy of the measured parameters must be estimated. This information provides the basis at which level discussion of the data is appropriate, and allows insight into the significance of comparisons with other data. The aim of this article is to provide the reader with basic understanding of the ITC technique and the experimental practices commonly applied, in order to foster an appreciation for how much measured thermodynamic parameters can deviate from ideal, error-free values. Particular attention is paid to the shape of the recorded isotherm (c-value), the influence of the applied buffer used for the reaction (protonation reactions, pH), the chosen experimental settings (temperature), impurities of protein and ligand, sources of systematic errors (solution concentration, solution activity, and device calibration) and to the applied analysis software. Furthermore, we comment on enthalpy-entropy compensation, heat capacities and van't Hoff enthalpies.

  8. Thermodynamic analysis of chromium solubility data in liquid lithium containing nitrogen: Comparison between experimental data and computer simulation

    NASA Astrophysics Data System (ADS)

    Krasin, Valery P.; Soyustova, Svetlana I.

    2015-10-01

    The mathematical formalism for description of solute interactions in dilute solution of chromium and nitrogen in liquid lithium have been applied for calculating of the temperature dependence of the solubility of chromium in liquid lithium with the various nitrogen contents. It is shown that the derived equations are useful to provide understanding of a relationship between thermodynamic properties and local ordering in the Li-Cr-N melt. Comparison between theory and data reported in the literature for solubility of chromium in nitrogen-contaminated liquid lithium, was allowed to explain the reasons of the deviation of the experimental semi-logarithmic plot of chromium content in liquid lithium as a function of the reciprocal temperature from a straight line.

  9. Effects of surface charge on interfacial interactions related to membrane fouling in a submerged membrane bioreactor based on thermodynamic analysis.

    PubMed

    Cai, Huihui; Fan, Hao; Zhao, Leihong; Hong, Huachang; Shen, Liguo; He, Yiming; Lin, Hongjun; Chen, Jianrong

    2016-03-01

    Effects of both membrane and sludge foulant surface zeta potentials on interfacial interactions between membrane and sludge foulant in different interaction scenarios were systematically investigated based on thermodynamic methods. Under conditions in this study, it was found that zeta potential had marginal effects on total interfacial interaction between two infinite planar surfaces, and the total interfacial interaction between foulant particles and membrane would be more repulsive with increase of absolute value of zeta potential. Adhesion of foulant particles on membrane surface should overcome an energy barrier. There exists a critical zeta potential below which energy barrier would disappear. Results also showed that rough surface membrane corresponded to significantly low strength of interfacial interactions. This study not only provided a series of methods to quantitatively assess the interfacial interactions between membrane and sludge foulants, but also reconciled the contradictory conclusions regarding effects of zeta potential in literature, giving important implications for membrane fouling mitigation.

  10. Kinetics and thermodynamics of interaction between sulfonamide antibiotics and humic acids: Surface plasmon resonance and isothermal titration microcalorimetry analysis.

    PubMed

    Xu, Juan; Yu, Han-Qing; Sheng, Guo-Ping

    2016-01-25

    The presence of sulfonamide antibiotics in the environments has been recognized as a crucial issue. Their migration and transformation in the environment is determined by natural organic matters that widely exist in natural water and soil. In this study, the kinetics and thermodynamics of interactions between humic acids (HA) and sulfamethazine (SMZ) were investigated by employing surface plasmon resonance (SPR) combined with isothermal titration microcalorimetry (ITC) technologies. Results show that SMZ could be effectively bound with HA. The binding strength could be enhanced by increasing ionic strength and decreasing temperature. High pH was not favorable for the interaction. Hydrogen bond and electrostatic interaction may play important roles in driving the binding process, with auxiliary contribution from hydrophobic interaction. The results implied that HA existed in the environment may have a significant influence on the migration and transformation of organic pollutants through the binding process.

  11. Kinetic and thermodynamic analysis of the inhibitory effects of maltose, glucose, and related carbohydrates on wheat β-amylase.

    PubMed

    Daba, Tadessa; Kojima, Kenji; Inouye, Kuniyo

    2013-04-10

    Inhibition of wheat β-amylase (WBA) by glucose and maltose was studied by kinetics and thermodynamics. The inhibitory effects of fructose, difructose, sucrose, trehalose, cellobiose, acarbose, and 1-deoxynojirimycin on WBA were also evaluated. The half maximal inhibitory concentrations (IC50) of acarbose, maltose and glucose were 0.06±0.01M, 0.22±0.09M, and 1.41±0.17M, respectively. The inhibitor constant (Ki) and the thermodynamic parameters such as changes in Gibbs energy (ΔG), enthalpy (ΔH), and entropy (ΔS) of the dissociation reactions of the WBA-glucose and WBA-maltose complexes were temperature and pH-dependent. The dissociation reactions were endothermic and enthalpy-driven. Both glucose and maltose behaved as competitive inhibitors at pH 3.0 and 5.4 at a temperature of 25°C with respective Ki values of 0.33±0.02M and 0.12±0.03M. In contrast, both sugars exhibited uncompetitive inhibition at pH 9 at a temperature of 25°C with Ki values of 0.21±0.03M for glucose and 0.11±0.04M for maltose. The pH-dependence of the inhibition type and Ki values indicate that the ionizing groups of WBA influence drastically the interaction with these carbohydrates. This evidence enables us to consider temperature and pH in the WBA-catalyzed hydrolysis to manipulate the inhibition by end-product, maltose, and even by glucose.

  12. Semiclassical methods in curved spacetime and black hole thermodynamics

    SciTech Connect

    Camblong, Horacio E.; Ordonez, Carlos R.

    2005-06-15

    Improved semiclassical techniques are developed and applied to a treatment of a real scalar field in a D-dimensional gravitational background. This analysis, leading to a derivation of the thermodynamics of black holes, is based on the simultaneous use of (i) a near-horizon description of the scalar field in terms of conformal quantum mechanics; (ii) a novel generalized WKB framework; and (iii) curved-spacetime phase-space methods. In addition, this improved semiclassical approach is shown to be asymptotically exact in the presence of hierarchical expansions of a near-horizon type. Most importantly, this analysis further supports the claim that the thermodynamics of black holes is induced by their near-horizon conformal invariance.

  13. Oxygen nonstoichiometry and thermodynamic characterization of Zr doped ceria in the 1573–1773 K temperature range† †Electronic supplementary information (ESI) available: XRD patterns and SEM images. See DOI: 10.1039/c4cp04916k Click here for additional data file.

    PubMed Central

    Takacs, M.; Steinfeld, A.

    2015-01-01

    This work encompasses the thermodynamic characterization and critical evaluation of Zr4+ doped ceria, a promising redox material for the two-step solar thermochemical splitting of H2O and CO2 to H2 and CO. As a case study, we experimentally examine 5 mol% Zr4+ doped ceria and present oxygen nonstoichiometry measurements at elevated temperatures ranging from 1573 K to 1773 K and oxygen partial pressures ranging from 4.50 × 10–3 atm to 2.3 × 10–4 atm, yielding higher reduction extents compared to those of pure ceria under all conditions investigated, especially at the lower temperature range and at higher p O2. In contrast to pure ceria, a simple ideal solution model accounting for the formation of isolated oxygen vacancies and localized electrons accurately describes the defect chemistry. Thermodynamic properties are determined, namely: partial molar enthalpy, entropy, and Gibbs free energy. In general, partial molar enthalpy and entropy values of Zr4+ doped ceria are lower. The equilibrium hydrogen yields are subsequently extracted as a function of the redox conditions for dopant concentrations as high as 20%. Although reduction extents increase greatly with dopant concentration, the oxidation of Zr4+ doped ceria is thermodynamically less favorable compared to pure ceria. This leads to substantially larger temperature swings between reduction and oxidation steps, ultimately resulting in lower theoretical solar energy conversion efficiencies compared to ceria under most conditions. In effect, these results point to the importance of considering oxidation thermodynamics in addition to reduction when screening potential redox materials. PMID:25714616

  14. Changes of pore systems and infiltration analysis in two degraded soils after rock fragment addition

    NASA Astrophysics Data System (ADS)

    Gargiulo, Laura; Coppola, Antonio; De Mascellis, Roberto; Basile, Angelo; Mele, Giacomo; Terribile, Fabio

    2015-04-01

    Many soils in arid and semi-arid environments contain high amounts of rock fragments as a result of both natural soil forming processes and human activities. The amount, dimension and shape of rock fragment strongly influence soil structure development and therefore many soil processes (e.g. infiltration, water storage, solute transport, etc.). The aim of this work was to test the effects on both infiltration process and soil pore formation following an addition of rock fragments. The test was performed on two different soils: a clayey soil (Alfisol) and a clay loamy soil (Entisol) showing both a natural compact structure and water stagnation problems in field. Three concentrations of 4-8mm rock fragments (15%, 25% and 35%) were added to air-dried soils and the repacked samples have been subject to nine wet/dry cycles in order to induce soil structure formation and its stabilization. The process of infiltration was monitored at -12 cm of pressure heads imposed at the soil surface and kept constant for a certain time by a tension infiltrometer. Moreover, k(h) was determined imposing -9, -6,-3 and -1 cm at soil surface and applying a steady-state solution. After the hydrological measurements the soil samples were resin-impregnated and images of vertical sections of the samples, acquired at 20µm resolution, were analyzed in order to quantify the pore size distribution. This latter was calculated using the "successive opening" approach. The Entisol samples showed similar infiltration curves I(t) among the 4 treatments, with higher percentage of stones (i.e. 25 and 35%) showing a faster rising in the early-time (< 2 min) infiltration; the Alfisol samples are spread, showing a higher variability: limiting the analysis to the first three, despite they show a similar shape, the higher the stones content the lower the cumulated infiltration. The behavior of the 35% sample diverges from the others: it shows a fast rising step at the very early time (< 2 min) followed by a

  15. Analysis of Time to Event Outcomes in Randomized Controlled Trials by Generalized Additive Models

    PubMed Central

    Argyropoulos, Christos; Unruh, Mark L.

    2015-01-01

    Background Randomized Controlled Trials almost invariably utilize the hazard ratio calculated with a Cox proportional hazard model as a treatment efficacy measure. Despite the widespread adoption of HRs, these provide a limited understanding of the treatment effect and may even provide a biased estimate when the assumption of proportional hazards in the Cox model is not verified by the trial data. Additional treatment effect measures on the survival probability or the time scale may be used to supplement HRs but a framework for the simultaneous generation of these measures is lacking. Methods By splitting follow-up time at the nodes of a Gauss Lobatto numerical quadrature rule, techniques for Poisson Generalized Additive Models (PGAM) can be adopted for flexible hazard modeling. Straightforward simulation post-estimation transforms PGAM estimates for the log hazard into estimates of the survival function. These in turn were used to calculate relative and absolute risks or even differences in restricted mean survival time between treatment arms. We illustrate our approach with extensive simulations and in two trials: IPASS (in which the proportionality of hazards was violated) and HEMO a long duration study conducted under evolving standards of care on a heterogeneous patient population. Findings PGAM can generate estimates of the survival function and the hazard ratio that are essentially identical to those obtained by Kaplan Meier curve analysis and the Cox model. PGAMs can simultaneously provide multiple measures of treatment efficacy after a single data pass. Furthermore, supported unadjusted (overall treatment effect) but also subgroup and adjusted analyses, while incorporating multiple time scales and accounting for non-proportional hazards in survival data. Conclusions By augmenting the HR conventionally reported, PGAMs have the potential to support the inferential goals of multiple stakeholders involved in the evaluation and appraisal of clinical trial

  16. Comparative proteomic analysis of drug sodium iron chlorophyllin addition to Hep 3B cell line.

    PubMed

    Zhang, Jun; Wang, Wenhai; Yang, Fengying; Zhou, Xinwen; Jin, Hong; Yang, Peng-yuan

    2012-09-21

    The human hepatoma 3B cell line was chosen as an experimental model for in vitro test of drug screening. The drugs included chlorophyllin and its derivatives such as fluo-chlorophyllin, sodium copper chlorophyllin, and sodium iron chlorophyllin. The 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-tetrazolium bromide (MTT) method was used in this study to obtain the primary screening results. The results showed that sodium iron chlorophyllin had the best LC(50) value. Proteomic analysis was then performed for further investigation of the effect of sodium iron chlorophyllin addition to the Hep 3B cell line. The proteins identified from a total protein extract of Hep 3B before and after the drug addition were compared by two-dimensional-gel-electrophoresis. Then 32 three-fold differentially expressed proteins were successfully identified by MALDI-TOF-TOF-MS. There are 29 unique proteins among those identified proteins. These proteins include proliferating cell nuclear antigen (PCNA), T-complex protein, heterogeneous nuclear protein, nucleophosmin, heat shock protein A5 (HspA5) and peroxiredoxin. HspA5 is one of the proteins which are involved in protecting cancer cells against stress-induced apoptosis in cultured cells, protecting them against apoptosis through various mechanisms. Peroxiredoxin has anti-oxidant function and is related to cell proliferation, and signal transduction. It can protect the oxidation of other proteins. Peroxiredoxin has a close relationship with cancer and can eventually become a disease biomarker. This might help to develop a novel treatment method for carcinoma cancer.

  17. Methane flux in non-wetland soils in response to nitrogen addition: a meta-analysis.

    PubMed

    Aronson, E L; Helliker, B R

    2010-11-01

    The controls on methane (CH4) flux into and out of soils are not well understood. Environmental variables including temperature, precipitation, and nitrogen (N) status can have strong effects on the magnitude and direction (e.g., uptake vs. release) of CH4 flux. To better understand the interactions between CH4-cycling microorganisms and N in the non-wetland soil system, a meta-analysis was performed on published literature comparing CH4 flux in N amended and matched control plots. An appropriate study index was developed for this purpose. It was found that smaller amounts of N tended to stimulate CH4 uptake while larger amounts tended to inhibit uptake by the soil. When all other variables were accounted for, the switch occurred at 100 kg N x ha(-1) x yr(-1). Managed land and land with a longer duration of fertilization showed greater inhibition of CH4 uptake with added N. These results support the hypotheses that large amounts of available N can inhibit methanotrophy, but also that methanotrophs in upland soils can be N limited in their consumption of CH4 from the atmosphere. There were interactions between other variables and N addition on the CH4 flux response: lower temperature and, to a lesser extent, higher precipitation magnified the inhibition of CH4 uptake due to N addition. Several mechanisms that may cause these trends are discussed, but none could be conclusively supported with this approach. Further controlled and in situ study should be undertaken to isolate the correct mechanism(s) responsible and to model upland CH4 flux. PMID:21141185

  18. A comparative analysis of British and Taiwanese students' conceptual and procedural knowledge of fraction addition

    NASA Astrophysics Data System (ADS)

    Li, Hui-Chuan

    2014-10-01

    This study examines students' procedural and conceptual achievement in fraction addition in England and Taiwan. A total of 1209 participants (561 British students and 648 Taiwanese students) at ages 12 and 13 were recruited from England and Taiwan to take part in the study. A quantitative design by means of a self-designed written test is adopted as central to the methodological considerations. The test has two major parts: the concept part and the skill part. The former is concerned with students' conceptual knowledge of fraction addition and the latter is interested in students' procedural competence when adding fractions. There were statistically significant differences both in concept and skill parts between the British and Taiwanese groups with the latter having a higher score. The analysis of the students' responses to the skill section indicates that the superiority of Taiwanese students' procedural achievements over those of their British peers is because most of the former are able to apply algorithms to adding fractions far more successfully than the latter. Earlier, Hart [1] reported that around 30% of the British students in their study used an erroneous strategy (adding tops and bottoms, for example, 2/3 + 1/7 = 3/10) while adding fractions. This study also finds that nearly the same percentage of the British group remained using this erroneous strategy to add fractions as Hart found in 1981. The study also provides evidence to show that students' understanding of fractions is confused and incomplete, even those who are successfully able to perform operations. More research is needed to be done to help students make sense of the operations and eventually attain computational competence with meaningful grounding in the domain of fractions.

  19. Structures and thermodynamics of the mixed alkali alanates

    NASA Astrophysics Data System (ADS)

    Graetz, J.; Lee, Y.; Reilly, J. J.; Park, S.; Vogt, T.

    2005-05-01

    The thermodynamics and structural properties of the hexahydride alanates (M2M'AlH6) with the elpasolite structure have been investigated. A series of mixed alkali alanates ( Na2LiAlH6, K2LiAlH6 , and K2NaAlH6 ) were synthesized and found to reversibly absorb and desorb hydrogen without the need for a catalyst. Pressure-composition isotherms were measured to investigate the thermodynamics of the absorption and desorption reactions with hydrogen. Isotherms for catalyzed (4 mol% TiCl3 ) and uncatalyzed Na2LiAlH6 exhibited an increase in kinetics, but no change in the bulk thermodynamics with the addition of a dopant. A structural analysis using synchrotron x-ray diffraction showed that these compounds favor the Fm3¯m space group with the smaller ion (M') occupying an octahedral site. These results demonstrate that appropriate cation substitutions can be used to stabilize or destabilize the material and may provide an avenue to improving the unfavorable thermodynamics of a number of materials with promising gravimetric hydrogen densities.

  20. Thermodynamics and H2 Transfer in a Methanogenic, Syntrophic Community.

    PubMed

    Hamilton, Joshua J; Calixto Contreras, Montserrat; Reed, Jennifer L

    2015-07-01

    Microorganisms in nature do not exist in isolation but rather interact with other species in their environment. Some microbes interact via syntrophic associations, in which the metabolic by-products of one species serve as nutrients for another. These associations sustain a variety of natural communities, including those involved in methanogenesis. In anaerobic syntrophic communities, energy is transferred from one species to another, either through direct contact and exchange of electrons, or through small molecule diffusion. Thermodynamics plays an important role in governing these interactions, as the oxidation reactions carried out by the first community member are only possible because degradation products are consumed by the second community member. This work presents the development and analysis of genome-scale network reconstructions of the bacterium Syntrophobacter fumaroxidans and the methanogenic archaeon Methanospirillum hungatei. The models were used to verify proposed mechanisms of ATP production within each species. We then identified additional constraints and the cellular objective function required to match experimental observations. The thermodynamic S. fumaroxidans model could not explain why S. fumaroxidans does not produce H2 in monoculture, indicating that current methods might not adequately estimate the thermodynamics, or that other cellular processes (e.g., regulation) play a role. We also developed a thermodynamic coculture model of the association between the organisms. The coculture model correctly predicted the exchange of both H2 and formate between the two species and suggested conditions under which H2 and formate produced by S. fumaroxidans would be fully consumed by M. hungatei.

  1. Thermodynamic equilibrium at heterogeneous pressure

    NASA Astrophysics Data System (ADS)

    Vrijmoed, J. C.; Podladchikov, Y. Y.

    2015-07-01

    Recent advances in metamorphic petrology point out the importance of grain-scale pressure variations in high-temperature metamorphic rocks. Pressure derived from chemical zonation using unconventional geobarometry based on equal chemical potentials fits 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 constrained Gibbs minimization using linear programming techniques. In addition to constraining the system composition, a certain proportion of the system is constrained at a specified pressure. Input pressure variations need to be discretized, and each discrete pressure defines an additional constraint for the minimization. The Gibbs minimization method provides identical results to a geobarometry approach based on chemical potentials, thus validating the inferred pressure gradient. The thermodynamic consistency of the calculation is supported by the similar result obtained from two different approaches. In addition, the method can be used for multi-component, multi-phase systems of which several applications are given. A good fit to natural observations in multi-phase, multi-component systems demonstrates the possibility to explain phase assemblages and zoning by spatial pressure variations at equilibrium as an alternative to pressure variation in time due to disequilibrium.

  2. Thermodynamics of hCG--monoclonal antibody interaction: an analysis of real time kinetics data obtained using radiolabeled hCG probe.

    PubMed

    Ashish, Banerjee; Tamil Selvi, P; Murthy, Gundlupet Satyanarayana

    2002-08-15

    A thermodynamic analysis of the interaction of 125I-labeled human chorionic gonadotropin (IhCG) with two of its monoclonal antibodies (MAbs) was carried out. The dissociation profile of IhCG-MAb complex conforms to a two-step model. vant Hoff enthalpies were calculated with the K(A) (equilibrium constant) values obtained from dissociation at different temperatures. Free energy and entropy changes were calculated using the standard equations. DeltaH values for one of the MAbs, viz. VM7 were favorable at temperatures beyond 30 degrees C. Interestingly, the DeltaS values were also favorable at all temperatures. In the case of MAb VM4a, however, the interaction throughout the temperature range was driven by large favorable entropic contributions, indicating the importance of hydrophobic interaction in the binding of this MAb to hCG. The energetics of the interaction of these two monoclonals with hCG is discussed. PMID:12204330

  3. Structural study, NCA, FT-IR, FT-Raman spectral investigations, NBO analysis, thermodynamic functions of N-acetyl-L-phenylalanine

    NASA Astrophysics Data System (ADS)

    Raja, B.; Balachandran, V.; Revathi, B.

    2015-03-01

    The FT-IR and FT-Raman spectra of N-acetyl-L-phenylalanine were recorded and analyzed. Natural bond orbital analysis has been carried out for various intramolecular interactions that are responsible for the stabilization of the molecule. HOMO-LUMO energy gap has been computed with the help of density functional theory. The statistical thermodynamic functions (heat capacity, entropy, vibrational partition function and Gibbs energy) were obtained for the range of temperature 100-1000 K. The polarizability, first hyperpolarizability, anisotropy polarizability invariant has been computed using quantum chemical calculations. The infrared and Raman spectra were also predicted from the calculated intensities. Comparison of the experimental and theoretical spectra values provides important information about the ability of the computational method to describe the vibrational modes.

  4. Pediatric surgical capacity and demand: analysis reveals a modest gap in capacity and additional efficiency opportunities.

    PubMed

    Fixler, Tamas; Menaker, Rena J; Blair, Geoffrey K; Wright, James G

    2011-01-01

    The Canadian Paediatric Surgical Wait Times Project conducted an analysis of the alignment between capacity (supply) and demand for pediatric surgery at nine participating hospitals in five provinces. Demand for surgery was modelled using wait list data by assigning patients into monthly buckets of demand ("demand windows") based on the date on which a decision was made to proceed with their surgery plus their surgical wait time access target. Demand was then related to available capacity for various key resources (e.g., operating room availability, intensive care unit [ICU] and in-patient beds). The results indicate a small and not insurmountable gap of 8.5-11% in pediatric surgical capacity at these hospitals. A further capacity issue at many hospitals was ICU occupancy. In addition, an examination of several key performance indicators related to the management of peri-operative resources indicated that opportunities exist for deploying existing resources more efficiently, such as increasing on-time starts and reducing cancellation rates for elective surgery.

  5. Loophole-free Bell test using electron spins in diamond: second experiment and additional analysis

    NASA Astrophysics Data System (ADS)

    Hensen, B.; Kalb, N.; Blok, M. S.; Dréau, A. E.; Reiserer, A.; Vermeulen, R. F. L.; Schouten, R. N.; Markham, M.; Twitchen, D. J.; Goodenough, K.; Elkouss, D.; Wehner, S.; Taminiau, T. H.; Hanson, R.

    2016-08-01

    The recently reported violation of a Bell inequality using entangled electronic spins in diamonds (Hensen et al., Nature 526, 682–686) provided the first loophole-free evidence against local-realist theories of nature. Here we report on data from a second Bell experiment using the same experimental setup with minor modifications. We find a violation of the CHSH-Bell inequality of 2.35 ± 0.18, in agreement with the first run, yielding an overall value of S = 2.38 ± 0.14. We calculate the resulting P-values of the second experiment and of the combined Bell tests. We provide an additional analysis of the distribution of settings choices recorded during the two tests, finding that the observed distributions are consistent with uniform settings for both tests. Finally, we analytically study the effect of particular models of random number generator (RNG) imperfection on our hypothesis test. We find that the winning probability per trial in the CHSH game can be bounded knowing only the mean of the RNG bias. This implies that our experimental result is robust for any model underlying the estimated average RNG bias, for random bits produced up to 690 ns too early by the random number generator.

  6. Loophole-free Bell test using electron spins in diamond: second experiment and additional analysis

    PubMed Central

    Hensen, B.; Kalb, N.; Blok, M. S.; Dréau, A. E.; Reiserer, A.; Vermeulen, R. F. L.; Schouten, R. N.; Markham, M.; Twitchen, D. J.; Goodenough, K.; Elkouss, D.; Wehner, S.; Taminiau, T. H.; Hanson, R.

    2016-01-01

    The recently reported violation of a Bell inequality using entangled electronic spins in diamonds (Hensen et al., Nature 526, 682–686) provided the first loophole-free evidence against local-realist theories of nature. Here we report on data from a second Bell experiment using the same experimental setup with minor modifications. We find a violation of the CHSH-Bell inequality of 2.35 ± 0.18, in agreement with the first run, yielding an overall value of S = 2.38 ± 0.14. We calculate the resulting P-values of the second experiment and of the combined Bell tests. We provide an additional analysis of the distribution of settings choices recorded during the two tests, finding that the observed distributions are consistent with uniform settings for both tests. Finally, we analytically study the effect of particular models of random number generator (RNG) imperfection on our hypothesis test. We find that the winning probability per trial in the CHSH game can be bounded knowing only the mean of the RNG bias. This implies that our experimental result is robust for any model underlying the estimated average RNG bias, for random bits produced up to 690 ns too early by the random number generator. PMID:27509823

  7. Characterization and analysis of surface notches on Ti-alloy plates fabricated by additive manufacturing techniques

    NASA Astrophysics Data System (ADS)

    Chan, Kwai S.

    2015-12-01

    Rectangular plates of Ti-6Al-4V with extra low interstitial (ELI) were fabricated by layer-by-layer deposition techniques that included electron beam melting (EBM) and laser beam melting (LBM). The surface conditions of these plates were characterized using x-ray micro-computed tomography. The depth and radius of surface notch-like features on the LBM and EBM plates were measured from sectional images of individual virtual slices of the rectangular plates. The stress concentration factors of individual surface notches were computed and analyzed statistically to determine the appropriate distributions for the notch depth, notch radius, and stress concentration factor. These results were correlated with the fatigue life of the Ti-6Al-4V ELI alloys from an earlier investigation. A surface notch analysis was performed to assess the debit in the fatigue strength due to the surface notches. The assessment revealed that the fatigue lives of the additively manufactured plates with rough surface topographies and notch-like features are dominated by the fatigue crack growth of large cracks for both the LBM and EBM materials. The fatigue strength reduction due to the surface notches can be as large as 60%-75%. It is concluded that for better fatigue performance, the surface notches on EBM and LBM materials need to be removed by machining and the surface roughness be improved to a surface finish of about 1 μm.

  8. Loophole-free Bell test using electron spins in diamond: second experiment and additional analysis.

    PubMed

    Hensen, B; Kalb, N; Blok, M S; Dréau, A E; Reiserer, A; Vermeulen, R F L; Schouten, R N; Markham, M; Twitchen, D J; Goodenough, K; Elkouss, D; Wehner, S; Taminiau, T H; Hanson, R

    2016-01-01

    The recently reported violation of a Bell inequality using entangled electronic spins in diamonds (Hensen et al., Nature 526, 682-686) provided the first loophole-free evidence against local-realist theories of nature. Here we report on data from a second Bell experiment using the same experimental setup with minor modifications. We find a violation of the CHSH-Bell inequality of 2.35 ± 0.18, in agreement with the first run, yielding an overall value of S = 2.38 ± 0.14. We calculate the resulting P-values of the second experiment and of the combined Bell tests. We provide an additional analysis of the distribution of settings choices recorded during the two tests, finding that the observed distributions are consistent with uniform settings for both tests. Finally, we analytically study the effect of particular models of random number generator (RNG) imperfection on our hypothesis test. We find that the winning probability per trial in the CHSH game can be bounded knowing only the mean of the RNG bias. This implies that our experimental result is robust for any model underlying the estimated average RNG bias, for random bits produced up to 690 ns too early by the random number generator. PMID:27509823

  9. Integrated stoichiometric, thermodynamic and kinetic modelling of steady state metabolism.

    PubMed

    Fleming, R M T; Thiele, I; Provan, G; Nasheuer, H P

    2010-06-01

    The quantitative analysis of biochemical reactions and metabolites is at frontier of biological sciences. The recent availability of high-throughput technology data sets in biology has paved the way for new modelling approaches at various levels of complexity including the metabolome of a cell or an organism. Understanding the metabolism of a single cell and multi-cell organism will provide the knowledge for the rational design of growth conditions to produce commercially valuable reagents in biotechnology. Here, we demonstrate how equations representing steady state mass conservation, energy conservation, the second law of thermodynamics, and reversible enzyme kinetics can be formulated as a single system of linear equalities and inequalities, in addition to linear equalities on exponential variables. Even though the feasible set is non-convex, the reformulation is exact and amenable to large-scale numerical analysis, a prerequisite for computationally feasible genome scale modelling. Integrating flux, concentration and kinetic variables in a unified constraint-based formulation is aimed at increasing the quantitative predictive capacity of flux balance analysis. Incorporation of experimental and theoretical bounds on thermodynamic and kinetic variables ensures that the predicted steady state fluxes are both thermodynamically and biochemically feasible. The resulting in silico predictions are tested against fluxomic data for central metabolism in Escherichia coli and compare favourably with in silico prediction by flux balance analysis.

  10. Soil nitrous oxide emissions following crop residue addition: a meta-analysis.

    PubMed

    Chen, Huaihai; Li, Xuechao; Hu, Feng; Shi, Wei

    2013-10-01

    Annual production of crop residues has reached nearly 4 billion metric tons globally. Retention of this large amount of residues on agricultural land can be beneficial to soil C sequestration. Such potential impacts, however, may be offset if residue retention substantially increases soil emissions of N(2)O, a potent greenhouse gas and ozone depletion substance. Residue effects on soil N(2)O emissions have gained considerable attention since early 1990s; yet, it is still a great challenge to predict the magnitude and direction of soil N(2)O emissions following residue amendment. Here, we used a meta-analysis to assess residue impacts on soil N(2)O emissions in relation to soil and residue attributes, i.e., soil pH, soil texture, soil water content, residue C and N input, and residue C : N ratio. Residue effects were negatively associated with C : N ratios, but generally residue amendment could not reduce soil N(2)O emissions, even for C : N ratios well above ca. 30, the threshold for net N immobilization. Residue effects were also comparable to, if not greater than, those of synthetic N fertilizers. In addition, residue effects on soil N(2)O emissions were positively related to the amounts of residue C input as well as residue effects on soil CO(2) respiration. Furthermore, most significant and stimulatory effects occurred at 60-90% soil water-filled pore space and soil pH 7.1-7.8. Stimulatory effects were also present for all soil textures except sand or clay content ≤10%. However, inhibitory effects were found for soils with >90% water-filled pore space. Altogether, our meta-analysis suggests that crop residues played roles beyond N supply for N(2)O production. Perhaps, by stimulating microbial respiration, crop residues enhanced oxygen depletion and therefore promoted anaerobic conditions for denitrification and N(2)O production. Our meta-analysis highlights the necessity to connect the quantity and quality of crop residues with soil properties for predicting

  11. Thermodynamics of proton transport coupled ATP synthesis.

    PubMed

    Turina, Paola; Petersen, Jan; Gräber, Peter

    2016-06-01

    The thermodynamic H(+)/ATP ratio of the H(+)-ATP synthase from chloroplasts was measured in proteoliposomes after energization of the membrane by an acid base transition (Turina et al. 2003 [13], 418-422). The method is discussed, and all published data obtained with this system are combined and analyzed as a single dataset. This meta-analysis led to the following results. 1) At equilibrium, the transmembrane ΔpH is energetically equivalent to the transmembrane electric potential difference. 2) The standard free energy for ATP synthesis (reference reaction) is ΔG°(ref)=33.8±1.3kJ/mol. 3) The thermodynamic H(+)/ATP ratio, as obtained from the shift of the ATP synthesis equilibrium induced by changing the transmembrane ΔpH (varying either pH(in) or pH(out)) is 4.0±0.1. The structural H(+)/ATP ratio, calculated from the ratio of proton binding sites on the c-subunit-ring in F(0) to the catalytic nucleotide binding sites on the β-subunits in F(1), is c/β=14/3=4.7. We infer that the energy of 0.7 protons per ATP that flow through the enzyme, but do not contribute to shifting the ATP/(ADP·Pi) ratio, is used for additional processes within the enzyme, such as activation, and/or energy dissipation, due e.g. to internal uncoupling. The ratio between the thermodynamic and the structural H(+)/ATP values is 0.85, and we conclude that this value represents the efficiency of the chemiosmotic energy conversion within the chloroplast H(+)-ATP synthase.

  12. Methanol conversion to light olefins over nanostructured CeAPSO-34 catalyst: Thermodynamic analysis of overall reactions and effect of template type on catalytic properties and performance

    SciTech Connect

    Aghamohammadi, Sogand; Haghighi, Mohammad; Charghand, Mojtaba

    2014-02-01

    Graphical abstract: In this research nanostructured CeAPSO-34 was synthesized to explore the effect of TEAOH and morpholine on its physiochemical properties and MTO performance. Prepared catalysts were characterized with XRD, FESEM, BET, FTIR and NH3-TPD techniques. The results indicated that the nature of the template determines the physiochemical properties of CeAPSO-34 due to different rate of crystal growth. The catalyst obtained by using morpholine showed longer life time as well as sustaining light olefins selectivity at higher values. Furthermore, a comprehensive thermodynamic analysis of overall reactions network was carried out to address the major channels of methanol to olefins conversion. - Highlights: • Introduction of Ce into SAPO-34 framework. • Comparison of CeAPSO-34 synthesized using morpholine and TEAOH. • The nature of the template determines the physiochemical properties of CeAPSO-34. • Morpholine enhances catalyst lifetime in MTO process. • Presenting a complete reaction network for MTO process. - Abstract: TEAOH and morpholine were employed in synthesis of nanostructured CeAPSO-34 molecular sieve and used in methanol to olefins conversion. Prepared samples were characterized by XRD, FESEM, EDX, BET, FTIR and NH{sub 3}-TPD techniques. XRD patterns reflected the higher crystallinity of the catalyst synthesized with morpholine. The FESEM results indicated that the nature of the template determines the morphology of nanostructured CeAPSO-34 due to different rate of crystal growth. There was a meaningful difference in the strength of both strong and weak acid sites for CeAPSO-34 catalysts synthesized with TEAOH and morpholine templates. The catalyst synthesized with morpholine showed higher desorption temperature of both weak and strong acid sites evidenced by NH{sub 3}-TPD characterization. The catalyst obtained using morpholine template had the longer lifetime and sustained desired light olefins at higher values. A comprehensive

  13. Monomeric nature of dengue virus NS3 helicase and thermodynamic analysis of the interaction with single-stranded RNA

    PubMed Central

    Gebhard, Leopoldo G.; Incicco, J. Jeremías; Smal, Clara; Gallo, Mariana; Gamarnik, Andrea V.; Kaufman, Sergio B.

    2014-01-01

    Dengue virus nonstructural protein 3 (NS3) is a multifunctional protein formed by a superfamily-2 RNA helicase linked to a protease domain. In this work, we report results from in vitro experiments designed to determine the oligomeric state of dengue virus NS3 helicase (NS3h) and to characterize fundamental properties of the interaction with single-stranded (ss)RNA. Pulsed field gradient-NMR spectroscopy was used to determine the effective hydrodynamic radius of NS3h, which was constant over a wide range of protein concentrations in the absence and presence of ssRNA. Size exclusion chromatography-static light scattering experiments showed that NS3h eluted as a monomeric molecule even in the presence of ssRNA. Binding of NS3h to ssRNA was studied by quantitative fluorescence titrations using fluorescein-labeled and unlabeled ssRNA oligonucleotides of different lengths, and the effect of the fluorescein label on the interaction parameters was also analyzed. Experimental results were well described by a statistical thermodynamic model based on the theory of non-specific interactions of large ligands to a one-dimensional lattice. We found that binding of NS3h to ssRNA oligonucleotides and to poly(A) is characterized by minimum and occluded binding site sizes both of 10 nucleotides and by a weak positive cooperativity between adjacent proteins. PMID:25223789

  14. Thermodynamic modeling and experimental analysis of oxidation/sulfidation of nickel-chromium-aluminum model alloy coatings

    NASA Astrophysics Data System (ADS)

    Mueller, Erik M.

    With the current focus on finding future energy sources, land-based power gas turbines offer a desirable alternative to common coal-fired steam power generation. Ni-Cr-Al-X alloys are the material basis for producing overlay bond coats for the turbine blades used in sections of the turbine engine experiencing the most extreme environments. These overlay coatings are designed to provide environmental protection for the blades and vanes. While the oxidation of such alloys has been investigated and modeled in-depth, the concurrent sulfidation attack has not. This corrosion mode is now being heavily researched with the desire to use gasified coal, biomass, and other renewable fuel sources in gas turbines that often contain significant amounts of sulfur. The purpose of this dissertation was to use thermodynamic calculations to describe and predict the oxidation/sulfidation processes of two Ni-Cr-Al model alloys regarding phase evolution, composition, and component activities. These calculations, in the form of potential and phase fraction diagrams, combined with sulfidation experiments using kinetic measurements and materials characterization techniques, were able to describe and predict the simultaneous oxidation and sulfidation that occurred in these alloys.

  15. Kinetic, thermodynamic and structural analysis of tamiphosphor binding to neuraminidase of H1N1 (2009) pandemic influenza.

    PubMed

    Albiñana, Carlos Berenguer; Machara, Aleš; Řezáčová, Pavlína; Pachl, Petr; Konvalinka, Jan; Kožíšek, Milan

    2016-10-01

    Influenza virus causes severe respiratory infections that are responsible for up to half a million deaths worldwide each year. Two inhibitors targeting viral neuraminidase have been approved to date (oseltamivir, zanamivir). However, the rapid development of antiviral drug resistance and the efficient transmission of resistant viruses among humans represent serious threats to public health. The approved influenza neuraminidase inhibitors have (oxa)cyclohexene scaffolds designed to mimic the oxonium transition state during enzymatic cleavage of sialic acid. Their active forms contain a carboxylate that interacts with three arginine residues in the enzyme active site. Recently, the phosphonate group was successfully used as an isostere of the carboxylate in oseltamivir, and the resulting compound, tamiphosphor, was identified as a highly active neuraminidase inhibitor. However, the structure of the complex of this promising inhibitor with neuraminidase has not yet been reported. Here, we analyzed the interaction of a set of oseltamivir and tamiphosphor derivatives with neuraminidase from the A/California/07/2009 (H1N1) influenza virus. We thermodynamically characterized the binding of oseltamivir carboxylate or tamiphosphor to the neuraminidase catalytic domain by protein microcalorimetry, and we determined crystal structure of the catalytic domain in complex with tamiphosphor at 1.8 Å resolution. This structural information should aid rational design of the next generation of neuraminidase inhibitors.

  16. Adsorption of methylene blue onto poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol) nanotubes: kinetics, isotherm and thermodynamics analysis.

    PubMed

    Chen, Zhonghui; Zhang, Jianan; Fu, Jianwei; Wang, Minghuan; Wang, Xuzhe; Han, Runping; Xu, Qun

    2014-05-30

    Poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol) (PZS) nanotubes, an excellent adsorbent, were successfully synthesized by an in situ template method and used for the removal of methylene blue (MB) from aqueous solution. The morphology and structures of as-synthesized PZS nanotubes were characterized by scanning electron microscopy, transmission electron microscope, Fourier transform infrared spectroscopy and N2 adsorption/desorption isotherms. The effects of temperature, concentration, pH and contact time on MB adsorption were studied. It was favorable for adsorption under the condition of basic and high temperature. The pseudo-first-order, pseudo-second-order and intraparticle diffusion models were used to fit adsorption data in the kinetic studies. And results showed that the adsorption kinetics were more accurately described by the pseudo-second-order model. The equilibrium isotherms were conducted using Freundlich and Langmuir models. It has been demonstrated that the better agreement was Langmuir isotherm with correlation coefficient of 0.9933, equilibrium absorption capacity of 69.16mg/g and the corresponding contact time of 15min. Thermodynamic analyses showed that MB adsorption onto the PZS nanotubes was endothermic and spontaneous and it was also a physisorption process.

  17. Thermodynamic Analysis of the 3-Stage ADR for the Astro-H Soft X-Ray Spectrometer Instrument

    NASA Technical Reports Server (NTRS)

    Shirron, Peter; Kimball, Mark; DiPirro, Michael; Bialas, Tom; Sneiderman, Gary; Porter, Scott; Kelley, Richard

    2015-01-01

    The Soft X-ray Spectrometer (SXS) instrument on Astro-H will use a 3-stage ADR to cool the microcalorimeter array to 50 mK. In the primary operating mode, two stages of the ADR cool the detectors using superfluid helium at 1.20 K as the heat sink. In the secondary mode, which is activated when the liquid helium is depleted, two of the stages continuously cool the (empty) helium tank using a 4.5 K Joule-Thomson cooler as the heat sink, and the third stage cools the detectors. In the design phase, a high-fidelity model of the ADR was developed in order to predict both the cooling capacity and heat rejection rates in both operating modes. The primary sources of heat flow are from the salt pills, hysteresis heat from the magnets and magnetic shields, and power dissipated by the heat switches. The flight instrument dewar, ADR, detectors and electronics were integrated in mid-2014 and have since undergone extensive performance testing, in part to validate the performance model. This paper will present the thermodynamic performance of the ADR, including cooling capacity, heat rejection to the heat sinks, and various measures of efficiency.

  18. Thermodynamic analysis of reaction equilibria in ionic and molecular liquid systems by high-temperature Raman spectroscopy.

    PubMed

    Kalampounias, Angelos G; Boghosian, Soghomon

    2009-09-01

    A formalism for correlating relative Raman band intensities with the stoichiometric coefficients, the equilibrium constant, and the thermodynamics of reaction equilibria in solution is derived. The proposed method is used for studying: (1) the thermal dissociation of molten KHSO(4) in the temperature range 240-450 degrees C; (2) the dinuclear complex formation in molten TaCl(5)-AlCl(3) mixtures at temperatures between 125 and 235 degrees C. The experimental and calculational procedures for exploiting the temperature-dependent Raman band intensities in the molten phase as well as (if applicable) in the vapors thereof are described and used for determining the enthalpy of the equilibria: (1) 2HSO(4)(-)(l) <--> S(2)O(7)(2-)(l) + H(2)O(g), DeltaH(0)=64.9 +/- 2.9 kJ mol(-1); and (2) 1/2Ta(2)Cl(10)(l) + 1/2Al(2)Cl(6)(l) <--> TaAlCl(8)(l), DeltaH(0)=-12.1 +/- 1.5 kJ mol(-1).

  19. Thermodynamic analysis of Glycerol Steam Reforming for hydrogen production with in situ hydrogen and carbon dioxide separation

    NASA Astrophysics Data System (ADS)

    Silva, Joel M.; Soria, M. A.; Madeira, Luis M.

    2015-01-01

    A thermodynamic study of Glycerol Steam Reforming (GSR) for hydrogen production with in situ carbon dioxide and hydrogen (reaction products) simultaneous removal was performed. The sorption-enhanced membrane reactor (SEMR) was divided into multiple sub-Gibbs reactors and the Gibbs free energy minimization method was employed. The effects of temperature (600-800 K), molar water-to-glycerol feed ratio (WGFR) (3-9), pressure (1-5 atm) and fraction of hydrogen and carbon dioxide removal (f, 0-0.99) on the GSR process were target of investigation. A hydrogen yield (total moles of hydrogen produced/mole of reacted glycerol) very close to the stoichiometric value of 7 was obtained at 700 K, WGFR of 9, 1 atm and for fCO2 = 0.99 and fH2 = 0.80. This corresponds to an enhancement of 217%, 47% and 22% in terms of hydrogen yield comparatively to the traditional reactor (TR), sorption-enhanced reactor (SER) with carbon dioxide capture (fCO2 = 0.99) and membrane reactor (MR) with hydrogen separation (fH2 = 0.80) , respectively. In terms of coke, its formation was only observed under WGFRs below the stoichiometric value of 3.

  20. Numerical investigation and thermodynamic analysis of the effect of electrolyte flow rate on performance of all vanadium redox flow batteries

    NASA Astrophysics Data System (ADS)

    Khazaeli, Ali; Vatani, Ali; Tahouni, Nassim; Panjeshahi, Mohammad Hassan

    2015-10-01

    In flow batteries, electrolyte flow rate plays a crucial role on the minimizing mass transfer polarization which is at the compensation of higher pressure drop. In this work, a two-dimensional numerical method is applied to investigate the effect of electrolyte flow rate on cell voltage, maximum depth of discharge and pressure drop a six-cell stack of VRFB. The results show that during the discharge process, increasing electrolyte flow rate can raise the voltage of each cell up to 50 mV on average. Moreover, the maximum depth of discharge dramatically increases with electrolyte flow rate. On the other hand, the pressure drop also positively correlates with electrolyte flow rate. In order to investigate all these effects simultaneously, average energy and exergy efficiencies are introduced in this study for the transient process of VRFB. These efficiencies give insight into choosing an appropriate strategy for the electrolyte flow rate. Finally, the energy efficiency of electricity storage using VRFB is investigated and compared with other energy storage systems. The results illustrate that this kind of battery has at least 61% storage efficiency based on the second law of thermodynamics, which is considerably higher than that of their counterparts.

  1. Thermodynamics and combustion modeling

    NASA Technical Reports Server (NTRS)

    Zeleznik, Frank J.

    1986-01-01

    Modeling fluid phase phenomena blends the conservation equations of continuum mechanics with the property equations of thermodynamics. The thermodynamic contribution becomes especially important when the phenomena involve chemical reactions as they do in combustion systems. The successful study of combustion processes requires (1) the availability of accurate thermodynamic properties for both the reactants and the products of reaction and (2) the computational capabilities to use the properties. A discussion is given of some aspects of the problem of estimating accurate thermodynamic properties both for reactants and products of reaction. Also, some examples of the use of thermodynamic properties for modeling chemically reacting systems are presented. These examples include one-dimensional flow systems and the internal combustion engine.

  2. Performance of the Tariff Method: validation of a simple additive algorithm for analysis of verbal autopsies

    PubMed Central

    2011-01-01

    Background Verbal autopsies provide valuable information for studying mortality patterns in populations that lack reliable vital registration data. Methods for transforming verbal autopsy results into meaningful information for health workers and policymakers, however, are often costly or complicated to use. We present a simple additive algorithm, the Tariff Method (termed Tariff), which can be used for assigning individual cause of death and for determining cause-specific mortality fractions (CSMFs) from verbal autopsy data. Methods Tariff calculates a score, or "tariff," for each cause, for each sign/symptom, across a pool of validated verbal autopsy data. The tariffs are summed for a given response pattern in a verbal autopsy, and this sum (score) provides the basis for predicting the cause of death in a dataset. We implemented this algorithm and evaluated the method's predictive ability, both in terms of chance-corrected concordance at the individual cause assignment level and in terms of CSMF accuracy at the population level. The analysis was conducted separately for adult, child, and neonatal verbal autopsies across 500 pairs of train-test validation verbal autopsy data. Results Tariff is capable of outperforming physician-certified verbal autopsy in most cases. In terms of chance-corrected concordance, the method achieves 44.5% in adults, 39% in children, and 23.9% in neonates. CSMF accuracy was 0.745 in adults, 0.709 in children, and 0.679 in neonates. Conclusions Verbal autopsies can be an efficient means of obtaining cause of death data, and Tariff provides an intuitive, reliable method for generating individual cause assignment and CSMFs. The method is transparent and flexible and can be readily implemented by users without training in statistics or computer science. PMID:21816107

  3. Thermodynamics of Oligonucleotide Duplex Melting

    NASA Astrophysics Data System (ADS)

    Schreiber-Gosche, Sherrie; Edwards, Robert A.

    2009-05-01

    Melting temperatures of oligonucleotides are useful for a number of molecular biology applications, such as the polymerase chain reaction (PCR). Although melting temperatures are often calculated with simplistic empirical equations, application of thermodynamics provides more accurate melting temperatures and an opportunity for students to apply rigorous thermodynamic analysis to an important biochemical problem. Because the stacking of base pairs on top of one another is a significant factor in the energetics of oligonucleotide melting, several investigators have applied van't Hoff analysis to melting temperature data using a nearest-neighbor model and have obtained entropies and enthalpies for the stacking of bases. The present article explains how the equilibrium constant for the dissociation of strands from double-stranded oligonucleotides can be expressed in terms of the total strand concentration and thus how the total strand concentration influences the melting temperature. It also presents a simplified analysis based on the entropies and enthalpies of stacking that is manually tractable so that students can work examples to help them understand the thermodynamics of oligonucleotide melting.

  4. Thermodynamics of rock forming crystalline solutions

    NASA Technical Reports Server (NTRS)

    Saxena, S. K.

    1971-01-01

    Analysis of phase diagrams and cation distributions within crystalline solutions as means of obtaining thermodynamic data on rock forming crystalline solutions is discussed along with some aspects of partitioning of elements in coexisting phases. Crystalline solutions, components in a silicate mineral, and chemical potentials of these components were defined. Examples were given for calculating thermodynamic mixing functions in the CaW04-SrW04, olivine-chloride solution, and orthopyroxene systems.

  5. A model-driven quantitative metabolomics analysis of aerobic and anaerobic metabolism in E. coli K-12 MG1655 that is biochemically and thermodynamically consistent.

    PubMed

    McCloskey, Douglas; Gangoiti, Jon A; King, Zachary A; Naviaux, Robert K; Barshop, Bruce A; Palsson, Bernhard O; Feist, Adam M

    2014-04-01

    The advent of model-enabled workflows in systems biology allows for the integration of experimental data types with genome-scale models to discover new features of biology. This work demonstrates such a workflow, aimed at establishing a metabolomics platform applied to study the differences in metabolomes between anaerobic and aerobic growth of Escherichia coli. Constraint-based modeling was utilized to deduce a target list of compounds for downstream method development. An analytical and experimental methodology was developed and tailored to the compound chemistry and growth conditions of interest. This included the construction of a rapid sampling apparatus for use with anaerobic cultures. The resulting genome-scale data sets for anaerobic and aerobic growth were validated by comparison to previous small-scale studies comparing growth of E. coli under the same conditions. The metabolomics data were then integrated with the E. coli genome-scale metabolic model (GEM) via a sensitivity analysis that utilized reaction thermodynamics to reconcile simulated growth rates and reaction directionalities. This analysis highlighted several optimal network usage inconsistencies, including the incorrect use of the beta-oxidation pathway for synthesis of fatty acids. This analysis also identified enzyme promiscuity for the pykA gene, that is critical for anaerobic growth, and which has not been previously incorporated into metabolic models of E coli.

  6. Trend Analysis of Tropical Ozone From the Southern Hemisphere Additional Ozonesondes (SHADOZ) Data

    NASA Astrophysics Data System (ADS)

    Morioka, H.; Fujiwara, M.; Shiotani, M.; Thompson, A. M.; Witte, J. C.; Oltmans, S. J.

    2007-12-01

    Linear trends of ozone for 1998-2007 are estimated for the troposphere through the lower stratosphere at ten tropical ozonesonde stations participating in the Southern Hemisphere Additional Ozonesondes (SHADOZ) project. Most stations cover the period from early 1998 to the end of 2006, but some stations have a shorter or longer record. Soundings are made once to four times per month, varying for station and year, but cover basically all seasons. The total sounding number ranges from 102 for Malindi to 429 for Ascension Island. Trends are calculated for vertically averaged values in each 1-km bin from 0-1 km to 30-31 km, and expressed as percent per year. Statistical test is also made. Around the tropopause, between 15 and 20 km, negative trends are seen for most stations. At San Cristobal (in the eastern Pacific) at 16-17 km, the trend is -4.3 ± 3.0 percent per year, and at Watukosek (in Indonesia) at 17-18 km, it is -4.8 ± 3.9 percent per year, both statistically significant. However, at Ascension (in the Atlantic) and at Natal (in South America), the tropopause trend is near zero and not statistically significant. At Natal at 12-13 km, the trend is +3.7 ± 3.0 percent per year, and at Malindi (in Africa) at 11-12 km, it is +5.0 ± 4.6 percent per year, both statistically significant. Generally in the free troposphere, positive trends are seen, but are statistically not significant for most regions. In the planetary boundary layer, statistically significant positive trends are seen at Kuala Lumpur (in Southeast Asia) and at Fiji (in the southwestern Pacific), and a statistically significant negative trend is seen at Paramaribo (in South America). The trend analysis is also made for four different seasons. Around the tropopause, seasonality in trend is small for all stations. In the upper troposphere, at Fiji and at Samoa, negative trends are seen in SON, but positive trends are seen in DJF.

  7. Responses of ecosystem nitrogen cycle to nitrogen addition: a meta-analysis.

    PubMed

    Lu, Meng; Yang, Yuanhe; Luo, Yiqi; Fang, Changming; Zhou, Xuhui; Chen, Jiakuan; Yang, Xin; Li, Bo

    2011-03-01

    • Anthropogenic nitrogen (N) addition may substantially alter the terrestrial N cycle. However, a comprehensive understanding of how the ecosystem N cycle responds to external N input remains elusive. • Here, we evaluated the central tendencies of the responses of 15 variables associated with the ecosystem N cycle to N addition, using data extracted from 206 peer-reviewed papers. • Our results showed that the largest changes in the ecosystem N cycle caused by N addition were increases in soil inorganic N leaching (461%), soil NO₃⁻ concentration (429%), nitrification (154%), nitrous oxide emission (134%), and denitrification (84%). N addition also substantially increased soil NH₄+ concentration (47%), and the N content in belowground (53%) and aboveground (44%) plant pools, leaves (24%), litter (24%) and dissolved organic N (21%). Total N content in the organic horizon (6.1%) and mineral soil (6.2%) slightly increased in response to N addition. However, N addition induced a decrease in microbial biomass N by 5.8%. • The increases in N effluxes caused by N addition were much greater than those in plant and soil pools except soil NO₃⁻, suggesting a leaky terrestrial N system.

  8. Effects of additives on the co-pyrolysis of municipal solid waste and paper sludge by using thermogravimetric analysis.

    PubMed

    Fang, Shiwen; Yu, Zhaosheng; Lin, Yan; Lin, Yousheng; Fan, Yunlong; Liao, Yanfen; Ma, Xiaoqian

    2016-06-01

    By using thermogravimetric analysis (TGA), the effects of different additives (MgO, Al2O3 and ZnO) on the pyrolysis characteristics and activation energy of municipal solid waste (MSW), paper sludge (PS) and their blends in N2 atmosphere had been investigated in this study. The experiments resulted that these additives were effective in reducing the initial temperature and activation energy. However, not all the additives were beneficial to reduce the residue mass and enhance the index D. For the different ratios of MSW and PS, the same additive even had the different influences. The catalytic effects of additives were not obvious and the pyrolysis became difficult with the increase of the proportion of PS. Based on all the contrast of the pyrolysis characteristics, MgO was the best additive and 70M30P was the best ratio, respectively. PMID:26985626

  9. Electrochemical thermodynamic measurement system

    DOEpatents

    Reynier, Yvan; Yazami, Rachid; Fultz, Brent T.

    2009-09-29

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

  10. Thermodynamics: A Stirling effort

    NASA Astrophysics Data System (ADS)

    Horowitz, Jordan M.; Parrondo, Juan M. R.

    2012-02-01

    The realization of a single-particle Stirling engine pushes thermodynamics into stochastic territory where fluctuations dominate, and points towards a better understanding of energy transduction at the microscale.

  11. Thermodynamics and Frozen Foods.

    ERIC Educational Resources Information Center

    Kerr, William L.; Reid, David S.

    1993-01-01

    The heat content of a food at a given temperature can be described by the thermodynamic property of enthalpy. Presents a method to construct a simple calorimeter for measuring the enthalpy changes of different foods during freezing. (MDH)

  12. Limits to catalysis in quantum thermodynamics

    NASA Astrophysics Data System (ADS)

    Ng, N. H. Y.; Mančinska, L.; Cirstoiu, C.; Eisert, J.; Wehner, S.

    2015-08-01

    Quantum thermodynamics is a research field that aims at fleshing out the ultimate limits of thermodynamic processes in the deep quantum regime. A complete picture of thermodynamical processes naturally allows for auxiliary systems dubbed ‘catalysts’, i.e., any physical systems facilitating state transformations while remaining essentially intact in their state, like an auxiliary system, a clock, or an actual catalyst. In this work, we present a comprehensive analysis of the power and limitation of such thermal catalysis. Specifically, we provide a family of optimal catalysts that can be returned with minimal trace distance error after facilitating a state transformation process. To incorporate the genuine physical role of a catalyst, we identify very significant restrictions on arbitrary state transformations under dimension or mean energy bounds, using methods of convex relaxations. We discuss the implication of these findings on possible thermodynamic state transformations in the quantum regime.

  13. Thermodynamic benchmark study using Biacore technology.

    PubMed

    Navratilova, Iva; Papalia, Giuseppe A; Rich, Rebecca L; Bedinger, Daniel; Brophy, Susan; Condon, Brad; Deng, Ta; Emerick, Anne W; Guan, Hann-Wen; Hayden, Tanya; Heutmekers, Thomas; Hoorelbeke, Bart; McCroskey, Mark C; Murphy, Mary M; Nakagawa, Terry; Parmeggiani, Fabio; Qin, Xiaochun; Rebe, Sabina; Tomasevic, Nenad; Tsang, Tiffany; Waddell, M Brett; Zhang, Fred Feiyu; Leavitt, Stephanie; Myszka, David G

    2007-05-01

    A total of 22 individuals participated in this benchmark study to characterize the thermodynamics of small-molecule inhibitor-enzyme interactions using Biacore instruments. Participants were provided with reagents (the enzyme carbonic anhydrase II, which was immobilized onto the sensor surface, and four sulfonamide-based inhibitors) and were instructed to collect response data from 6 to 36 degrees C. van't Hoff enthalpies and entropies were calculated from the temperature dependence of the binding constants. The equilibrium dissociation and thermodynamic constants determined from the Biacore analysis matched the values determined using isothermal titration calorimetry. These results demonstrate that immobilization of the enzyme onto the sensor surface did not alter the thermodynamics of these interactions. This benchmark study also provides insights into the opportunities and challenges in carrying out thermodynamic studies using optical biosensors.

  14. Spectroscopic investigation, natural bond orbital analysis, HOMO-LUMO and thermodynamic functions of 2-tert-butyl-5-methyl anisole using DFT (B3LYP) calculations.

    PubMed

    Balachandran, V; Santhi, G; Karpagam, V; Revathi, B; Karabacak, M

    2015-02-01

    The optimized molecular structure and corresponding vibrational assignments of 2-tert-butyl-5-methyl anisole (TBMA) have been investigated using density functional theory (DFT)/B3LYP with 6-31G(d,p) and 6-311++G(d,p) basis sets investigation of the relative orientation of the methoxy group has shown two conformers (O-cis) and (O-trans) exist. The vibrational analysis of the stable conformer of the title compound is performed by means of infrared absorption and Raman spectroscopy in combination with theoretical simultaneously. The natural bond orbital (NBO) analysis is useful to understand the intra-molecular hyper conjugative interaction lone pair and π(∗)(C-C), σ(∗)(C-H) bond orbital. HOMO and LUMO energies show that charge transfer occurs in the molecule, therefore; HOMO, LUMO and molecular electrostatic potential (MEP) were calculated and analyzed. (1)H and (13)C NMR spectra by using gauge including atomic orbital (GIAO) method of studied compound were compared with experimental data. The thermodynamic functions of TBMA were calculated by B3LYP/6-311+G(d,p) basis set.

  15. Conformational stability, vibrational spectra, NLO properties, NBO and thermodynamic analysis of 2-amino-5-bromo-6-methyl-4-pyrimidinol for dye sensitized solar cells by DFT methods

    NASA Astrophysics Data System (ADS)

    Gladis Anitha, E.; Joseph Vedhagiri, S.; Parimala, K.

    2015-04-01

    The Fourier transform infrared (FT-IR) and Fourier transform Raman (FT-Raman) spectra of 2-amino-5-bromo-6-methyl-4-pyrimidinol (ABrMP) were recorded in the region 4000-400 and 3500-100 cm-1, respectively. The conformational stability, geometrical structure, vibrational frequencies, infrared intensities and Raman activities were carried out by DFT (B3LYP and LSDA) methods with 6-311++G(d,p) basis set. The calculated results show good agreement with observed spectra. The charge delocalization have been analyzed using NBO analysis by LSDA/6-311++G(d,p) level of theory. The NLO properties (μ, α0, Δα, β0 and βvec) have been computed quantum mechanically. The calculated HOMO and LUMO energies show that, the charge transfer occurs within the molecule. The solvent effects have been calculated using TD-DFT and the results are in good agreement with experimental measurements. The other molecular properties like Mulliken population analysis, electrostatic potential (ESP) and thermodynamic properties of the title compound at the different temperatures have been calculated.

  16. Conformational stability, vibrational spectra, NLO properties, NBO and thermodynamic analysis of 2-amino-5-bromo-6-methyl-4-pyrimidinol for dye sensitized solar cells by DFT methods.

    PubMed

    Anitha, E Gladis; Vedhagiri, S Joseph; Parimala, K

    2015-04-01

    The Fourier transform infrared (FT-IR) and Fourier transform Raman (FT-Raman) spectra of 2-amino-5-bromo-6-methyl-4-pyrimidinol (ABrMP) were recorded in the region 4000-400 and 3500-100 cm(-1), respectively. The conformational stability, geometrical structure, vibrational frequencies, infrared intensities and Raman activities were carried out by DFT (B3LYP and LSDA) methods with 6-311++G(d,p) basis set. The calculated results show good agreement with observed spectra. The charge delocalization have been analyzed using NBO analysis by LSDA/6-311++G(d,p) level of theory. The NLO properties (μ, α0, Δα, β0 and βvec) have been computed quantum mechanically. The calculated HOMO and LUMO energies show that, the charge transfer occurs within the molecule. The solvent effects have been calculated using TD-DFT and the results are in good agreement with experimental measurements. The other molecular properties like Mulliken population analysis, electrostatic potential (ESP) and thermodynamic properties of the title compound at the different temperatures have been calculated.

  17. Thermodynamic laws in isolated systems.

    PubMed

    Hilbert, Stefan; Hänggi, Peter; Dunkel, Jörn

    2014-12-01

    The recent experimental realization of exotic matter states in isolated quantum systems and the ensuing controversy about the existence of negative absolute temperatures demand a careful analysis of the conceptual foundations underlying microcanonical thermostatistics. Here we provide a detailed comparison of the most commonly considered microcanonical entropy definitions, focusing specifically on whether they satisfy or violate the zeroth, first, and second laws of thermodynamics. Our analysis shows that, for a broad class of systems that includes all standard classical Hamiltonian systems, only the Gibbs volume entropy fulfills all three laws simultaneously. To avoid ambiguities, the discussion is restricted to exact results and analytically tractable examples.

  18. Thermodynamic laws in isolated systems.

    PubMed

    Hilbert, Stefan; Hänggi, Peter; Dunkel, Jörn

    2014-12-01

    The recent experimental realization of exotic matter states in isolated quantum systems and the ensuing controversy about the existence of negative absolute temperatures demand a careful analysis of the conceptual foundations underlying microcanonical thermostatistics. Here we provide a detailed comparison of the most commonly considered microcanonical entropy definitions, focusing specifically on whether they satisfy or violate the zeroth, first, and second laws of thermodynamics. Our analysis shows that, for a broad class of systems that includes all standard classical Hamiltonian systems, only the Gibbs volume entropy fulfills all three laws simultaneously. To avoid ambiguities, the discussion is restricted to exact results and analytically tractable examples. PMID:25615053

  19. Analysis of Glass-Filled Nylon in Laser Powder Bed Fusion Additive Manufacturing

    NASA Astrophysics Data System (ADS)

    Slotwinski, John; LaBarre, Erin; Forrest, Ryan; Crane, Emily

    2016-03-01

    At the Johns Hopkins University Applied Physics Laboratory (APL), glass bead-filled polyamide (a.k.a. nylon) (GFN) is being used frequently for functional parts and systems, built using a laser-based powder bed fusion (PBF) additive manufacturing (AM) system. Since these parts have performance requirements, it is important to understand the mechanical properties of the additively-made GFN as a function of build orientation and build parameters. In addition, the performance of the AM system used to manufacture these parts must be evaluated in order to understand its capabilities, especially in order to determine the dimensional precision and repeatability of features built with this system. This paper summarizes recent APL efforts to characterize the GFN powder, the mechanical properties of parts made with GFN, and the performance of the laser PBF machine while running GFN using an AM test artifact.

  20. Analysis of economics of a TV broadcasting satellite for additional nationwide TV programs

    NASA Technical Reports Server (NTRS)

    Becker, D.; Mertens, G.; Rappold, A.; Seith, W.

    1977-01-01

    The influence of a TV broadcasting satellite, transmitting four additional TV networks was analyzed. It is assumed that the cost of the satellite systems will be financed by the cable TV system operators. The additional TV programs increase income by attracting additional subscribers. Two economic models were established: (1) each local network is regarded as an independent economic unit with individual fees (cost price model) and (2) all networks are part of one public cable TV company with uniform fees (uniform price model). Assumptions are made for penetration as a function of subscription rates. Main results of the study are: the installation of a TV broadcasting satellite improves the economics of CTV-networks in both models; the overall coverage achievable by the uniform price model is significantly higher than that achievable by the cost price model.

  1. Thermodynamic Cycle and CFD Analyses for Hydrogen Fueled Air-breathing Pulse Detonation Engines

    NASA Technical Reports Server (NTRS)

    Povinelli, Louis A.; Yungster, Shaye

    2002-01-01

    This paper presents the results of a thermodynamic cycle analysis of a pulse detonation engine (PDE) using a hydrogen-air mixture at static conditions. The cycle performance results, namely the specific thrust, fuel consumption and impulse are compared to a single cycle CFD analysis for a detonation tube which considers finite rate chemistry. The differences in the impulse values were indicative of the additional performance potential attainable in a PDE.

  2. An Analysis of Word Problems in School Mathematics Texts: Operation of Addition and Subtraction

    ERIC Educational Resources Information Center

    Singh, Parmjit

    2006-01-01

    This paper discusses the types of word problems represented in Malaysia's primary one, primary two and primary three mathematics texts based on Van De Walle's model (1998) in the operations of addition and subtraction. A test was constructed to measure students' success based on this model. The data from this study indicates that the Malaysian…

  3. Vector generalized additive models for extreme rainfall data analysis (study case rainfall data in Indramayu)

    NASA Astrophysics Data System (ADS)

    Utami, Eka Putri Nur; Wigena, Aji Hamim; Djuraidah, Anik

    2016-02-01

    Rainfall pattern are good indicators for potential disasters. Global Circulation Model (GCM) contains global scale information that can be used to predict the rainfall data. Statistical downscaling (SD) utilizes the global scale information to make inferences in the local scale. Essentially, SD can be used to predict local scale variables based on global scale variables. SD requires a method to accommodate non linear effects and extreme values. Extreme value Theory (EVT) can be used to analyze the extreme value. One of methods to identify the extreme events is peak over threshold that follows Generalized Pareto Distribution (GPD). The vector generalized additive model (VGAM) is an extension of the generalized additive model. It is able to accommodate linear or nonlinear effects by involving more than one additive predictors. The advantage of VGAM is to handle multi response models. The key idea of VGAM are iteratively reweighted least square for maximum likelihood estimation, penalized smoothing, fisher scoring and additive models. This works aims to analyze extreme rainfall data in Indramayu using VGAM. The results show that the VGAM with GPD is able to predict extreme rainfall data accurately. The prediction in February is very close to the actual value at quantile 75.

  4. Molecular cytogenetic analysis of Brassica rapa-Brassica oleracea var. alboglabra monosomic addition lines.

    PubMed

    Hasterok, Robert; Wolny, Elzbieta; Kulak, Sylwia; Zdziechiewicz, Aleksandra; Maluszynska, Jolanta; Heneen, Waheeb K

    2005-07-01

    Interspecific alien chromosome addition lines can be very useful for gene mapping and studying chromosome homoeology between closely related species. In this study we demonstrate a simple but robust manner of identifying individual C-genome chromosomes (C5, C8 and C9) in the A-genome background through the simultaneous use of 5S and 25S ribosomal probes on mitotic and meiotic chromosomes of three different Brassica rapa-B. oleracea var. alboglabra monosomic addition lines. Sequential silver staining and fluorescence in situ hybridisation indicated that 18S-5.8S-25S rRNA genes on the additional chromosome C9 are expressed in the A-genome background. Meiotic behaviour of the additional chromosomes was studied in pollen mother cells at diakinesis and metaphase I. In all of the addition lines the alien chromosome was most frequently observed as a univalent. The alien chromosome C5, which carries an intercalary 5S rDNA locus, occasionally formed trivalents that involved either rDNA- or non rDNA-carrying chromosomes from the A genome. In the case of chromosomes C8 and C9, the most frequently observed intergenomic associations involved the regions occupied by 18S-5.8S-25S ribosomal RNA genes. It is possible that not all such associations represent true pairing but are remnants of nucleolar associations from the preceding interphase. Variations in the numbers and distribution of 5S and 25S rDNA sites between cultivars of B. oleracea, B. oleracea var. alboglabra and B. rapa are discussed.

  5. EBSD analysis of magnesium addition on inclusion formation in SS400 structural steel

    SciTech Connect

    Luo, Sin-Jie; Su, Yen-Hao Frank; Lu, Muh-Jung; Kuo, Jui-Chao

    2013-08-15

    In this study, the effect of magnesium addition on the inclusion formation in SS400 steel was investigated. The experimental specimens with and without Mg addition treatment were compared. The microstructure was observed using optical microscopy after etching with 3% nital. The morphology and chemical composition of the inclusions were analyzed via scanning electron microscopy and energy dispersive spectrometry. The lattice structure and orientation of the inclusions were identified by electron backscattering diffraction. The average size of inclusions in SS400 was between 0.67 and 0.75 μm, and between 0.65 and 0.68 μm in SS400 + Mg. The 2 ppm Mg addition resulted in the oxide formation change from Al{sub 2}O{sub 3} to MgO·Al{sub 2}O{sub 3} and in the inclusion formation change from Al{sub 2}O{sub 3}–MnS to MgO·Al{sub 2}O{sub 3}–MnS. Moreover, a simple-phase MnS with an average grain size of 1 μm to 2 μm was observed in rod-like, globular, and polyhedron forms. - Highlights: • The effect of magnesium addition was investigated for SS400 steel. • 2 ppm Mg addition changes the inclusion formation from Al2O3-MnS to MgO·Al2O3-MnS. • MnS observed in inclusions exhibits rod-like, globular, and polyhedron forms.

  6. Thermodynamical journey in plant biology

    PubMed Central

    Barbacci, Adelin; Magnenet, Vincent; Lahaye, Marc

    2015-01-01

    Nonequilibrium irreversible thermodynamics constitute a meaningful point of view suitable to explore life with a rich paradigm. This analytical framework can be used to span the gap from molecular processes to plant function and shows great promise to create a holistic description of life. Since living organisms dissipate energy, exchange entropy and matter with their environment, they can be assimilated to dissipative structures. This concept inherited from nonequilibrium thermodynamics has four properties which defines a scale independent framework suitable to provide a simpler and more comprehensive view of the highly complex plant biology. According to this approach, a biological function is modeled as a cascade of dissipative structures. Each dissipative structure, corresponds to a biological process, which is initiated by the amplification of a fluctuation. Evolution of the process leads to the breakage of the system symmetry and to the export of entropy. Exporting entropy to the surrounding environment corresponds to collecting information about it. Biological actors which break the symmetry of the system and which store information are by consequence, key actors on which experiments and data analysis focus most. This paper aims at illustrating properties of dissipative structure through familiar examples and thus initiating the dialogue between nonequilibrium thermodynamics and plant biology. PMID:26175747

  7. Analysis And Control Of Copper Plating Bath Additives And By-Products

    NASA Astrophysics Data System (ADS)

    Newton, Beverly; Kaiser, Edward

    2003-09-01

    New copper plating bath chemisties are being developed to meet the emerging need of plating copper into submicron features on semiconductor wafers. These chemistries are designed to provide a fast, efficient, fill for even the most challenging wafer terrain. It has been found that maintaining the concentration of the additives in these plating baths at certain levels is critical to the performance of the bath. Plating technology for semiconductor applications requires rigid bath control and disciplined methodology. Establishing correlations between what is found in the plated film and bath chemistry control parameters is fundamental in producing interconnects that are consistent and reliable. To establish these correlations, it is important to have a clear understanding of the chemical composition of the bath. It is theorized that the "suppressor" bath components help moderate the deposition rate of the copper fill and the "leveler" additives improve the topology of the copper overfill. Too much or too little of these components in the bath can be detrimental to the quality of the copper deposition and may result in "fill failure" leading to a higher than necessary scrap rate for the wafers. Indirect bath measurements, such as Cyclic Voltammetric Stripping (CVS), tell an incomplete story as these techniques only measures the combined effect of the additives and by-products on the plating quality. High Performance Liquid (HPLC) and Ion Chromatography are analytical techniques which provide important information on the concentration, chemical balance and trend measurement of major constituents such as additives, brighteners, boosters, stabilizers, carriers, levelers, inhibitors, accelerators, transition metals, metal complexes and contaminants in the plating bath. This information provides for improved device quality, reduced scrap rate and reduced costs of bath maintenance. This, however, is not the end of the story. In addition to additives, copper plating baths

  8. Application of multivariate analysis to the effects of additives on chemical and sensory quality of stored coffee brew.

    PubMed

    Pérez-Martínez, Mónica; Sopelana, Patricia; de Peña, M Paz; Cid, Concepción

    2008-12-24

    The aim of this work was to obtain a black coffee brew to be consumed hot by extension of its shelf life, by addition of additives. Four pH-regulator agents (sodium and potassium carbonates and bicarbonates), one pH regulator and antioxidant (sodium citrate), three antioxidants [sodium ascorbate, ethylenediaminetetracetic acid (EDTA), and sodium sulfite], and lactoserum were tested by sensory analysis. Sodium carbonate and bicarbonate were selected for a study of the physicochemical (soluble and volatile compounds related to the sensory properties) and sensorial quality of coffee brew stored for 90 days at 4 degrees C. Although both additives extended the shelf life of the coffee brew up to 60 days, sodium carbonate was the chosen additive because it was the most useful in limiting the pH decrease and perception of sourness, which are some of the main factors involved in the rejection of stored coffee brews, and it better maintained the aroma and taste/flavor. Moreover, the application of multivariate analysis facilitated first the description of the global changes of the coffee brews with or without additives throughout the storage using principal component analysis and second the obtainment of a simple equation only with pH and caffeic acid parameters to discriminate the three types of coffee brews and simplify the analytical process, by means of the stepwise discriminant analysis.

  9. Computer code for single-point thermodynamic analysis of hydrogen/oxygen expander-cycle rocket engines

    NASA Technical Reports Server (NTRS)

    Glassman, Arthur J.; Jones, Scott M.

    1991-01-01

    This analysis and this computer code apply to full, split, and dual expander cycles. Heat regeneration from the turbine exhaust to the pump exhaust is allowed. The combustion process is modeled as one of chemical equilibrium in an infinite-area or a finite-area combustor. Gas composition in the nozzle may be either equilibrium or frozen during expansion. This report, which serves as a users guide for the computer code, describes the system, the analysis methodology, and the program input and output. Sample calculations are included to show effects of key variables such as nozzle area ratio and oxidizer-to-fuel mass ratio.

  10. [Analysis of constituents of ester-type gum bases used as natural food additives].

    PubMed

    Tada, Atsuko; Masuda, Aino; Sugimoto, Naoki; Yamagata, Kazuo; Yamazaki, Takeshi; Tanamoto, Kenichi

    2007-12-01

    The differences in the constituents of ten ester-type gum bases used as natural food additives in Japan (urushi wax, carnauba wax, candelilla wax, rice bran wax, shellac wax, jojoba wax, bees wax, Japan wax, montan wax, and lanolin) were investigated. Several kinds of gum bases showed characteristic TLC patterns of lipids. In addition, compositions of fatty acid and alcohol moieties of esters in the gum bases were analyzed by GC/MS after methanolysis and hydrolysis, respectively. The results indicated that the varieties of fatty acids and alcohols and their compositions were characteristic for each gum base. These results will be useful for identification and discrimination of the ester-type gum bases. PMID:18203503

  11. Consequence analysis of a NaOH solution spray release during addition to waste tank

    SciTech Connect

    Himes, D.A., Westinghouse Hanford Co.

    1996-10-09

    Toxicological consequences were calculated for a postulated maximum caustic soda (NaOH) solution spray leak during addition to a waste tank to adjust tank pH. Although onsite risk guidelines were exceeded for the unmitigated release, site boundary consequences were below the level of concern. Means of mitigating the release so as to greatly reduce the onsite consequences were recommended. Consequences for the mitigated release were estimated and both onsite and offsite consequences were found to negligible.

  12. Analysis of Tank 43H Samples at the Conclusion of Uranyl Carbonate Addition

    SciTech Connect

    Oji, L.N.

    2002-10-15

    Tank 43H serves as the feed Tank to the 2H evaporator. In the months of July and August 2001, about 21,000 gallons of a depleted uranyl carbonate solution were added to Tank 43H and agitated with two Flygt mixers. The depleted uranium addition served to decrease the U-235 enrichment in the Tank 43H supernate so that the supernate could be evaporated with no risk of accumulating enriched uranium.

  13. Analysis of hydraulic fracturing additives by LC/Q-TOF-MS.

    PubMed

    Ferrer, Imma; Thurman, E Michael

    2015-08-01

    The chemical additives used in fracturing fluids can be used as tracers of water contamination caused by hydraulic fracturing operations. For this purpose, a complete chemical characterization is necessary using advanced analytical techniques. Liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (LC/Q-TOF-MS) was used to identify chemical additives present in flowback and produced waters. Accurate mass measurements of main ions and fragments were used to characterize the major components of fracking fluids. Sodium adducts turned out to be the main molecular adduct ions detected for some additives due to oxygen-rich structures. Among the classes of chemical components analyzed by mass spectrometry include gels (guar gum), biocides (glutaraldehyde and alkyl dimethyl benzyl ammonium chloride), and surfactants (cocamidopropyl dimethylamines, cocamidopropyl hydroxysultaines, and cocamidopropyl derivatives). The capabilities of accurate mass and MS-MS fragmentation are explored for the unequivocal identification of these compounds. A special emphasis is given to the mass spectrometry elucidation approaches used to identify a major class of hydraulic fracturing compounds, surfactants.

  14. Analysis and Modeling of soil hydrology under different soil additives in artificial runoff plots

    NASA Astrophysics Data System (ADS)

    Ruidisch, M.; Arnhold, S.; Kettering, J.; Huwe, B.; Kuzyakov, Y.; Ok, Y.; Tenhunen, J. D.

    2009-12-01

    The impact of monsoon events during June and July in the Korean project region Haean Basin, which is located in the northeastern part of South Korea plays a key role for erosion, leaching and groundwater pollution risk by agrochemicals. Therefore, the project investigates the main hydrological processes in agricultural soils under field and laboratory conditions on different scales (plot, hillslope and catchment). Soil hydrological parameters were analysed depending on different soil additives, which are known for prevention of soil erosion and nutrient loss as well as increasing of water infiltration, aggregate stability and soil fertility. Hence, synthetic water-soluble Polyacrylamides (PAM), Biochar (Black Carbon mixed with organic fertilizer), both PAM and Biochar were applied in runoff plots at three agricultural field sites. Additionally, as control a subplot was set up without any additives. The field sites were selected in areas with similar hillslope gradients and with emphasis on the dominant land management form of dryland farming in Haean, which is characterised by row planting and row covering by foil. Hydrological parameters like satured water conductivity, matrix potential and water content were analysed by infiltration experiments, continuous tensiometer measurements, time domain reflectometry as well as pressure plates to indentify characteristic water retention curves of each horizon. Weather data were observed by three weather stations next to the runoff plots. Measured data also provide the input data for modeling water transport in the unsatured zone in runoff plots with HYDRUS 1D/2D/3D and SWAT (Soil & Water Assessment Tool).

  15. Analysis of hydraulic fracturing additives by LC/Q-TOF-MS.

    PubMed

    Ferrer, Imma; Thurman, E Michael

    2015-08-01

    The chemical additives used in fracturing fluids can be used as tracers of water contamination caused by hydraulic fracturing operations. For this purpose, a complete chemical characterization is necessary using advanced analytical techniques. Liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (LC/Q-TOF-MS) was used to identify chemical additives present in flowback and produced waters. Accurate mass measurements of main ions and fragments were used to characterize the major components of fracking fluids. Sodium adducts turned out to be the main molecular adduct ions detected for some additives due to oxygen-rich structures. Among the classes of chemical components analyzed by mass spectrometry include gels (guar gum), biocides (glutaraldehyde and alkyl dimethyl benzyl ammonium chloride), and surfactants (cocamidopropyl dimethylamines, cocamidopropyl hydroxysultaines, and cocamidopropyl derivatives). The capabilities of accurate mass and MS-MS fragmentation are explored for the unequivocal identification of these compounds. A special emphasis is given to the mass spectrometry elucidation approaches used to identify a major class of hydraulic fracturing compounds, surfactants. PMID:26044738

  16. Studies on Pidotimod Enantiomers With Chiralpak-IA: Crystal Structure, Thermodynamic Parameters and Molecular Docking.

    PubMed

    Dou, Xiaorui; Su, Xin; Wang, Yue; Chen, Yadong; Shen, Weiyang

    2015-11-01

    Pidotimod, a synthetic dipeptide, has two chiral centers with biological and immunological activity. Its enantiomers were characterized by x-ray crystallographic analysis. A chiral stationary phase (CSP) Chiralpak-IA based on amylose derivatized with tris-(3, 5-dimethylphenyl carbamate) was used to separate pidotimod enantiomers. The mobile phase was prepared in a ratio of 35:65:0.2 of methyl-tert-butyl-ether and acetonitrile trifluoroaceticacid. In addition, thermodynamics and molecular docking methods were used to explain the enantioseparation mechanism by Chiralpak-IA. Thermodynamic studies were carried out from 10 to 45 °C. In general, both retention and enantioselectivity decreased as the temperature increased. Thermodynamic parameters indicate that the interaction force between the pidotimod enantiomer (4S, 2'R) and IA CSP is stronger and their complex model is more stable. According to GOLD molecular docking simulation, Van der Waals force is the leading cause of pidotimod enantiomers separation by IA CSP.

  17. Studies on Pidotimod Enantiomers With Chiralpak-IA: Crystal Structure, Thermodynamic Parameters and Molecular Docking.

    PubMed

    Dou, Xiaorui; Su, Xin; Wang, Yue; Chen, Yadong; Shen, Weiyang

    2015-11-01

    Pidotimod, a synthetic dipeptide, has two chiral centers with biological and immunological activity. Its enantiomers were characterized by x-ray crystallographic analysis. A chiral stationary phase (CSP) Chiralpak-IA based on amylose derivatized with tris-(3, 5-dimethylphenyl carbamate) was used to separate pidotimod enantiomers. The mobile phase was prepared in a ratio of 35:65:0.2 of methyl-tert-butyl-ether and acetonitrile trifluoroaceticacid. In addition, thermodynamics and molecular docking methods were used to explain the enantioseparation mechanism by Chiralpak-IA. Thermodynamic studies were carried out from 10 to 45 °C. In general, both retention and enantioselectivity decreased as the temperature increased. Thermodynamic parameters indicate that the interaction force between the pidotimod enantiomer (4S, 2'R) and IA CSP is stronger and their complex model is more stable. According to GOLD molecular docking simulation, Van der Waals force is the leading cause of pidotimod enantiomers separation by IA CSP. PMID:26340373

  18. Subsonic flutter analysis addition to NASTRAN. [for use with CDC 6000 series digital computers

    NASA Technical Reports Server (NTRS)

    Doggett, R. V., Jr.; Harder, R. L.

    1973-01-01

    A subsonic flutter analysis capability has been developed for NASTRAN, and a developmental version of the program has been installed on the CDC 6000 series digital computers at the Langley Research Center. The flutter analysis is of the modal type, uses doublet lattice unsteady aerodynamic forces, and solves the flutter equations by using the k-method. Surface and one-dimensional spline functions are used to transform from the aerodynamic degrees of freedom to the structural degrees of freedom. Some preliminary applications of the method to a beamlike wing, a platelike wing, and a platelike wing with a folded tip are compared with existing experimental and analytical results.

  19. Different responses of soil respiration and its components to nitrogen addition among biomes: a meta-analysis.

    PubMed

    Zhou, Lingyan; Zhou, Xuhui; Zhang, Baocheng; Lu, Meng; Luo, Yiqi; Liu, Lingli; Li, Bo

    2014-07-01

    Anthropogenic activities have increased nitrogen (N) deposition by threefold to fivefold over the last century, which may considerably affect soil respiration (Rs). Although numerous individual studies and a few meta-analyses have been conducted, it remains controversial as to how N addition affects Rs and its components [i.e., autotrophic (Ra) and heterotrophic respiration (Rh)]. To reconcile the difference, we conducted a comprehensive meta-analysis of 295 published studies to examine the responses of Rs and its components to N addition in terrestrial ecosystems. We also assessed variations in their responses in relation to ecosystem types, environmental conditions, and experimental duration (DUR). Our results show that N addition significantly increased Rs by 2.0% across all biomes but decreased by 1.44% in forests and increased by 7.84% and 12.4% in grasslands and croplands, respectively (P < 0.05). The differences may largely result from diverse responses of Ra to N addition among biomes with more stimulation of Ra in croplands and grasslands compared with no significant change in forests. Rh exhibited a similar negative response to N addition among biomes except that in croplands, tropical and boreal forests. Methods of partitioning Rs did not induce significant differences in the responses of Ra or Rh to N addition, except that Ra from root exclusion and component integration methods exhibited the opposite responses in temperate forests. The response ratios (RR) of Rs to N addition were positively correlated with mean annual temperature (MAT), with being more significant when MAT was less than 15 °C, but negatively with DUR. In addition, the responses of Rs and its components to N addition largely resulted from the changes in root and microbial biomass and soil C content as indicated by correlation analysis. The response patterns of Rs to N addition as revealed in this study can be benchmarks for future modeling and experimental studies.

  20. A theoretical investigation of thermodynamic effects on developed cavitation

    NASA Technical Reports Server (NTRS)

    Weir, D. S.

    1976-01-01

    The results of a theoretical investigation of thermodynamic effects on developed cavitation are presented. An approximate solution to the conservation equations for a two-phase laminar boundary layer is obtained. This analysis produces an expression for the temperature difference between the liquid and vapor phases which can be applied to developed cavity flows. Experimental data of cavity temperature depressions are correlated using this result. In addition, a theoretical estimate of the Nusselt number for the cavity is made using a turbulent boundary layer cavity model proposed by Brennen. The result agrees in part with empirically determined expressions for the cavity Nusselt number.

  1. Crystal structure and thermodynamic analysis of diagnostic mAb 106.3 complexed with BNP 5-13 (C10A)

    SciTech Connect

    Longenecker, Kenton L.; Ruan, Qiaoqiao; Fry, Elizabeth H.; Saldana, Sylvia C.; Brophy, Susan E.; Richardson, Paul L.; Tetin, Sergey Y.

    2010-09-02

    B-type natriuretic peptide (BNP) is a naturally secreted regulatory hormone that influences blood pressure and vascular water retention in human physiology. The plasma BNP concentration is a clinically recognized biomarker for various cardiovascular diseases. Quantitative detection of BNP can be achieved in immunoassays using the high-affinity monoclonal IgG1 antibody 106.3, which binds an epitope spanning residues 5-13 of the mature bioactive peptide. To understand the structural basis of this molecular recognition, we crystallized the Fab fragment complexed with the peptide epitope and determined the three-dimensional structure by X-ray diffraction to 2.1 {angstrom} resolution. The structure reveals the detailed interactions that five of the complementarity-determining regions make with the partially folded peptide. Thermodynamic measurements using fluorescence spectroscopy suggest that the interaction is enthalpy driven, with an overall change in free energy of binding, {Delta}G = -54 kJ/mol, at room temperature. The parameters are interpreted on the basis of the structural information. The kinetics of binding suggest a diffusion-limited mechanism, whereby the peptide easily adopts a bound conformation upon interaction with the antibody. Moreover, comparative analysis with alanine-scanning results of the epitope explains the basis of selectivity for BNP over other related natriuretic peptides.

  2. Thermodynamic analysis of interactions between Ni-based solid oxide fuel cells (SOFC) anodes and trace species in a survey of coal syngas

    SciTech Connect

    Andrew Martinez; Kirk Gerdes; Randall Gemmen; James Postona

    2010-03-20

    A thermodynamic analysis was conducted to characterize the effects of trace contaminants in syngas derived from coal gasification on solid oxide fuel cell (SOFC) anode material. The effluents from 15 different gasification facilities were considered to assess the impact of fuel composition on anode susceptibility to contamination. For each syngas case, the study considers the magnitude of contaminant exposure resulting from operation of a warm gas cleanup unit at two different temperatures and operation of a nickel-based SOFC at three different temperatures. Contaminant elements arsenic (As), phosphorous (P), and antimony (Sb) are predicted to be present in warm gas cleanup effluent and will interact with the nickel (Ni) components of a SOFC anode. Phosphorous is the trace element found in the largest concentration of the three contaminants and is potentially the most detrimental. Poisoning was found to depend on the composition of the syngas as well as system operating conditions. Results for all trace elements tended to show invariance with cleanup operating temperature, but results were sensitive to syngas bulk composition. Synthesis gas with high steam content tended to resist poisoning.

  3. Thermodynamic analysis of interactions between Ni-based solid oxide fuel cells (SOFC) anodes and trace species in a survey of coal syngas

    NASA Astrophysics Data System (ADS)

    Martinez, Andrew; Gerdes, Kirk; Gemmen, Randall; Poston, James

    A thermodynamic analysis was conducted to characterize the effects of trace contaminants in syngas derived from coal gasification on solid oxide fuel cell (SOFC) anode material. The effluents from 15 different gasification facilities were considered to assess the impact of fuel composition on anode susceptibility to contamination. For each syngas case, the study considers the magnitude of contaminant exposure resulting from operation of a warm gas cleanup unit at two different temperatures and operation of a nickel-based SOFC at three different temperatures. Contaminant elements arsenic (As), phosphorous (P), and antimony (Sb) are predicted to be present in warm gas cleanup effluent and will interact with the nickel (Ni) components of a SOFC anode. Phosphorous is the trace element found in the largest concentration of the three contaminants and is potentially the most detrimental. Poisoning was found to depend on the composition of the syngas as well as system operating conditions. Results for all trace elements tended to show invariance with cleanup operating temperature, but results were sensitive to syngas bulk composition. Synthesis gas with high steam content tended to resist poisoning.

  4. Thermodynamic Analysis of V-concentrating Phase Formation in V-bearing Steelmaking Slag Modified by MgO

    NASA Astrophysics Data System (ADS)

    Wu, Liushun; Gao, Wei; Xie, Dawei; Li, Liaosha; Dong, Yuanchi

    2015-10-01

    In the study, magnesium oxide acting as modifier was added to V-bearing steelmaking slag to concentrate vanadium, and then the effect of magnesium oxide on the formation of V-concentrating phase during cooling was investigated. Experimental results show that, in the case of the original slag, di-calcium silicate along with most of vanadate and phosphate in the slag forms solid solution, calcium ferrite which contains small part of vanadium in the slag and matrix without vanadium in turn precipitate during slowly cooling; For the sample with 8% MgO addition, two new phases (merwinite and V-concentrating phase) generate during slowly cooling, and the amount of di-calcium silicate decreases. Merwinite phase doesn't contain vanadium, and V-concentrating phase (Ca3(V,P)2O8·nCa2SiO4) contains 17-19% V2O5 by mass; For the sample with 16% MgO addition, another new phase (monticellite) precipitates from liquid slag, the phase of di-calcium silicate disappears, and most of vanadium concentrates in V-concentrating phase-Ca3(V,P)2O8·nCa2SiO4 (18-21%V2O5).

  5. Work producing reservoirs: Stochastic thermodynamics with generalized Gibbs ensembles

    NASA Astrophysics Data System (ADS)

    Horowitz, Jordan M.; Esposito, Massimiliano

    2016-08-01

    We develop a consistent stochastic thermodynamics for environments composed of thermodynamic reservoirs in an external conservative force field, that is, environments described by the generalized or Gibbs canonical ensemble. We demonstrate that small systems weakly coupled to such reservoirs exchange both heat and work by verifying a local detailed balance relation for the induced stochastic dynamics. Based on this analysis, we help to rationalize the observation that nonthermal reservoirs can increase the efficiency of thermodynamic heat engines.

  6. Work producing reservoirs: Stochastic thermodynamics with generalized Gibbs ensembles.

    PubMed

    Horowitz, Jordan M; Esposito, Massimiliano

    2016-08-01

    We develop a consistent stochastic thermodynamics for environments composed of thermodynamic reservoirs in an external conservative force field, that is, environments described by the generalized or Gibbs canonical ensemble. We demonstrate that small systems weakly coupled to such reservoirs exchange both heat and work by verifying a local detailed balance relation for the induced stochastic dynamics. Based on this analysis, we help to rationalize the observation that nonthermal reservoirs can increase the efficiency of thermodynamic heat engines. PMID:27627226

  7. Qualitative Analysis of Additives in Plastic Marine Debris and Its New Products.

    PubMed

    Rani, Manviri; Shim, Won Joon; Han, Gi Myung; Jang, Mi; Al-Odaini, Najat Ahmed; Song, Young Kyong; Hong, Sang Hee

    2015-10-01

    Due to their formulation and/or processing, plastics contain additives and impurities that may leach out under conditions of use and accumulate in the environment. To evaluate their role as vectors of chemical contaminants in marine environment, plastic debris (n = 19) collected from coastal beaches along with new plastics (n = 25; same or same brand) bought from local markets were screened by gas chromatography-mass spectrometry in full scan mode. Detected peaks were identified using NIST library in different polymers (polypropylene (PP) > polyethylene (PE) > PP + PE > polyethyl terephthalate > poly(acylene:styrene) with different use (food, fishery, and general use). A database on the presence of 231 different chemicals were grouped into hydrocarbons, ultra-violet (UV)-stabilizers, antioxidants, plasticizers, lubricants, intermediates, compounds for dyes and inks, flame retardants, etc. The UV326, UV327, UV328, UV320, UvinualMC80, irganox 1076, DEHP, antioxidant no 33, di-n-octylisophthalate, diisooctyl phthalate, hexanoic acid 2-ethyl-hexadecyl ester, and hydrocarbons were most frequently detected. Finding of toxic phthalates and UV stabilizers in those products having moisture contact (like bottles with short use) raised concern to humans and indicated their irregular use. The comparison between new and debris plastics clearly indicated the leaching and absorption of chemicals and supports our assumption of plastic as media for transferring these additives in marine environment.

  8. Qualitative Analysis of Additives in Plastic Marine Debris and Its New Products.

    PubMed

    Rani, Manviri; Shim, Won Joon; Han, Gi Myung; Jang, Mi; Al-Odaini, Najat Ahmed; Song, Young Kyong; Hong, Sang Hee

    2015-10-01

    Due to their formulation and/or processing, plastics contain additives and impurities that may leach out under conditions of use and accumulate in the environment. To evaluate their role as vectors of chemical contaminants in marine environment, plastic debris (n = 19) collected from coastal beaches along with new plastics (n = 25; same or same brand) bought from local markets were screened by gas chromatography-mass spectrometry in full scan mode. Detected peaks were identified using NIST library in different polymers (polypropylene (PP) > polyethylene (PE) > PP + PE > polyethyl terephthalate > poly(acylene:styrene) with different use (food, fishery, and general use). A database on the presence of 231 different chemicals were grouped into hydrocarbons, ultra-violet (UV)-stabilizers, antioxidants, plasticizers, lubricants, intermediates, compounds for dyes and inks, flame retardants, etc. The UV326, UV327, UV328, UV320, UvinualMC80, irganox 1076, DEHP, antioxidant no 33, di-n-octylisophthalate, diisooctyl phthalate, hexanoic acid 2-ethyl-hexadecyl ester, and hydrocarbons were most frequently detected. Finding of toxic phthalates and UV stabilizers in those products having moisture contact (like bottles with short use) raised concern to humans and indicated their irregular use. The comparison between new and debris plastics clearly indicated the leaching and absorption of chemicals and supports our assumption of plastic as media for transferring these additives in marine environment. PMID:26329499

  9. Thermodynamic and molecular-scale analysis of new systems of water-soluble hydrate formers + CH4.

    PubMed

    Lee, Jong-Won; Lu, Hailong; Moudrakovski, Igor L; Ratcliffe, Christopher I; Ripmeester, John A

    2010-10-28

    Among a variety of cyclic ether, cyclic ester, and cyclic ketone compounds, six new formers were found to form binary sII or sH hydrates with CH(4) gas. Hydrate-phase equilibria for all the hydrate formers were measured. The results obtained showed distinct relationships between the hydrate-phase equilibrium curve and the molecular size of the guests. In addition, 2-methyltetrahydrofuran and 3-methyltetrahydrofuran, or 4-methyl-1,3-dioxane and 4-methyl-1,3-dioxolane, showed different hydrate structures even though they have similar chemical structures. Such structural differences can provide useful information on the critical guest size, which determines hydrate crystal structures according to the size of the captured guest. PMID:20925355

  10. Gravimetric approach to the standard addition method in instrumental analysis. 1.

    PubMed

    Kelly, W Robert; MacDonald, Bruce S; Guthrie, William F

    2008-08-15

    A mathematical formulation for a gravimetric approach to the univariate standard addition method (SAM) is presented that has general applicability for both liquids and solids. Using gravimetry rather than volumetry reduces the preparation time, increases design flexibility, and makes increased accuracy possible. SAM has most often been used with analytes in aqueous solutions that are aspirated into flames or plasmas and determined by absorption, emission, or mass spectrometric techniques. The formulation presented here shows that the method can also be applied to complex matrixes, such as distillate and residual fuel oils, using techniques such as X-ray fluorescence (XRF) or combustion combined with atomic fluorescence or absorption. These techniques, which can be subject to matrix-induced interferences, could realize the same benefits that have been demonstrated for dilute aqueous solutions.

  11. PAT-1 safety analysis report addendum author responses to request for additional information.

    SciTech Connect

    Weiner, Ruth F.; Schmale, David T.; Kalan, Robert J.; Akin, Lili A.; Miller, David Russell; Knorovsky, Gerald Albert; Yoshimura, Richard Hiroyuki; Lopez, Carlos; Harding, David Cameron; Jones, Perry L.; Morrow, Charles W.

    2010-09-01

    The Plutonium Air Transportable Package, Model PAT-1, is certified under Title 10, Code of Federal Regulations Part 71 by the U.S. Nuclear Regulatory Commission (NRC) per Certificate of Compliance (CoC) USA/0361B(U)F-96 (currently Revision 9). The National Nuclear Security Administration (NNSA) submitted SAND Report SAND2009-5822 to NRC that documented the incorporation of plutonium (Pu) metal as a new payload for the PAT-1 package. NRC responded with a Request for Additional Information (RAI), identifying information needed in connection with its review of the application. The purpose of this SAND report is to provide the authors responses to each RAI. SAND Report SAND2010-6106 containing the proposed changes to the Addendum is provided separately.

  12. Analysis of additives in dairy products by liquid chromatography coupled to quadrupole-orbitrap mass spectrometry.

    PubMed

    Jia, Wei; Ling, Yun; Lin, Yuanhui; Chang, James; Chu, Xiaogang

    2014-04-01

    A new method combining QuEChERS with ultrahigh-performance liquid chromatography and electrospray ionization quadrupole Orbitrap high-resolution mass spectrometry (UHPLC/ESI Q-Orbitrap) was developed for the highly accurate and sensitive screening of 43 antioxidants, preservatives and synthetic sweeteners in dairy products. Response surface methodology was employed to optimize a quick, easy, cheap, effective, rugged, and safe (QuEChERS) sample preparation method for the determination of 42 different analytes in dairy products for the first time. After optimization, the maximum predicted recovery was 99.33% rate for aspartame under the optimized conditions of 10 mL acetionitrile, 1.52 g sodium acetate, 410 mg PSA and 404 mgC18. For the matrices studied, the recovery rates of the other 42 compounds ranged from 89.4% to 108.2%, with coefficient of variation <6.4%. UHPLC/ESI Q-Orbitrap Mass full scan mode acquired full MS data was used to identify and quantify additives, and data-dependent scan mode obtained fragment ion spectra for confirmation. The mass accuracy typically obtained is routinely better than 1.5ppm, and only need to calibrate once a week. The 43 compounds behave dynamic in the range 0.001-1000 μg kg(-1) concentration, with correlation coefficient >0.999. The limits of detection for the analytes are in the range 0.0001-3.6 μg kg(-1). This method has been successfully applied on screening of antioxidants, preservatives and synthetic sweeteners in commercial dairy product samples, and it is very useful for fast screening of different food additives.

  13. The quantitative surface analysis of an antioxidant additive in a lubricant oil matrix by desorption electrospray ionization mass spectrometry

    PubMed Central

    Da Costa, Caitlyn; Reynolds, James C; Whitmarsh, Samuel; Lynch, Tom; Creaser, Colin S

    2013-01-01

    RATIONALE Chemical additives are incorporated into commercial lubricant oils to modify the physical and chemical properties of the lubricant. The quantitative analysis of additives in oil-based lubricants deposited on a surface without extraction of the sample from the surface presents a challenge. The potential of desorption electrospray ionization mass spectrometry (DESI-MS) for the quantitative surface analysis of an oil additive in a complex oil lubricant matrix without sample extraction has been evaluated. METHODS The quantitative surface analysis of the antioxidant additive octyl (4-hydroxy-3,5-di-tert-butylphenyl)propionate in an oil lubricant matrix was carried out by DESI-MS in the presence of 2-(pentyloxy)ethyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate as an internal standard. A quadrupole/time-of-flight mass spectrometer fitted with an in-house modified ion source enabling non-proximal DESI-MS was used for the analyses. RESULTS An eight-point calibration curve ranging from 1 to 80 µg/spot of octyl (4-hydroxy-3,5-di-tert-butylphenyl)propionate in an oil lubricant matrix and in the presence of the internal standard was used to determine the quantitative response of the DESI-MS method. The sensitivity and repeatability of the technique were assessed by conducting replicate analyses at each concentration. The limit of detection was determined to be 11 ng/mm2 additive on spot with relative standard deviations in the range 3–14%. CONCLUSIONS The application of DESI-MS to the direct, quantitative surface analysis of a commercial lubricant additive in a native oil lubricant matrix is demonstrated. © 2013 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons, Ltd. PMID:24097398

  14. Thermodynamic and elastic fluctuation analysis of Langmuir mixed monolayers composed by dehydrocholic acid (HDHC) and didodecyldimethylammonium bromide (DDAB).

    PubMed

    Messina, Paula V; Prieto, Gerardo; Ruso, Juan Manuel; Fernández-Leyes, Marcos D; Schulz, Pablo C; Sarmiento, Félix

    2010-01-01

    The physicochemical and elastic properties of Langmuir mixed monolayers composed by dehydrocholic acid (HDHC) and didodecyldimethylammonium bromide (DDAB) were evaluated. The experiments were performed with a constant surface pressure penetration Langmuir balance based on Axisymmetric Drop Shape Analysis (ADSA). The behavior of such amphiphiles in monolayer was clearly non-ideal and would be seriously influenced by the amount of HDHC molecules present. The presence of bile acid type molecules caused the monolayer be more condensed (A(c) diminution) and the intermolecular attractive interactions be stronger (high epsilon(0) values). This fact would be related to H-bond formation between water and carboxilate and carbonile groups in the cholesteric ring and agreed with the existence of laterally structured microdomains at the monolayer (determined by the analysis of the first virial coefficient, b(0)<1, of the state equation). The miscibility of both surfactants in the monolayer, their high bulk hydrophobicity (pi(c)>35 mJ m(-2)) just with the obtained negative values of the free energy of mixing Delta G(mix), and the excess second virial coefficient (b(1))(E) obtained allows us to infer that net attractive interaction existed between HDHC and DDAB molecules at the monolayer and that mixed systems would be able to be used in the formulation of supramolecular assemblies.

  15. Submonolayer Ag films on Fe(100): A first-principles analysis of energetics controlling adlayer thermodynamics and kinetics

    NASA Astrophysics Data System (ADS)

    Li, Wei; Huang, Li; Evans, James W.; Han, Yong

    2016-04-01

    Epitaxial growth of Ag on Fe(100) and postdeposition relaxation have been studied in several experiments. We provide a first-principles density functional theory analysis of key adatom interaction energies and diffusion barriers controlling growth and relaxation kinetics for the submonolayer regime, as these have not been assessed previously. A cluster expansion approach is used to obtain an extensive set of conventional lateral interactions between adatoms on fourfold hollow adsorption sites. We find robust oscillatory decay of pair interactions with increasing separation, and of trio interactions with increasing perimeter length. First- and second-nearest-neighbor pair interactions, as well as compact linear and bent trio interactions, dominate. The adatom terrace diffusion barrier is estimated to be Ed≈0.39 eV. We also provide a limited analysis of unconventional interactions for which one adatom is at the bridge-site transition state for hopping and one or more others are at fourfold hollow sites. Energy barriers for diffusion along island edges can be determined with the aid of both conventional and unconventional interactions.

  16. JTHERGAS: Thermodynamic Estimation from 2D Graphical Representations of Molecules

    PubMed Central

    Blurock, Edward; Warth, V.; Grandmougin, X.; Bounaceur, R.; Glaude, P.A.; Battin-Leclerc, F.

    2013-01-01

    JTHERGAS is a versatile calculator (implemented in JAVA) to estimate thermodynamic information from two dimensional graphical representations of molecules and radicals involving covalent bonds based on the Benson additivity method. The versatility of JTHERGAS stems from its inherent philosophy that all the fundamental data used in the calculation should be visible, to see exactly where the final values came from, and modifiable, to account for new data that can appear in the literature. The main use of this method is within automatic combustion mechanism generation systems where fast estimation of a large number and variety of chemical species is needed. The implementation strategy is based on meta-atom definitions and substructure analysis allowing a highly extensible database without modification of the core algorithms. Several interfaces for the database and the calculations are provided from terminal line commands, to graphical interfaces to web-services. The first order estimation of thermodynamics is based summing up the contributions of each heavy atom bonding description. Second order corrections due to steric hindrance and ring strain are made. Automatic estimate of contributions due to internal, external and optical symmetries are also made. The thermodynamical data for radicals is calculated by taking the difference due to the lost of a hydrogen radical taking into account changes in symmetry, spin, rotations, vibrations and steric hindrances. The software is public domain and is based on standard libraries such as CDK and CML. PMID:23761949

  17. Surface Emissivity Effects on Thermodynamic Retrieval of IR Spectral Radiance

    NASA Technical Reports Server (NTRS)

    Zhou, Daniel K.; Larar, Allen M.; Smith, William L.; Liu, Xu

    2006-01-01

    The surface emissivity effect on the thermodynamic parameters (e.g., the surface skin temperature, atmospheric temperature, and moisture) retrieved from satellite infrared (IR) spectral radiance is studied. Simulation analysis demonstrates that surface emissivity plays an important role in retrieval of surface skin temperature and terrestrial boundary layer (TBL) moisture. NAST-I ultraspectral data collected during the CLAMS field campaign are used to retrieve thermodynamic properties of the atmosphere and surface. The retrievals are then validated by coincident in-situ measurements, such as sea surface temperature, radiosonde temperature and moisture profiles. Retrieved surface emissivity is also validated by that computed from the observed radiance and calculated emissions based on the retrievals of surface temperature and atmospheric profiles. In addition, retrieved surface skin temperature and emissivity are validated together by radiance comparison between the observation and retrieval-based calculation in the window region where atmospheric contribution is minimized. Both simulation and validation results have lead to the conclusion that variable surface emissivity in the inversion process is needed to obtain accurate retrievals from satellite IR spectral radiance measurements. Retrieval examples are presented to reveal that surface emissivity plays a significant role in retrieving accurate surface skin temperature and TBL thermodynamic parameters.

  18. Thermodynamics of Biological Processes

    PubMed Central

    Garcia, Hernan G.; Kondev, Jane; Orme, Nigel; Theriot, Julie A.; Phillips, Rob

    2012-01-01

    There is a long and rich tradition of using ideas from both equilibrium thermodynamics and its microscopic partner theory of equilibrium statistical mechanics. In this chapter, we provide some background on the origins of the seemingly unreasonable effectiveness of ideas from both thermodynamics and statistical mechanics in biology. After making a description of these foundational issues, we turn to a series of case studies primarily focused on binding that are intended to illustrate the broad biological reach of equilibrium thinking in biology. These case studies include ligand-gated ion channels, thermodynamic models of transcription, and recent applications to the problem of bacterial chemotaxis. As part of the description of these case studies, we explore a number of different uses of the famed Monod–Wyman–Changeux (MWC) model as a generic tool for providing a mathematical characterization of two-state systems. These case studies should provide a template for tailoring equilibrium ideas to other problems of biological interest. PMID:21333788

  19. Compositional GC-FID analysis of the additives to PVC, focusing on the gaskets of lids for glass jars.

    PubMed

    Biedermann-Brem, Sandra; Biedermann, Maurus; Fiselier, Katell; Grob, Koni

    2005-12-01

    A gas chromatographic (FID) method is described which aims at the quantitative compositional analysis of the additives in plasticized PVC, particularly the plastisols used as gaskets for lids of glass jars. An extract of the PVC is analysed directly as well as after transesterification to ethyl esters. Transesterification enables the analysis of epoxidized soya bean and linseed oil (ESBO and ELO) as well as polyadipates. For most other additives, the shifts in the chromatogram resulting from transesterification is used to confirm the identifications made by direct analysis. In the gaskets of 69 lids from the European market used for packaging oily foods, a broad variety of plastisol compositions was found, many or possibly all of which do not comply with legal requirements. In 62% of these lids, ESBO was the principal plasticizer, whereas in 25% a phthalate had been used. PMID:16356892

  20. Thermodynamic and alkylation interference analysis of the lac repressor-operator substituted with the analogue 7-deazaguanine.

    PubMed

    Zhang, X; Gottlieb, P A

    1993-10-26

    Guanine residues in the lac operator were substituted with the isosteric analogue of 7-deazaguanine. The observed equilibrium dissociation constants for lac repressor binding to substituted operators were measured in 10 mM Tris, 150 mM KCl, 0.1 mM EDTA, and 0.1 mM DTE, pH 7.6, at 25 degrees C, using either a standard equilibrium assay or a competition assay. Of the seven individual sites tested, only three significantly altered the complex affinity. Two of these sites are symmetrically related and are positioned in the major grooves that are known to interact directly with repressor, and the third site is located in the central core region of the operator. The alkylation interference assay, which identifies essential phosphate sites, was used to define the extent of perturbation on the protein-DNA complex by the modified nucleotide. Chemical footprinting data for the singly substituted operator done at a single concentration of protein reflected the alignment of sterically incompatible groups or disruption in the local conformation, but did not appear to alter general phosphate backbone interactions. Similar experiments with a doubly substituted operator revealed that the free energy of binding was an additive combination of each of the individual sites, and the alkylation interference data were similar to the singly substituted and wild-type operators. A constitutive mutant which also had a higher binding constant had a similar alkylation interference pattern. PMID:8218202

  1. Thermodynamic analysis of sol-gel transition of gelatin in terms of water activity in various solutions.

    PubMed

    Miyawaki, Osato; Omote, Chiaki; Matsuhira, Keiko

    2015-12-01

    Sol-gel transition of gelatin was analyzed as a multisite stoichiometric reaction of a gelatin molecule with water and solute molecules. The equilibrium sol-gel transition temperature, Tt , was estimated from the average of gelation and melting temperature measured by differential scanning calorimetry. From Tt and the melting enthalpy, ΔHsol , the equilibrium sol-to-gel ratio was estimated by the van't Hoff equation. The reciprocal form of the Wyman-Tanford equation, which describes the sol-to-gel ratio as a function of water activity, was successfully applied to obtain a good linear relationship. From this analysis, the role of water activity on the sol-gel transition of gelatin was clearly explained and the contributions of hydration and solute binding to gelatin molecules were separately discussed in sol-gel transition. The general solution for the free energy for gel-stabilization in various solutions was obtained as a simple function of solute concentration.

  2. [High Throughput Screening Analysis of Preservatives and Sweeteners in Carbonated Beverages Based on Improved Standard Addition Method].

    PubMed

    Wang, Su-fang; Liu, Yun; Gong, Li-hua; Dong, Chun-hong; Fu, De-xue; Wang, Guo-qing

    2016-02-01

    Simulated water samples of 3 kinds of preservatives and 4 kinds of sweeteners were formulated by using orthogonal design. Kernel independent component analysis (KICA) was used to process the UV spectra of the simulated water samples and the beverages added different amounts of the additive standards, then the independent components (ICs), i. e. the UV spectral profiles of the additives, and the ICs' coefficient matrices were used to establish UV-KICA-SVR prediction model of the simulated preservatives and sweeteners solutions using support vector regression (SVR) analysis. The standards added beverages samples were obtained by adding different amounts level of additives in carbonated beverages, their UV spectra were processed by KICA, then IC information represented to the additives and other sample matrix were obtained, and the sample background can be deducted by removing the corresponding IC, other ICs' coefficient matrices were used to estimate the amounts of the additives in the standard added beverage samples based on the UV-KICA-SVR model, while the intercept of linear regression equation of predicted amounts and the added amounts in the standard added samples is the additive content in the raw beverage sample. By utilization of chemometric "blind source separation" method for extracting IC information of the tested additives in the beverage and other sample matrix, and using SVR regression modeling to improve the traditional standard addition method, a new method was proposed for the screening of the preservatives and sweeteners in carbonated beverages. The proposed UV-KICA-SVR method can be used to determine 3 kinds of preservatives and 4 kinds of sweetener in the carbonate beverages with the limit of detection (LOD) are located with the range 0.2-1.0 mg · L⁻¹, which are comparable to that of the traditional high performance liquid chromatographic (HPLC) method. PMID:27209754

  3. [High Throughput Screening Analysis of Preservatives and Sweeteners in Carbonated Beverages Based on Improved Standard Addition Method].

    PubMed

    Wang, Su-fang; Liu, Yun; Gong, Li-hua; Dong, Chun-hong; Fu, De-xue; Wang, Guo-qing

    2016-02-01

    Simulated water samples of 3 kinds of preservatives and 4 kinds of sweeteners were formulated by using orthogonal design. Kernel independent component analysis (KICA) was used to process the UV spectra of the simulated water samples and the beverages added different amounts of the additive standards, then the independent components (ICs), i. e. the UV spectral profiles of the additives, and the ICs' coefficient matrices were used to establish UV-KICA-SVR prediction model of the simulated preservatives and sweeteners solutions using support vector regression (SVR) analysis. The standards added beverages samples were obtained by adding different amounts level of additives in carbonated beverages, their UV spectra were processed by KICA, then IC information represented to the additives and other sample matrix were obtained, and the sample background can be deducted by removing the corresponding IC, other ICs' coefficient matrices were used to estimate the amounts of the additives in the standard added beverage samples based on the UV-KICA-SVR model, while the intercept of linear regression equation of predicted amounts and the added amounts in the standard added samples is the additive content in the raw beverage sample. By utilization of chemometric "blind source separation" method for extracting IC information of the tested additives in the beverage and other sample matrix, and using SVR regression modeling to improve the traditional standard addition method, a new method was proposed for the screening of the preservatives and sweeteners in carbonated beverages. The proposed UV-KICA-SVR method can be used to determine 3 kinds of preservatives and 4 kinds of sweetener in the carbonate beverages with the limit of detection (LOD) are located with the range 0.2-1.0 mg · L⁻¹, which are comparable to that of the traditional high performance liquid chromatographic (HPLC) method.

  4. Viscoplasticity: A thermodynamic formulation

    NASA Technical Reports Server (NTRS)

    Freed, A. D.; Chaboche, J. L.

    1989-01-01

    A thermodynamic foundation using the concept of internal state variables is given for a general theory of viscoplasticity, as it applies to initially isotropic materials. Three fundamental internal state variables are admitted. They are: a tensor valued back stress for kinematic effects, and the scalar valued drag and yield strengths for isotropic effects. All three are considered to phenomenologically evolve according to competitive processes between strain hardening, strain induced dynamic recovery, and time induced static recovery. Within this phenomenological framework, a thermodynamically admissible set of evolution equations is put forth. This theory allows each of the three fundamental internal variables to be composed as a sum of independently evolving constituents.

  5. Beyond Equilibrium Thermodynamics

    NASA Astrophysics Data System (ADS)

    Öttinger, Hans Christian

    2005-01-01

    Beyond Equilibrium Thermodynamics fills a niche in the market by providing a comprehensive introduction to a new, emerging topic in the field. The importance of non-equilibrium thermodynamics is addressed in order to fully understand how a system works, whether it is in a biological system like the brain or a system that develops plastic. In order to fully grasp the subject, the book clearly explains the physical concepts and mathematics involved, as well as presenting problems and solutions; over 200 exercises and answers are included. Engineers, scientists, and applied mathematicians can all use the book to address their problems in modelling, calculating, and understanding dynamic responses of materials.

  6. Determination of 3D paleostress systems: An additional technique for basin analysis

    SciTech Connect

    Bakker, H.E.

    1988-08-01

    The present structure of the western Mediterranean has been largely determined by several phases of rifting and oceanic spreading which began during the Oligocene. The main rifting event took place during the middle Oligocene-earliest Miocene. This is indicated by structural, stratigraphic, metamorphic, and volcanic data. During this event Corsica and Sardinia drifted eastward from the previously amalgamated Iberian-European plate, and the Provencal and Algerian basins were developed. The plate movements related to the development of these basins have been reconstructed by using the orientation of the present plate boundaries, the strike of transform faults, the age and trend of magnetic anomalies, and paleomagnetic data. An additional approach is proposed, based on detailed field study of faults at specific locations on the continental plates. From fault-plane and slip-direction data the author can calculate the responsible 3D paleostress systems. These stress systems apparently can be used to reconstruct in detail the kinematics of the rifting and drifting processes on both a local and regional scale. The method is illustrated by the geodynamic evolution of Mallorca, Menorca, and the Gulf of Valencia.

  7. Temperature Profile and Imaging Analysis of Laser Additive Manufacturing of Stainless Steel

    NASA Astrophysics Data System (ADS)

    Islam, M.; Purtonen, T.; Piili, H.; Salminen, A.; Nyrhilä, O.

    Powder bed fusion is a laser additive manufacturing (LAM) technology which is used to manufacture parts layer-wise from powdered metallic materials. The technology has advanced vastly in the recent years and current systems can be used to manufacture functional parts for e.g. aerospace industry. The performance and accuracy of the systems have improved also, but certain difficulties in the powder fusion process are reducing the final quality of the parts. One of these is commonly known as the balling phenomenon. The aim of this study was to define some of the process characteristics in powder bed fusion by performing comparative studies with two different test setups. This was done by comparing measured temperature profiles and on-line photography of the process. The material used during the research was EOS PH1 stainless steel. Both of the test systems were equipped with 200 W single mode fiber lasers. The main result of the research was that some of the process instabilities are resulting from the energy input during the process.

  8. Additive analysis of nano silicon under the influence of neutron irradiation

    NASA Astrophysics Data System (ADS)

    Garibli, Aydan; Huseynov, Elchin; Garibov, Adil; Mehdiyeva, Ravan

    2016-04-01

    Nano silicon with 80m2g‑1 specific surface area, 100 nm size and 0.08 g/cm3 density has been irradiated continuously with neutrons (2 × 1013n ṡcm‑2s‑1) up to 20 h at various periods in TRIGA Mark II type research reactor. After the neutron irradiation, cooling time of the samples is taken approximately 360 h. It is found that the initial radioactivity of the irradiated samples changes within 0.1 kBq-3.1 GBq range. Definition of elements’ concentration is determined based on the activities formed in the relevant energy range. After the irradiation, the result of activity analysis carried out the element content of 1% mixture existing in nano Si which has been defined with radionuclides of the relevant element. Moreover, from activities of mixed radioisotopes, their amounts in percentage has been determined.

  9. Protein-Protein Interaction Analysis Highlights Additional Loci of Interest for Multiple Sclerosis

    PubMed Central

    Ragnedda, Giammario; Disanto, Giulio; Giovannoni, Gavin; Ebers, George C.; Sotgiu, Stefano; Ramagopalan, Sreeram V.

    2012-01-01

    Genetic factors play an important role in determining the risk of multiple sclerosis (MS). The strongest genetic association in MS is located within the major histocompatibility complex class II region (MHC), but more than 50 MS loci of modest effect located outside the MHC have now been identified. However, the relative candidate genes that underlie these associations and their functions are largely unknown. We conducted a protein-protein interaction (PPI) analysis of gene products coded in loci recently reported to be MS associated at the genome-wide significance level and in loci suggestive of MS association. Our aim was to identify which suggestive regions are more likely to be truly associated, which genes are mostly implicated in the PPI network and their expression profile. From three recent independent association studies, SNPs were considered and divided into significant and suggestive depending on the strength of the statistical association. Using the Disease Association Protein-Protein Link Evaluator tool we found that direct interactions among genetic products were significantly higher than expected by chance when considering both significant regions alone (p<0.0002) and significant plus suggestive (p<0.007). The number of genes involved in the network was 43. Of these, 23 were located within suggestive regions and many of them directly interacted with proteins coded within significant regions. These included genes such as SYK, IL-6, CSF2RB, FCLR3, EIF4EBP2 and CHST12. Using the gene portal BioGPS, we tested the expression of these genes in 24 different tissues and found the highest values among immune-related cells as compared to non-immune tissues (p<0.001). A gene ontology analysis confirmed the immune-related functions of these genes. In conclusion, loci currently suggestive of MS association interact with and have similar expression profiles and function as those significantly associated, highlighting the fact that more common variants remain to be

  10. Thermodynamics of the hydrodenitrogenation of carbazole

    SciTech Connect

    Steele, W.V.; Chirico, R.D.

    1991-10-01

    A thermodynamic analysis, based on accurate experimental Gibbs energies of formation, was completed for the key hydrogen-consuming steps in the HDN reaction network for carbazole. The results were compared with literature reaction studies. The concept of crossover temperature'' is shown to be a valuable tool in the interpretation of literature reaction-study results. Methods of nitrogen removal from aromatic materials are discussed in light of the findings of the thermodynamic analysis. It is concluded that the removal of nitrogen from heterocyclic aromatic nitrogen-containing compounds with conventional hydrodesulfurization catalysts, temperatures, and hydrogen pressures occurs under thermodynamic control'' with unavoidably high hydrogen consumption. The report also concludes that to reduce hydrogen consumption in the HDN of carbazole, pathways via 1,2,3,4a,9a-hexahydrocarbazole must be followed. Conditions under which these processes are possible are discussed. 36 refs., 9 figs.

  11. The inclusion complex of rosmarinic acid into beta-cyclodextrin: A thermodynamic and structural analysis by NMR and capillary electrophoresis.

    PubMed

    Aksamija, Amra; Polidori, Ange; Plasson, Raphaël; Dangles, Olivier; Tomao, Valérie

    2016-10-01

    This work focuses on the characterization of the rosmarinic acid (RA)-β-cyclodextrin (CD) complex in aqueous solution by (1)H NMR (1D- and 2D-ROESY), completed with studies by capillary electrophoresis (CE). From the (1)H NMR data, the stoichiometry of the complex was determined by a Job's plot and the binding constant was estimated from a linear regression (Scott's method). At pH 2.9, the results showed that RA binds CD with a 1:1 stoichiometry and a binding constant Kb of 445 (±53) M(-1) or 465 (±81) M(-1) depending on the CD protons (H-5 or H-3) selected for the evaluation. The Kb value was also calculated from the CD-induced chemical shifts of each RA proton in order to collect information on the structure of the complex. The pH dependence of Kb revealed that the RA carboxylic form displays the highest affinity for CD. An investigation by capillary electrophoresis fully confirmed these results. 2D ROESY analysis provided detailed structural information on the complex and showed a strong correlation between H-3 and H-5 of CD and most RA protons. In conclusion, RA, an efficient phenolic antioxidant from rosemary with a marketing authorization, spontaneously forms a relatively stable inclusion complex with CD in water. PMID:27132848

  12. Analysis of a new thermodynamic cycle for combined power and cooling using low and mid temperature solar collectors

    SciTech Connect

    Goswami, D.Y.; Xu, F.

    1999-05-01

    A combined thermal power and cooling cycle is proposed which combines the Rankine and absorption refrigeration cycles. It can provide power output as well as refrigeration with power generation as a primary goal. Ammonia-water mixture is used as a working fluid. The boiling temperature of the ammonia-water mixture increases as the boiling process proceeds until all liquid is vaporized, so that a better thermal match is obtained in the boiler. The proposed cycle takes advantage of the low boiling temperature of ammonia vapor so that it can be expanded to a low temperature while it is still in a vapor state or a high quality two phase state. This cycle is ideally suited for solar thermal power using low cost concentrating collectors, with the potential to reduce the capital cost of a solar thermal power plant. The cycle can also be used as a bottoming cycle for any thermal power plant. This paper presents a parametric analysis of the proposed cycle.

  13. The impact of binding thermodynamics on medicinal chemistry optimizations.

    PubMed

    Ferenczy, György G; Keserű, György M

    2015-01-01

    Ligand binding thermodynamics has been attracted considerable interest in the past decade owing to the recognized relation between binding thermodynamic profile and the physicochemical and druglike properties of compounds. In this review, the relation between optimization strategies and ligand properties is presented based on the structural and thermodynamic analysis of ligand-protein complex formation. The control of the binding thermodynamic profile is beneficial for the balanced affinity and physicochemical properties of drug candidates, and early phase optimization gives more opportunity to this control.

  14. Mass analysis addition to the Differential Ion Flux Probe (DIFP) study

    NASA Technical Reports Server (NTRS)

    Wright, K. H., Jr.; Jolley, Richard

    1994-01-01

    The objective of this study is to develop a technique to measure the characteristics of space plasmas under highly disturbed conditions; e.g., non-Maxwellian plasmas with strong drifting populations and plasmas contaminated by spacecraft outgassing. The approach, conducted in conjunction with current MSFC activities, is to extend the capabilities of the Differential Ion Flux Probe (DIFP) to include a high throughput mass measurement that does not require either high voltage or contamination sensitive devices such as channeltron electron multipliers or microchannel plates. This will significantly reduce the complexity and expense of instrument fabrication, testing, and integration of flight hardware compared to classical mass analyzers. The feasibility of the enhanced DIFP has been verified by using breadboard test models in a controlled plasma environment. The ability to manipulate particles through the instrument regardless of incident angle, energy, or ionic component has been amply demonstrated. The energy analysis mode is differential and leads directly to a time-of-flight mass measurement. With the new design, the DIFP will separate multiple ion streams and analyze each stream independently for ion flux intensity, velocity (including direction of motion), mass, and temperature (or energy distribution). In particular, such an instrument will be invaluable on follow-on electrodynamic TSS missions and, possibly, for environmental monitoring on the space station.

  15. Uncovering hidden variance: pair-wise SNP analysis accounts for additional variance in nicotine dependence

    PubMed Central

    Culverhouse, Robert C.; Saccone, Nancy L.; Stitzel, Jerry A.; Wang, Jen C.; Steinbach, Joseph H.; Goate, Alison M.; Schwantes-An, Tae-Hwi; Grucza, Richard A.; Stevens, Victoria L.; Bierut, Laura J.

    2010-01-01

    Results from genome-wide association studies of complex traits account for only a modest proportion of the trait variance predicted to be due to genetics. We hypothesize that joint analysis of polymorphisms may account for more variance. We evaluated this hypothesis on a case–control smoking phenotype by examining pairs of nicotinic receptor single-nucleotide polymorphisms (SNPs) using the Restricted Partition Method (RPM) on data from the Collaborative Genetic Study of Nicotine Dependence (COGEND). We found evidence of joint effects that increase explained variance. Four signals identified in COGEND were testable in independent American Cancer Society (ACS) data, and three of the four signals replicated. Our results highlight two important lessons: joint effects that increase the explained variance are not limited to loci displaying substantial main effects, and joint effects need not display a significant interaction term in a logistic regression model. These results suggest that the joint analyses of variants may indeed account for part of the genetic variance left unexplained by single SNP analyses. Methodologies that limit analyses of joint effects to variants that demonstrate association in single SNP analyses, or require a significant interaction term, will likely miss important joint effects. PMID:21079997

  16. Mechanism of interaction of optimized Limulus-derived cyclic peptides with endotoxins: thermodynamic, biophysical and microbiological analysis.

    PubMed

    Andrä, Jörg; Howe, Jörg; Garidel, Patrick; Rössle, Manfred; Richter, Walter; Leiva-León, José; Moriyon, Ignacio; Bartels, Rainer; Gutsmann, Thomas; Brandenburg, Klaus

    2007-09-01

    On the basis of formerly investigated peptides corresponding to the endotoxin-binding domain from LALF [Limulus anti-LPS (lipopolysaccharide) factor], a protein from Limulus polyphemus, we have designed and synthesized peptides of different lengths with the aim of obtaining potential therapeutic agents against septic shock syndrome. For an understanding of the mechanisms of action, we performed a detailed physicochemical and biophysical analysis of the interaction of rough mutant LPS with these peptides by applying FTIR (Fourier-transform infrared) spectroscopy, SAXS (small-angle X-ray scattering), calorimetric techniques [DSC (differential scanning calorimetry) and ITC (isothermal titration calorimetry)] and FFTEM (freeze-fracture transmission electron microscopy). Also, the action of the peptides on bacteria of different origin in microbial assays was investigated. Using FTIR and DSC, our results indicated a strong fluidization of the lipid A acyl chains due to peptide binding, with a decrease in the endothermic melting enthalpy change of the acyl chains down to a complete disappearance in the 1:0.5 to 1:2 [LPS]:[peptide] molar ratio range. Via ITC, it was deduced that the binding is a clearly exothermic process which becomes saturated at a 1:0.5 to 1:2 [LPS]:[peptide] molar ratio range. The results obtained with SAXS indicated a drastic change of the aggregate structures of LPS into a multilamellar stack, which was visualized in electron micrographs as hundreds of lamellar layers. This can be directly correlated with the inhibition of the LPS-induced production of tumour necrosis factor alpha in human mononuclear cells, but not with the action of the peptides on bacteria.

  17. Flavoured aspects of the QCD thermodynamics

    NASA Astrophysics Data System (ADS)

    Kaczmarek, O.

    2016-01-01

    We discuss recent progress in lattice QCD studies on various aspects involving strange and heavy quarks. Appropriate combinations of conserved net strange and net charm fluctuations and their correlations with other conserved charges provide evidence that in the hadronic phase so far unobserved hadrons contribute to the thermodynamics and need to be included in hadron resonance gas models. In the strange sector this leads to significant reductions of the chemical freeze-out temperature of strange hadrons. We have found that a description of the thermodynamics of open strange and open charm degrees of freedom in terms of an uncorrelated hadron gas is valid only up to temperatures close to the chiral crossover temperature. This suggests that in addition to light and strange hadrons also open charm hadrons start to dissolve already close to the chiral crossover. Further indications that open charm mesons start to melt in the vicinity of Tc is obtained from an analysis of screening masses, while in the charmonium sector these screening masses show a behavior compatible with a sequential melting pattern. In the last section we discuss resent progress in extracting a transport coefficient, the heavy quark momentum diffusion coefficient, based on continuum extrapolated color-electric field correlation functions and estimate the time scale associated with the kinetic equilibration of heavy quarks. Close to Tc this suggests that charm quark kinetic equilibration appears almost as fast as that of light partons in agreement with qualitative discoveries at RHIC and LHC that charm quarks appear to flow about as effectively as light quarks.

  18. Black Hole Thermodynamics in an Undergraduate Thermodynamics Course.

    ERIC Educational Resources Information Center

    Parker, Barry R.; McLeod, Robert J.

    1980-01-01

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

  19. Thermodynamics of Resource Recycling.

    ERIC Educational Resources Information Center

    Hauserman, W. B.

    1988-01-01

    Evaluates the overall economic efficiency of a closed resource cycle. Uses elementary thermodynamic definitions of overall thermal efficiency for determining an economically quantifiable basis. Selects aluminum for investigation and includes a value-entropy diagram for a closed aluminum cycle. (MVL)

  20. Program Computes Thermodynamic Functions

    NASA Technical Reports Server (NTRS)

    Mcbride, Bonnie J.; Gordon, Sanford

    1994-01-01

    PAC91 is latest in PAC (Properties and Coefficients) series. Two principal features are to provide means of (1) generating theoretical thermodynamic functions from molecular constants and (2) least-squares fitting of these functions to empirical equations. PAC91 written in FORTRAN 77 to be machine-independent.

  1. Focus on stochastic thermodynamics

    NASA Astrophysics Data System (ADS)

    Van den Broeck, Christian; Sasa, Shin-ichi; Seifert, Udo

    2016-02-01

    We introduce the thirty papers collected in this ‘focus on’ issue. The contributions explore conceptual issues within and around stochastic thermodynamics, use this framework for the theoretical modeling and experimental investigation of specific systems, and provide further perspectives on and for this active field.

  2. Thermodynamics in dynamical spacetimes

    NASA Astrophysics Data System (ADS)

    Tresguerres, Romualdo

    2014-03-01

    We derive a general formulation of the laws of irreversible thermodynamics in the presence of electromagnetism and gravity. For the handling of macroscopic material media, we use as a guide the field equations and the Noether identities of fundamental matter as deduced in the framework of gauge theories of the Poincaré ⊗ U(1) group.

  3. On Teaching Thermodynamics

    ERIC Educational Resources Information Center

    Debbasch, F.

    2011-01-01

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

  4. Thermodynamics of Dilute Solutions.

    ERIC Educational Resources Information Center

    Jancso, Gabor; Fenby, David V.

    1983-01-01

    Discusses principles and definitions related to the thermodynamics of dilute solutions. Topics considered include dilute solution, Gibbs-Duhem equation, reference systems (pure gases and gaseous mixtures, liquid mixtures, dilute solutions), real dilute solutions (focusing on solute and solvent), terminology, standard states, and reference systems.…

  5. Fluctuating Thermodynamics for Biological Processes

    NASA Astrophysics Data System (ADS)

    Ham, Sihyun

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

  6. A thermodynamic formulation of root water uptake

    NASA Astrophysics Data System (ADS)

    Hildebrandt, Anke; Kleidon, Axel; Bechmann, Marcel

    2016-08-01

    By extracting bound water from the soil and lifting it to the canopy, root systems of vegetation perform work. Here we describe how root water uptake can be evaluated thermodynamically and demonstrate that this evaluation provides additional insights into the factors that impede root water uptake. We derive an expression that relates the energy export at the base of the root system to a sum of terms that reflect all fluxes and storage changes along the flow path in thermodynamic terms. We illustrate this thermodynamic formulation using an idealized setup of scenarios with a simple model. In these scenarios, we demonstrate why heterogeneity in soil water distribution and rooting properties affect the impediment of water flow even though the mean soil water content and rooting properties are the same across the scenarios. The effects of heterogeneity can clearly be identified in the thermodynamics of the system in terms of differences in dissipative losses and hydraulic energy, resulting in an earlier start of water limitation in the drying cycle. We conclude that this thermodynamic evaluation of root water uptake conveniently provides insights into the impediments of different processes along the entire flow path, which goes beyond resistances and also accounts for the role of heterogeneity in soil water distribution.

  7. The second laws of quantum thermodynamics.

    PubMed

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

    2015-03-17

    The second law of thermodynamics places constraints on state transformations. It applies to systems composed of many particles, however, we are seeing that one can formulate laws of thermodynamics when only a small number of particles are interacting with a heat bath. Is there a second law of thermodynamics in this regime? Here, we find that for processes which are approximately cyclic, the second law for microscopic systems takes on a different form compared to the macroscopic scale, imposing not just one constraint on state transformations, but an entire family of constraints. We find a family of free energies which generalize the traditional one, and show that they can never increase. The ordinary second law relates to one of these, with the remainder imposing additional constraints on thermodynamic transitions. We find three regimes which determine which family of second laws govern state transitions, depending on how cyclic the process is. In one regime one can cause an apparent violation of the usual second law, through a process of embezzling work from a large system which remains arbitrarily close to its original state. These second laws are relevant for small systems, and also apply to individual macroscopic systems interacting via long-range interactions. By making precise the definition of thermal operations, the laws of thermodynamics are unified in this framework, with the first law defining the class of operations, the zeroth law emerging as an equivalence relation between thermal states, and the remaining laws being monotonicity of our generalized free energies. PMID:25675476

  8. The second laws of quantum thermodynamics.

    PubMed

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

    2015-03-17

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

  9. The thermodynamics of simple biomembrane mimetic systems

    PubMed Central

    Raudino, Antonio; Sarpietro, Maria Grazia; Pannuzzo, Martina

    2011-01-01

    Insight into the forces governing a system is essential for understanding its behavior and function. Thermodynamic investigations provide a wealth of information that is not, or is hardly, available from other methods. This article reviews thermodynamic approaches and assays to measure collective properties such as heat adsorption / emission and volume variations. These methods can be successfully applied to the study of lipid vesicles (liposomes) and biological membranes. With respect to instrumentation, differential scanning calorimetry, pressure perturbation calorimetry, isothermal titration calorimetry, dilatometry, and acoustic techniques aimed at measuring the isothermal and adiabatic processes, two- and three-dimensional compressibilities are considered. Applications of these techniques to lipid systems include the measurement of different thermodynamic parameters and a detailed characterization of thermotropic, barotropic, and lyotropic phase behavior. The membrane binding and / or partitioning of solutes (proteins, peptides, drugs, surfactants, ions, etc.) can also be quantified and modeled. Many thermodynamic assays are available for studying the effect of proteins and other additives on membranes, characterizing non-ideal mixing, domain formation, bilayer stability, curvature strain, permeability, solubilization, and fusion. Studies of membrane proteins in lipid environments elucidate lipid–protein interactions in membranes. Finally, a plethora of relaxation phenomena toward equilibrium thermodynamic structures can be also investigated. The systems are described in terms of enthalpic and entropic forces, equilibrium constants, heat capacities, partial volume changes, volume and area compressibility, and so on, also shedding light on the stability of the structures and the molecular origin and mechanism of the structural changes. PMID:21430953

  10. Thermodynamics of Inozemtsev's elliptic spin chain

    NASA Astrophysics Data System (ADS)

    Klabbers, Rob

    2016-06-01

    We study the thermodynamic behaviour of Inozemtsev's long-range elliptic spin chain using the Bethe ansatz equations describing the spectrum of the model in the infinite-length limit. We classify all solutions of these equations in that limit and argue which of these solutions determine the spectrum in the thermodynamic limit. Interestingly, some of the solutions are not selfconjugate, which puts the model in sharp contrast to one of the model's limiting cases, the Heisenberg XXX spin chain. Invoking the string hypothesis we derive the thermodynamic Bethe ansatz equations (TBA-equations) from which we determine the Helmholtz free energy in thermodynamic equilibrium and derive the associated Y-system. We corroborate our results by comparing numerical solutions of the TBA-equations to a direct computation of the free energy for the finite-length hamiltonian. In addition we confirm numerically the interesting conjecture put forward by Finkel and González-López that the original and supersymmetric versions of Inozemtsev's elliptic spin chain are equivalent in the thermodynamic limit.

  11. pH-Manipulated Underwater-Oil Adhesion Wettability Behavior on the Micro/Nanoscale Semicircular Structure and Related Thermodynamic Analysis.

    PubMed

    Tie, Lu; Guo, Zhiguang; Liu, Weimin

    2015-05-20

    Controlling oil of wettability behavior in response to the underwater out stimulation has shown promising applications in understanding and designing novel micro- or nanofluidic devices. In this article, the pH-manipulated underwater-oil adhesion wetting phenomenon and superoleophobicity on the micro- and nanotexture copper mesh films (CMF) were investigated. It should be noted that the surface exhibits underwater superoleophobicity under different pH values of the solution; however, the underwater-oil adhesion behavior on the surface is dramatically influenced by the pH value of the solution. On the basis of the thermodynamic analysis, a plausible mechanism to explain the pH-controllable underwater-oil adhesion and superoleophobic wetting behavior observed on a micro- and nanoscale semicircular structure has been revealed. Furthermore, variation of chemistry (intrinsic oil contact angle (OCA)) of the responsive surface that due to the carboxylic acid groups is protonated or deprotonated by the acidic or basic solution on free energy (FE) with its barrier (FEB) and equilibrium oil contact angle (EOCA) with it hysteresis (OCAH) are discussed. The result shows that a critical intrinsic OCA on the micro- and nano- semicircular texture is necessary for conversion from the oil Cassie impregnating to oil Cassie wetting state. In a water/oil/solid system, the mechanism reveals that the differences between the underwater OCA and oil adhesive force of the responsive copper mesh film under different pH values of solution are ascribed to the different oil wetting state that results from combining the changing intrinsic OCA and micro-/nanosemicircular structures. These results are well in agreement with the experiment.

  12. The Statistical Interpretation of Classical Thermodynamic Heating and Expansion Processes

    ERIC Educational Resources Information Center

    Cartier, Stephen F.

    2011-01-01

    A statistical model has been developed and applied to interpret thermodynamic processes typically presented from the macroscopic, classical perspective. Through this model, students learn and apply the concepts of statistical mechanics, quantum mechanics, and classical thermodynamics in the analysis of the (i) constant volume heating, (ii)…

  13. Thermodynamic indicators for environmental certification.

    PubMed

    Panzieri, Margherita; Porcelli, Marcello; Pulselli, Federico Maria

    2002-09-01

    The Earth is an open thermodynamic system, that remains in a steady state far from the equilibrium, through energy and matter exchanges with the surrounding environment. These natural constraints, which prevent the system from maximizing its entropy, are threatened by human action and our ecosystem needs urgent protection. In this viewpoint the environmental certification was born, according to international standards ISO 14001, ISO 14040, and European Regulation EMAS. These are voluntary adhesions to a program of environmental protection by companies, administrations and organizations which, starting from the respect of the existing environmental laws and regulations, decide to further improve their environmental performance. To obtain and maintain certification of a system is necessary to apply some indicators to evaluate its environmental performance and to demonstrate its progressive improvement. Here we propose to use for this purpose the thermodynamic indicators produced from energy analysis by Odum. The case study is Montalcino city (Italy) and energy indicators are used to evaluate environmental performance of this system where exist different activities, from agricultural productions, to tourism. Results show that energy analysis could become a valid standard monitoring method for environmental certification, especially in consideration of its wide application field.

  14. A Genome-Wide Association Analysis Reveals Epistatic Cancellation of Additive Genetic Variance for Root Length in Arabidopsis thaliana.

    PubMed

    Lachowiec, Jennifer; Shen, Xia; Queitsch, Christine; Carlborg, Örjan

    2015-01-01

    Efforts to identify loci underlying complex traits generally assume that most genetic variance is additive. Here, we examined the genetics of Arabidopsis thaliana root length and found that the genomic narrow-sense heritability for this trait in the examined population was statistically zero. The low amount of additive genetic variance that could be captured by the genome-wide genotypes likely explains why no associations to root length could be found using standard additive-model-based genome-wide association (GWA) approaches. However, as the broad-sense heritability for root length was significantly larger, and primarily due to epistasis, we also performed an epistatic GWA analysis to map loci contributing to the epistatic genetic variance. Four interacting pairs of loci were revealed, involving seven chromosomal loci that passed a standard multiple-testing corrected significance threshold. The genotype-phenotype maps for these pairs revealed epistasis that cancelled out the additive genetic variance, explaining why these loci were not detected in the additive GWA analysis. Small population sizes, such as in our experiment, increase the risk of identifying false epistatic interactions due to testing for associations with very large numbers of multi-marker genotypes in few phenotyped individuals. Therefore, we estimated the false-positive risk using a new statistical approach that suggested half of the associated pairs to be true positive associations. Our experimental evaluation of candidate genes within the seven associated loci suggests that this estimate is conservative; we identified functional candidate genes that affected root development in four loci that were part of three of the pairs. The statistical epistatic analyses were thus indispensable for confirming known, and identifying new, candidate genes for root length in this population of wild-collected A. thaliana accessions. We also illustrate how epistatic cancellation of the additive genetic variance

  15. A Genome-Wide Association Analysis Reveals Epistatic Cancellation of Additive Genetic Variance for Root Length in Arabidopsis thaliana

    PubMed Central

    Lachowiec, Jennifer; Shen, Xia; Queitsch, Christine; Carlborg, Örjan

    2015-01-01

    Efforts to identify loci underlying complex traits generally assume that most genetic variance is additive. Here, we examined the genetics of Arabidopsis thaliana root length and found that the genomic narrow-sense heritability for this trait in the examined population was statistically zero. The low amount of additive genetic variance that could be captured by the genome-wide genotypes likely explains why no associations to root length could be found using standard additive-model-based genome-wide association (GWA) approaches. However, as the broad-sense heritability for root length was significantly larger, and primarily due to epistasis, we also performed an epistatic GWA analysis to map loci contributing to the epistatic genetic variance. Four interacting pairs of loci were revealed, involving seven chromosomal loci that passed a standard multiple-testing corrected significance threshold. The genotype-phenotype maps for these pairs revealed epistasis that cancelled out the additive genetic variance, explaining why these loci were not detected in the additive GWA analysis. Small population sizes, such as in our experiment, increase the risk of identifying false epistatic interactions due to testing for associations with very large numbers of multi-marker genotypes in few phenotyped individuals. Therefore, we estimated the false-positive risk using a new statistical approach that suggested half of the associated pairs to be true positive associations. Our experimental evaluation of candidate genes within the seven associated loci suggests that this estimate is conservative; we identified functional candidate genes that affected root development in four loci that were part of three of the pairs. The statistical epistatic analyses were thus indispensable for confirming known, and identifying new, candidate genes for root length in this population of wild-collected A. thaliana accessions. We also illustrate how epistatic cancellation of the additive genetic variance

  16. Thermodynamic Curvature and Black Holes

    NASA Astrophysics Data System (ADS)

    Ruppeiner, George

    In my talk, I will discuss black hole thermodynamics, particularly what happens when you add thermodynamic curvature to the mix. Although black hole thermodynamics is a little off the main theme of this workshop, I hope nevertheless that my message will be of some interest to researchers in supersymmetry and supergravity.

  17. Thermodynamic States in Explosion Fields

    SciTech Connect

    Kuhl, A L

    2009-10-16

    Here we investigate the thermodynamic states occurring in explosion fields from the detonation of condensed explosives in air. In typical applications, the pressure of expanded detonation products gases is modeled by a Jones-Wilkins-Lee (JWL) function: P{sub JWL} = f(v,s{sub CJ}); constants in that function are fit to cylinder test data. This function provides a specification of pressure as a function of specific volume, v, along the expansion isentrope (s = constant = s{sub CJ}) starting at the Chapman-Jouguet (CJ) state. However, the JWL function is not a fundamental equation of thermodynamics, and therefore gives an incomplete specification of states. For example, explosions inherently involve shock reflections from surfaces; this changes the entropy of the products, and in such situations the JWL function provides no information on the products states. In addition, most explosives are not oxygen balanced, so if hot detonation products mix with air, they after-burn, releasing the heat of reaction via a turbulent combustion process. This raises the temperature of explosion products cloud to the adiabatic flame temperature ({approx}3,000K). Again, the JWL function provides no information on the combustion products states.

  18. Evaluating the combustion reactivity of drop tube furnace and thermogravimetric analysis coal chars with a selection of metal additives

    SciTech Connect

    Katherine Le Manquais; Colin E. Snape; Ian McRobbie; Jim Barker

    2011-03-17

    Opportunities exist for effective coal combustion additives that can reduce the carbon content of pulverized fuel ash (PFA) to below 6%, thereby making it saleable for filler/building material applications without the need for postcombustion treatment. However, with only limited combustion data currently available for the multitude of potential additives, catalytic performance under pulverized fuel (PF) boiler conditions has received relatively little attention. This paper therefore compares the reactivity of catalyzed bituminous coal chars from thermogravimetric analysis (TGA) with those generated by devolatilization in a drop tube furnace (DTF). The principal aim was to explore the fundamental chemistry behind the chosen additives' relative reactivities. Accordingly, all eight of the investigated additives increased the TGA burnout rate of the TGA and DTF chars, with most of the catalysts demonstrating consistent reactivity levels across chars from both devolatilization methods. Copper(I) chloride, silver chloride, and copper nitrate were thus identified as the most successful additives tested, but it proved difficult to establish a definitive reactivity ranking. This was largely due to the use of physical mixtures for catalyst dispersion, the relatively narrow selection of additives examined, and the inherent variability of the DTF chars. Nevertheless, one crucial exception to normal additive behavior was discovered, with copper(I) chloride perceptibly deactivating during devolatilization in the DTF, even though it remained the most effective catalyst tested. As a prolonged burnout at over 1000{sup o}C was required to replicate this deactivation effect on the TGA, the phenomenon could not be detected by typical testing procedures. Subsequently, a comprehensive TGA study showed no obvious relationship between the catalyst-induced reductions in the reaction's apparent activation energy and the samples recorded burnout rates.

  19. Thermodynamic significance of human basal metabolism

    NASA Astrophysics Data System (ADS)

    Wang, Cuncheng

    1993-06-01

    The human basal state, a non-equilibrium steady state, is analysed in this paper in the light of the First and Second Laws of Thermodynamics whereby the thermodynamic significance of the basal metabolic rate and its distinction to the dissipation function and exergy loss are identified. The analysis demonstrates the correct expression of the effects of the blood flow on the heat balance in a human-body bio-heat model and the relationship between the basal metabolic rate and the blood perfusion.

  20. Black hole entropy and isolated horizons thermodynamics.

    PubMed

    Ghosh, Amit; Perez, Alejandro

    2011-12-01

    We present a statistical mechanical calculation of the thermodynamical properties of (nonrotating) isolated horizons. The introduction of the Planck scale allows for the definition of a universal horizon temperature (independent of the mass of the black hole) and a well-defined notion of energy (as measured by suitable local observers) proportional to the horizon area in Planck units. The microcanonical and canonical ensembles associated with the system are introduced. Black hole entropy and other thermodynamical quantities can be consistently computed in both ensembles and results are in agreement with Hawking's semiclassical analysis for all values of the Immirzi parameter.