Science.gov

Sample records for addition thermodynamic analysis

  1. Evaluation of Five Additional Enhancements to the Building Loads Analysis and System Thermodynamics (BLAST) Program

    DTIC Science & Technology

    1993-04-01

    FINDINGS AND RECOMMENDATIONS OF TEST/DEMONSTRATION U’ WORK UNIT NO./TITLE OF TEST: T3B, Blast Enhancements Evaluation PERFORMING LABORATORY: USACERL...gram, work unit EA-KAI, "Test New BLAST Enhancements," and project 4A162784AT45, "Energy and Energy Conservation," work unit XG2, "Energy Analysis...air economy cycle. 2. SZDT-DX. Single zone draw-through fan systems with a direct expansion condensing unit tor zones 1, 2, and 3. Zone I

  2. 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.

  3. 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).

  4. 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.

  5. 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.

  6. 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.

  7. Thermodynamic analysis of coal gasification processes

    NASA Astrophysics Data System (ADS)

    Singh, S. P.; Weil, S. A.; Babu, S. P.

    1980-09-01

    Thermodynamic analysis for evaluating and improving coal gasification process efficiency requires estimation of enthalpy, entropy, and availability transformations in various process steps. A compilation of procedures and data relevant to coal gasification processes is presented for calculating the above thermodynamic properties. Enthalpy and availability transformations are estimated for significant process steps in the HYGAS process for producing substitute natural gas from coal. The thermal efficiencies based on the first law of thermodynamics are compared with the availability efficiencies based on the second law. Work intensive process steps, such as gas compression and separation, are shown to have extremely low thermal efficiencies and fairly high availability efficiencies. Heat intensive process steps, such as steam generation, have high thermal efficiencies but generally poor availability efficiencies.

  8. Why Are Addition Reactions to N2 Thermodynamically Unfavorable?

    PubMed

    Borden, Weston Thatcher

    2017-02-09

    Thermochemical data are used to show that, of the 89.9 kcal/mol difference between the endothermicity of H2 addition to N2 (ΔH = 47.9 kcal/mol) and the exothermicity of H2 addition to acetylene (ΔH = -42.0 kcal/mol), less than half is due to a stronger π bond in N2 than in acetylene. The other major contributor to the difference of 89.9 kcal/mol between the enthalpies of hydrogenation of N2 and acetylene is that the pair of N-H bonds that are created in the addition of H2 to N2 are significantly weaker than the pair of C-H bonds that are created in the addition of H2 to acetylene. The reasons for this large difference between the strengths of the N-H bonds in E-HN═NH and the C-H bonds in H2C═CH2 are analyzed and discussed.

  9. Residue cluster additivity of thermodynamic stability in the hydrophobic core of mesophile vs. hyperthermophile rubredoxins.

    PubMed

    LeMaster, David M; Hernández, Griselda

    2007-02-01

    The branched sidechain residues 24 and 33 in the hydrophobic core of rubredoxin differ between the Clostridium pasteurianum (Cp) and Pyrococcus furiosus (Pf) sequences. Their X-ray structures indicate that these two sidechains are in van der Waals contact with each other, while neither appears to significantly interact with the other nonconserved residues. The simultaneous interchange of residues 24 and 33 between the Cp and Pf rubredoxin sequences yield a complementary pair of hybrid proteins for which the sum of their thermodynamic stabilities equals that of the parental rubredoxins. The 1.2 kcal/mol change arising from this two residues interchange accounts for 21% of the differential thermodynamic stability between the mesophile and hyperthermophile proteins. The additional interchange of the sole nonconserved aromatic residue in the hydrophobic core yields a 0.78 kcal/mol deviation from thermodynamic additivity.

  10. Thermodynamic method of calculating the effect of alloying additives on interphase interaction in composite materials

    NASA Technical Reports Server (NTRS)

    Tuchinsky, L. I.

    1986-01-01

    The effect of alloying additives to the matrix of a composite on the high temperature solubility rate of a single component fiber was analyzed thermodynamically. With an example of binary Ni alloys, with Group IV-VI transition metals reinforced with W fibers, agreement between the calculated and experimental data was demonstrated.

  11. 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.

  12. CFD analysis of thermodynamic cycles in a pulse tube refrigerator

    NASA Astrophysics Data System (ADS)

    Chen, Ling; Zhang, Yu; Luo, Ercang; Li, Teng; Wei, Xiaolin

    2010-11-01

    The objectives of this paper are to study the thermodynamic cycles in an inertance tube pulse tube refrigerator (ITPTR) by means of CFD method. The simulation results show that gas parcels working in different parts of ITPTR undergo different thermodynamic cycles. The net effects of those thermodynamic cycles are pumping heat from the low temperature part to the high temperature part of the system. The simulation results also show that under different frequencies of piston movement, the gas parcels working in the same part of the system will undergo the same type of thermodynamic cycles. The simulated thermal cycles are compared with those thermodynamic analysis results from a reference. Comparisons show that both CFD simulations and theoretical analysis predict the same type of thermal cycles at the same location. However, only CFD simulation can give the quantitative results, while the thermodynamic analysis is still remaining in quality.

  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. Additional strange hadrons from QCD thermodynamics and strangeness freezeout in heavy ion collisions.

    PubMed

    Bazavov, A; Ding, H-T; Hegde, P; Kaczmarek, O; Karsch, F; Laermann, E; Maezawa, Y; Mukherjee, Swagato; Ohno, H; Petreczky, P; Schmidt, C; Sharma, S; Soeldner, W; Wagner, M

    2014-08-15

    We compare lattice QCD results for appropriate combinations of net strangeness fluctuations and their correlations with net baryon number fluctuations with predictions from two hadron resonance gas (HRG) models having different strange hadron content. The conventionally used HRG model based on experimentally established strange hadrons fails to describe the lattice QCD results in the hadronic phase close to the QCD crossover. Supplementing the conventional HRG with additional, experimentally uncharted strange hadrons predicted by quark model calculations and observed in lattice QCD spectrum calculations leads to good descriptions of strange hadron thermodynamics below the QCD crossover. We show that the thermodynamic presence of these additional states gets imprinted in the yields of the ground-state strange hadrons leading to a systematic 5-8 MeV decrease of the chemical freeze-out temperatures of ground-state strange baryons.

  15. A Simple Thermodynamic Analysis of Photosynthesis

    NASA Astrophysics Data System (ADS)

    Albarrán-Zavala, E.; Angulo-Brown, F.

    2007-12-01

    In this paper we present a comparative study of nine photosynthetic pathways bymeans of their thermodynamic performance. The comparison is made by using the thermalefficiency of light-to-chemical energy conversion and the so-called ecological criterionarising from finite-time thermodynamics. The application of both criteria leads tophotosynthesis made by metaphytes and non sulfur purple bacteria as those of bestthermodynamic performance. In spite of the simplicity of our thermodynamic approachsome insights over the low overall efficiency of photosynthesis is suggested.

  16. 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…

  17. Quantum-chemical model evaluations of thermodynamics and kinetics of oxygen atom additions to narrow nanotubes.

    PubMed

    Slanina, Zdenĕk; Stobinski, Leszek; Tomasik, Piotr; Lin, Hong-Ming; Adamowicz, Ludwik

    2003-01-01

    This paper reports a computational study of oxygen additions to narrow nanotubes, a problem frequently studied with fullerenes. In fact, fullerene oxides were the first observed fullerene derivatives, and they have naturally attracted the attention of both experiment and theory. C60O had represented a long-standing case of experiment-theory disagreement, and there has been a similar problem with C60O2. The disagreement has been explained by kinetic rather than thermodynamic control. In this paper a similar computational approach is applied to narrow nanotubes. Recently, very narrow nanotubes have been observed with a diameter of 5 A and even with a diameter of 4 A. It has been supposed that the narrow nanotubes are closed by fragments of small fullerenes like C36 or C20. In this report we perform calculations for oxygen additions to such model nanotubes capped by fragments of D2d C36, D4d C32, and Ih C20 fullerenic cages (though the computational models have to be rather short). The three models have the following carbon contents: C84, C80, and C80. Both thermodynamic enthalpy changes and kinetic activation barriers for oxygen addition to six selected bonds are computed and analyzed. The lowest isomer (thermodynamically the most stable) is never of the 6/6 type, that is, the enthalpically favored structures are produced by oxygen additions to the nanotube tips. Interestingly enough, the lowest energy isomer has, for the D2d C36 and D4d C32 cases, the lowest kinetic activation barrier as well.

  18. Thermodynamic Analysis of Ionic Compounds: Synthetic Applications.

    ERIC Educational Resources Information Center

    Yoder, Claude H.

    1986-01-01

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

  19. 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.

  20. The thermodynamic analysis of weak protein interactions using sedimentation equilibrium

    PubMed Central

    Dolinska, Monika B.; Wingfield, Paul T.

    2014-01-01

    Proteins self-associate to form dimers and tetramers. Purified proteins are used to study the thermodynamics of protein interactions using the analytical ultracentrifuge. In this approach, monomer – dimer equilibrium constants are directly measured at various temperatures. Data analysis is used to derive thermodynamic parameters such as Gibbs free energy, enthalpy and entropy which can predict which major forces are involved in protein association. PMID:25081741

  1. 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.

  2. 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.

  3. Thermodynamic and Structural Properties of Methanol-Water Solutions Using Non-Additive Interaction Models

    PubMed Central

    Zhong, Yang; Warren, G. Lee; Patel, Sandeep

    2014-01-01

    We study bulk structural and thermodynamic properties of methanol-water solutions via molecular dynamics simulations using novel interaction potentials based on the charge equilibration (fluctuating charge) formalism to explicitly account for molecular polarization at the atomic level. The study uses the TIP4P-FQ potential for water-water interactions, and the CHARMM-based (Chemistry at HARvard Molecular Mechanics) fluctuating charge potential for methanol-methanol and methanol-water interactions. In terms of bulk solution properties, we discuss liquid densities, enthalpies of mixing, dielectric constants, self-diffusion constants, as well as structural properties related to local hydrogen bonding structure as manifested in radial distribution functions and cluster analysis. We further explore the electronic response of water and methanol in the differing local environments established by the interaction of each species predominantly with molecules of the other species. The current force field for the alcohol-water interaction performs reasonably well for most properties, with the greatest deviation from experiment observed for the excess mixing enthalpies, which are predicted to be too favorable. This is qualitatively consistent with the overestimation of the methanol-water gas-phase interaction energy for the lowest-energy conformer (methanol as proton donor). Hydration free energies for methanol in TIP4P-FQ water are predicted to be −5.6±0.2 kcal/mole, in respectable agreement with the experimental value of −5.1 kcal/mole. With respect to solution micro-structure, the present cluster analysis suggests that the micro-scale environment for concentrations where select thermodynamic quantities reach extremal values is described by a bi-percolating network structure. PMID:18074339

  4. Thermodynamic analysis of volatile organometallic fission products.

    PubMed

    Auxier, John D; Jordan, Jacob A; Stratz, S Adam; Shahbazi, Shayan; Hanson, Daniel E; Cressy, Derek; Hall, Howard L

    The ability to perform rapid separations in a post nuclear weapon detonation scenario is an important aspect of national security. In the past, separations of fission products have been performed using solvent extraction, precipitation, etc. The focus of this work is to explore the feasibility of using thermochromatography, a technique largely employed in superheavy element chemistry, to expedite the separation of fission products from fuel components. A series of fission product complexes were synthesized and the thermodynamic parameters were measured using TGA/DSC methods. Once measured, these parameters were used to predict their retention times using thermochromatography.

  5. Microtextured superhydrophobic surfaces: a thermodynamic analysis.

    PubMed

    Li, W; Amirfazli, A

    2007-04-28

    Superhydrophobic surfaces with a contact angle (CA) larger than 150 degrees have recently attracted great interest in both academic research and practical applications due to their water-repellent or self-cleaning properties. However, thermodynamic mechanisms responsible for the effects of various factors such as surface geometry and chemistry, liquids, and environmental sources have not been well understood. In this study, a pillar microtexture, which has been intensively investigated in experiments, is chosen as a typical example and thermodynamically analyzed in detail. To gain a comprehensive insight into superhydrophobic behavior, the roles of pillar height, width and spacing (or roughness and solid fraction), intrinsic CA, drop size, and vibrational energy are systematically investigated. Free energy (FE) and free energy barrier (FEB) are calculated using a simple and robust model. Based on the calculations of FE and FEB, various CAs, including apparent, equilibrium (stable), advancing and receding CAs, and contact angle hysteresis (CAH) can be determined. Especially, the design of practical superhydrophobic surfaces is emphasized in connection with the transition between noncomposite and composite states; a criterion for judging such transition is proposed. The theoretical results are consistent with the Wenzel's and the Cassie's equations for equilibrium CA values and experimental observations. Furthermore, based on these results and the proposed criterion, some general principles to achieve superhydrophobic performance are suggested.

  6. 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.

  7. 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.

  8. Thermodynamics-based Metabolite Sensitivity Analysis in metabolic networks.

    PubMed

    Kiparissides, A; Hatzimanikatis, V

    2017-01-01

    The increasing availability of large metabolomics datasets enhances the need for computational methodologies that can organize the data in a way that can lead to the inference of meaningful relationships. Knowledge of the metabolic state of a cell and how it responds to various stimuli and extracellular conditions can offer significant insight in the regulatory functions and how to manipulate them. Constraint based methods, such as Flux Balance Analysis (FBA) and Thermodynamics-based flux analysis (TFA), are commonly used to estimate the flow of metabolites through genome-wide metabolic networks, making it possible to identify the ranges of flux values that are consistent with the studied physiological and thermodynamic conditions. However, unless key intracellular fluxes and metabolite concentrations are known, constraint-based models lead to underdetermined problem formulations. This lack of information propagates as uncertainty in the estimation of fluxes and basic reaction properties such as the determination of reaction directionalities. Therefore, knowledge of which metabolites, if measured, would contribute the most to reducing this uncertainty can significantly improve our ability to define the internal state of the cell. In the present work we combine constraint based modeling, Design of Experiments (DoE) and Global Sensitivity Analysis (GSA) into the Thermodynamics-based Metabolite Sensitivity Analysis (TMSA) method. TMSA ranks metabolites comprising a metabolic network based on their ability to constrain the gamut of possible solutions to a limited, thermodynamically consistent set of internal states. TMSA is modular and can be applied to a single reaction, a metabolic pathway or an entire metabolic network. This is, to our knowledge, the first attempt to use metabolic modeling in order to provide a significance ranking of metabolites to guide experimental measurements.

  9. Revisiting thermodynamics and kinetic diffusivities of uranium–niobium with Bayesian uncertainty analysis

    DOE PAGES

    Duong, Thien C.; Hackenberg, Robert Errol; Landa, Alex; ...

    2016-09-20

    In this paper, thermodynamic and kinetic diffusivities of uranium–niobium (U–Nb) are re-assessed by means of the CALPHAD (CALculation of PHAse Diagram) methodology. In order to improve the consistency and reliability of the assessments, first-principles calculations are coupled with CALPHAD. In particular, heats of formation of γ -U–Nb are estimated and verified using various density-functional theory (DFT) approaches. These thermochemistry data are then used as constraints to guide the thermodynamic optimization process in such a way that the mutual-consistency between first-principles calculations and CALPHAD assessment is satisfactory. In addition, long-term aging experiments are conducted in order to generate new phase equilibriamore » data at the γ2/α+γ2 boundary. These data are meant to verify the thermodynamic model. Assessment results are generally in good agreement with experiments and previous calculations, without showing the artifacts that were observed in previous modeling. The mutual-consistent thermodynamic description is then used to evaluate atomic mobility and diffusivity of γ-U–Nb. Finally, Bayesian analysis is conducted to evaluate the uncertainty of the thermodynamic model and its impact on the system's phase stability.« less

  10. Revisiting thermodynamics and kinetic diffusivities of uranium–niobium with Bayesian uncertainty analysis

    SciTech Connect

    Duong, Thien C.; Hackenberg, Robert Errol; Landa, Alex; Honarmandi, Pejman; Talapatra, Anjana; Volz, Heather Michelle; Llobet, Anna Megias; Smith, Alice Iulia; King, Graham Missell; Bajaj, Saurabh; Ruban, Andrei; Vitos, Levente; Turchi, Patrice E. A.; Arroyave, Raymundo

    2016-09-20

    In this paper, thermodynamic and kinetic diffusivities of uranium–niobium (U–Nb) are re-assessed by means of the CALPHAD (CALculation of PHAse Diagram) methodology. In order to improve the consistency and reliability of the assessments, first-principles calculations are coupled with CALPHAD. In particular, heats of formation of γ -U–Nb are estimated and verified using various density-functional theory (DFT) approaches. These thermochemistry data are then used as constraints to guide the thermodynamic optimization process in such a way that the mutual-consistency between first-principles calculations and CALPHAD assessment is satisfactory. In addition, long-term aging experiments are conducted in order to generate new phase equilibria data at the γ2/α+γ2 boundary. These data are meant to verify the thermodynamic model. Assessment results are generally in good agreement with experiments and previous calculations, without showing the artifacts that were observed in previous modeling. The mutual-consistent thermodynamic description is then used to evaluate atomic mobility and diffusivity of γ-U–Nb. Finally, Bayesian analysis is conducted to evaluate the uncertainty of the thermodynamic model and its impact on the system's phase stability.

  11. 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.

  12. Thermodynamic analysis and optimization of the cycle parameters of regenerative gas-turbine converters for solar power stations /SGTS/

    NASA Astrophysics Data System (ADS)

    Drabkin, L. M.

    A thermodynamic analysis compares the efficiency of a simple solar-driven helium gas turbine generator with two improved schemes employing regeneration of heat from the recirculating working fluid. One scheme uses a recuperator based on direct heat exchange while the other recovers heat by thermoelectric conversion in addition to the recuperator. The specific area of the heat exchange surface is calculated along with other system parameters for maximum thermodynamic cycle efficiency. Gains of up to 15% are demonstrated.

  13. 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.

  14. Protein conjugation with PAMAM nanoparticles: Microscopic and thermodynamic analysis.

    PubMed

    Chanphai, P; Froehlich, E; Mandeville, J S; Tajmir-Riahi, H A

    2017-02-01

    PAMAM dendrimers form strong protein conjugates that are used in drug delivery systems. We report the thermodynamic and binding analysis of polyamidoamine (PAMAM-G4) conjugation with human serum albumin (HSA), bovine serum albumin (BSA) and milk beta-lactoglobulin (b-LG) in aqueous solution at physiological pH. Hydrophobicity played a major role in PAMAM-protein interactions with more hydrophobic b-LG forming stronger polymer-protein conjugates. Thermodynamic parameters showed PAMAM-protein bindings occur via hydrophobic and H-bonding contacts for b-LG, while van der waals and H-bonding interactions prevail in HSA and BSA-polymer conjugates. The protein loading efficacy was 45-55%. PAMAM complexation induced major alterations of protein conformation. TEM images show major polymer morphological changes upon protein conjugation.

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

    PubMed

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

    2014-12-07

    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.

  16. Thermodynamic analysis of resources used in manufacturing processes.

    PubMed

    Gutowski, Timothy G; Branham, Matthew S; Dahmus, Jeffrey B; Jones, Alissa J; Thiriez, Alexandre

    2009-03-01

    In this study we use a thermodynamic framework to characterize the material and energy resources used in manufacturing processes. The analysis and data span a wide range of processes from "conventional" processes such as machining, casting, and injection molding, to the so-called "advanced machining" processes such as electrical discharge machining and abrasive waterjet machining, and to the vapor-phase processes used in semiconductor and nanomaterials fabrication. In all, 20 processes are analyzed. The results show that the intensity of materials and energy used per unit of mass of material processed (measured either as specific energy or exergy) has increased by at least 6 orders of magnitude over the past several decades. The increase of material/energy intensity use has been primarily a consequence of the introduction of new manufacturing processes, rather than changes in traditional technologies. This phenomenon has been driven by the desire for precise small-scale devices and product features and enabled by stable and declining material and energy prices over this period. We illustrate the relevance of thermodynamics (including exergy analysis) for all processes in spite of the fact that long-lasting focus in manufacturing has been on product quality--not necessarily energy/material conversion efficiency. We promote the use of thermodynamics tools for analysis of manufacturing processes within the context of rapidly increasing relevance of sustainable human enterprises. We confirm that exergy analysis can be used to identify where resources are lost in these processes, which is the first step in proposing and/or redesigning new more efficient processes.

  17. 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.

  18. Thermodynamics of small systems embedded in a reservoir: a detailed analysis of finite size effects

    NASA Astrophysics Data System (ADS)

    Schnell, Sondre K.; Vlugt, Thijs J. H.; Simon, Jean-Marc; Bedeaux, Dick; Kjelstrup, Signe

    2012-06-01

    We present a detailed study on the finite size scaling behaviour of thermodynamic properties for small systems of particles embedded in a reservoir. Previously, we derived that the leading finite size effects of thermodynamic properties for small systems scale with the inverse of the linear length of the small system, and we showed how this can be used to describe systems in the thermodynamic limit [Chem. Phys. Lett. 504, 199 (2011)]. This approach takes into account an effective surface energy, as a result of the non-periodic boundaries of the small embedded system. Deviations from the linear behaviour occur when the small system becomes very small, i.e. smaller than three times the particle diameter in each direction. At this scale, so-called nook- and corner effects will become important. In this work, we present a detailed analysis to explain this behaviour. In addition, we present a model for the finite size scaling when the size of the small system is of the same order of magnitude as the reservoir. The developed theory is validated using molecular simulations of systems containing Lennard-Jones and WCA particles, and leads to significant improvements over our previous approach. Our approach eventually leads to an efficient method to compute the thermodynamic factor of macroscopic systems from finite size scaling, which is for example required for converting Fick and Maxwell-Stefan transport diffusivities.

  19. 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

  20. Thermodynamic performance analysis of ramjet engine at wide working conditions

    NASA Astrophysics Data System (ADS)

    Ou, Min; Yan, Li; Tang, Jing-feng; Huang, Wei; Chen, Xiao-qian

    2017-03-01

    Although ramjet has the advantages of high-speed flying and higher specific impulse, the performance parameters will decline seriously with the increase of flight Mach number and flight height. Therefore, the investigation on the thermodynamic performance of ramjet is very crucial for broadening the working range. In the current study, a typical ramjet model has been employed to investigate the performance characteristics at wide working conditions. First of all, the compression characteristic analysis is carried out based on the Brayton cycle. The obtained results show that the specific cross-section area (A2 and A5) and the air-fuel ratio (f) have a great influence on the ramjet performance indexes. Secondly, the thermodynamic calculation process of ramjet is given from the view of the pneumatic thermal analysis. Then, the variable trends of the ramjet performance indexes with the flow conditions, the air-fuel ratio (f), the specific cross-sectional area (A2 and A5) under the fixed operating condition, equipotential dynamic pressure condition and variable dynamic pressure condition have been discussed. Finally, the optimum value of the specific cross-sectional area (A5) and the air-fuel ratio (f) of the ramjet model at a fixed work condition (Ma=3.5, H=12 km) are obtained.

  1. 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.

  2. Thermodynamic Analysis and Optimization Based on Exergy Flow for a Two-Staged Pulse Tube Refrigerator

    DTIC Science & Technology

    2010-01-01

    model is convenient for thermodynamic analysis and optimization and shows the important characteristics of two-stage PTRs. Exergy comes into the system ...THERMODYNAMIC ANALYSIS AND OPTIMIZATION BASED ON EXERGY FLOW FOR A TWOSTAGED PULSE TUBE REFRIGERATOR A. Razani, T. Fraser, C. Dodson, and T. Roberts...Prescribed by ANSI Std Z39-18 THERMODYNAMIC ANALYSIS AND OPTIMIZATION BASED ON EXERGY FLOW FOR A TWO-STAGED PULSE TUBE REFRIGERATOR A. Razani 1,3

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Thermodynamic analysis of a seeded magnetogasdynamic combustion plasma

    NASA Astrophysics Data System (ADS)

    Bose, T. K.

    1986-06-01

    A Faraday type magnetogasdynamic (MGD) seeded combustion gas plasma generated by burning fuel gas in air with up to 50 percent oxygen enrichment in stoichiometric ratio to determine the sources of thermodynamic irreversibility has been studied. For preliminary determination of the adiabatic flame temperature at one bar, five different fuel gases are studied, out of which four are derivatives of coal: water gas, Lurgi gas, Koppers-Totzek gas, producer gas, and methane. As seed, cesium, potassium and sodium in seed to fuel gas mass ratio of 0.01 to 0.03 in appropriate compound form are used and the equilibrium composition is calculated at 1 bar and temperature from 1500 to 3000 K by considering 14 species in the mixture. Subsequently, a Mollier enthalpy-entropy chart is produced for water gas burning with 50 percent oxygen enriched air and one percent potassium seed to fuel gas mass ratio in the above temperature range and in the pressure range of 0.01 to 100 bars. Finally, from the thermodynamic analysis it is shown that the electrical power generation per unit length is more and irreversibility due to the ohmic heating is less if the temperature is high.

  8. 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.

  9. Thermodynamic analysis and optimization of air-cooled heat exchangers

    NASA Astrophysics Data System (ADS)

    Salimpour, Mohammad Reza; Bahrami, Zabihollah

    2011-01-01

    In the present study, a thermodynamic second-law analysis was performed to investigate the effects of different geometry and flow parameters on the air-cooled heat exchanger performance. For this purpose, the entropy generation due to heat transfer and pressure loss of internal and external flows of the air-cooled heat exchanger was calculated; and it was observed that the total entropy generation has a minimum at special tube-side Reynolds number. Also, it was seen that the increasing of the tube-side Reynolds number resulted in the rise of the irreversibility of the air-cooled heat exchanger. The results also showed when air-side Reynolds number decreased, the entropy generation rate of the external flow reduced. Finally, based on the computed results, a new correlation was developed to predict the optimum Reynolds number of the tube-side fluid flow.

  10. 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.

  11. Thermodynamical analysis of acoustical perturbations in the bronchial tree

    NASA Astrophysics Data System (ADS)

    Puente, Margarita; Perez-Guerrero, Armando; Alvarado, Manuel

    2002-11-01

    In the airways, very complex flows occur because of different conditions and the existence of a lot of complications: constantly changing temperature and pressure during the respiration process, a normally turbulent flow in the trachea which, in heavy breathing, remains so in the first three or four generations of airways, changes of the direction of the flow over the breathing cycle, from inspiration to expiration, etc. We also know the air that flows in the bronchial tree is perturbed by several sources such as the heart and the circulatory system, the diaphragm and stomach movements, etc., which produce sound waves. Thus an acoustical analysis of the phenomenon can lead us to a physical model which could help us to better understand the phenomena and to demonstrate the importance to clinical applications such as the pneumocardiograms. To this purpose we use a thermodynamical model that originally was developed to analyze supersonic air jets to explain the production of shock waves in the bronchial tree.

  12. Thermodynamic analysis of the carbothermic reduction of a high-phosphorus oolitic iron ore by FactSage

    NASA Astrophysics Data System (ADS)

    Yu, Wen; Tang, Qiong-yao; Chen, Jiang-an; Sun, Ti-chang

    2016-10-01

    A thermodynamic analysis of the carbothermic reduction of high-phosphorus oolitic iron ore (HPOIO) was conducted by the FactSage thermochemical software. The effects of temperature, C/O ratio, additive types, and dosages both on the reduction of fluorapatite and the formation of liquid slag were studied. The results show that the minimum thermodynamic reduction temperature of fluorapatite by carbon decreases to about 850°C, which is mainly ascribed to the presence of SiO2, Al2O3, and Fe. The reduction rate of fluorapatite increases and the amount of liquid slag decreases with the rise of C/O ratio. The reduction of fluorapatite is hindered by the addition of CaO and Na2CO3, thereby allowing the selective reduction of iron oxides upon controlled C/O ratio. The thermodynamic results obtain in the present work are in good agreement with the experimental results available in the literatures.

  13. Influence of Temperature on Thermodynamic Properties of Methyl t-Butyl Ether (MTBE) + Gasoline Additives

    NASA Astrophysics Data System (ADS)

    Gonzalez-Olmos, R.; Iglesias, M.; Goenaga, J. M.; Resa, J. M.

    2007-08-01

    The densities and sound speeds of binary mixtures of methyl tert-butyl ether (MTBE) + (benzene, toluene, ethylbenzene, isooctane, tert-butyl alcohol) have been measured at temperatures from 288.15 to 323.15 K and at atmospheric pressure over the complete concentration range. The experimental excess volumes and deviations of isentropic compressibility were calculated. The deviation of isentropic compressibility data have been analyzed in terms of different theoretical models; adequate agreement between the experimental and predicted values is obtained. The data from this study improve the data situation related to gasoline additives and help to understand the MTBE volumetric and acoustic behavior for various chemical systems.

  14. Brownian dynamics of subunit addition-loss kinetics and thermodynamics in linear polymer self-assembly.

    PubMed

    Castle, Brian T; Odde, David J

    2013-12-03

    The structure and free energy of multistranded linear polymer ends evolves as individual subunits are added and lost. Thus, the energetic state of the polymer end is not constant, as assembly theory has assumed. Here we utilize a Brownian dynamics approach to simulate the addition and loss of individual subunits at the polymer tip. Using the microtubule as a primary example, we examined how the structure of the polymer tip dictates the rate at which units are added to and lost from individual protofilaments. We find that freely diffusing subunits arrive less frequently to lagging protofilaments but bind more efficiently, such that there is no kinetic difference between leading and lagging protofilaments within a tapered tip. However, local structure at the nanoscale has up to an order-of-magnitude effect on the rate of addition. Thus, the kinetic on-rate constant, integrated across the microtubule tip (kon,MT), is an ensemble average of the varying individual protofilament on-rate constants (kon,PF). Our findings have implications for both catastrophe and rescue of the dynamic microtubule end, and provide a subnanoscale framework for understanding the mechanism of action of microtubule-associated proteins and microtubule-directed drugs. Although we utilize the specific example of the microtubule here, the findings are applicable to multistranded polymers generally.

  15. 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.

  16. 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.

  17. 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.

  18. 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

  19. 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

  20. 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.

  1. The experimental investigation and thermodynamic analysis of vortex tubes

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

    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.

  2. 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.

  3. 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.

  4. Binding of λ-carrageenan (a food additive) to almond cystatin: An insight involving spectroscopic and thermodynamic approach.

    PubMed

    Siddiqui, Azad Alam; Feroz, Anna; Khaki, Peerzada Shariq Shaheen; Bano, Bilqees

    2017-05-01

    Carrageenan is a high molecular weight linear sulphated polysaccharide, primarily used in food industry as gelling, thickening, and stabilizing agent. Almond milk prepared from almonds is low in fat, but high in antioxidants, energy, proteins, lipids and fibre. Purified almond cystatin was incubated with increasing concentrations of carrageenan at 25°C for different time interval and significant loss in inhibitory activity was observed. Interaction between carrageenan and cystatin resulted in complex formation as depicted by the decrease in fluorescence intensity with increase in the concentration of carrageenan. Stern-volmer analysis of fluorescence quenching data showed binding constant to be 1.84±0.20×10(4)M(-1) and number of binding sites close to unity. These results were further confirmed by supporting results obtained in UV-vis spectroscopy. FTIR analysis shows significant shift in the peak intensity and this change clearly depict change in the structure of cystatin from that of α helix to β-sheet. CD spectra further confirmed the structural transition of the cystatin from α helix to β-sheet structure on interaction with increased concentrations of carrageenan. The contributing thermodynamic parameters were determined by ITC. The negative ΔH° and positive TΔS° values suggest involvement of electrostatic forces and hydrophobic interaction in the formation of the λ-carrageenan-cystatin complex.

  5. 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.

  6. 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.

  7. 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.

  8. Thermodynamic analysis of antagonist and agonist interactions with dopamine receptors.

    PubMed

    Duarte, E P; Oliveira, C R; Carvalho, A P

    1988-03-01

    The binding of [3H]spiperone to dopamine D-2 receptors and its inhibition by antagonists and agonists were examined in microsomes derived from the sheep caudate nucleus, at temperatures between 37 and 1 degree C, and the thermodynamic parameters of the binding were evaluated. The affinity of the receptor for the antagonists, spiperone and (+)-butaclamol, decreased as the incubation temperature decreased; the affinity for haloperidol did not further decrease at temperatures below 15 degrees C. The binding of the antagonists was associated with very large increases in entropy, as expected for hydrophobic interactions. The enthalpy and entropy changes associated with haloperidol binding were dependent on temperature, in contrast to those associated with spiperone and (+)-butaclamol. The magnitude of the entropy increase associated with the specific binding of the antagonists did not correlate with the degree of lipophilicity of these drugs. The data suggest that, in addition to hydrophobic forces, other forces are also involved in the antagonist-dopamine receptor interactions, and that a conformational change of the receptor could occur when the antagonist binds. Agonist binding data are consistent with a two-state model of the receptor, a high-affinity state (RH) and a low-affinity state (RL). The affinity of dopamine binding to the RH decreased with decreasing temperatures below 20 degrees C, whereas the affinity for the RL increased at low temperatures. In contrast, the affinity of apomorphine for both states of receptor decreased as the temperature decreased from 30 to 8 degrees C. A clear distinction between the energetics of high-affinity and low-affinity agonist binding was observed. The formation of the high-affinity complex was associated with larger increases in enthalpy and entropy than the interaction with the low-affinity state was. The results suggest that the interaction of the receptor with the G-proteins, induced or stabilized by the binding of

  9. 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.

  10. 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.

  11. 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.

  12. The Analysis of Spontaneous Processes Using Equilibrium Thermodynamics

    ERIC Educational Resources Information Center

    Honig, J. M.; Ben-Amotz, Dor

    2006-01-01

    The derivations based on the use of deficit functions provide a simple means of demonstrating the extremism conditions that are applicable to various thermodynamics function. The method shows that the maximum quantity of work is available from a system only when the processes are carried out reversibly since irreversible (spontaneous)…

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

    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.

  14. 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.

  15. Thermodynamic Mechanism Analysis of Calcification Roasting Process of Bastnaesite Concentrates

    NASA Astrophysics Data System (ADS)

    Cen, Peng; Wu, Wenyuan; Bian, Xue

    2017-03-01

    A novel calcification roasting decomposition method for bastnaesite concentrates has been proposed previously. In this work, the thermodynamic mechanism was investigated via simultaneous measurements of thermogravimetry and differential thermal analyses, combined with X-ray diffraction analyses. Rare earth oxides and calcium fluorides were generated after bastnaesite and calcium hydroxide broke down, respectively. The generation and decomposition of calcium carbonate occurred at the same time. Considering the difficulties in obtaining pure substances, theoretical calculations were applied to determine the standard enthalpy of formation (Δf H 298), Gibbs free energies of formation (Δf G 298), and heat capacities at constant pressure (C p) of some rare earth minerals (CeFCO3 and CeOF). Based on these results, the standard Gibbs energy of reaction at different temperatures (Δr G T) was ascertained, and the major reactions were verified to be thermodynamically reasonable.

  16. Self-association of plant wax components: a thermodynamic analysis.

    PubMed

    Casado, C G; Heredia, A

    2001-01-01

    Excess specific heat, C(p)()(E), of binary mixtures of selected components of plant cuticular waxes has been determined. This thermodynamic parameter gives an explanation of the special molecular arrangement in crystalline and amorphous zones of plant waxes. C(p)()(E) values indicate that hydrogen bonding between chains results in the formation of amorphous zones. Conclusions on the self-asembly process of plant waxes have been also made.

  17. 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.

  18. Thermodynamic analysis of ecosystem based on remote sensing data

    NASA Astrophysics Data System (ADS)

    Sandlerskiy, Robert; Puzachenko, Yurii

    2010-05-01

    key words: ecosystem thermodynamic, energy balance, exergy, Transformation of matter and energy in plant associations and their relationship with other parts of the ecosystem are being determined by the physiological processes in plants. Accordingly, to identify general patterns of ecosystem energy transformation, assessment of an energy balance components reflecting the nature of physiological processes: photosynthesis, transpiration (of which carbon balance is evaluated), water and minerals exchange, is required. Assessment of the main energy variables for ecosystems is possible on the basis of information-thermodynamic approach in which the ecosystem - is an open system, producing yield for self-maintenance on its structure through the conversion of solar energy. In doing so, the distribution of energy absorbed by balance components depends on the structure of the system that determines the nonequilibrium energy conversion. In the information-thermodynamic approach essential component in the transformation of solar energy is exergy - the maximum work that a thermodynamic system may commit during its transition from the current state to the state of equilibrium with the environment. Exergy sometimes called system yield, it is the function of the distance between the current state of the system and thermodynamic equilibrium. Relating to ecosystems, exergy - part of absorbed solar energy, spend on biological productivity and evapotranspiration (exergy of solar radiation). The rest goes into the bound energy - energy transition in the heat flow and entropy, and in increment of internal energy - system energy accumulation wich in its turn spend on maintenance of intercomponent and interspecific interactions, local cycles. Get estimation of energy balance for the entire set of ecosystems based on ground-based measurements is virtually impossible. Such assessments are possible on the basis of remote sensing data, which show the energetic state of the Earth's surface at

  19. [Total analysis of organic rubber additives].

    PubMed

    He, Wen-Xuan; Robert, Shanks; You, Ye-Ming

    2010-03-01

    In the present paper, after middle pressure chromatograph separation using both positive phase and reversed-phase conditions, the organic additives in ethylene-propylene rubber were identified by infrared spectrometer. At the same time, by using solid phase extraction column to maintain the main component-fuel oil in organic additves to avoid its interfering with minor compounds, other organic additves were separated and analysed by GC/Ms. In addition, the remaining active compound such as benzoyl peroxide was identified by CC/Ms, through analyzing acetone extract directly. Using the above mentioned techniques, soften agents (fuel oil, plant oil and phthalte), curing agent (benzoylperoxide), vulcanizing accelerators (2-mercaptobenzothiazole, ethyl thiuram and butyl thiuram), and antiagers (2, 6-Di-tert-butyl-4-methyl phenol and styrenated phenol) in ethylene-propylene rubber were identified. Although the technique was established in ethylene-propylene rubber system, it can be used in other rubber system.

  20. 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.

  1. 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.

  2. Plasma gasification of carbonaceous wastes: thermodynamic analysis and experiment

    NASA Astrophysics Data System (ADS)

    Messerle, V. E.; Mosse, A. L.; Ustimenko, A. B.

    2016-07-01

    Thermodynamic calculations of the plasma gasification process of carbonaceous wastes in air and steam ambient were carried out. A maximum yield of synthesis gas in such processes is predicted to be achieved at a temperature of 1600 K. On a specially developed plasma facility, plasma gasification experiments were performed for carbonaceous wastes. From the organic mass of carbonaceous waste and from its mineral mass, respectively, a high-calorific syngas and a neutral slag consisting predominantly of ferric carbide, calcium monosilicate, silica and iron, were obtained. A comparison between the experiment and the calculations has shown a good consistency between the data.

  3. 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.

  4. Thermodynamic analysis of contamination by alloying elements in aluminum recycling.

    PubMed

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

    2010-07-15

    In previous studies on the physical chemistry of pyrometallurgical processing of aluminum scrap, only a limited number of thermodynamic parameters, such as the Gibbs free energy change of impurity reactions and the variation of activity of an impurity in molten aluminum, were taken into account. In contrast, in this study we thermodynamically evaluated the quantitative removal limit of impurities during the remelting of aluminum scrap; all relevant parameters, such as the total pressure, the activity coefficient of the target impurity, the temperature, the oxygen partial pressure, and the activity coefficient of oxidation product, were considered. For 45 elements that usually occur in aluminum products, the distribution ratios among the metal, slag, and gas phases in the aluminum remelting process were obtained. Our results show that, except for elements such as Mg and Zn, most of the impurities occurred as troublesome tramp elements that are difficult to remove, and our results also indicate that the extent to which the process parameters such as oxygen partial pressure, temperature, and flux composition can be changed in aluminum production is quite limited compared to that for iron and copper production, owing to aluminum's relatively low melting point and strong affinity for oxygen. Therefore, the control of impurities in the disassembly process and the quality of scrap play important roles in suppressing contamination in aluminum recycling.

  5. 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.

  6. Thermodynamic and structural analysis of homodimeric proteins: model of β-lactoglobulin.

    PubMed

    Burgos, Inés; Dassie, Sergio A; Villarreal, Marcos A; Fidelio, Gerardo D

    2012-02-01

    The energetics of protein homo-oligomerization was analyzed in detail with the application of a general thermodynamic model. We have studied the thermodynamic aspects of protein-protein interaction employing β-lactoglobulin A from bovine milk at pH=6.7 where the protein is mainly in its dimeric form. We performed differential calorimetric scans at different total protein concentration and the resulting thermograms were analyzed with the thermodynamic model for oligomeric proteins previously developed. The thermodynamic model employed, allowed the prediction of the sign of the enthalpy of dimerization, the analysis of complex calorimetric profiles without transitions baselines subtraction and the obtainment of the thermodynamic parameters from the unfolding and the association processes and the compared with association parameters obtained with Isothermal Titration Calorimetry performed at different temperatures. The dissociation and unfolding reactions were also monitored by Fourier-transform infrared spectroscopy and the results indicated that the dimer of β-lactoglobulin (N(2)) reversibly dissociates into monomeric units (N) which are structurally distinguishable by changes in their infrared absorbance spectra upon heating. Hence, it is proposed that β-lactoglobulin follows the conformational path induced by temperature:N(2)⇌2N⇌2D. The general model was validated with these results indicating that it can be employed in the study of the thermodynamics of other homo-oligomeric protein systems.

  7. Analysis of Arctic Cloud Thermodynamic Phase Susceptibility to Aerosols.

    NASA Astrophysics Data System (ADS)

    Coopman, Q.; Garrett, T. J.; Riedi, J.; Eckhardt, S.; Stohl, A.

    2014-12-01

    Even if Arctic is remote from industrialized areas, this region is influenced by elevated concentration of aerosols from mid-latitude, especially during winter. This is mainly due to the decrease of wet scavenging and the surface temperature inversion, both acting as a trap for the atmospheric particles. Aerosols play a key role on cloud's microphysics, because they act as Cloud Condensation Nuclei (CCN) or Ice Nuclei (IN). Both nuclei influence directly on cloud's presence and formation, potentially impacting also thermodynamic phase transition through different mechanisms, which in turn affect cloud radiative properties and forcing. In our study we used two sets of data: i) A combination of POLDER-3/PARASOL and MODIS/AQUA satellite measurements to retrieve cloud properties; ii) The numerical transport model FLEXPART which use carbon monoxide tracer to inform on concentration of biomass burning and anthropogenic aerosols. The main advantage of combining these two sets of data is to obtain large statistics about clouds that have been potentially influenced by varied concentrations of aerosol. We report here results of a study in which we analyze potential interaction between clouds and aerosols from biomass burning and anthropogenic sources. We first analyzed the temperature at which thermodynamic phase transition is most likely to occur according to the types and concentrations of aerosols. It is shown a correlation between the temperature of thermodynamic phase transition and aerosols concentrations and type. Unlike we could have expected from previous studies, preliminary analyses suggest that aerosols from anthropogenic sources accelerate the liquid-ice transition whereas aerosols from biomass burning inhibit the transition from water to ice. Different hypotheses can be responsible for this observation and we analyze parameters that can play a role on the transition temperature shift and how aerosols act as an inhibitor or activator of the phase transition, for

  8. Thermodynamics analysis of aluminum plasma transition induced by hypervelocity impact

    NASA Astrophysics Data System (ADS)

    Liu, Zhixiang; Zhang, Qingming; Ju, Yuanyuan

    2016-02-01

    The production of plasmas during hypervelocity meteoroid and space debris impact has been proposed to explain the presence of paleomagnetic fields on the lunar surface, and also the electromagnetic damage to spacecraft electronic devices. Based on Gibbs' ensemble theory, we deduce Saha equation of state and figure out the ionization degree; further, by using the derivation of Clausius-Clapeyron equation, we obtain the entropy increase and latent heat of plasma transition after vaporization; finally, we analyze the conversion efficiency of kinetic energy into internal energy, present two key contradictions, and revise them with the entropy increase, latent heat, and conversion efficiency. We analyze the aluminum plasma transition from multiple perspectives of the equation of state, latent heat of phase transition, and conversion efficiency and propose the internal energy and impact velocity criterion, based on the laws of thermodynamics.

  9. 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.

  10. 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.

  11. Thermodynamic analysis of metal ion-induced protein assembly.

    PubMed

    Herr, Andrew B; Conrady, Deborah G

    2011-01-01

    A large number of biological systems are regulated by metal ion-induced protein assembly. This phenomenon can play a critical role in governing protein function and triggering downstream biological responses. We discuss the basic thermodynamic principles of linked equilibria that pertain to metal ion-induced dimerization and describe experimental approaches useful for studying such systems. The most informative techniques for studying these systems are sedimentation velocity and sedimentation equilibrium analytical ultracentrifugation, although a wide range of other spectroscopic, chromatographic, or qualitative approaches can provide a wealth of useful information. These experimental procedures are illustrated with examples from two systems currently under study: zinc-induced assembly of a staphylococcal protein responsible for intercellular adhesion in bacterial biofilms and calcium-induced dimerization of a human nucleotidase.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. Thermodynamic Analysis of Chemically Reacting Mixtures and Their Kinetics: Example of a Mixture of Three Isomers.

    PubMed

    Pekař, Miloslav

    2016-10-18

    Thermodynamics provides consequences of and restrictions on chemically reacting mixtures, particularly their kinetics, which have not been fully explored. Herein, a comprehensive thermodynamic analysis is illustrated for a reacting mixture of three isomers. The rate equation is first derived on the basis of the results of nonequilibrium continuum thermodynamics of linear fluids, and is then subjected to the requirement of consistency with entropic inequality (the second law). This consistency test involves the correct representation of the reaction rate as a function of affinities. It is shown that entropic inequality restricts the signs or values of coefficients in the constitutive equations for reaction rates/rate constants. The use of reverse rate constants and the identification of thermodynamic and kinetic equilibrium constants are not necessary in this approach. Although the presented thermodynamic analysis works only for independent reactions, the rates of dependent reactions are not excluded from having effects on kinetics. It is shown that the rates of dependent reactions are combined from the rates of independent reactions differently than dependent reactions are combined from independent reactions. The results are compared to the classical mass-action rate equations, and new restrictions on the values of the classical rate constants are derived.

  18. 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

    2014-05-06

    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

  19. Benchmarking the thermodynamic analysis of water molecules around a model beta sheet.

    PubMed

    Huggins, David J

    2012-06-05

    Water molecules play a vital role in biological and engineered systems by controlling intermolecular interactions in the aqueous phase. Inhomogeneous fluid solvation theory provides a method to quantify solvent thermodynamics from molecular dynamics or Monte Carlo simulations and provides an insight into intermolecular interactions. In this study, simulations of TIP4P-2005 and TIP5P-Ewald water molecules around a model beta sheet are used to investigate the orientational correlations and predicted thermodynamic properties of water molecules at a protein surface. This allows the method to be benchmarked and provides information about the effect of a protein on the thermodynamics of nearby water molecules. The results show that the enthalpy converges with relatively little sampling, but the entropy and thus the free energy require considerably more sampling to converge. The two water models yield a very similar pattern of hydration sites, and these hydration sites have very similar thermodynamic properties, despite notable differences in their orientational preferences. The results also predict that a protein surface affects the free energy of water molecules to a distance of approximately 4.0 Å, which is in line with previous work. In addition, all hydration sites have a favorable free energy with respect to bulk water, but only when the water-water entropy term is included. A new technique for calculating this term is presented and its use is expected to be very important in accurately calculating solvent thermodynamics for quantitative application.

  20. Kinetics and Thermodynamics of Reversible Thiol Additions to Mono- and Diactivated Michael Acceptors: Implications for the Design of Drugs That Bind Covalently to Cysteines.

    PubMed

    Krenske, Elizabeth H; Petter, Russell C; Houk, K N

    2016-12-02

    Additions of cysteine thiols to Michael acceptors underpin the mechanism of action of several covalent drugs (e.g., afatinib, osimertinib, ibrutinib, neratinib, and CC-292). Reversible Michael acceptors have been reported in which an additional electron-withdrawing group was added at the α-carbon of a Michael acceptor. We have performed density functional theory calculations to determine why thiol additions to these Michael acceptors are reversible. The α-EWG group stabilizes the anionic transition state and intermediate of the Michael addition, but less intuitively, it destabilizes the neutral adduct. This makes the reverse reaction (elimination) both faster and more thermodynamically favorable. For thiol addition to be reversible, the Michael acceptor must also contain a suitable substituent on the β-carbon, such as an aryl or branched alkyl group. Computations explain how these structural elements contribute to reversibility and the ability to tune the binding affinities and the residence times of covalent inhibitors.

  1. Thermodynamic Behavior Research Analysis of Twin-roll Casting Lead Alloy Strip Process

    NASA Astrophysics Data System (ADS)

    Jiang, Chengcan; Rui, Yannian

    2017-03-01

    The thermodynamic behavior of twin-roll casting (TRC) lead alloy strip process directly affects the forming of the lead strip, the quality of the lead strip and the production efficiency. However, there is little research on the thermodynamics of lead alloy strip at home and abroad. The TRC lead process is studied in four parameters: the pouring temperature of molten lead, the depth of molten pool, the roll casting speed, and the rolling thickness of continuous casting. Firstly, the thermodynamic model for TRC lead process is built. Secondly, the thermodynamic behavior of the TRC process is simulated with the use of Fluent. Through the thermodynamics research and analysis, the process parameters of cast rolling lead strip can be obtained: the pouring temperature of molten lead: 360-400 °C, the depth of molten pool: 250-300 mm, the roll casting speed: 2.5-3 m/min, the rolling thickness: 8-9 mm. Based on the above process parameters, the optimal parameters(the pouring temperature of molten lead: 375-390 °C, the depth of molten pool: 285-300 mm, the roll casting speed: 2.75-3 m/min, the rolling thickness: 8.5-9 mm) can be gained with the use of the orthogonal experiment. Finally, the engineering test of TRC lead alloy strip is carried out and the test proves the thermodynamic model is scientific, necessary and correct. In this paper, a detailed study on the thermodynamic behavior of lead alloy strip is carried out and the process parameters of lead strip forming are obtained through the research, which provide an effective theoretical guide for TRC lead alloy strip process.

  2. 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.

  3. 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

  4. Flavonoid interactions with human transthyretin: combined structural and thermodynamic analysis.

    PubMed

    Trivella, Daniela B B; dos Reis, Caio V; Lima, Luís Maurício T R; Foguel, Débora; Polikarpov, Igor

    2012-10-01

    Transthyretin (TTR) is a carrier protein involved in human amyloidosis. The development of small molecules that may act as TTR amyloid inhibitors is a promising strategy to treat these pathologies. Here we selected and characterized the interaction of flavonoids with the wild type and the V30M amyloidogenic mutant TTR. TTR acid aggregation was evaluated in vitro in the presence of the different flavonoids. The best TTR aggregation inhibitors were studied by Isothermal Titration Calorimetry (ITC) in order to reveal their thermodynamic signature of binding to TTRwt. Crystal structures of TTRwt in complex with the top binders were also obtained, enabling us to in depth inspect TTR interactions with these flavonoids. The results indicate that changing the number and position of hydroxyl groups attached to the flavonoid core strongly influence flavonoid recognition by TTR, either by changing ligand affinity or its mechanism of interaction with the two sites of TTR. We also compared the results obtained for TTRwt with the V30M mutant structure in the apo form, allowing us to pinpoint structural features that may facilitate or hamper ligand binding to the V30M mutant. Our data show that the TTRwt binding site is labile and, in particular, the central region of the cavity is sensible for the small differences in the ligands tested and can be influenced by the Met30 amyloidogenic mutation, therefore playing important roles in flavonoid binding affinity, mechanism and mutant protein ligand binding specificities.

  5. 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.

  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. 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.

  8. 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.

  9. 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.

  10. Analysis of energy disposal - Thermodynamic aspects of the entropy deficiency of a product state distribution

    NASA Technical Reports Server (NTRS)

    Levine, R. D.; Bernstein, R. B.

    1973-01-01

    A thermodynamic-like approach to the characterization of product state distributions is outlined. A moment analysis of the surprisal and the entropy deficiency is presented from a statistical mechanical viewpoint. The role of reactant state selection is discussed using the 'state function' property of the entropy.

  11. Systematic analysis of transverse momentum distribution and non-extensive thermodynamics theory

    SciTech Connect

    Sena, I.; Deppman, A.

    2013-03-25

    A systematic analysis of transverse momentum distribution of hadrons produced in ultrarelativistic p+p and A+A collisions is presented. We investigate the effective temperature and the entropic parameter from the non-extensive thermodynamic theory of strong interaction. We conclude that the existence of a limiting effective temperature and of a limiting entropic parameter is in accordance with experimental data.

  12. 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.

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

    NASA Astrophysics Data System (ADS)

    Sega, Marcello; Fábián, Balázs; Jedlovszky, Pál

    2015-09-01

    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.

  14. A thermodynamic analysis of gas adsorption on microporous materials: evaluation of energy heterogeneity.

    PubMed

    Llorens, Joan; Pera-Titus, Marc

    2009-03-15

    This paper presents a thermodynamic isotherm derived from solution thermodynamics principles to describe gas adsorption on microporous materials. This isotherm relies on a potential relationship between the integral free energy of adsorption relative to saturation, Psi/RT, expressed by the Kiselev equation, and the variable Z = 1/-Ln(Pi), being Pi the relative pressure. A mathematical analysis reveals that the adsorption energy heterogeneity in the micropores is collected in a characteristic parameter of the isotherm, m, that can be related to the alpha parameter of the Dubinin-Astakhov isotherm in a simple way (m = alpha + 1). The isotherm also predicts a plateau in Psi/RT at extremely low pressures (Pi < 10(-7)). Neimark's thermodynamic equation accounting for gas adsorption on mesoporous solids is found to be a particular case of the isotherm presented in this study. The Langmuir isotherm only shows consistency with the thermodynamic isotherm for a reduced combination of values of the relevant parameters, not usually found in common adsorbents. The suitability of the thermodynamic isotherm is experimentally assessed by testing a collection of microporous materials, including activated carbons, carbon nanotubes, and zeolites.

  15. Thermodynamic analysis of biogenic and synthetic polyamines conjugation with PAMAM-G4 nanoparticles.

    PubMed

    Chanphai, P; Tajmir-Riahi, H A

    2016-02-01

    We report the thermodynamic analysis of the bindings of poly(amidoamine) (PAMAM-G4) nanoparticles with biogenic polyamines spermine (spm), spermidine (spmd) and synthetic polyamines 3,7,11,15-tetrazaheptadecane·4HCl (BE-333) in aqueous solution at physiological conditions. Multiple spectroscopic methods, thermodynamic parameters and molecular modelling were used to analyse polyamine bindings to PAMAM dendrimers. Thermodynamic parameters ΔS, ΔH and ΔG parameters showed that polyamines bind polymer through H-bonding and van der Waals contacts with biogenic polyamines form more stable conjugates than synthetic polyamines. Modelling showed that polyamines are located at the surface of PAMAM with the free binding energy of -3.56 (spermine), -3.88 (spermidine) and -3.13 kcal/mol (BE-333), indicating spontaneous polyamine-polymer interaction at room temperature.

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

    NASA Astrophysics Data System (ADS)

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

    1993-09-01

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

  17. Thermodynamic analysis of the basic pulse-tube refrigerator

    NASA Astrophysics Data System (ADS)

    de Boer, P. C. T.

    The basic pulse-tube refrigerator is modelled as a tube with one end closed and with a movable piston at the other end. Both ends contain heat exchangers. The piston is capable of moving through the heat exchanger at its end. The thermodynamic model consists of four steps: adiabatic compression of the gas in the pulse tube; isobaric heat transfer from the gas to the wall of the pulse tube; adiabatic expansion of the gas in the pulse tube; and isobaric heat transfer from the wall of the pulse tube to the gas. During the entire cycle the pressure is taken to be uniform, and the gas inside either heat exchanger is assumed to be at the temperature of that exchanger. Upon neglecting gas motion during the isobaric heat transfer steps, complete analytical results are obtained for the temperature profiles of the wall, of the gas after compression, and of the gas after expansion. Each of these profiles is piecewise adiabatic. The profiles are used in finding the coefficient of performance and the net work done per cycle. The coefficient of performance is derived by noting that the basic heat transfer process consists of several reverse Brayton cycles, staged in series. The net work done per cycle is found by constructing the p-V diagram for the piston. This diagram represents a modified reverse Brayton cycle, with each of the compression and expansion steps consisting of two hyperbolic segments. The parameters determining these segments depend on the temperature at which gas enters the heat exchangers. Results are presented for the coefficient of performance and the heat removed per cycle as a function of the temperature ratio of the heat exchangers, for various values of the pressure ratio π and the non-dimensional length Lh of the heat exchanger at the closed end. The model is non-linear and permits study of the effect of large values of π and Lh.

  18. 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.

  19. 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.

  20. 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.

  1. Thermodynamic analysis of five compressed-air energy-storage cycles. [Using CAESCAP computer code

    SciTech Connect

    Fort, J. A.

    1983-03-01

    One important aspect of the Compressed-Air Energy-Storage (CAES) Program is the evaluation of alternative CAES plant designs. The thermodynamic performance of the various configurations is particularly critical to the successful demonstration of CAES as an economically feasible energy-storage option. A computer code, the Compressed-Air Energy-Storage Cycle-Analysis Program (CAESCAP), was developed in 1982 at the Pacific Northwest Laboratory. This code was designed specifically to calculate overall thermodynamic performance of proposed CAES-system configurations. The results of applying this code to the analysis of five CAES plant designs are presented in this report. The designs analyzed were: conventional CAES; adiabatic CAES; hybrid CAES; pressurized fluidized-bed CAES; and direct coupled steam-CAES. Inputs to the code were based on published reports describing each plant cycle. For each cycle analyzed, CAESCAP calculated the thermodynamic station conditions and individual-component efficiencies, as well as overall cycle-performance-parameter values. These data were then used to diagram the availability and energy flow for each of the five cycles. The resulting diagrams graphically illustrate the overall thermodynamic performance inherent in each plant configuration, and enable a more accurate and complete understanding of each design.

  2. Thermodynamic analysis of universes with the initial and final de Sitter eras

    NASA Astrophysics Data System (ADS)

    Moradpour, H.; Sabet, M. T. Mohammadi; Ghasemi, A.

    2015-08-01

    Our aim is studying the thermodynamics of cosmological models including initial and final de Sitter eras. For this propose, bearing Cai-Kim temperature in mind, we investigate the thermodynamic properties of a dark energy (DE) candidate with variable energy density, and show that the state parameter of this dark energy candidate (ωD) should obey the ωD≠ - 1 constraint, whiles there is no interaction between the fluids filled the universe, and the universe is not in the de Sitter eras. Additionally, based on the thermal fluctuation theory, we study the possibility of inducing fluctuations to the entropy of the DE candidate due to a mutual interaction between the cosmos sectors. Therefore, we find a relation between the thermal fluctuations and the mutual interaction between the cosmos sectors, whiles the DE candidate has a varying energy density. Finally, bearing the coincidence problem in mind, we derive a constraint on the vacuum energy, and investigate its relation with the entropy evolution of the DE candidate. We also point to a model with initial and final de Sitter eras in which a gravitationally induced particle production process leads to change the expansion eras, whiles the corresponding pressure is considered as the cause of current accelerated phase. We study its thermodynamics, and show that such processes may also leave thermal fluctuations into the system. We also find an expression between the thermal fluctuations and the particle production rate. Finally, we use Hayward-Kodama temperature to get a relation for the horizon entropy in models including the gravitationally induced particle production process. Our study shows that the first law of thermodynamics is available on the apparent horizon whiles, the gravitationally induced particle production process, as the DE candidate, may add an additional term to the Bekenstein limit of the horizon. The relation between the validity of the second law of thermodynamics and the gravitationally particle

  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. 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.

  6. 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.

  7. Superposition-additive approach in the description of thermodynamic parameters of formation and clusterization of substituted alkanes at the air/water interface.

    PubMed

    Vysotsky, Yu B; Belyaeva, E A; Fomina, E S; Vasylyev, A O; Vollhardt, D; Fainerman, V B; Aksenenko, E V; Miller, R

    2012-12-01

    The superposition-additive approach developed previously was shown to be applicable for the calculations of the thermodynamic parameters of formation and atomization of conjugate systems, their dipole polarizability, molecular diamagnetic susceptibility, π-electronic ring currents, etc. In the present work, the applicability of this approach for the calculation of the thermodynamic parameters of formation and clusterization at the water/air interface of alkanes, fatty alcohols, thioalcohols, amines, nitriles, fatty acids (C(n)H(2n+1)X, X is the functional group) and cis-unsaturated carboxylic acids (C(n)H(2n-1)COOH) is studied. Using the proposed approach the thermodynamic quantities determined agree well with the available data, either calculated using the semiempirical (PM3) quantum chemical method, or obtained in experiments. In particular, for enthalpy and Gibbs' energy of the formation of substituted alkane monomers from the elementary substances, and their absolute entropy, the standard deviations of the values calculated according to the superposition-additive scheme with the mutual superimposition domain C(n-2)H(2n-4) (n is the number of carbon atoms in the alkyl chain) from the results of PM3 calculations for alkanes, alcohols, thioalcohols, amines, fatty acids, nitriles and cis-unsaturated carboxylic acids are respectively: 0.05, 0.004, 2.87, 0.02, 0.01, 0.77, and 0.01 kJ/mol for enthalpy; 2.32, 5.26, 4.49, 0.53, 1.22, 1.02, 5.30 J/(molK) for absolute entropy; 0.69, 1.56, 3.82, 0.15, 0.37, 0.69, 1.58 kJ/mol for Gibbs' energy, whereas the deviations from the experimental data are: 0.52, 5.75, 1.40, 1.00, 4.86 kJ/mol; 0.52, 0.63, 1.40, 6.11, 2.21 J/(molK); 2.52, 5.76, 1.58, 1.78, 4.86 kJ/mol, respectively (for nitriles and cis-unsaturated carboxylic acids experimental data are not available). The proposed approach provides also quite accurate estimates of enthalpy, entropy and Gibbs' energy of boiling and melting, critical temperatures and standard heat

  8. 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.

  9. Group additivity calculation of the standard molal thermodynamic properties of aqueous amino acids, polypeptides and unfolded proteins as a function of temperature, pressure and ionization state

    NASA Astrophysics Data System (ADS)

    Dick, J. M.; Larowe, D. E.; Helgeson, H. C.

    2005-10-01

    Thermodynamic calculation of the chemical speciation of proteins and the limits of protein metastability affords a quantitative understanding of the biogeochemical constraints on the distribution of proteins within and among different organisms and chemical environments. These calculations depend on accurate determination of the ionization states and standard molal Gibbs free energies of proteins as a function of temperature and pressure, which are not generally available. Hence, to aid predictions of the standard molal thermodynamic properties of ionized proteins as a function of temperature and pressure, calculated values are given below of the standard molal thermodynamic properties at 25°C and 1 bar and the revised Helgeson-Kirkham-Flowers equations of state parameters of the structural groups comprising amino acids, polypeptides and unfolded proteins. Group additivity and correlation algorithms were used to calculate contributions by ionized and neutral sidechain and backbone groups to the standard molal Gibbs free energy (Δ G°), enthalpy (Δ H°), entropy (S°), isobaric heat capacity (C°P), volume (V°) and isothermal compressibility (κ°T) of multiple reference model compounds. Experimental values of C°P, V° and κ°T at high temperature were taken from the recent literature, which ensures an internally consistent revision of the thermodynamic properties and equations of state parameters of the sidechain and backbone groups of proteins, as well as organic groups. As a result, Δ G°, Δ H°, S° C°P, V° and κ°T of unfolded proteins in any ionization state can be calculated up to T~-300°C and P~-5000 bars. In addition, the ionization states of unfolded proteins as a function of not only pH, but also temperature and pressure can be calculated by taking account of the degree of ionization of the sidechain and backbone groups present in the sequence. Calculations of this kind represent a first step in the prediction of chemical affinities of many

  10. 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

  11. A THERMODYNAMIC ANALYSIS OF HIGH ENERGY SYNTHETIC FOODS.

    DTIC Science & Technology

    An analysis is presented of the possibilities of incorporating synthetic foods into the diets of personnel engaged in long duration, manned space...appropriate substitutes for the lower energy carbohydrates that normally make up approximately 50 percent of the diet . Various classes or organic...synthetic alpha-amino acids and their peptides of chain lengths in excess of that found in leucine. Methods of reducing possible ketogenic effects are discussed. (Author)

  12. Grüneisen analysis of thermodynamic properties of δ-phase Pu-Ga alloys

    NASA Astrophysics Data System (ADS)

    Lawson, A. C.

    2014-07-01

    We present a Grüneisen analysis of the intriguing temperature dependence of the thermal expansion and bulk modulus of delta phase plutonium alloys. This analysis exploits the thermodynamic relationship between these quantities and the heat capacity and reduces the description of complicated behaviour to the determination of a manageable number of numerical constants. We conclude from the analysis (1) that there is a small Schottky-like heat capacity anomaly at high temperatures and (2) that the size of this anomaly depends strongly on alloy concentration. Grüneisen analysis provides an economical description of the thermal expansion and bulk modulus of δ-Pu.

  13. Temperature, pressure, and electrochemical constraints on protein speciation: Group additivity calculation of the standard molal thermodynamic properties of ionized unfolded proteins

    NASA Astrophysics Data System (ADS)

    Dick, J. M.; Larowe, D. E.; Helgeson, H. C.

    2006-07-01

    Thermodynamic calculations can be used to quantify environmental constraints on the speciation of proteins, such as the pH and temperature dependence of ionization state, and the relative chemical stabilities of proteins in different biogeochemical settings. These calculations depend in part on values of the standard molal Gibbs energies of proteins and their ionization reactions as a function of temperature and pressure. Because these values are not generally available, we calculated values of the standard molal thermodynamic properties at 25°C and 1 bar as well as the revised Helgeson-Kirkham-Flowers equations of state parameters of neutral and charged zwitterionic reference model compounds including aqueous amino acids, polypeptides, and unfolded proteins. The experimental calorimetric and volumetric data for these species taken from the literature were combined with group additivity algorithms to calculate the properties and parameters of neutral and ionized sidechain and backbone groups in unfolded proteins. The resulting set of group contributions enables the calculation of the standard molal Gibbs energy, enthalpy, entropy, isobaric heat capacity, volume, and isothermal compressibility of unfolded proteins in a range of proton ionization states to temperatures and pressures exceeding 100°C and 1000 bar. This approach provides a useful frame of reference for thermodynamic studies of protein folding and complexation reactions. It can also be used to assign provisional values of the net charge and Gibbs energy of ionized proteins as a function of temperature and pH. Using these values, an Eh-pH diagram for a reaction representing the speciation of extracellular proteins from Pyrococcus furiosus and Bacillus subtilis was generated. The predicted predominance limits of these proteins correspond with the different electrochemical conditions of hydrothermal vents and soils. More comprehensive calculations of this kind may reveal pervasive chemical potential

  14. 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

  15. 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.

  16. Conserved variable analysis of the convective boundary layer thermodynamic structure over the tropical oceans

    NASA Technical Reports Server (NTRS)

    Betts, Alan K.; Albrecht, Bruce A.

    1987-01-01

    An analysis of FGGE dropwindsonde data using conserved thermodynamic variables shows mixing line structures for the convective boundary layer over the equatorial Pacific. Deeper boundary layers show a double structure. Reversals of the gradients of mixing ratio and equivalent potential temperature above the boundary-layer top are present in all the averages and suggest that the origin of the air sinking into the boundary layer needs further study.

  17. Thermodynamic analysis of four magnetic heat-pump cycles

    NASA Astrophysics Data System (ADS)

    Chen, F. C.; Murphy, R. W.; Mei, V. C.; Chen, G. L.

    1992-10-01

    The characteristics of four thermomagnetic heat pump cycles (Carnot, Ericsson, Stirling, and regenerative) are analyzed over extended ranges of temperature lift. The analysis is carried out for gadolinium operating between 0 and 7 Tesla, with a heat-rejection temperature of 320 K. A 42-percent reduction in the coefficient of performance at 260 K cooling temperature and a 15-percent reduction in capacity at 232 K cooling temperature is predicted for the magnetic Ericsson cycle as compared with the ideal regenerative cycle. It is suggested that the potential irreversibilities from this one source alone may adversely affect the viability of certain proposed magnetic heat pump concepts if the relevant loss mechanisms are not adequately addressed.

  18. Thermodynamic analysis of small ligand binding to the Escherichia coli repressor of biotin biosynthesis.

    PubMed

    Xu, Y; Johnson, C R; Beckett, D

    1996-04-30

    BirA is the transcriptional repressor of biotin biosynthesis and a biotin holoenzyme synthetase. It catalyzes synthesis of biotinyl-5'-AMP from the substrates biotin and ATP. The adenylate is the activated intermediate in the biotin transfer reaction as well as the positive allosteric effector for site-specific DNA binding. The affinity of BirA for the adenylate is considerably greater than its affinity for biotin, and both binding reactions are coupled to changes in the conformation of the protein. The temperature dependencies of the two binding interactions have been determined using kinetic techniques. Van't Hoff analysis of the equilibrium dissociation constants derived from the kinetic data indicate that while the two binding processes are characterized by large negative enthalpies, the entropic contributions are small for both. Binding enthalpies have also been determined by isothermal titration calorimetry. Consistent with the results of the van't Hoff analyses, the calorimetric enthalpies are large and negative. The greater precision of the calorimetric measurements allowed more accurate estimation of the entropic contributions to the binding processes, which are of opposite sign for the two ligands. In addition, the heat capacity changes associated with the two binding reactions are small. The measured thermodynamic parameters for binding of biotin and bio-5'-AMP to BirA have been utilized to dissect out structural contributions to the binding energetics. Results of these calculations indicate equivalent contributions of burial of polar and apolar surface area to both binding processes. The total loss of solvent accessible surface area is, however, greater for biotin binding. The analysis indicates furthermore that although both binding reactions are coupled to losses in configurational entropy, the magnitude of the conformational change is significantly larger for biotin binding.

  19. Effect of Ni and Pd Addition on Mechanical, Thermodynamic, and Electronic Properties of AuSn4-Based Intermetallics: A Density Functional Investigation

    NASA Astrophysics Data System (ADS)

    Tian, Yali; Zhou, Wei; Wu, Ping

    2016-08-01

    The effects of Ni and Pd addition on the mechanical, thermodynamic, and electronic properties of AuSn4-based intermetallic compounds (IMCs) have been investigated by first-principles calculations to reveal the essence of Au embrittlement. Three kinds of doped (namely Ni-doped, Pd-doped, and Ni/Pd-codoped) IMCs are considered in this work. The polycrystalline elastic properties are deduced from single-crystal elastic constants. It is found that the doped systems together with nondoped AuSn4 are all ductile phases. For Ni-doped AuSn4, the modulus, hardness, brittleness, Debye temperature, and minimum thermal conductivity increase with the Ni fraction, but this is not the case for the Pd-doped material, since Au0.75Pd0.25Sn4 is the more brittle phase. For Au0.5Pd0.25Ni0.25Sn4, the mechanical, thermodynamic, and electronic properties are similar to those of Au0.5Pd0.5Sn4.

  20. 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.

  1. Carbon deposition in an SOFC fueled by tar-laden biomass gas: a thermodynamic analysis

    NASA Astrophysics Data System (ADS)

    Singh, Devinder; Hernández-Pacheco, Eduardo; Hutton, Phillip N.; Patel, Nikhil; Mann, Michael D.

    This work presents a thermodynamic analysis of the carbon deposition in a solid oxide fuel cell (SOFC) fueled by a biomass gasifier. Integrated biomass-SOFC units offer considerable benefits in terms of efficiency and fewer emissions. SOFC-based power plants can achieve a system efficiency of 70-80% (including heat utilization) as compared to 30-37% for conventional systems. The fuel from the biomass gasifier can contain considerable amounts of tars depending on the type of gasifier used. These tars can lead to the deposition of carbon at the anode side of SOFCs and affect the performance of the fuel cells. This paper thermodynamically studies the risk of carbon deposition due to the tars present in the feed stream and the effect various parameters like current density, steam, and temperature have on carbon deposition. Since tar is a complex mixture of aromatics, it is represented by a mixture of toluene, naphthalene, phenol, and pyrene. A total of 32 species are considered for the thermodynamic analysis, which is done by the Gibbs energy minimization technique. The carbon deposition is shown to decrease with an increase in current density and becomes zero after a critical current density. Steam in the feed stream also decreases the amount of carbon deposition. With the increase in temperature the amount of carbon first decreases and then increases.

  2. A novel thermodynamic state recursion method for description of nonideal nonlinear chromatographic process of frontal analysis.

    PubMed

    Liu, Qian; OuYang, Liangfei; Liang, Heng; Li, Nan; Geng, Xindu

    2012-06-01

    A novel thermodynamic state recursion (TSR) method, which is based on nonequilibrium thermodynamic path described by the Lagrangian-Eulerian representation, is presented to simulate the whole chromatographic process of frontal analysis using the spatial distribution of solute bands in time series like as a series of images. TSR differs from the current numerical methods using the partial differential equations in Eulerian representation. The novel method is used to simulate the nonideal, nonlinear hydrophobic interaction chromatography (HIC) processes of lysozyme and myoglobin under the discrete complex boundary conditions. The results show that the simulated breakthrough curves agree well with the experimental ones. The apparent diffusion coefficient and the Langmuir isotherm parameters of the two proteins in HIC are obtained by the state recursion inverse method. Due to its the time domain and Markov characteristics, TSR is applicable to the design and online control of the nonlinear multicolumn chromatographic systems.

  3. 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.

  4. Group additivity equations of state for calculating the standard molal thermodynamic properties of aqueous organic species at elevated temperatures and pressures

    NASA Astrophysics Data System (ADS)

    Amend, Jan P.; Helgeson, Harold C.

    1997-01-01

    Group additivity equations of state for aqueous organic molecules have been generated by combining the revised Helgeson-Kirkham-Flowers (HKF) equations of state ( Shock and Helgeson, 1988, 1990; Tanger and Helgeson, 1988; Shock et al., 1989, 1992) with experimental values of the standard molal properties of aqueous alkanes, alkanols, alkylbenzenes, car☐ylic acids, amides, and amines. Equations of state parameters for the groups represented by -CH 2-, -CH 3, -CHCH 3-, -C 6H 5, -CH 2OH, -COOH, -CONH 2, and -CH 2NH 2 were determined by regression of the experimental data. This procedure permits calculation of the standard molal thermodynamic properties of these groups at elevated temperatures and pressures. Although curves representing the apparent standard molal Gibbs free energies (Δ G°) and enthalpies (Δ H°) of formation, and the standard molal entropies ( S°) of the groups as a function of temperature and pressure are respectively similar for each of them, the temperature dependence of the standard molal heat capacities ( Cp°) and volumes ( V°) of a number of the groups are quite different from one another. For example, the standard molal heat capacities of the hydrocarbon groups minimize with increasing temperature, but those of -CH 2OH and -CH 2NH 2 maximize. Computed values of Δ G°, Δ H°, S°, Cp°, V°, and the equations of state parameters for the various groups were used together with group additivity relations to generate corresponding values of these properties for aqueous n-alkanes, 2-methylalkanes, n-alkylbenzenes, n-alkanols, n-car☐ylic acids, n-amides, and n-amines at temperatures ≤ 250°C and pressures ≤ 1 kbar. The validity and generality of the equations of state are supported by the fact that predicted equilibrium constants for liquid n-alkane solubility reactions in water compare favorably with experimental values reported in the literature for temperatures as high as 200°C. Furthermore, equilibrium constants for aqueous ethane

  5. 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.

  6. Thermodynamic analysis of porphyrin binding to Momordica charantia (bitter gourd) lectin.

    PubMed

    Sultan, Nabil A M; Maiya, Bhaskar G; Swamy, Musti J

    2004-08-01

    Owing to the use of porphyrins in photodynamic therapy for the treatment of malignant tumors, and the preferential interaction of lectins with tumor cells, studies on lectin-porphyrin interaction are of significant interest. In this study, the interaction of several free-base and metalloporphyrins with Momordica charantia (bitter gourd) lectin (MCL) was investigated by absorption spectroscopy. Difference absorption spectra revealed that significant changes occur in the Soret band region of the porphyrins on binding to MCL. These changes were monitored to obtain association constants (Ka) and stoichiometry of binding. The tetrameric MCL binds four porphyrin molecules, and the stoichiometry was unaffected by the presence of the specific sugar, lactose. In addition, the agglutination activity of MCL was unaffected by the presence of the porphyrins used in this study, clearly indicating that porphyrin and carbohydrate ligands bind at different sites. Both cationic and anionic porphyrins bind to the lectin with comparable affinity (Ka =10(3)-10(5) m(-1)). The thermodynamic parameters associated with the interaction of several porphyrins, obtained from the temperature dependence of the Ka values, were found to be in the range: DeltaH degrees = -98.1 to -54.4 kJ.mol(-1) and DeltaS degrees =-243.9 to -90.8 J.mol(-1).K(-1). These results indicate that porphyrin binding to MCL is governed by enthalpic forces and that the contribution from binding entropy is negative. Enthalpy-entropy compensation was observed in the interaction of different porphyrins with MCL, underscoring the role of water structure in the overall binding process. Analysis of CD spectra of MCL indicates that this protein contains about 13%alpha-helix, 36%beta-sheet, 21%beta-turn, and the rest unordered structures. Binding of porphyrins does not significantly alter the secondary and tertiary structures of MCL.

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

    NASA Astrophysics Data System (ADS)

    Banerjee, Kinshuk

    2015-05-01

    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.

  8. 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.

  9. 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.

  10. 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.

  11. Surface analysis and evaluation of progressive addition lens

    NASA Astrophysics Data System (ADS)

    Li, Zhiying; Li, Dan

    2016-10-01

    The Progressive addition lens is used increasingly extensive with its advantages of meeting the requirements of distant and near vision at the same time. Started from the surface equations of progressive addition lens, combined with evaluation method of spherical power and cylinder power, the relationship equations between the surface sag and optical power distribution are derived. According to the requirements on difference of actual and nominal optical power from Chinese National Standard, the tolerance analysis and evaluation of prototype progressive addition surface with addition of 2.5m-1 ( 7.5m-1 10m-1 ) is given in detail. The tolerance analysis method provides theoretical proof for lens processing control accuracy, and the processing feasibility of lens is evaluated much more reasonably.

  12. 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.

  13. Using principal component analysis to find correlations between loop-related and thermodynamic variables for G-quadruplex-forming sequences.

    PubMed

    Jaumot, Joaquim; Gargallo, Raimundo

    2010-08-01

    The application of Principal Component Analysis (PCA) is proposed here as a simple means of revealing correlations between thermodynamic variables corresponding to folding equilibria of intramolecular G-quadruplexes and Watson-Crick duplexes, and the length of loops in the corresponding guanine-rich DNA sequences. To this end, two previously studied data sets were analyzed (Arora and Maiti, J. Phys. Chem. B. 2009 and Kumar and Maiti, Nucleic Acids. Res. 2008). All of the sequences considered shared the common structure 5'- GGG - loop1 - GGG - loop2 - GGG - loop3 - GGG -3'. PCA of these data sets supported a series of correlations between the variables studied. First, the association of loop length with thermodynamic stability and quadruplex structure was corroborated. Secondly, it is proposed that the addition of ethylene glycol produces a stronger stabilization on those sequences showing long loop1 and/or loop3. Thirdly, it is proposed that a low content of adenine in loop1 and/or loop3 will produce an increase in the stability of G-quadruplex and its related Watson-Crick duplex.

  14. Calculation of ionization energy, electron affinity, and hydride affinity trends in pincer-ligated d(8)-Ir((tBu4)PXCXP) complexes: implications for the thermodynamics of oxidative H2 addition.

    PubMed

    Baroudi, Abdulkader; El-Hellani, Ahmad; Bengali, Ashfaq A; Goldman, Alan S; Hasanayn, Faraj

    2014-12-01

    DFT methods are used to calculate the ionization energy (IE) and electron affinity (EA) trends in a series of pincer ligated d(8)-Ir((tBu4)PXCXP) complexes (1-X), where C is a 2,6-disubstituted phenyl ring with X = O, NH, CH2, BH, S, PH, SiH2, and GeH2. Both C2v and C2 geometries are considered. Two distinct σ-type ((2)A1 or (2)A) and π-type ((2)B1 or (2)B) electronic states are calculated for each of the free radical cation and anion. The results exhibit complex trends, but can be satisfactorily accounted for by invoking a combination of electronegativity and specific π-orbital effects. The calculations are also used to study the effects of varying X on the thermodynamics of oxidative H2 addition to 1-X. Two closed shell singlet states differentiated in the C2 point group by the d(6)-electon configuration are investigated for the five-coordinate Ir(III) dihydride product. One electronic state has a d(6)-(a)(2)(b)(2)(b)(2) configuration and a square pyramidal geometry, the other a d(6)-(a)(2)(b)(2)(a)(2) configuration with a distorted-Y trigonal bipyramidal geometry. No simple correlations are found between the computed reaction energies of H2 addition and either the IEs or EAs. To better understand the origin of the computed trends, the thermodynamics of H2 addition are analyzed using a cycle of hydride and proton addition steps. The analysis highlights the importance of the electron and hydride affinities, which are not commonly used in rationalizing trends of oxidative addition reactions. Thus, different complexes such as 1-O and 1-CH2 can have very similar reaction energies for H2 addition arising from opposing hydride and proton affinity effects. Additional calculations on methane C-H bond addition to 1-X afford reaction and activation energy trends that correlate with the reaction energies of H2 addition leading to the Y-product.

  15. Critical analysis of the thermodynamic properties of the In-Se gaseous and solid phases

    NASA Astrophysics Data System (ADS)

    Chatillon, Christian

    1993-03-01

    The thermodynamic properties of the In4Se3(s), InSe(s), In6Se7(s), In2Se3(s) compounds and of the In2Se(g), InSe(g) and In2Se2(g) molecules are established from literature data after a critical analysis of primary data. Using the congruent vaporization property of the In2Se3(s) compound, the discrepancies between data are analysed and new values are proposed that allow the calculation of vaporization processes in the In-Se system to be carried out.

  16. Thermodynamic analysis and comparison on oxy-fuel power generation process - article no. 053001

    SciTech Connect

    Deng, S.M.; Hynes, R.

    2009-09-15

    In this paper, pressurized oxy-fuel combustion power generation processes are modeled and analyzed based on a 350 MW subcritical reheat boiler associated with a condensing steam turbine. The performance results are obtained. Furthermore, the influences of slurry concentration and coal properties on power plant performance are investigated. An oxy-fuel configuration operating at ambient pressure is studied to compare the performance with pressurized oxy-fuel configuration. Thermodynamic analysis reveals the true potentials of the pressurized oxy-fuel process. Based on the system integration, an improved configuration is proposed in which plant efficiency of pressurized oxy-fuel process is increased by 1.36%.

  17. Thermodynamic analysis of liquid bridge for fixed volume in atomic force microscope

    NASA Astrophysics Data System (ADS)

    Wei, Zheng; He, MengFu; Zhao, WenBin; Li, Yang

    2013-10-01

    In ambient condition, capillary forces are the major contributors to the adhesive forces between the tip of an atomic force microscope (AFM) and the sample. In general, capillary forces are thought to be related to water film thickness, contact time and relative humidity and so on. In this paper, an original analysis regarding the liquid bridge, based on the surface and interface thermodynamic theory, is proposed. The cases covered in the study include the capillary forces and temperature of liquid bridge for quickly drawn liquid bridge, and for nonvolatile liquid bridge. The study results show that variation in temperature may occur in the liquid bridge when it is stretched.

  18. 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.

  19. Thermodynamic analysis of a geopressured geothermal hybrid wellhead power system. Final report

    SciTech Connect

    Chang, I.; Williams, J.R.

    1985-01-01

    This research project is designed to evaluate the performance and operating characteristics of hybrid power cycles applied to geopressured and geothermal resources. The power systems evaluated are from the EPRI geopressured wellheat project and data used for the analysis are from the Pleasant Bayou well site. Three types of hybrid power systems are analyzed thermodynamically. They are (A) the single flash system, (B) the double flash system, and (C) the binary system. The studies of the first two systems are more extensive than the third one, although the binary system is the one chosen for testing at the Pleasant Bayou well site.

  20. The Building Loads Analysis System Thermodynamics (BLAST) Program, Version 2.0: Input Booklet.

    DTIC Science & Technology

    1979-06-01

    Z ); Delete all handwritten text i.e., form should be blank Input Form. Delete all hyphens between words. Accession For " 7 MIS GfSki rry DOC...NO 4. TITLE f«nd Subtitle) THE BUILDING LOADS ANALYSIS SYSTEM THERMODYNAMICS (BLAST) PROGRAM, VERSION 2.0: INPUT BOOkLET 7 . AUTHORf»; E... 7 I quipmenl Types 8 Speeial Parameters Applicability Al Other System Parameters A2 Speeial Parameters Page 30 34 7 5 ->b 46 77 [08 110

  1. Improved thermodynamic analysis of gas reactions for compound semiconductor growth by vapor-phase epitaxy

    NASA Astrophysics Data System (ADS)

    Inatomi, Yuya; Kangawa, Yoshihiro; Kakimoto, Koichi; Koukitu, Akinori

    2017-03-01

    An improved thermodynamic analysis method for vapor-phase epitaxy is proposed. In the conventional method, the mass-balance constraint equations are expressed in terms of variations in partial pressure. Although the conventional method is appropriate for gas–solid reactions occurring near the growth surface, it is not suitable for gas reactions that involve changes in the number of gas molecules. We reconsider the constraint equations in order to predict the effect of gas reactions on semiconductor growth processes. To demonstrate the feasibility of the improved method, the growth process of group-III nitrides by metalorganic vapor-phase epitaxy has been investigated.

  2. 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…

  3. Appreciating the role of thermodynamics in LCA improvement analysis via an application to titanium dioxide nanoparticles.

    PubMed

    Grubb, Geoffrey F; Bakshi, Bhavik R

    2011-04-01

    Although many regard it as the most important step of life cycle assessment, improvement analysis is given relatively little attention in the literature. Most available improvement approaches are highly subjective, and traditional LCA methods often do not account for resources other than fossil fuels. In this work exergy is evaluated as a thermodynamically rigorous way of identifying process improvement opportunities. As a case study, a novel process for producing titanium dioxide nanoparticles is considered. A traditional impact assessment, a first law energy analysis, and an exergy analysis are done at both the process and life cycle scales. The results indicate that exergy analysis provides insights not available via other methods, especially for identifying unit operations with the greatest potential for improvement. Exergetic resource accounting at the life cycle scale shows that other materials are at least as significant as fossil fuels for the production of TiO2 nanoparticles in this process.

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

    NASA Astrophysics Data System (ADS)

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

    2013-09-01

    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 CO2 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. At the request of the authors and the Proceedings Editor the above article has been replaced with a corrected version. The original PDF file supplied to AIP Publishing contained several equations with incorrect/missing characters resulting from processes used to create the PDF file. The article has been replaced and the equations now display correctly.

  5. 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.

  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. 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.

  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. [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.

  12. 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.

  13. 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.

  14. 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.

  15. Thermodynamic and structural analysis of phosphotyrosine polypeptide binding to Grb2-SH2.

    PubMed

    McNemar, C; Snow, M E; Windsor, W T; Prongay, A; Mui, P; Zhang, R; Durkin, J; Le, H V; Weber, P C

    1997-08-19

    A thermodynamic analysis using isothermal titration calorimetry (ITC) has been performed to examine the binding interaction between the SH2 (Src homology 2) domain of growth factor receptor binding protein 2 (Grb2-SH2) and one of its phosphotyrosine (pY) polypeptide ligands. Interaction of the Shc-derived phosphotyrosine hexapeptide Ac-SpYVNVQ-NH2 with Grb2-SH2 was both enthalpically and entropically favorable (DeltaH = -7.55 kcal mol-1, -TDeltaS = -1.46 kcal mol-1 , DeltaG = -9.01 kcal mol-1, T = 20 degrees C). ITC experiments using five alanine-substituted peptides were performed to examine the role of each side chain in binding. The results were consistent with homology models of the Grb2-SH2-Shc hexapeptide complex which identified several possible hydrogen bonds between Grb2-SH2 and the phosphotyrosine and conserved asparagine(+2) side chains of the Shc hexapeptide. These studies also demonstrated that the hydrophobic valine(+1) side chain contributes significantly to the favorable entropic component of binding. The thermodynamic and structural data are consistent with a Grb2-SH2 recognition motif of pY-hydrophobic-N-X (where X is any amino acid residue). The measured heat capacity of binding (DeltaCp = -146 cal mol-1 K-1) was very similar to computed values using semiempirical estimates (DeltaCp = -106 to -193 cal mol-1 K-1) derived from apolar and polar accessible surface area values calculated from several homology models of the Grb2-SH2-Shc hexapeptide complex. The homology model which most closely reproduced the measured DeltaCp value is also the model which had the lowest RMS deviation from the subsequently determined crystal structure. Calculations based on the thermodynamic data and these semiempirical estimates indicated that the binding event involves burial of nearly comparable apolar (677 A2) and polar (609 A2) surface areas.

  16. Economic and Thermodynamic Analysis for Preliminary Design of Dry Steam Geothermal Power Plant (GPP) with Multifarious Gas Removal System (GRS) in Kamojang, West Java, Indonesia

    NASA Astrophysics Data System (ADS)

    Damar Pranadi, Aloysius; Sihana; Suryopratomo, Kutut; Rahmatika Salis, Fiki

    2016-09-01

    Indonesia has great number of geothermal potential separated by two kind of potential, 16.13 GW for high enthalpy and 7.88 GW for low enthalpy speculative resources [4]. In the end of 2013, Ministry of Energy and Mineral Resources stated that Geothermal Power Plant (GPP) in Indonesia have been built about 1.34 GW in capacity and wanted to seriously develop geothermal potential up to 6.64 GW by 2025 [8]. Cost is one of famous obstacle in Indonesia's GPP Development. To reduce grand total cost of GPP, this paper will present the relation between thermodynamic and economic analysis in purpose to find the most economical gas removal system in GPP. By gleaning data at Kamojang Steam Field on behalf of PT Pertamina Geothermal Energy, this study will thermodynamically analyze and calculate a GPP preliminary design with software, named as Cycle Tempo 5.0. In additional, writers create motive steam calculator (based on C++ language) to enhance thermodynamic analysis for gas removal system (GRS) and adapted the results in Cycle Tempo 5.0. After thermodynamic analysis has been done, economic study will be undertaken by Net Present Value Analysis to compare the utilization cost of three different GRS and find which kind of GRS is more economical for nearly 30 years operation. For the result, Dual LRVP has higher performance than the others, spend less utilization cost and more economical for nearly 30 years operation. Moreover, the economic analysis for replacement of gas removal system shown in this paper too. In conclusion, GPP with Dual LRVP is proper to be developed in the future Geothermal Power Plant or to replace the existing GRS in some existing GPP in Indonesia.

  17. Thermodynamic analysis on HVPE growth of InGaN ternary alloy

    NASA Astrophysics Data System (ADS)

    Hanaoka, Koshi; Murakami, Hisashi; Kumagai, Yoshinao; Koukitu, Akinori

    2011-03-01

    Growth of InGaN alloy using hydride vapor phase epitaxy (HVPE) was investigated. Thermodynamic analysis was performed, taking account of the source zones. It was found that InCl3 and GaCl3, which are known to be essential for appreciable InGaN growth by HVPE, could be generated preferentially at the source zone by using a group-III metal and Cl2 gas. The analysis for the growth zone revealed that a significantly large driving force for both InN and GaN deposition is possible. The calculated vapor-solid distribution was close to a linear relationship by using a high V/III ratio, inert carrier gas, and high temperature. These facts suggest that an InGaN thick layer can be grown with a high growth rate and enough controllability of solid composition by employing InCl3 and GaCl3 precursors.

  18. 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.

  19. An approach to rational ligand-design based on a thermodynamic analysis.

    PubMed

    Ui, Mihoko; Tsumoto, Kouhei

    2010-11-01

    Thermodynamic analysis is an effective tool in screening of lead-compounds for development of potential drug candidates. In most cases, a ligand achieve high affinity and specificity to a target protein by means of both favorable enthalpy and entropy terms, which can be reflected in binding profiles of Isothermal Titration Calorimetry (ITC). A favorable enthalpy change suggests the contribution of noncovalent contacts such as hydrogen bonding and van der Waals interaction between a ligand and its target protein. In general, optimization of binding enthalpy is more difficult than that of entropies in ligand-design; therefore, it is desirable to choose firstly a lead-compound based on its binding enthalpic gain. In this paper, we demonstrate the utility of thermodynamic approach to ligand screening using anti-ciguatoxin antibody 10C9 as a model of a target protein which possesses a large hydrophobic pocket. As a result of this screening, we have identified three compounds that could bind to the antigen-binding pocket of 10C9 with a few kcal/mol of favorable binding enthalpy. Comparison of their structure with the proper antigen ciguatoxin CTX3C revealed that 10C9 rigorously identifies their cyclic structure and a characteristic hydroxyl group. ITC measurement might be useful and powerful for a rational ligand screening and the optimization of the ligand; the enthalpic gain is an effective index for ligand-design studies.

  20. 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.

  1. Thermodynamic analysis of helium boil-off experiments with pressure variations

    NASA Astrophysics Data System (ADS)

    Cha, Y. S.; Niemann, R. C.; Hull, J. R.

    A thermodynamic analysis by calorimetric experiments in a system with changing pressure is presented. A general equation is derived for use in calculating the rate of heat loss from measured mass flow rate. The results show that the largest contribution from pressure variation is the sensible heat of liquid helium in a Dewar. A dimensionless parameter that was identified provides an indication of the importance of pressure variation relative to the latent heat of vaporization during an experiment. This dimensionless parameter is a function of system pressure land the thermodynamic properties of helium), rate of change of system pressure, liquid helium inventory in the Dewar and measured mass flow rate. In the special case when the effect of pressure variation is small compared to the latent heat of vaporization, the heat loss rate is the product of the measured mass flow rate and the latent heat of vaporization, multiplied by a correction factor that is a function of the ratio of vapour density to liquid density. This correction factor is significant for helium at pressures near or above 1 atm and should always be included in the calculation.

  2. Thermodynamic analysis of the efficiency of high-temperature steam electrolysis system for hydrogen production

    NASA Astrophysics Data System (ADS)

    Mingyi, Liu; Bo, Yu; Jingming, Xu; Jing, Chen

    High-temperature steam electrolysis (HTSE), a reversible process of solid oxide fuel cell (SOFC) in principle, is a promising method for highly efficient large-scale hydrogen production. In our study, the overall efficiency of the HTSE system was calculated through electrochemical and thermodynamic analysis. A thermodynamic model in regards to the efficiency of the HTSE system was established and the quantitative effects of three key parameters, electrical efficiency (η el), electrolysis efficiency (η es), and thermal efficiency (η th) on the overall efficiency (η overall) of the HTSE system were investigated. Results showed that the contribution of η el, η es, η th to the overall efficiency were about 70%, 22%, and 8%, respectively. As temperatures increased from 500 °C to 1000 °C, the effect of η el on η overall decreased gradually and the η es effect remained almost constant, while the η th effect increased gradually. The overall efficiency of the high-temperature gas-cooled reactor (HTGR) coupled with the HTSE system under different conditions was also calculated. With the increase of electrical, electrolysis, and thermal efficiency, the overall efficiencies were anticipated to increase from 33% to a maximum of 59% at 1000 °C, which is over two times higher than that of the conventional alkaline water electrolysis.

  3. 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.

  4. A Simple, Approximate Method for Analysis of Kerr-Newman Black Hole Dynamics and Thermodynamics

    NASA Astrophysics Data System (ADS)

    Pankovic, V.; Ciganovic, S.; Glavatovic, R.

    2009-06-01

    In this work we present a simple approximate method for analysis of the basic dynamical and thermodynamical characteristics of Kerr-Newman black hole. Instead of the complete dynamics of the black hole self-interaction, we consider only the stable (stationary) dynamical situations determined by condition that the black hole (outer) horizon "circumference" holds the integer number of the reduced Compton wave lengths corresponding to mass spectrum of a small quantum system (representing the quantum of the black hole self-interaction). Then, we show that Kerr-Newman black hole entropy represents simply the ratio of the sum of static part and rotation part of the mass of black hole on one hand, and the ground mass of small quantum system on the other hand. Also we show that Kerr-Newman black hole temperature represents the negative value of the classical potential energy of gravitational interaction between a part of black hole with reduced mass and a small quantum system in the ground mass quantum state. Finally, we suggest a bosonic great canonical distribution of the statistical ensemble of given small quantum systems in the thermodynamical equilibrium with (macroscopic) black hole as thermal reservoir. We suggest that, practically, only the ground mass quantum state is significantly degenerate while all the other, excited mass quantum states, are non-degenerate. Kerr-Newman black hole entropy is practically equivalent to the ground mass quantum state degeneration. Given statistical distribution admits a rough (qualitative) but simple modeling of Hawking radiation of the black hole too.

  5. 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

  6. 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.

  7. 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).

  8. Spectral Envelopes and Additive + Residual Analysis/Synthesis

    NASA Astrophysics Data System (ADS)

    Rodet, Xavier; Schwarz, Diemo

    The subject of this chapter is the estimation, representation, modification, and use of spectral envelopes in the context of sinusoidal-additive-plus-residual analysis/synthesis. A spectral envelope is an amplitude-vs-frequency function, which may be obtained from the envelope of a short-time spectrum (Rodet et al., 1987; Schwarz, 1998). [Precise definitions of such an envelope and short-time spectrum (STS) are given in Section 2.] The additive-plus-residual analysis/synthesis method is based on a representation of signals in terms of a sum of time-varying sinusoids and of a non-sinusoidal residual signal [e.g., see Serra (1989), Laroche et al. (1993), McAulay and Quatieri (1995), and Ding and Qian (1997)]. Many musical sound signals may be described as a combination of a nearly periodic waveform and colored noise. The nearly periodic part of the signal can be viewed as a sum of sinusoidal components, called partials, with time-varying frequency and amplitude. Such sinusoidal components are easily observed on a spectral analysis display (Fig. 5.1) as obtained, for instance, from a discrete Fourier transform.

  9. Carbothermic Synthesis of 820 m UN Kernels: Literature Review, Thermodynamics, Analysis, and Related Experiments

    SciTech Connect

    Lindemer, Terrence; Voit, Stewart L; Silva, Chinthaka M; Besmann, Theodore M; Hunt, Rodney Dale

    2014-01-01

    The U.S. Department of Energy is considering 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 large, dense uranium nitride (UN) kernels. This effort explores many factors involved in using gel-derived uranium oxide-carbon microspheres to make large UN kernels. Analysis of recent studies with sufficient experimental details is provided. Extensive thermodynamic calculations are used to predict carbon monoxide and other pressures for several different reactions that may be involved in conversion of uranium oxides and carbides to UN. Experimentally, the method for making the gel-derived microspheres is described. These were used in a microbalance with an attached mass spectrometer to determine details of carbothermic conversion in argon, nitrogen, or vacuum. A quantitative model is derived from experiments for vacuum conversion to an uranium oxide-carbide kernel.

  10. Thermodynamics analysis of diffusion in spark plasma sintering welding Cr3C2 and Ni

    NASA Astrophysics Data System (ADS)

    Zhang, Fan; Zhang, Jinyong; Leng, Xiaoxuan; Lei, Liwen; Fu, Zhengyi

    2017-03-01

    Spark plasma sintering (SPS) welding of chromium carbide (Cr3C2) and nickel (Ni) was used to investigate the atomic diffusion caused by bypassing current. It was found that the diffusion coefficient with bypassing current was enhanced by almost 3.57 times over that without bypassing current. Different from the previous researches, the thermodynamics analysis conducted herein showed that the enhancement included a current direction-independent part besides the known current direction-dependent part. A local temperature gradient (LTG) model was proposed to explain the current direction-independent effect. Assuming that the LTG was mainly due to the interfacial electric resistance causing heterogeneous Joule heating, the theoretical results were in good agreement with the experimental results both in the present and previous studies. This new LTG model provides a reasonable physical meaning for the low-temperature advantage of SPS welding and should be useful in a wide range of applications.

  11. Thermodynamic Analysis of Beam down Solar Gas Turbine Power Plant equipped with Concentrating Receiver System

    NASA Astrophysics Data System (ADS)

    Azharuddin; Santarelli, Massimo

    2016-09-01

    Thermodynamic analysis of a closed cycle, solar powered Brayton gas turbine power plant with Concentrating Receiver system has been studied. A Brayton cycle is simpler than a Rankine cycle and has an advantage where the water is scarce. With the normal Brayton cycle a Concentrating Receiver System has been analysed which has a dependence on field density and optical system. This study presents a method of optimization of design parameter, such as the receiver working temperature and the heliostats density. This method aims at maximizing the overall efficiency of the three major subsystem that constitute the entire plant, namely, the heliostat field and the tower, the receiver and the power block. The results of the optimization process are shown and analysed.

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

    PubMed Central

    Goo, Eden; Chapman, Brian; Hickey, Anthony J.R.

    2016-01-01

    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

  13. Thermodynamic analysis of the nondenaturational conformational change of baker's yeast phosphoglycerate kinase at 24 degrees C.

    PubMed

    Ijeoma, Opral; Hollowell, Heather N; Bodnar, Melissa A; Britt, B Mark

    2008-10-15

    A plot of the Gibbs free energy of unfolding vs. temperature is calculated for baker's yeast phosphoglycerate kinase in 150 mM sodium phosphate (pH=7.0) from a combination of reversible differential scanning calorimetry measurements and isothermal guanidine hydrochloride titrations. The stability curve reveals the existence of two stable, folded conformers with an abrupt conformational transition occurring at 24 degrees C. The transition state thermodynamics for the low- to high-temperature conformational change are calculated from slow-scan-rate differential scanning calorimetry measurements where it is found that the free energy barrier for the conversion is 90 kJ/mol and the transition state possesses a significant unfolding quality. This analysis also confirms a nondenaturational conformational transition at 24 degrees C. The data therefore suggest that X-ray structures obtained from crystals grown below this temperature may differ considerably from the physiological structure and that the two conformers are not readily interconverted.

  14. Design and thermodynamic performance analysis of multichannel cryogenic transfer line for XFEL AMTF

    NASA Astrophysics Data System (ADS)

    Duda, P.; Chorowski, M.; Polinski, J.

    2017-02-01

    The XATL1 cryogenic transfer line for XFEL/AMTF is dedicated for transferring cryogenic cooling power from helium refrigerators to a cryogenic test facility by means of the continuous flows of cold helium in supercritical and gaseous state. The external envelope of the transfer line contains 4 cold process lines and a common radiation shield, as well as the system of supports and thermal contraction compensators. The XATL1 was designed and manufactured within the Polish in-kind contribution to the XFEL project. The line has been under operation since year 2012. The paper presents a design, including supporting and thermal compensation systems, of the XATL1 line. The line performance analysis based on the Second Law of Thermodynamics has been done, and the output has been compared with the design assumptions.

  15. Vibrational spectra, normal coordinate analysis and thermodynamics of 2, 5-difluorobenzonitrile

    NASA Astrophysics Data System (ADS)

    Rastogi, V. K.; Singhal, Surabhi; Palafox, M. A.; Ramana Rao, G.

    2010-02-01

    The FTIR spectrum of 2, 5-difluorobenzonitrile has been recorded in the region 200-4000 cm-1 (in liquid phase). The laser Raman spectrum in the range of 0-3500 cm-1 (in liquid phase) has also been recorded. The spectra have been analyzed assuming C s point group symmetry for the molecule. A zero-order normal coordinate analysis has been made for the molecule using force constants derived earlier. On the basis of potential energy distributions and eigen vectors unambiguous vibrational assignments have been made for all the fundamentals of the molecule. Thermodynamic functions have also been computed in the temperature range 200-1000 K by utilizing the observed fundamental frequencies assuming rigid-rotor harmonic oscillator approximation.

  16. Thermodynamic Analysis of Coherently Grown GaAsN/Ge: Effects of Different Gaseous Sources

    NASA Astrophysics Data System (ADS)

    Kawano, Jun; Kangawa, Yoshihiro; Yayama, Tomoe; Kakimoto, Koichi; Koukitu, Akinori

    2013-04-01

    Thermodynamic analysis of coherently grown GaAs1-xNx on Ge with low N content was performed to determine the relationship between solid composition and growth conditions. In this study, a new algorithm for the simulation code, which is applicable to wider combinations of gaseous sources than the traditional algorithm, was developed to determine the influence of different gaseous sources on N incorporation. Using this code, here we successfully compared two cases: one is a system using trimethylgallium (TMG), AsH3, and NH3, and the other uses dimethylhydrazine (DMHy) instead of NH3. It was found that the optimal N/As ratio of input gas in the system using DMHy was much lower than that using NH3. This shows that the newly developed algorithm could be a useful tool for analyzing the N incorporation during the vapor growth of GaAs1-xNx.

  17. 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.

  18. Thermodynamic analysis of two-dimensional crystal growth in nucleated isotactic polypropylene

    NASA Astrophysics Data System (ADS)

    Pieruccini, M.; Marco, G. Di; Lanza, M.

    1996-08-01

    A thermodynamic model is used to describe the two-dimensional crystallization kinetics (as observed by means of a calorimeter) of polypropylene nucleated with small amounts of indigo. The customary expression of the free enthalpy associated to secondary nucleation is initially used to analyze the experimental data. A significant dependence of the apparent surface tension (either basal or lateral) of the nuclei on the concentration of indigo is pointed out. To account for this effect, a phenomenological correction to the free enthalpy of nucleation is considered afterwards, which is connected with an entropy contribution arising from the formation of the crystal-melt interface. A more detailed data analysis is then carried out in light of this model.

  19. 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.

  20. Thermodynamics of Bioreactions.

    PubMed

    Held, Christoph; Sadowski, Gabriele

    2016-06-07

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

  1. 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.

  2. Thermodynamic analysis of interactions between cofactor and neuronal nitric oxide synthase.

    PubMed

    Sanae, Ryuhei; Kurokawa, Fumiaki; Oda, Masayuki; Ishijima, Sumio; Sagami, Ikuko

    2011-03-15

    The thermodynamics of cofactor binding to the isolated reductase domain (Red) of nNOS and its mutants have been studied by isothermal titration calorimetry. The NADP(+) and 2',5'-ADP binding stoichiometry to Red were both 1:1, consistent with a one-site kinetic model instead of a two-site model. The binding constant (K(D) = 71 nM) and the large heat capacity change (ΔC(p) = -440 cal mol(-1) K(-1)) for 2',5'-ADP were remarkably different from those for NADP(+) (1.7 μM and -140 cal mol(-1) K(-1), respectively). These results indicate that the nicotinamide moiety as well as the adenosine moiety has an important role in binding to nNOS. They also suggest that the thermodynamics of the conformational change in Red caused by cofactor binding are significantly different from the conformational changes that occur in cytochrome c reductase, in which the nicotinamide moiety of the cofactor is not essential for binding. Analysis of the deletion mutant of the autoinhibitory helix (RedΔ40) revealed that the deletion resulted in a decrease in the binding affinity of 2',5'-ADP with more unfavorable enthalpy gain. In the case of RedCaM, which contains a calmodulin (CaM) binding site, the presence of Ca(2+)/CaM caused a 6.7-fold increase in the binding affinity for 2',5'-ADP that was mostly due to the favorable entropy change. These results are consistent with a model in which Ca(2+)/CaM induces a conformational change in NOS to a flexible "open" form from a "closed" form that locked by cofactor binding, and this change facilitates the electron transfer required for catalysis.

  3. 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).

  4. 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.

  5. 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.

  6. Vibrational and electronic investigations, thermodynamic parameters, HOMO and LUMO analysis on Lornoxicam by density functional theory

    NASA Astrophysics Data System (ADS)

    Suhasini, M.; Sailatha, E.; Gunasekaran, S.; Ramkumaar, G. R.

    2015-11-01

    The Fourier transform infrared (FT-IR) and FT-Raman spectra of Lornoxicam were recorded in the region 4000-450 cm-1 and 4000-50 cm-1 respectively. Density functional theory (DFT) has been used to calculate the optimized geometrical parameters, atomic charges, and vibrational wavenumbers and intensity of the vibrational bands. The computed vibrational wave numbers were compared with the FT-IR and FT-Raman experimental data. The computational calculations at DFT/B3LYP level with 6-31G(d,p) and 6-31++G(d,p) basis sets. The complete vibrational assignments were performed on the basis of the potential energy distribution (PED) of the Vibrational modes calculated using Vibrational Energy Distribution Analysis (VEDA 4) program. The oscillator's strength calculated by TD-DFT and Lornoxicam is approach complement with the experimental findings. The NMR chemical shifts 13C and 1H were recorded and calculated using the gauge independent atomic orbital (GIAO) method. The Natural charges and intermolecular contacts have been interpreted using Natural Bond orbital (NBO) analysis and the HOMO-LUMO energy gap has been calculated. The thermodynamic properties like Entropy, Enthalpy, Specific heat capacity and zero vibrational energy have been calculated. Besides, molecular electrostatic potential (MEP) was investigated using theoretical calculations.

  7. Thermodynamic analysis of a combined gas turbine power plant with a solid oxide fuel cell for marine applications

    NASA Astrophysics Data System (ADS)

    Welaya, Yousri M. A.; Mosleh, M.; Ammar, Nader R.

    2013-12-01

    Strong restrictions on emissions from marine power plants (particularly SOx, NOx) will probably be adopted in the near future. In this paper, a combined solid oxide fuel cell (SOFC) and gas turbine fuelled by natural gas is proposed as an attractive option to limit the environmental impact of the marine sector. It includes a study of a heatrecovery system for 18 MW SOFC fuelled by natural gas, to provide the electric power demand onboard commercial vessels. Feasible heat-recovery systems are investigated, taking into account different operating conditions of the combined system. Two types of SOFC are considered, tubular and planar SOFCs, operated with either natural gas or hydrogen fuels. This paper includes a detailed thermodynamic analysis for the combined system. Mass and energy balances are performed, not only for the whole plant but also for each individual component, in order to evaluate the thermal efficiency of the combined cycle. In addition, the effect of using natural gas as a fuel on the fuel cell voltage and performance is investigated. It is found that a high overall efficiency approaching 70% may be achieved with an optimum configuration using SOFC system under pressure. The hybrid system would also reduce emissions, fuel consumption, and improve the total system efficiency.

  8. Synthesis, X-ray structure analysis, thermodynamic and electronic properties of 4-acetamido benzaldehyde using vibrational spectroscopy and DFT calculations

    NASA Astrophysics Data System (ADS)

    Jeeva Jasmine, N.; Arunagiri, C.; Subashini, A.; Stanley, N.; Thomas Muthiah, P.

    2017-02-01

    Theoretical Spectrograms, namely, FT-Raman (3500-50 cm-1) and FT-Infrared (4000-400 cm-1) spectra have been studied for 4-acetamido benzaldehyde (4ABA) and are assigned to different normal modes of the molecule. Vibrational spectral analysis was compared with the experimental and theoretical, FT-IR and FT-Raman spectra. The effect of polarity on the Harmonic vibrational frequencies, intensities, optimized geometrical parameters and several thermodynamic parameters in the ground state have been computed by the B3LYP method using 6-311 + G(d,p) basis set. The results of the optimized molecular structure is presented and compared with the XRD values. The global chemical reactivity relate to some parameters, such as HOMO, LUMO, gap energy (ΔE) and other parameters, including electronegativity (χ) and global hardness (η). The values of the reactivity descriptors indicated that the interaction between 4ABA molecules reduced its reactivity in comparison with the exhibited in gas phase. In addition, the local reactivity has been analyzed through the Fukui function and condensed softness indices.

  9. 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

    2015-05-07

    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.

  10. 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.

  11. 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.

  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. Thermodynamic analysis and experimental study on the oxidation of the Zn-Al-Mg coating baths

    NASA Astrophysics Data System (ADS)

    Su, Xuping; Zhou, Jie; Wang, Jianhua; Wu, Changjun; Liu, Ya; Tu, Hao; Peng, Haoping

    2017-02-01

    Surface oxidation of molten Zn-6Al baths containing 0.0, 3.0 and 6.0 wt. % Mg were analyzed using X-ray photoelectron spectroscopy. γ-Al2O3 is formed on the surface of the Zn-6Al bath, while MgAl2O4 and MgO occur at 460 °C in the Zn-6Al-3Mg and Zn-6Al-6Mg baths, respectively. Thermodynamic analysis on the oxidation of the Zn-Al-Mg baths was performed. Calculated phase diagrams at 460 °C and 560 °C show good agreements with the experimental results. MgO or MgAl2O4 exists in almost the entire composition range of the calculated oxidation diagrams. According to the calculation, oxidation products depend on the composition and temperature of the baths. The primary and secondary oxidation products of the Zn-Al-Mg baths can be reasonably explained by oxidation phase diagrams. Utilizing these results, the favorable practical bath melts and operating conditions can be designed.

  14. Thermodynamic Modeling and Analysis of an Optical Electric-Field Sensor

    PubMed Central

    Xiao, Xia; Xu, Yan; Dong, Zexing

    2015-01-01

    The stability of the optical electric field sensor (OEFS) in actual operation is affected by environmental factors such as temperature and SF6 (sulfur hexafluoride). To analyze the operational environment parameters affecting the optical properties of crystals, a thermodynamic model of the OEFS in which the optical properties of the crystal are changed by the first-order effects and the second-order effects was established. The intensity parameters such as electric, stress and temperature fields were introduced. The theoretical analysis results show that under temperature, stress and electric field conditions, the optical properties of the sensing crystals are no longer changed only by the electro-optic effect, but also by the temperature and the stress fields. Further synthesis suggests the expected optical property changes under the effect of the environment fields. OEFS tests show that the accuracy of OEFS is dependent on temperature with a ratio error of −0.8%~1.5% in the temperature range from −25 °C to +40 °C. PMID:25811225

  15. 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.

  16. 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.

  17. Collective Behaviour in Video Viewing: A Thermodynamic Analysis of Gaze Position

    PubMed Central

    2017-01-01

    Videos and commercials produced for large audiences can elicit mixed opinions. We wondered whether this diversity is also reflected in the way individuals watch the videos. To answer this question, we presented 65 commercials with high production value to 25 individuals while recording their eye movements, and asked them to provide preference ratings for each video. We find that gaze positions for the most popular videos are highly correlated. To explain the correlations of eye movements, we model them as “interactions” between individuals. A thermodynamic analysis of these interactions shows that they approach a “critical” point such that any stronger interaction would put all viewers into lock-step and any weaker interaction would fully randomise patterns. At this critical point, groups with similar collective behaviour in viewing patterns emerge while maintaining diversity between groups. Our results suggest that popularity of videos is already evident in the way we look at them, and that we maintain diversity in viewing behaviour even as distinct patterns of groups emerge. Our results can be used to predict popularity of videos and commercials at the population level from the collective behaviour of the eye movements of a few viewers. PMID:28045963

  18. 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.

  19. 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.

  20. 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.

  1. Navy Additive Manufacturing: Policy Analysis for Future DLA Material Support

    DTIC Science & Technology

    2014-12-01

    support programs. 14. SUBJECT TERMS additive manufacturing, 3D printing, technology adoption 15. NUMBER OF PAGES 69 16...LEFT BLANK xii LIST OF ACRONYMS AND ABBREVIATIONS 3D Three Dimensions or Three Dimensional 3DP 3D Printing AM Additive Manufacturing AMDO...this is about to change. Additive manufacturing (AM) systems (commonly known as “ 3D printing”) could bring the organic parts manufacturing capability

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  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 review and thermodynamic analysis of an external combustion, reciprocating engine

    SciTech Connect

    Caton, J.A.; West, J.E.

    1996-12-31

    The open cycle reciprocating Brayton engine concept uses separate and different cylinders for compression and expansion, and combustion occurs in an external burner at approximately constant pressure. Although this general engine concept dates back to Brayton in 1876, no known engine has been constructed or tested. Because of the nature of the combustion process (continuous) and the separation of the compression and expansion processes, the open cycle reciprocating Brayton engine has the potential to produce lower emissions and to possess higher efficiencies than conventional reciprocating engines. In contrast to conventional engines, the Brayton engine may use intercooling, recuperation and reduced heat loss technologies. This report reviews previous efforts concerning this concept, and describes the development and use of a thermodynamic based simulation for the open cycle reciprocating Brayton engine. Using this simulation, the indicated thermal efficiency of the base case open cycle reciprocating Brayton engine was 45.6%. In addition, the indicated thermal efficiency for high expander wall temperatures was as high as 50% for the highest wall temperatures. For a continuous flow combustor such as proposed for the open cycle reciprocating Brayton engine, the hydrocarbon and carbon monoxide emissions will be negligible for well designed combustors. Regarding nitric oxides, similar gas turbine combustors have been designed to minimize the nitric oxide emissions. Today`s gas turbines easily may produce less than 25 ppm of nitric oxide, and some are even as low as 10 ppm. For the more typical emission of 25 ppm, the open cycle reciprocating Brayton engine is expected to emit less than one-half of the Federal regulation for nitric oxides without any catalyst system.

  9. Composition analysis of oxide films formed on titanium surface under pulsed laser action by method of chemical thermodynamics

    NASA Astrophysics Data System (ADS)

    Ageev, E. I.; Andreeva, Ya M.; Karlagina, Yu Yu; Kolobov, Yu R.; Manokhin, S. S.; Odintsova, G. V.; Slobodov, A. A.; Veiko, V. P.

    2017-04-01

    A pulsed fiber laser with a wavelength of 1.06 µm was used to treat a commercial pure titanium surface in the air at intensities below the ablation threshold to provide oxide formation. Laser oxidation results are predicted by the chemical thermodynamic method and confirmed by experimental techniques (x-ray diffraction, energy dispersive x-ray spectroscopy). For the first time, the chemical thermodynamic method was used for determining the qualitative and quantitative phase-chemical composition of the compounds formed by a pulsed laser heating of commercial titanium in the air, and its applicability is proven. The simulation shows that multilayered composite film appears on a surface, the lower layers of which consist of Ti2O3 and TiO oxides with the addition of titanium nitride; and the thin upper layer consists of transparent titanium dioxide. Also, the chemical composition of films remains unchanged within a temperature range of 881–2000 K.

  10. 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

  11. 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.

  12. 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.

  13. Thermodynamic modeling and sensitivity analysis of porewater chemistry in compacted bentonite

    NASA Astrophysics Data System (ADS)

    Ochs, Michael; Lothenbach, Barbara; Shibata, Masahiro; Yui, Mikazu

    Compacted bentonite is typically foreseen as the main component of the engineered barrier system of high-level radioactive waste repositories. To derive Kd values and diffusion coefficients of radionuclides for performance assessment, it is critical to be able to describe the chemistry of the pore solution and to understand how it is influenced by different factors. The present paper presents a sensitivity analysis on the influence of important parameters on porewater chemistry in compacted bentonite. The principal parameters varied were the fractions of calcite, gypsum, and NaCl dissolving from bentonite, and pCO 2: Model calculations were done with the help of a surface chemical thermodynamic model that simultaneously treats solution/mineral equilibria as well as surface complexation and ion exchange reactions at the edge and siloxane surfaces of clay minerals. Some calculations were extended to take into account electric double layer effects in the porespace. The model results show that two powerful pH buffer systems are operative in compacted bentonite: Amphoteric edge SOH sites and the carbonate buffer system. If pCO 2 is imposed externally, the resulting porewater pH is mainly controlled by the carbonate buffer. If bentonite is treated as a closed system, the buffering action of the SOH sites becomes more important. In both cases, the dissolution of calcite and gypsum from the bentonite is important. The dissolution of impurities and the ion exchange reactions have an important influence in compacted bentonite, and porewater composition is relatively independent of groundwater composition. If the development of an electric double layer in the bentonite pores is considered, our results indicate that at higher dry densities (⩾1200 kg/m 3) the entire porespace may be occupied with (truncated) diffuse layers, leaving no space for free porewater.

  14. 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

  15. Limitations in xylose-fermenting Saccharomyces cerevisiae, made evident through comprehensive metabolite profiling and thermodynamic analysis.

    PubMed

    Klimacek, Mario; Krahulec, Stefan; Sauer, Uwe; Nidetzky, Bernd

    2010-11-01

    Little is known about how the general lack of efficiency with which recombinant Saccharomyces cerevisiae strains utilize xylose affects the yeast metabolome. Quantitative metabolomics was therefore performed for two xylose-fermenting S. cerevisiae strains, BP000 and BP10001, both engineered to produce xylose reductase (XR), NAD(+)-dependent xylitol dehydrogenase and xylulose kinase, and the corresponding wild-type strain CEN.PK 113-7D, which is not able to metabolize xylose. Contrary to BP000 expressing an NADPH-preferring XR, BP10001 expresses an NADH-preferring XR. An updated protocol of liquid chromatography/tandem mass spectrometry that was validated by applying internal (13)C-labeled metabolite standards was used to quantitatively determine intracellular pools of metabolites from the central carbon, energy, and redox metabolism and of eight amino acids. Metabolomic responses to different substrates, glucose (growth) or xylose (no growth), were analyzed for each strain. In BP000 and BP10001, flux through glycolysis was similarly reduced (∼27-fold) when xylose instead of glucose was metabolized. As a consequence, (i) most glycolytic metabolites were dramatically (≤ 120-fold) diluted and (ii) energy and anabolic reduction charges were affected due to decreased ATP/AMP ratios (3- to 4-fold) and reduced NADP(+) levels (∼3-fold), respectively. Contrary to that in BP000, the catabolic reduction charge was not altered in BP10001. This was due mainly to different utilization of NADH by XRs in BP000 (44%) and BP10001 (97%). Thermodynamic analysis complemented by enzyme kinetic considerations suggested that activities of pentose phosphate pathway enzymes and the pool of fructose-6-phosphate are potential factors limiting xylose utilization. Coenzyme and ATP pools did not rate limit flux through xylose pathway enzymes.

  16. Thermodynamic analysis and optimization of a high temperature triple absorption heat transformer.

    PubMed

    Khamooshi, Mehrdad; Parham, Kiyan; Yari, Mortaza; Egelioglu, Fuat; Salati, Hana; Babadi, Saeed

    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.

  17. 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.

  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. 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.

  20. 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

  1. Additional analysis of dendrochemical data of Fallon, Nevada.

    PubMed

    Sheppard, Paul R; Helsel, Dennis R; Speakman, Robert J; Ridenour, Gary; Witten, Mark L

    2012-04-05

    Previously reported dendrochemical data showed temporal variability in concentration of tungsten (W) and cobalt (Co) in tree rings of Fallon, Nevada, US. Criticism of this work questioned the use of the Mann-Whitney test for determining change in element concentrations. Here, we demonstrate that Mann-Whitney is appropriate for comparing background element concentrations to possibly elevated concentrations in environmental media. Given that Mann-Whitney tests for differences in shapes of distributions, inter-tree variability (e.g., "coefficient of median variation") was calculated for each measured element across trees within subsites and time periods. For W and Co, the metals of highest interest in Fallon, inter-tree variability was always higher within versus outside of Fallon. For calibration purposes, this entire analysis was repeated at a different town, Sweet Home, Oregon, which has a known tungsten-powder facility, and inter-tree variability of W in tree rings confirmed the establishment date of that facility. Mann-Whitney testing of simulated data also confirmed its appropriateness for analysis of data affected by point-source contamination. This research adds important new dimensions to dendrochemistry of point-source contamination by adding analysis of inter-tree variability to analysis of central tendency. Fallon remains distinctive by a temporal increase in W beginning by the mid 1990s and by elevated Co since at least the early 1990s, as well as by high inter-tree variability for W and Co relative to comparison towns.

  2. Analysis of fluorine addition to the vanguard first stage

    NASA Technical Reports Server (NTRS)

    Tomazic, William A; Schmidt, Harold W; Tischler, Adelbert O

    1957-01-01

    The effect of adding fluorine to the Vanguard first-stage oxidant was anlyzed. An increase in specific impulse of 5.74 percent may be obtained with 30 percent fluorine. This increase, coupled with increased mass ratio due to greater oxidant density, gave up to 24.6-percent increase in first-stage burnout energy with 30 percent fluorine added. However, a change in tank configuration is required to accommodate the higher oxidant-fuel ratio necessary for peak specific impulse with fluorine addition.

  3. 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 ...

  4. 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.

  5. 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…

  6. 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

  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.

  8. Analysis of Saccharides by the Addition of Amino Acids

    NASA Astrophysics Data System (ADS)

    Ozdemir, Abdil; Lin, Jung-Lee; Gillig, Kent J.; Gulfen, Mustafa; Chen, Chung-Hsuan

    2016-06-01

    In this work, we present the detection sensitivity improvement of electrospray ionization (ESI) mass spectrometry of neutral saccharides in a positive ion mode by the addition of various amino acids. Saccharides of a broad molecular weight range were chosen as the model compounds in the present study. Saccharides provide strong noncovalent interactions with amino acids, and the complex formation enhances the signal intensity and simplifies the mass spectra of saccharides. Polysaccharides provide a polymer-like ESI spectrum with a basic subunit difference between multiply charged chains. The protonated spectra of saccharides are not well identified because of different charge state distributions produced by the same molecules. Depending on the solvent used and other ions or molecules present in the solution, noncovalent interactions with saccharides may occur. These interactions are affected by the addition of amino acids. Amino acids with polar side groups show a strong tendency to interact with saccharides. In particular, serine shows a high tendency to interact with saccharides and significantly improves the detection sensitivity of saccharide compounds.

  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. 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

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Thermodynamic holography

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

    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.

  16. Thermodynamic analysis on an anisotropically superhydrophobic surface with a hierarchical structure

    NASA Astrophysics Data System (ADS)

    Zhao, Jieliang; Su, Zhengliang; Yan, Shaoze

    2015-12-01

    Superhydrophobic surfaces, which refer to the surfaces with contact angle higher than 150° and hysteresis less than 10°, have been reported in various studies. However, studies on the superhydrophobicity of anisotropic, hierarchical surfaces are limited and the corresponding thermodynamic mechanisms could not be explained thoroughly. Here we propose a simplified surface model of anisotropic patterned surface with dual scale roughness. Based on the thermodynamic method, we calculate the equilibrium contact angle (ECA) and the contact angle hysteresis (CAH) on the given surface. We show here that the hierarchical structure has much better anisotropic wetting properties than the single-scale one, and the results shed light on the potential application in controllable micro-/nano-fluidic systems. Our studies can be potentially applied for the fabrication of anisotropically superhydrophobic surfaces.

  17. 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.

  18. 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.

  19. 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

  20. A model for exergy analysis and thermodynamic bounds of Stirling refrigerators

    NASA Astrophysics Data System (ADS)

    Razani, A.; Dodson, C.; Roberts, T.

    2010-04-01

    A thermodynamic model based on exergy flow through a Stirling Refrigerator is developed. Important irreversibilities of the refrigerator due to external heat transfer with the reservoirs, heat leak, flow and heat transfer in regenerator are included in the model. Expansion and compression efficiencies are introduced in the model to account for the losses in these processes. The effect of a control phase shift between the mass flow rate and pressure across regenerator on the performance of the refrigerator is presented. Analytical solutions representing important quantities in the design of Stirling refrigerators such as the load curve, cooling power and efficiency in terms of basic system input parameters are developed. Thermodynamic bounds for the performance of Stirling refrigerators are obtained. Results indicating a compromise between cooling power and efficiency that are dependent on the constraint of the system are presented and discussed.

  1. 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

  2. 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.

  3. 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.

  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. Thermodynamic analysis of fermentation and anaerobic growth of baker's yeast for ethanol production.

    PubMed

    Teh, Kwee-Yan; Lutz, Andrew E

    2010-05-17

    Thermodynamic concepts have been used in the past to predict microbial growth yield. This may be the key consideration in many industrial biotechnology applications. It is not the case, however, in the context of ethanol fuel production. In this paper, we examine the thermodynamics of fermentation and concomitant growth of baker's yeast in continuous culture experiments under anaerobic, glucose-limited conditions, with emphasis on the yield and efficiency of bio-ethanol production. We find that anaerobic metabolism of yeast is very efficient; the process retains more than 90% of the maximum work that could be extracted from the growth medium supplied to the chemostat reactor. Yeast cells and other metabolic by-products are also formed, which reduces the glucose-to-ethanol conversion efficiency to less than 75%. Varying the specific ATP consumption rate, which is the fundamental parameter in this paper for modeling the energy demands of cell growth, shows the usual trade-off between ethanol production and biomass yield. The minimum ATP consumption rate required for synthesizing cell materials leads to biomass yield and Gibbs energy dissipation limits that are much more severe than those imposed by mass balance and thermodynamic equilibrium constraints.

  6. 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

  7. Inflight thermodynamic properties

    NASA Technical Reports Server (NTRS)

    Brown, S. C.; Daniels, G. E.; Johnson, D. L.; Smith, O. E.

    1973-01-01

    The inflight thermodynamic parameters (temperature, pressure, and density) of the atmosphere are presented. Mean and extreme values of the thermodynamic parameters given here can be used in application of many aerospace problems, such as: (1) research and planning and engineering design of remote earth sensing systems; (2) vehicle design and development; and (3) vehicle trajectory analysis, dealing with vehicle thrust, dynamic pressure, aerodynamic drag, aerodynamic heating, vibration, structural and guidance limitations, and reentry analysis. Atmospheric density plays a very important role in most of the above problems. A subsection on reentry is presented, giving atmospheric models to be used for reentry heating, trajectory, etc., analysis.

  8. Thermodynamics of Nonadditive Systems.

    PubMed

    Latella, Ivan; Pérez-Madrid, Agustín; Campa, Alessandro; Casetti, Lapo; Ruffo, Stefano

    2015-06-12

    The usual formulation of thermodynamics is based on the additivity of macroscopic systems. However, there are numerous examples of macroscopic systems that are not additive, due to the long-range character of the interaction among the constituents. We present here an approach in which nonadditive systems can be described within a purely thermodynamics formalism. The basic concept is to consider a large ensemble of replicas of the system where the standard formulation of thermodynamics can be naturally applied and the properties of a single system can be consequently inferred. After presenting the approach, we show its implementation in systems where the interaction decays as 1/r(α) in the interparticle distance r, with α smaller than the embedding dimension d, and in the Thirring model for gravitational systems.

  9. 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.

  10. Comments to Irreversibility in Thermodynamics

    NASA Technical Reports Server (NTRS)

    Zak, M.

    1995-01-01

    The problem of irreversibility in thermodynamics was revisited and analyzed on the microscopic, stochastic, and macroscopic levels of description. It was demonstrated that Newtonian dynamics can be represented in the Reynolds form, a new phenomenological force with non-Lipschitz properties was introduced, and additional non- Lipschitz thermodynamical forces were incorporated into macroscopic models of transport phenomena.

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

    DOE PAGES

    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.

  13. Thermodynamic analysis of chain-melting transition temperatures for monounsaturated phospholipid membranes: dependence on cis-monoenoic double bond position.

    PubMed Central

    Marsh, D

    1999-01-01

    Unsaturated phospholipid is the membrane component that is essential to the dynamic environment needed for biomembrane function. The dependence of the chain-melting transition temperature, T(t), of phospholipid bilayer membranes on the position, n(u), of the cis double bond in the glycerophospholipid sn-2 chain can be described by an expression of the form T(t) = T(t)(c)(1 + h'(c)|n(u) - n(c)|)/(1 + s'(c)|n(u) - n(c)|), where n(c) is the chain position of the double bond corresponding to the minimum transition temperature, T(t)(c), for constant diacyl lipid chain lengths. This implies that the incremental transition enthalpy (and entropy) contributed by the sn-2 chain is greater for whichever of the chain segments, above or below the double-bond position, is the longer. The critical position, n(c), of the double bond is offset from the center of the sn-2 chain by an approximately constant amount, deltan(c) approximately 1. 5 C-atom units. The dependence of the parameters T(t)(c), h'(c), and s'(c) on sn-1 and sn-2 chain lengths can be interpreted consistently when allowance is made for the chain packing mismatch between the sn-1 and sn-2 chains. The length of the sn-2 chain is reduced by approximately 0.8 C-atom units by the cis double bond, in addition to a shortening by approximately 1.3 C-atom units by the bent configuration at the C-2 position. Based on this analysis, a general thermodynamic expression is proposed for the dependence of the chain-melting transition temperature on the position of the cis double bond and on the sn-1 and sn-2 chain lengths. The above treatment is restricted mostly to double-bond positions close to the center of the sn-2 chain. For double bonds positioned closer to the carboxyl or terminal methyl ends of the sn-2 chain, the effects on transition enthalpy can be considerably larger. They may be interpreted by the same formalism, but with different characteristic parameters, h'(c) and s'(c), such that the shorter of the chain segments

  14. 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.

  15. Thermodynamic analysis of molecular beam epitaxy of compounds in the In-Se system

    NASA Astrophysics Data System (ADS)

    Chatillon, Christian; Emery, Jean-Yves

    1993-03-01

    The molecular beam epitaxy of the compounds In4Se3(s), InSe(s) and In2Se3(s) is analysed using thermodynamics of vaporization and condensation phenomena. The growth conditions are studied as referred to equilibrium conditions in order to identify the main gaseous species that compete in the condensation and evaporation processes and to indicate the species which may have a low sticking coefficient. The general behaviour of MBE growth parameters is well described by thermodynamics, the domains of existence of In4Se3(s), InSe(s) and In2Se3(s) being directly correlated to the experimental results. The sticking or condensation coefficient of selenium is determined to be 0.52 on InSe(s) and 0.41 to 0.28 on In2Se3(s). The origin of this coefficient value is analysed and discussed in terms of thermal accommodation of the polymeric Sen(g) incident gaseous species.

  16. 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.

  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.

  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. Folding of a model three-helix bundle protein: a thermodynamic and kinetic analysis.

    PubMed

    Zhou, Y; Karplus, M

    1999-11-05

    The kinetics and thermodynamics of an off-lattice model for a three-helix bundle protein are investigated as a function of a bias gap parameter that determines the energy difference between native and non-native contacts. A simple dihedral potential is used to introduce the tendency to form right-handed helices. For each value of the bias parameter, 100 trajectories of up to one microsecond are performed. Such statistically valid sampling of the kinetics is made possible by the use of the discrete molecular dynamics method with square-well interactions. This permits much faster simulations for off-lattice models than do continuous potentials. It is found that major folding pathways can be defined, although ensembles with considerable structural variation are involved. The large gap models generally fold faster than those with a smaller gap. For the large gap models, the kinetic intermediates are non-obligatory, while both obligatory and non-obligatory intermediates are present for small gap models. Certain large gap intermediates have a two-helix microdomain with one helix extended outward (as in domain-swapped dimers); the small gap intermediates have more diverse structures. The importance of studying the kinetic, as well as the thermodynamics, of folding for an understanding of the mechanism is discussed and the relation between kinetic and equilibrium intermediates is examined. It is found that the behavior of this model system has aspects that encompass both the "new" view and the "old" view of protein folding.

  20. Non-Equilibrium Thermodynamic Analysis on the Performance of AN Irreversible Thermally Driven Brownian Motor

    NASA Astrophysics Data System (ADS)

    Gao, Tianfu; Chen, Jincan

    Based on the general model of thermally-driven Brownian motors, an equivalent cycle system is established and the Onsager coefficients and efficiency at the maximum power output of the system are analytically calculated from non-equilibrium thermodynamics. It is found that the Onsager reciprocity relation holds and the Onsager coefficients are affected by the main irreversibilities existing in practical systems. Only when the heat leak and the kinetic energy change of the particle in the system are negligible, can the determinant of the Onsager matrix vanish. It is also found that in the frame of non-equilibrium thermodynamics, the power output and efficiency of an irreversible Brownian motor can be expressed to be the same form as those of an irreversible Carnot heat engine, so the results obtained here are of general significance. Moreover, these results are used to analyze the performance characteristics of a class of thermally-driven Brownian motors so that some important conclusions in literature may be directly derived from the present paper.

  1. A DFT-GGA based thermodynamic analysis of the secondary structure of proteins

    NASA Astrophysics Data System (ADS)

    Ismer, Lars; Neugebauer, Jörg

    2005-03-01

    Studies of the thermodynamic stability of the secondary structure of proteins are important for understanding the protein folding process. We have therefore estimated the free energy change to fold a fully extended structure (FES) into the α-helical conformation for isolated infinite poly-glycine (Gly) and -alanine (Ala) chains. The calculations have been performed employing DFT-GGA, a plane-wave pseudo-potential approach and the harmonic approximation. Our results reveal [1], that this approach leads to a significantly improved description of thermodynamic data with respect to previous studies based on empirical force fields. Further we find, that the enthalpy to transform an α-helix into an FES strongly reduces with increasing temperature: at room temperature the free energy difference for Gly is close to zero within the numerical error bar (0.5 kcal/mol), whereas for Ala the α-helix is by 1.0 kcal/mol more stable. We conclude, without recoursing to any empirical input parameters, that an isolated Ala-FES will even at room temperature spontaneously fold into an α-helix.1. L. Ismer, J. Ireta, S. Boeck and J. Neugebauer submitted to Phys. Rev. E

  2. 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).

  3. Quantitative analysis of soil calcium by laser-induced breakdown spectroscopy using addition and addition-internal standardizations

    NASA Astrophysics Data System (ADS)

    Shirvani-Mahdavi, Hamidreza; Shafiee, Parisa

    2016-12-01

    Matrix mismatching in the quantitative analysis of materials through calibration-based laser-induced breakdown spectroscopy (LIBS) is a serious problem. In this paper, to overcome the matrix mismatching, two distinct approaches named addition standardization (AS) and addition-internal combinatorial standardization (A-ICS) are demonstrated for LIBS experiments. Furthermore, in order to examine the efficiency of these methods, the concentration of calcium in ordinary garden soil without any fertilizer is individually measured by each of the two procedures. To achieve this purpose, ten standard samples with different concentrations of calcium (as the analyte) and copper (as the internal standard) are prepared in the form of cylindrical tablets, so that the soil plays the role of the matrix in all of them. The measurements indicate that the relative error of concentration compared to a certified value derived by induced coupled plasma optical emission spectroscopy is 3.97% and 2.23% for AS and A-ICS methods, respectively. Furthermore, calculations related to standard deviation indicates that A-ICS method may be more accurate than AS one.

  4. 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

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

    SciTech Connect

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

    2014-04-07

    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.

  6. Breaking the Carnot limit without violating the second law: A thermodynamic analysis of off-resonant quantum light generation

    NASA Astrophysics Data System (ADS)

    Boukobza, E.; Ritsch, H.

    2013-06-01

    The Carnot limit, formulated in 1824, represents the maximal efficiency of a classical heat engine. In this work we present a thermodynamical analysis of a light amplifier based on a three-level atom coupled off-resonantly to a single quantized cavity mode and to two heat reservoirs with positive temperatures. Based on standard work and heat flow equilibrium, we show that for a cavity blue-detuned with respect to the atomic resonance, the system can surpass the Carnot limit. Nevertheless, the second law of thermodynamics is still obeyed, as the total entropy always increases. By analyzing a semiclassical version of the model, we derive a formula for the critical frequency for which the Carnot limit is broken and a formula for the amplifier efficiency which agrees with its quantum counterpart. In the semiclassical regime, however, the second law is not satisfied and hence it does not offer a physically acceptable description of the system. Finally, we show that breaking the Carnot limit occurs also in a blue-detuned quantum amplifier with output coupling, which represents a realistic model of a laser or maser.

  7. Thermodynamic analysis of the heterodimerization of leucine zippers of Jun and Fos transcription factors

    SciTech Connect

    Seldeen, Kenneth L.; McDonald, Caleb B.; Deegan, Brian J.

    2008-10-31

    Jun and Fos are components of the AP1 family of transcription factors and bind to the promoters of a diverse multitude of genes involved in critical cellular responses such as cell growth and proliferation, cell cycle regulation, embryonic development and cancer. Here, using the powerful technique of isothermal titration calorimetry, we characterize the thermodynamics of heterodimerization of leucine zippers of Jun and Fos. Our data suggest that the heterodimerization of leucine zippers is driven by enthalpic forces with unfavorable entropy change at physiological temperatures. Furthermore, the basic regions appear to modulate the heterodimerization of leucine zippers and may undergo at least partial folding upon heterodimerization. Large negative heat capacity changes accompanying the heterodimerization of leucine zippers are consistent with the view that leucine zippers do not retain {alpha}-helical conformations in isolation and that the formation of the native coiled-coil {alpha}-helical dimer is attained through a coupled folding-dimerization mechanism.

  8. Experimental analysis of the thermodynamic mechanism of Langmuir-Blodgett film transfer

    SciTech Connect

    Egusa, Syun; Gemma, Nobuhiro, Azuma, Makoto )

    1990-03-22

    An experimental investigation was made on the mechanism for the transfer of a Langmuir-Blodgett (LB) film. The transfer ratio ({rho}) and the interfacial force (f) were observed for stearyl alcohol and cadmium stearate monolayers on silicon substrates, by systematically varying both the surface pressures ({pi}) of the monolayer and the hydrophilicities of the substrate characterized by contact angle ({theta}{sub 0}). It was found that the ratios {rho} observed both for up- and down-stroke depositions changed discretely within zero and unity, divided at the critical values of {pi} and {theta}{sub 0}. To examine the film-transfer characteristics, on the basis of thermodynamics, the interfacial forces applied to the moving substrate were measured during the deposition process.

  9. Doppler-width thermodynamic thermometry by means of line-absorbance analysis

    SciTech Connect

    Castrillo, A.; De Vizia, M. D.; Gianfrani, L.; Moretti, L.; Galzerano, G.; Laporta, P.; Merlone, A.

    2011-09-15

    A clean and effective implementation of Doppler-width thermometry is described. Exploiting the relationship between line-center absorbance and integrated absorbance, the Doppler width of a molecular spectral line can be retrieved from a set of profiles resulting from different gas pressures. The method is validated by its application to numerically simulated spectra. Preliminary experiments, in water vapor samples, turn out to be successful, demonstrating Doppler-widths' retrieval in the near-infrared with a precision of 8x10{sup -5}, at the water triple point temperature. The direct link to the Boltzmann constant makes the proposed method very attractive for temperature metrology as a tool for the realization of a new thermodynamic temperature scale.

  10. 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.

  11. THERMODYNAMIC ANALYSIS OF OPEN-CYCLE MULTISHAFT POWER SYSTEM WITH MULTIPLE REHEAT AND INTERCOOL

    NASA Technical Reports Server (NTRS)

    Glassman, A. J.

    1994-01-01

    This program computes the specific power output, specific fuel consumption, and cycle efficiency functions of turbine-inlet temperature, compressor pressure ratio, and component performance factors for power systems having any number of shafts up to a maximum of five. On each shaft there can be any number of compressors and turbines up to a maximum of five each, along with any specified number of intervening intercoolers and reheaters. A recuperator can be included in the system and turbine coolant flow can be accounted for. The combustion-gas thermodynamic properties are valid for any fuel consisting of hydrogen and/or carbon only. The program should be used with maximum temperatures no higher than about 2000 K (3140 degrees Fahrenheit) because molecular dissociation is not included in the stoichiometry. Improvements in cycle performance resulting from the use of intercooling, reheating, and recuperation can also be determined. This program has been implemented on the IBM 7094.

  12. Thermodynamic analysis of the plasma production of ferroniobium from a loparite concentrate

    NASA Astrophysics Data System (ADS)

    Nikolaev, A. A.; Kirpichev, D. E.; Nikolaev, A. V.; Tsvetkov, Yu. V.

    2013-11-01

    The possibility of pyrometallurgical processing of a loparite concentrate at a temperature of 2000-4000 K and a pressure of 0.1 MPa is thermodynamically studied using the TERRA software package. It is found that the niobium concentration in the concentrate almost doubles during plasma heating as a result of thermal decomposition and the precipitation of rare-earth metals into a gas phase. Crude niobium can be extracted from the thermally decomposed concentrate by carbothermic or aluminothermic reduction. After plasma-arc vacuum refining, crude niobium can be used for making commercial ferroniobium. The calculated energy consumed for the plasma production of ferroniobium from the loparite concentrate by carbothermic or aluminothermic reduction under adiabatic conditions is 46.6 or 79.0 GJ/(t ferroniobium), respectively. The energy consumption can even be increased severalfold, and the implementation of the process remains economically efficient at the existing market price of ferroniobium.

  13. A parametric analysis microcomputer model for evaluating the thermodynamic performance of a reciprocating Brayton cycle engine

    SciTech Connect

    Tsongas, G.A. ); White, T.J. )

    1989-10-01

    A Brayton open-cycle engine is under development. It operates similarly to a gas turbine engine, but uses reciprocating piston compressor and expander components. The design appears to have a number of advantages, including multifuel capability, the potential for lower cost, and the ability to be scaled to small sizes without significant loss in efficiency. An interactive microcomputer model has been developed that analyzes the thermodynamic performance of the engine. The model incorporates all the important irreversibilities found in piston devices, including heat transfer, mechanical friction, pressure losses, and mass loss and recirculation. There are 38 input parameters to the model. Key independent operating parameters are maximum temperature, compressor rpm, and pressure ratio. The development of the model and its assumptions are outlined in this paper. The emphasis is on model applications.

  14. A thermodynamic and mutational analysis of an RNA purine loop as a protein binding site.

    PubMed

    White, S A; Li, H; Rauch, M E

    1995-10-01

    The thermal stability and protein binding of a 36 nucleotide RNA hairpin containing an internal loop were studied under various solution conditions. Yeast ribosomal protein L32 binds to its transcript and small RNAs which reproduce the L32 transcript's secondary structure have been examined. Replacement of the internal loop with canonical base pairs did not affect the salt dependence of the melting temperature suggesting that both molecules adopt a linear shape. Several electrostatic contacts are formed on binding to a ribosomal fusion protein, but Mg+2 is not required for binding. The RNA protein complex is stable up to 50 degrees C. Two internal loop deletion mutants have similar thermodynamic stabilities and chemical and enzymatic reactivities, but fail to bind the fusion protein. However, several of the internal loop bases of the deletion mutants are moderately reactive to chemical agents whereas the wild type loop sequence displayed a mixed pattern of protection and hyperreactivity.

  15. Analysis of water sorption isotherms of amorphous food materials by solution thermodynamics with relevance to glass transition: evaluation of plasticizing effect of water by the thermodynamic parameters.

    PubMed

    Shimazaki, Eriko; Tashiro, Akiko; Kumagai, Hitomi; Kumagai, Hitoshi

    2017-04-01

    Relation between the thermodynamic parameters obtained from water sorption isotherms and the degree of reduction in the glass transition temperature (Tg), accompanied by water sorption, was quantitatively studied. Two well-known glassy food materials namely, wheat gluten and maltodextrin were used as samples. The difference between the chemical potential of water in a solution and that of pure water ([Formula: see text]), the difference between the chemical potential of solid in a solution and that of a pure solid ([Formula: see text]), and the change in the integral Gibbs free energy ([Formula: see text]) were obtained by analyzing the water sorption isotherms using solution thermodynamics. The parameter [Formula: see text] correlated well with ΔTg (≡Tg - Tg0; where Tg0 is the glass transition temperature of dry material), which had been taken to be an index of plasticizing effect. This indicates that plasticizing effect of water on foods can be evaluated through the parameter [Formula: see text].

  16. Mechanics, Waves and Thermodynamics

    NASA Astrophysics Data System (ADS)

    Ranjan Jain, Sudhir

    2016-05-01

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

  17. Thermodynamic analysis of effects of contact angle on interfacial interactions and its implications for membrane fouling control.

    PubMed

    Chen, Jianrong; Shen, Liguo; Zhang, Meijia; Hong, Huachang; He, Yiming; Liao, Bao-Qiang; Lin, Hongjun

    2016-02-01

    Concept of hydrophobicity always fails to accurately assess the interfacial interaction and membrane fouling, which calls for reliable parameters for this purpose. In this study, effects of contact angle on interfacial interactions related to membrane fouling were investigated based on thermodynamic analysis. It was found that, total interaction energy between sludge foulants and membrane monotonically decreases and increases with water and glycerol contact angle, respectively, indicating that these two parameters can be reliable indicators predicting total interaction energy and membrane fouling. Membrane roughness decreases interaction strength for over 20 times, and effects of membrane roughness on membrane fouling should consider water and glycerol contact angle on membrane. It was revealed existence of a critical water and glycerol contact angle for a given membrane bioreactor. Meanwhile, diiodomethane contact angle has minor effect on the total interaction, and cannot be regarded as an effective indicator assessing interfacial interactions and membrane fouling.

  18. 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.

  19. 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.

  20. 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

  1. Thermodynamic analysis and optimization of fuel cell based Combined Cycle Cogeneration plant

    NASA Astrophysics Data System (ADS)

    Odukoya, Adedoyin

    Power plants operating in combined cycle cogeneration configuration are becoming increasingly popular because of high energy conversion efficiency and reduced pollutant and green-house gas emissions. On the other hand, fuel cell technology continues to be of global interest because it can operate with very low to 0% green-house gas emission depending on the fuel. The aim of the present work is to investigate the effect of co-firing of natural gas with synthetic gas generated from coal gasification on the thermodynamic performance of an air blown coal gasification Combined Cycle Cogeneration unit with a solid oxide fuel cell (SOFC) arrangement. The effects of the operating temperature of the SOFC and the pressure ratio and turbine inlet temperature of the gas turbine on the net work output and efficiency of the power cycles on the cogeneration unit are simulated. Simulations are also conducted on the thermal and cogeneration efficiencies of the individual power cycle as well as the overall plants respectively. The optimal pressure ratio, temperature of operation of the SOFC and, gas turbine inlet temperature was determined using a sequential quadratic program solver base on the Quasi-Newton algorithm.

  2. 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.

  3. 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.

  4. 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

    2016-12-01

    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.

  5. A numerical model on thermodynamic analysis of free piston Stirling engines

    NASA Astrophysics Data System (ADS)

    Mou, Jian; Hong, Guotong

    2017-02-01

    In this paper, a new numerical thermodynamic model which bases on the energy conservation law has been used to analyze the free piston Stirling engine. In the model all data was taken from a real free piston Stirling engine which has been built in our laboratory. The energy conservation equations have been applied to expansion space and compression space of the engine. The equation includes internal energy, input power, output power, enthalpy and the heat losses. The heat losses include regenerative heat conduction loss, shuttle heat loss, seal leakage loss and the cavity wall heat conduction loss. The numerical results show that the temperature of expansion space and the temperature of compression space vary with the time. The higher regeneration effectiveness, the higher efficiency and bigger output work. It is also found that under different initial pressures, the heat source temperature, phase angle and engine work frequency pose different effects on the engine’s efficiency and power. As a result, the model is expected to be a useful tool for simulation, design and optimization of Stirling engines.

  6. Effects of polydisperse crowders on aggregation reactions: A molecular thermodynamic analysis

    NASA Astrophysics Data System (ADS)

    Shah, Dhawal; Tan, Aik Lee; Ramakrishnan, Vigneshwar; Jiang, Jianwen; Rajagopalan, Raj

    2011-02-01

    Intracellular crowding in biological systems is usually mimicked in in vitro experiments by adding single crowders at high volume fractions, without taking into consideration the polydispersity of the crowders in the cellular environment. Here, we develop a molecular thermodynamic formalism to examine the effects of size-polydispersity of crowders on aggregation reaction equilibria. Although the predominantly common practice so far has been to appeal to the entropic (excluded-volume) effects in describing crowding effects, we show that the internal energy (hence, the enthalpy) of the system could dramatically alter the effects, even qualitatively, particularly in the case of a mixture of crowders, depending on the changes in the covolume of the products relative to that of the reactants and on the preferential binding or exclusion of the crowders by the reactants and products. We also show that in the case of polydisperse crowders the crowders with the largest size difference dominate the overall changes in the yield of the reaction, depending on the individual concentrations of the crowders.

  7. Conversion of heat to light using Townes' maser-laser engine: Quantum optics and thermodynamic analysis

    SciTech Connect

    Ooi, C. H. Raymond

    2011-04-15

    It is shown that thermal energy from a heat source can be converted to useful work in the form of maser-laser light by using a combination of a Stern-Gerlach device and stimulated emissions of excited particles in a maser-laser cavity. We analyze the populations of atoms or quantum dots exiting the cavity, the photon statistics, and the internal entropy as a function of atomic transit time, using the quantum theory of masers and lasers. The power of the laser light is estimated to be sufficiently high for device applications. The thermodynamics of the heat converter is analyzed as a heat engine operating between two reservoirs of different temperature but is generalized to include the change of internal quantum states. The von Neumann entropies for the internal degree are obtained. The sum of the internal and external entropies increases after each cycle and the second law is not violated, even if the photon entropy due to finite photon number distribution is not included. An expression for efficiency relating to the Carnot efficiency is obtained. We resolve the subtle paradox on the reduction of the internal entropy with regards to the path separation after the Stern-Gerlach device.

  8. Thermodynamic analysis of framework deformation in Na,Cs-RHO zeolite upon CO2 adsorption.

    PubMed

    Pera-Titus, M; Palomino, M; Valencia, S; Rey, F

    2014-11-28

    Fully dehydrated and partially sodium-cesium containing RHO zeolite (Na,Cs-RHO) shows a genuine inflection in the CO2 isotherms in the temperature range 293-333 K that can be attributed to a sorbate-induced framework deformation from an acentric (A) to a centric (C) phase due to a partial cation rearrangement. This peculiar sorption pattern can be captured by the formulation of thermodynamic isotherms, providing a direct enthalpic and entropic signature of the CO2 adsorption-desorption process during deformation. Using this formulation, the energy barrier between the acentric and centric phases for CO2 adsorption-desorption was estimated in the range 4.7-9.6 J g(-1) of solid (15-32 kJ mol(-1)), reflecting a higher CO2 affinity for the acentric phase, whereas the elastic energy involved during framework distortion was estimated in the range 6-12 J g(-1) of solid (19-39 kJ mol(-1)) with a relative maximum at 303 K and showing a dominant entropic contribution.

  9. Enhanced weathering of olivine in seawater: The efficiency as revealed by thermodynamic scenario analysis.

    PubMed

    Griffioen, Jasper

    2017-01-01

    Enhanced weathering of olivine has been suggested as a measure to lower the atmospheric CO2 level and it might also mitigate ocean acidification. This study aimed to characterise how olivine can weather in seawater, to elucidate the role of secondary precipitation and to ascertain the efficiency in terms of molar CO2 removal per mole of olivine dissolution. Geochemical thermodynamic equilibrium modelling was used, which considered both the variable mineralogical composition of olivine and the kinds of secondary precipitates that may be formed. The advantage is that such an approach is independent from local or regional factors as temperature, related kinetics, mineralogy, etc. The results show that the efficiency falls when secondary precipitates are formed. When Fe-bearing olivine undergoes weathering in an oxic environment, Fe(III) hydroxides will inevitably be formed, and as a result of this acidifying process, CO2 could be released to the atmosphere. This might also enhance ocean acidification when Fe-rich olivine becomes used. Ocean alkalinisation only happens when more than 1mol/kgH2O Mg-rich olivine weathers. Maintenance of supersaturation for calcite or aragonite as holds in seawater reduces the efficiency by about a factor of two compared to the efficiency without secondary precipitation. Precipitation of sepiolite as Mg silicate reduces the efficiency even more. Magnesite precipitation has a similar effect to Ca carbonate precipitation, but according to the literature magnesite precipitation is improbable at ambient conditions and relatively low supersaturation. When less than 0.05mmololivine/kg(seawater) weathers the efficiency is slightly different than at higher intensities, due to strong buffering by seawater alkalinity.

  10. A First-Law Thermodynamic Analysis of the Corn-Ethanol Cycle

    SciTech Connect

    Patzek, Tad W.

    2006-12-15

    This paper analyzes energy efficiency of the industrial corn-ethanol cycle. In particular, it critically evaluates earlier publications by DOE, USDA, and UC Berkeley Energy Resources Group. It is demonstrated that most of the current First Law net-energy models of the industrial corn-ethanol cycle are based on nonphysical assumptions and should be viewed with caution. In particular, these models do not (i) define the system boundaries, (ii) conserve mass, and (iii) conserve energy. The energy cost of producing and refining carbon fuels in real time, for example, corn and ethanol, is high relative to that of fossil fuels deposited and concentrated over geological time. Proper mass and energy balances of corn fields and ethanol refineries that account for the photosynthetic energy, part of the environment restoration work, and the coproduct energy have been formulated. These balances show that energetically production of ethanol from corn is 2-4 times less favorable than production of gasoline from petroleum. From thermodynamics it also follows that ecological damage wrought by industrial biofuel production must be severe. With the DDGS coproduct energy credit, 3.9 gallons of ethanol displace on average the energy in 1 gallon of gasoline. Without the DDGS energy credit, this average number is 6.2 gallons of ethanol. Equivalent CO{sub 2} emissions from corn ethanol are some 50% higher than those from gasoline, and become 100% higher if methane emissions from cows fed with DDGS are accounted for. From the mass balance of soil it follows that ethanol coproducts should be returned to the fields.

  11. Thermodynamic and kinetic analysis of carbohydrate binding to the basic lectin from winged bean (Psophocarpus tetragonolobus).

    PubMed

    Khan, M I; Sastry, M V; Surolia, A

    1986-03-05

    A basic lectin (pI approximately 10.0) was purified to homogeneity from the seeds of winged bean (Psophocarpus tetragonolobus) by affinity chromatography on Sepharose 6-aminocaproyl-D-galactosamine. The lectin agglutinated trypsinized rabbit erythrocytes and had a relative molecular mass of 58,000 consisting of two subunits of Mr 29,000. The lectin binds to N-dansylgalactosamine, leading to a 15-fold increase in dansyl fluorescence with a concomitant 25-nm blue shift in the emission maximum. The lectin has two binding sites/dimer for this sugar and an association constant of 4.17 X 10(5) M-1 at 25 degrees C. The strong binding to N-dansylgalactosamine is due to a relatively positive entropic contribution as revealed by the thermodynamic parameters: delta H = -33.62 kJ mol-1 and delta S0 = -5.24 J mol-1 K-1. Binding of this sugar to the lectin shows that it can accommodate a large hydrophobic substituent on the C-2 carbon of D-galactose. Studies with other sugars indicate that a hydrophobic substituent in alpha-conformation at the anomeric position increases the affinity of binding. The C-4 and C-6 hydroxyl groups are critical for sugar binding to this lectin. Lectin difference absorption spectra in the presence of N-acetylgalactosamine indicate perturbation of tryptophan residues on sugar binding. The results of stopped flow kinetics with N-dansylgalactosamine and the lectin are consistent with a simple one-step mechanism for which k+1 = 1.33 X 10(4) M-1 s-1 and k-1 = 3.2 X 10(-2) s-1 at 25 degrees C. This k-1 is slower than any reported for a lectin-monosaccharide complex so far. The activation parameters indicate an enthalpically controlled association process.

  12. Chemical and biochemical thermodynamics: Is it time for a reunification?

    PubMed

    Iotti, Stefano; Raff, Lionel; Sabatini, Antonio

    2017-02-01

    The thermodynamics of chemical reactions in which all species are explicitly considered with atoms and charge balanced is compared with the transformed thermodynamics generally used to treat biochemical reactions where atoms and charges are not balanced. The transformed thermodynamic quantities suggested by Alberty are obtained by execution of Legendre transformation of the usual thermodynamic potentials. The present analysis demonstrates that the transformed values for ΔrG'(0) and ΔrH'(0)can be obtained directly without performing Legendre transformations by simply writing the chemical reactions with all the pseudoisomers explicitly included and charges balanced. The appropriate procedures for computing the stoichiometric coefficients for the pseudoisomers are fully explained by means of an example calculation for the biochemical ATP hydrolysis reaction. It is concluded that the analysis has reunited the "two separate worlds" of conventional thermodynamics and transformed thermodynamics. In addition, it is also shown that the value of the conditional Gibbs energy of reaction, ΔrG', for a biochemical reaction is the same of the value of ΔrG for any chemical reaction involving pseudoisomers of the biochemical reagents.

  13. Expression QTL analysis of top loci from GWAS meta-analysis highlights additional schizophrenia candidate genes.

    PubMed

    de Jong, Simone; van Eijk, Kristel R; Zeegers, Dave W L H; Strengman, Eric; Janson, Esther; Veldink, Jan H; van den Berg, Leonard H; Cahn, Wiepke; Kahn, René S; Boks, Marco P M; Ophoff, Roel A

    2012-09-01

    There is genetic evidence that schizophrenia is a polygenic disorder with a large number of loci of small effect on disease susceptibility. Genome-wide association studies (GWASs) of schizophrenia have had limited success, with the best finding at the MHC locus at chromosome 6p. A recent effort of the Psychiatric GWAS consortium (PGC) yielded five novel loci for schizophrenia. In this study, we aim to highlight additional schizophrenia susceptibility loci from the PGC study by combining the top association findings from the discovery stage (9394 schizophrenia cases and 12 462 controls) with expression QTLs (eQTLs) and differential gene expression in whole blood of schizophrenia patients and controls. We examined the 6192 single-nucleotide polymorphisms (SNPs) with significance threshold at P<0.001. eQTLs were calculated for these SNPs in a sample of healthy controls (n=437). The transcripts significantly regulated by the top SNPs from the GWAS meta-analysis were subsequently tested for differential expression in an independent set of schizophrenia cases and controls (n=202). After correction for multiple testing, the eQTL analysis yielded 40 significant cis-acting effects of the SNPs. Seven of these transcripts show differential expression between cases and controls. Of these, the effect of three genes (RNF5, TRIM26 and HLA-DRB3) coincided with the direction expected from meta-analysis findings and were all located within the MHC region. Our results identify new genes of interest and highlight again the involvement of the MHC region in schizophrenia susceptibility.

  14. 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…

  15. 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

  16. 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

  17. 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...

  18. 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.

  19. Thermodynamic analysis of ligand binding and ligand binding-induced tertiary structure formation by the thiamine pyrophosphate riboswitch.

    PubMed

    Kulshina, Nadia; Edwards, Thomas E; Ferré-D'Amaré, Adrian R

    2010-01-01

    The thi-box riboswitch regulates gene expression in response to the intracellular concentration of thiamine pyrophosphate (TPP) in archaea, bacteria, and eukarya. To complement previous biochemical, genetic, and structural studies of this phylogenetically widespread RNA domain, we have characterized its interaction with TPP by isothermal titration calorimetry. This shows that TPP binding is highly dependent on Mg(2+) concentration. The dissociation constant decreases from approximately 200 nM at 0.5 mM Mg(2+) concentration to approximately 9 nM at 2.5 mM Mg(2+) concentration. Binding is enthalpically driven, but the unfavorable entropy of binding decreases as Mg(2+) concentration rises, suggesting that divalent cations serve to pre-organize the RNA. Mutagenesis, biochemical analysis, and a new crystal structure of the riboswitch suggest that a critical element that participates in organizing the riboswitch structure is the tertiary interaction formed between the P3 and L5 regions. This tertiary contact is distant from the TPP binding site, but calorimetric analysis reveals that even subtle mutations in L5 can have readily detectable effects on TPP binding. The thermodynamic signatures of these mutations, namely decreased favorable enthalpy of binding and small effects on entropy of binding, are consistent with the P3-L5 association contributing allosterically to TPP-induced compaction of the RNA.

  20. Morphometric Image Analysis of Giant Vesicles: A New Tool for Quantitative Thermodynamics Studies of Phase Separation in Lipid Membranes

    PubMed Central

    Husen, Peter; Arriaga, Laura R.; Monroy, Francisco; Ipsen, John H.; Bagatolli, Luis A.

    2012-01-01

    We have developed a strategy to determine lengths and orientations of tie lines in the coexistence region of liquid-ordered and liquid-disordered phases of cholesterol containing ternary lipid mixtures. The method combines confocal-fluorescence-microscopy image stacks of giant unilamellar vesicles (GUVs), a dedicated 3D-image analysis, and a quantitative analysis based in equilibrium thermodynamic considerations. This approach was tested in GUVs composed of 1,2-dioleoyl-sn-glycero-3-phosphocholine/1,2-palmitoyl-sn-glycero-3-phosphocholine/cholesterol. In general, our results show a reasonable agreement with previously reported data obtained by other methods. For example, our computed tie lines were found to be nonhorizontal, indicating a difference in cholesterol content in the coexisting phases. This new, to our knowledge, analytical strategy offers a way to further exploit fluorescence-microscopy experiments in GUVs, particularly retrieving quantitative data for the construction of three lipid-component-phase diagrams containing cholesterol. PMID:23283229

  1. Metabolic network analysis of perfused livers under fed and fasted states: incorporating thermodynamic and futile-cycle-associated regulatory constraints.

    PubMed

    Orman, Mehmet A; Androulakis, Ioannis P; Berthiaume, Francois; Ierapetritou, Marianthi G

    2012-01-21

    Isolated liver perfusion systems have been extensively used to characterize intrinsic metabolic changes in liver under various conditions, including systemic injury, hepatotoxin exposure, and warm ischemia. Most of these studies were performed utilizing fasted animals prior to perfusion so that a simplified metabolic network could be used in order to determine intracellular fluxes. However, fasting induced metabolic alterations might interfere with disease related changes. Therefore, there is a need to develop a "unified" metabolic flux analysis approach that could be similarly applied to both fed and fasted states. In this study we explored a methodology based on elementary mode analysis in order to determine intracellular fluxes and active pathways simultaneously. In order to decrease the solution space, thermodynamic constraints, and enzymatic regulatory properties for the formation of futile cycles were further considered in the model, resulting in a mixed integer quadratic programming problem. Given the published experimental observations describing the perfused livers under fed and fasted states, the proposed approach successfully determined that gluconeogenesis, glycogenolysis and fatty acid oxidation were active in both states. However, fasting increased the fluxes in gluconeogenic reactions whereas it decreased fluxes associated with glycogenolysis, TCA cycle, fatty acid oxidation and electron transport reactions. This analysis further identified that more pathways were found to be active in fed state while their weight values were relatively lower compared to fasted state. Glucose, lactate, glutamine, glutamate and ketone bodies were also found to be important external metabolites whose extracellular fluxes should be used in the hepatic metabolic network analysis. In conclusion, the mathematical formulation explored in this study is an attractive tool to analyze the metabolic network of perfused livers under various disease conditions. This approach could

  2. Thermodynamic analysis and kinetic modelling of dioxin formation and emissions from power boilers firing salt-laden hog fuel.

    PubMed

    Duo, Wenli; Leclerc, Denys

    2007-04-01

    Both organic chlorine (e.g. PVC) and inorganic chlorides (e.g. NaCl) can be significant chlorine sources for dioxin and furan (PCDD/F) formation in combustion processes. This paper presents a thermodynamic analysis of high temperature salt chemistry. Its influence on PCDD/F formation in power boilers burning salt-laden wood waste is examined through the relationships between Cl2, HCl, NaCl(g) and NaCl(c). These analyses show that while HCl is a product of combustion of PVC-laden municipal solid waste, NaCl can be converted to HCl in hog fuel boilers by reactions with SO2 or alumino-silicate materials. Cl2 is a strong chlorinating agent for PCDD/F formation. HCl can be oxidized to Cl2 by O2, and Cl2 can be reduced back to HCl by SO2. The presence of sulphur at low concentrations thus enhances PCDD/F formation by increasing HCl concentrations. At high concentrations, sulphur inhibits de novo formation of PCDD/Fs through Cl2 reduction by excess SO2. The effect of NH3, CO and NOx on PCDD/F formation is also discussed. A semi-empirical kinetic model is proposed. This model considers both precursor and de novo formation mechanisms. A simplified version is used as a stack emission model. The kinetic model indicates that stack dioxin emissions will increase linearly with decreasing electrostatic precipitator (ESP) efficiency and exponentially with increasing ESP temperature.

  3. Polyoxomolybdate formation - A thermodynamic analysis from density functional/PCM calculations

    NASA Astrophysics Data System (ADS)

    Steffler, Fernando; de Lima, Guilherme Ferreira; Duarte, Hélio Anderson

    2017-02-01

    Polyoxomolybdates have been intensely investigated, but their mechanisms of formation are not completely understood. The complex equilibrium of different species is affected by concentration, pH, ionic strength and temperature. It is a challenging system to model using computational chemistry. In the present work, density functional calculations were carried out using the polarizable continuum method to include solvent effects in an effort to provide insight into the mechanism of polyoxomolybdate formation in aqueous solution. We establish a possible sequence of reactions for the formation of small polyoxomolybdates containing up to 8 Mo by addition of the monomeric unit [MoO4]2-.

  4. Thermodynamics of Asymptotically Conical Geometries.

    PubMed

    Cvetič, Mirjam; Gibbons, Gary W; Saleem, Zain H

    2015-06-12

    We study the thermodynamical properties of a class of asymptotically conical geometries known as "subtracted geometries." We derive the mass and angular momentum from the regulated Komar integral and the Hawking-Horowitz prescription and show that they are equivalent. By deriving the asymptotic charges, we show that the Smarr formula and the first law of thermodynamics hold. We also propose an analog of Christodulou-Ruffini inequality. The analysis can be generalized to other asymptotically conical geometries.

  5. Ab initio molecular orbital study of substituent effects in vaska type complexes (trans-IrL{sub 2}(CO)X): Electron affinities, ionization potentials, carbonyl stretch frequencies, and the thermodynamics of H{sub 2} dissociative addition

    SciTech Connect

    Abu-Hasanayn, F.; Goldman, A.S.; Krogh-Jespersen, K.

    1994-10-26

    Ab initio electronic structure calculations are used to study substituent effects in Vaska-type complexes, trans-IrL{sub 2}(CO)X (1-X) (X = F, Cl, Br, I, CN, H, CH{sub 3}, SiH{sub 3}, OH, and SH; L = PH{sub 3}). Both the electron affinity and the ionization potential of 1-X are computed to increase upon descending the halogen series of complexes, which indicates, surprisingly, that the complexes with more electronegative halogens are more difficult to reduce and easier to oxidize. The computed electron affinity trend is consistent with the half-wave reduction potential trend known for 1-X (L = PPh{sub 3}; X = F, Cl, Br, and I). Computed carbonyl stretch frequencies for 1-X are greater than experimental values (L = PPh{sub 3}), but observed trends are well reproduced. The redox and spectroscopic trends are discussed in terms of the substituent effects on the electronic structure of 1-X, particularly as revealed in the molecular orbital energy level diagrams of these complexes. The reaction energy for H{sub 2} addition to 1-X, leading to the cis,trans-(H){sub 2}IrL{sub 2}(CO)X (2-X) product, has been computed. After electron correlation effects are included (MP4(SDTQ)), the reaction enthalpy computed for 1-CI is {minus}18.4 kcal/mol (L = PH{sub 3}) as compared to a reported experimental value of {minus}14 kcal/mol (L = PPh{sub 3}). Compared with available experimental data, the electronic effects of L(L = PH{sub 3}, NH{sub 3}, or AsH{sub 3}) and X on the thermodynamics of the H{sub 2} addition reaction are accurately reproduced by the model calculations at all levels of theory (HF and MPn). Formation of the hypothetical products cis,trans- and trans,trans-(H){sub 2}IrL{sub 2}(CO)X(2-X and 3-X) (X = BH{sub 2}, NH{sub 2}, and PH{sub 2}) is used to demonstrate that {pi}-acceptor substituents promote the H{sub 2} addition reaction to 1-X while {pi}-donor substituents disfavor addition.

  6. Spatial Analysis and Quantification of the Thermodynamic Driving Forces in Protein-Ligand Binding: Binding Site Variability

    PubMed Central

    Raman, E. Prabhu; MacKerell, Alexander D.

    2015-01-01

    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 provides an unprecedented level of detail into the mechanisms of binding. Direct protein-ligand interaction energies play a significant role in both non-polar 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. Notable is 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

  7. Thermodynamics of weight loss diets.

    PubMed

    Fine, Eugene J; Feinman, Richard D

    2004-12-08

    BACKGROUND: It is commonly held that "a calorie is a calorie", i.e. that diets of equal caloric content will result in identical weight change independent of macronutrient composition, and appeal is frequently made to the laws of thermodynamics. We have previously shown that thermodynamics does not support such a view and that diets of different macronutrient content may be expected to induce different changes in body mass. Low carbohydrate diets in particular have claimed a "metabolic advantage" meaning more weight loss than in isocaloric diets of higher carbohydrate content. In this review, for pedagogic clarity, we reframe the theoretical discussion to directly link thermodynamic inefficiency to weight change. The problem in outline: Is metabolic advantage theoretically possible? If so, what biochemical mechanisms might plausibly explain it? Finally, what experimental evidence exists to determine whether it does or does not occur? RESULTS: Reduced thermodynamic efficiency will result in increased weight loss. The laws of thermodynamics are silent on the existence of variable thermodynamic efficiency in metabolic processes. Therefore such variability is permitted and can be related to differences in weight lost. The existence of variable efficiency and metabolic advantage is therefore an empiric question rather than a theoretical one, confirmed by many experimental isocaloric studies, pending a properly performed meta-analysis. Mechanisms are as yet unknown, but plausible mechanisms at the metabolic level are proposed. CONCLUSIONS: Variable thermodynamic efficiency due to dietary manipulation is permitted by physical laws, is supported by much experimental data, and may be reasonably explained by plausible mechanisms.

  8. 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.

  9. Complete determination of the Pin1 catalytic domain thermodynamic cycle by NMR lineshape analysis.

    PubMed

    Greenwood, Alexander I; Rogals, Monique J; De, Soumya; Lu, Kun Ping; Kovrigin, Evgenii L; Nicholson, Linda K

    2011-09-01

    The phosphorylation-specific peptidyl-prolyl isomerase Pin1 catalyzes the isomerization of the peptide bond preceding a proline residue between cis and trans isomers. To best understand the mechanisms of Pin1 regulation, rigorous enzymatic assays of isomerization are required. However, most measures of isomerase activity require significant constraints on substrate sequence and only yield rate constants for the cis isomer, [Formula: see text] and apparent Michaelis constants, [Formula: see text]. By contrast, NMR lineshape analysis is a powerful tool for determining microscopic rates and populations of each state in a complex binding scheme. The isolated catalytic domain of Pin1 was employed as a first step towards elucidating the reaction scheme of the full-length enzyme. A 24-residue phosphopeptide derived from the amyloid precurser protein intracellular domain (AICD) phosphorylated at Thr668 served as a biologically-relevant Pin1 substrate. Specific (13)C labeling at the Pin1-targeted proline residue provided multiple reporters sensitive to individual isomer binding and on-enzyme catalysis. We have performed titration experiments and employed lineshape analysis of phosphopeptide (13)C-(1)H constant time HSQC spectra to determine [Formula: see text], [Formula: see text], [Formula: see text], and [Formula: see text] for the catalytic domain of Pin1 acting on this AICD substrate. The on-enzyme equilibrium value of [E·trans]/[E·cis] = 3.9 suggests that the catalytic domain of Pin1 is optimized to operate on this substrate near equilibrium in the cellular context. This highlights the power of lineshape analysis for determining the microscopic parameters of enzyme catalysis, and demonstrates the feasibility of future studies of Pin1-PPIase mutants to gain insights on the catalytic mechanism of this important enzyme.

  10. 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.

  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 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.

  13. 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.

  14. Thermodynamic property evaluation and magnetic refrigeration cycle analysis for gadolinium gallium garnet

    SciTech Connect

    Murphy, R.W.

    1994-12-01

    Based on relevant material property data and previous model formulations, a magnetothermodynamic property map for gadolinium gallium garnet (Gd{sub 3}Ga{sub 5}O{sub 12}) was adapted for refrigeration cycle analysis in the temperature range 4-40 K and the magnetic field range 0-6 T. Employing methods similar to those previously developed for other materials and temperature ranges, assessments of limitations and relative performance were made for Carnot, ideal regenerative, and pseudo-constant field regenerative cycles. It was found that although Carnot cycle limitations on available temperature lift for gadolinium gallium garnet are not as severe as the limitations for materials previously examined, considerable improvement in cooling capacity and temperature lift combinations can be achieved by using regenerative cycles if serious loss mechanisms are avoided.

  15. 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.

  16. Nonequilibrium thermodynamics of nucleation.

    PubMed

    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.

  17. Nonequilibrium thermodynamics of nucleation

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  18. Modeling anaerobic digestion of blue algae: stoichiometric coefficients of amino acids acidogenesis and thermodynamics analysis.

    PubMed

    Yuan, Xian-Zheng; Shi, Xiao-Shuang; Yuan, Chun-Xin; Wang, Yu-Ping; Qiu, Yan-Ling; Guo, Rong-Bo; Wang, Li-Sheng

    2014-02-01

    In order to facilitate the application of Anaerobic Digestion Model No. 1 (ADM1), an approach for a detailed calculation of stoichiometric coefficients for amino acids acidogenesis during the anaerobic digestion of blue algae is presented. The simulation results obtained support the approach by good predictions of the dynamic behavior of cumulative methane production, pH values as well as the concentrations of acetate, propionate, butyrate, valerate and inorganic nitrogen. The sensitivity analysis based on Monte Carlo simulation showed that the stoichiometric coefficients for amino acids acidogenesis had high sensitivities to the outputs of the model. The model further indicated that the Gibbs free energies from the uptake of long-chain fatty acids (LCFA), valerate and butyrate were positive through the digestion, while the free energies for other components were negative. During the digestion, the cumulative heat productions from microbial activities and methane were 77.69 kJ and 185.76 kJ, respectively. This result suggested that proper heat preservation of anaerobic digesters could minimize the external heating needs due to the heat produced from microbial activities.

  19. Effect of silicate structure on thermodynamic properties of calcium silicate melts: Quantitative analysis of Raman spectra

    NASA Astrophysics Data System (ADS)

    Park, Joo Hyun

    2013-05-01

    The distribution of silicate anionic species (Qn units, n=0, 1, 2, 3) and the chemical speciation of oxygen in CaO-SiO2-MO (M=Mn and Mg) slags were investigated by micro-Raman spectroscopic analysis. Furthermore, the thermochemical properties were evaluated using a concentration of free oxygen and a degree of polymerization. A good linear relationship was obtained between sulfide capacity and concentration of free oxygen in the CaO-SiO2 (-MnO) melts at 1500 to 1600 °C. However, even though there was more abundant free oxygen in the CaO-SiO2-MgO system than in the CaO-SiO2 system, the sulfide capacity of the former was lower than the latter, indicating that the sulfur dissolution behavior in the silicate melts cannot be simply explained by the content of free oxygen, because the composition dependency of the stability ratio of oxygen and sulfide ions should be taken into account. The excess free energy of CaO, MgO and MnO linearly decreased as the ln (Q3/Q2) increased. The effect of the degree of polymerization on the excess free energy of mixing of MgO-containing slag was larger than that of MnO-containing slag, which was explained by the difference of the ionization potential between Mn2+ and Mg2+ ions.

  20. 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.

  1. 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.

  2. 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…

  3. 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.

  4. 7 CFR 91.38 - Additional fees for appeal of analysis.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 7 Agriculture 3 2011-01-01 2011-01-01 false Additional fees for appeal of analysis. 91.38 Section 91.38 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Standards, Inspections, Marketing Practices), DEPARTMENT OF AGRICULTURE (CONTINUED)...

  5. 7 CFR 91.38 - Additional fees for appeal of analysis.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 3 2010-01-01 2010-01-01 false Additional fees for appeal of analysis. 91.38 Section 91.38 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Standards, Inspections, Marketing Practices), DEPARTMENT OF AGRICULTURE (CONTINUED)...

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. Reducing the matrix effects in chemical analysis: fusion of isotope dilution and standard addition methods

    NASA Astrophysics Data System (ADS)

    Pagliano, Enea; Meija, Juris

    2016-04-01

    The combination of isotope dilution and mass spectrometry has become an ubiquitous tool of chemical analysis. Often perceived as one of the most accurate methods of chemical analysis, it is not without shortcomings. Current isotope dilution equations are not capable of fully addressing one of the key problems encountered in chemical analysis: the possible effect of sample matrix on measured isotope ratios. The method of standard addition does compensate for the effect of sample matrix by making sure that all measured solutions have identical composition. While it is impossible to attain such condition in traditional isotope dilution, we present equations which allow for matrix-matching between all measured solutions by fusion of isotope dilution and standard addition methods.

  11. 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

  12. Thermodynamic efficiency out of equilibrium

    NASA Astrophysics Data System (ADS)

    Sivak, David; Crooks, Gavin

    2011-03-01

    Molecular-scale machines typically operate far from thermodynamic equilibrium, limiting the applicability of equilibrium statistical mechanics to understand their efficiency. Thermodynamic length analysis relates a non-equilibrium property (dissipation) to equilibrium properties (equilibrium fluctuations and their relaxation time). Herein we demonstrate that the thermodynamic length framework follows directly from the assumptions of linear response theory. Uniting these two frameworks provides thermodynamic length analysis a firmer statistical mechanical grounding, and equips linear response theory with a metric structure to facilitate the prediction and discovery of optimal (minimum dissipation) paths in complicated free energy landscapes. To explore the applicability of this theoretical framework, we examine its accuracy for simple bistable systems, parametrized to model single-molecule force-extension experiments. Through analytic derivation of the equilibrium fluctuations and numerical calculation of the dissipation and relaxation time, we verify that thermodynamic length analysis (though derived in a near-equilibrium limit) provides a strikingly good approximation even far from equilibrium, and thus provides a useful framework for understanding molecular motor efficiency.

  13. Falcon: Visual analysis of large, irregularly sampled, and multivariate time series data in additive manufacturing

    DOE PAGES

    Steed, Chad A.; Halsey, William; Dehoff, Ryan; ...

    2017-02-16

    Flexible visual analysis of long, high-resolution, and irregularly sampled time series data from multiple sensor streams is a challenge in several domains. In the field of additive manufacturing, this capability is critical for realizing the full potential of large-scale 3D printers. Here, we propose a visual analytics approach that helps additive manufacturing researchers acquire a deep understanding of patterns in log and imagery data collected by 3D printers. Our specific goals include discovering patterns related to defects and system performance issues, optimizing build configurations to avoid defects, and increasing production efficiency. We introduce Falcon, a new visual analytics system thatmore » allows users to interactively explore large, time-oriented data sets from multiple linked perspectives. Falcon provides overviews, detailed views, and unique segmented time series visualizations, all with adjustable scale options. To illustrate the effectiveness of Falcon at providing thorough and efficient knowledge discovery, we present a practical case study involving experts in additive manufacturing and data from a large-scale 3D printer. The techniques described are applicable to the analysis of any quantitative time series, though the focus of this paper is on additive manufacturing.« less

  14. Dental indications for the instrumental functional analysis in additional consideration of health-economic aspects

    PubMed Central

    Tinnemann, Peter; Stöber, Yvonne; Roll, Stephanie; Vauth, Christoph; Willich, Stefan N.; Greiner, Wolfgang

    2010-01-01

    Background Besides clinical and radiological examination instrumental functional analyses are performed as diagnostic procedures for craniomandibular dysfunctions. Instrumental functional analyses cause substantial costs and shows a considerable variability between individual dentist practices. Objectives On the basis of published scientific evidence the validity of the instrumental functional analysis for the diagnosis of craniomandibular dysfunctions compared to clinical diagnostic procedures; the difference of the various forms of the instrumental functional analysis; the existence of a dependency on additional other factors and the need for further research are determined in this report. In addition, the cost effectiveness of the instrumental functional analysis is analysed in a health-policy context, and social, legal and ethical aspects are considered. Methods A literature search is performed in over 27 databases and by hand. Relevant companies and institutions are contacted concerning unpublished studies. The inclusion criteria for publications are (i) diagnostic studies with the indication “craniomandibular malfunction”, (ii) a comparison between clinical and instrumental functional analysis, (iii) publications since 1990, (iv) publications in English or German. The identified literature is evaluated by two scientists regarding the relevance of content and methodical quality. Results The systematic database search resulted in 962 hits. 187 medical and economic complete publications are evaluated. Since the evaluated studies are not relevant enough to answer the medical or health economic questions no study is included. Discussion The inconsistent terminology concerning craniomandibular dysfunctions and instrumental functional analyses results in a broad literature search in databases and an extensive search by hand. Since no relevant results concerning the validity of the instrumental functional analysis in comparison to the clinical functional analysis

  15. Comparative analysis of electric field influence on the quantum wells with different boundary conditions: II. Thermodynamic properties.

    PubMed

    Olendski, Oleg

    2015-04-01

    Thermodynamic properties of the one-dimensional (1D) quantum well (QW) with miscellaneous permutations of the Dirichlet (D) and Neumann (N) boundary conditions (BCs) at its edges in the perpendicular to the surfaces electric field [Formula: see text] are calculated. For the canonical ensemble, analytical expressions involving theta functions are found for the mean energy and heat capacity [Formula: see text] for the box with no applied voltage. Pronounced maximum accompanied by the adjacent minimum of the specific heat dependence on the temperature T for the pure Neumann QW and their absence for other BCs are predicted and explained by the structure of the corresponding energy spectrum. Applied field leads to the increase of the heat capacity and formation of the new or modification of the existing extrema what is qualitatively described by the influence of the associated electric potential. A remarkable feature of the Fermi grand canonical ensemble is, at any BC combination in zero fields, a salient maximum of [Formula: see text] observed on the T axis for one particle and its absence for any other number N of corpuscles. Qualitative and quantitative explanation of this phenomenon employs the analysis of the chemical potential and its temperature dependence for different N. It is proved that critical temperature [Formula: see text] of the Bose-Einstein (BE) condensation increases with the applied voltage for any number of particles and for any BC permutation except the ND case at small intensities [Formula: see text] what is explained again by the modification by the field of the interrelated energies. It is shown that even for the temperatures smaller than [Formula: see text] the total dipole moment [Formula: see text] may become negative for the quite moderate [Formula: see text]. For either Fermi or BE system, the influence of the electric field on the heat capacity is shown to be suppressed with N growing. Different asymptotic cases of, e.g., the small and

  16. 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

  17. 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

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

    PubMed

    Marcus, R A

    2006-08-29

    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 12C/13C 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.

  19. 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.

  20. 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.

  1. 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

  2. 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%).

  3. 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.

  4. 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.

  5. Structural and thermodynamic investigations on the aggregation and folding of acylphosphatase by molecular dynamics simulations and solvation free energy analysis.

    PubMed

    Chong, Song-Ho; Lee, Chewook; Kang, Guipeun; Park, Mirae; Ham, Sihyun

    2011-05-11

    Protein engineering method to study the mutation effects on muscle acylphosphatase (AcP) has been actively applied to describe kinetics and thermodynamics associated with AcP aggregation as well as folding processes. Despite the extensive mutation experiments, the molecular origin and the structural motifs for aggregation and folding kinetics as well as thermodynamics of AcP have not been rationalized at the atomic resolution. To this end, we have investigated the mutation effects on the structures and thermodynamics for the aggregation and folding of AcP by using the combination of fully atomistic, explicit-water molecular dynamics simulations, and three-dimensional reference interaction site model theory. The results indicate that the A30G mutant with the fastest experimental aggregation rate displays considerably decreased α1-helical contents as well as disrupted hydrophobic core compared to the wild-type AcP. Increased solvation free energy as well as hydrophobicity upon A30G mutation is achieved due to the dehydration of hydrophilic side chains in the disrupted α1-helix region of A30G. In contrast, the Y91Q mutant with the slowest aggregation rate shows a non-native H-bonding network spanning the mutation site to hydrophobic core and α1-helix region, which rigidifies the native state protein conformation with the enhanced α1-helicity. Furthermore, Y91Q exhibits decreased solvation free energy and hydrophobicity compared to wild type due to more exposed and solvated hydrophilic side chains in the α1-region. On the other hand, the experimentally observed slower folding rates in both mutants are accompanied by decreased helicity in α2-helix upon mutation. We here provide the atomic-level structures and thermodynamic quantities of AcP mutants and rationalize the structural origin for the changes that occur upon introduction of those mutations along the AcP aggregation and folding processes.

  6. 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

  7. 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.

  8. 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.

  9. Analysis of error-prone survival data under additive hazards models: measurement error effects and adjustments.

    PubMed

    Yan, Ying; Yi, Grace Y

    2016-07-01

    Covariate measurement error occurs commonly in survival analysis. Under the proportional hazards model, measurement error effects have been well studied, and various inference methods have been developed to correct for error effects under such a model. In contrast, error-contaminated survival data under the additive hazards model have received relatively less attention. In this paper, we investigate this problem by exploring measurement error effects on parameter estimation and the change of the hazard function. New insights of measurement error effects are revealed, as opposed to well-documented results for the Cox proportional hazards model. We propose a class of bias correction estimators that embraces certain existing estimators as special cases. In addition, we exploit the regression calibration method to reduce measurement error effects. Theoretical results for the developed methods are established, and numerical assessments are conducted to illustrate the finite sample performance of our methods.

  10. Application of liquid chromatography in polymer non-ionic antistatic additives analysis.

    PubMed

    González-Rodríguez, M Victoria; Dopico-García, M Sonia; Noguerol-Cal, Rosalía; Carballeira-Amarelo, Tania; López-Vilariño, José M; Fernández-Martínez, Gerado

    2010-11-01

    This article investigates the applicability of HPLC-UV, ultra performance LC-evaporative light-scattering detection (UPLC-ELSD), HPLC-ESI(+)-MS and HPLC-hybrid linear ion trap (LTQ) Orbitrap MS for the analysis of different non-ionic antistatic additives, Span 20, Span 60, Span 65, Span 80, Span 85 (sorbitan fatty acid esters), Atmer 129 (glycerol fatty acid ester) and Atmer 163 (ethoxylated alkylamine). Several alkyl chain length or different degrees of esterification of polyol derivatives can be present in commercial mixtures of these polymer additives. Therefore, their identification and quantification is complicated. Qualitative composition of the studied compounds was analysed by MS. HPLC-UV, UPLC-ELSD and HPLC-LTQ Orbitrap MS methods were applied to the quantitative determination of the different Spans, Atmer 129 and Atmer 163, respectively. Quality parameters of these methods were established and no derivatization was necessary.

  11. 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.

  12. Results of investigations of Ethernet network fault-tolerance parameters by using additional analysis subsystem

    NASA Astrophysics Data System (ADS)

    Sultanov, Albert H.; Gayfulin, Renat R.; Vinogradova, Irina L.

    2008-04-01

    Fiber optic telecommunication systems with duplex data transmitting over single fiber require reflection minimization. Moreover reflections may be so high that causes system deactivating by misoperation of conventional alarm, and system can not automatically adjudge the collision, so operator manual control is required. In this paper we proposed technical solution of mentioned problem based on additional analysis subsystem, realized on the installed Ufa-city fiber optic CTV system "Crystal". Experience of it's maintenance and results of investigations of the fault tolerance parameters are represented

  13. In silico thermodynamics stability change analysis involved in BH4 responsive mutations in phenylalanine hydroxylase: QM/MM and MD simulations analysis.

    PubMed

    Chadha, Nidhi; Tiwari, Anjani K; Kumar, Vikas; Milton, Marilyn D; Mishra, Anil K

    2015-01-01

    The mammalian tetrahydrobiopterin (BH4)-dependent phenylalanine hydroxylases (PAH), involved in important metabolic pathways of phenylalanine, belong to non-heme iron-containing aromatic acid hydroxylases' enzyme (AAH) family. AAHs utilize BH4 as protein co-factor and thus promote hydroxylation reactions of their substrates. Any alterations in BH4 -mediated AAH's pathway or mutations in these enzymes are responsible for various disorders, and thus highlights the importance of mutational analysis to assess the effect on their biosynthetic pathways. Our present studies are aimed at single-site mutations in PAH that lead to thermodynamic stability change upon folding and further validation of designed non-reduced BH2 designed co-factors. We have presented single-site mutational analysis of PAH where single-site mutations have been identified from known literature. Further, in silico studies with the PAH, in silico mutant PAH, and crystallized known mutant A313T forms, involved QM/MM and Molecular Dynamics (MD) simulations analysis. The modified co-factor A showed high affinity with PAH and all mutant PAH with high G-score of -14.851. The best pose high affinity co-factor A subjected to QM/MM optimization which leads to square-pyramidal coordination of non-heme active site. The structural and energetic information obtained from the production phase of 20 ns MD simulation of co-factor-metalloprotein complex results helped to understand the binding mode and involvement of three molecules throughout the reaction pathways' catalysis of PAH. The free energies of binding (dG) of A were found to be -68.181 kcal/mol and -72.249 for 1DMW and 1TDW for A313T mutant. Binding of Co-factor A do not perturb the coordination environment of iron at the active site which resides in 2-Histdine and 1-Glutamate triad, and may enhance the percentage response towards co-factor-mediated therapy.

  14. Four Additional Cases of Diphyllobothrium nihonkaiense Infection Confirmed by Analysis of COX1 Gene in Korea

    PubMed Central

    Park, Sang Hyun; Jeon, Hyeong Kyu; Kim, Jin Bong

    2015-01-01

    Most of the diphyllobothriid tapeworms isolated from human samples in the Republic of Korea (= Korea) have been identified as Diphyllobothrium nihonkaiense by genetic analysis. This paper reports confirmation of D. nihonkaiense infections in 4 additional human samples obtained between 1995 and 2014, which were analyzed at the Department of Parasitology, Hallym University College of Medicine, Korea. Analysis of the mitochondrial cytochrome c oxidase 1 (cox1) gene revealed a 98.5-99.5% similarity with a reference D. nihonkaiense sequence in GenBank. The present report adds 4 cases of D. nihonkaiense infections to the literature, indicating that the dominant diphyllobothriid tapeworm species in Korea is D. nihonkaiense but not D. latum. PMID:25748716

  15. 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.

  16. Statins Have No Additional Benefit for Pulmonary Hypertension: A Meta-Analysis of Randomized Controlled Trials

    PubMed Central

    Wang, Lin; Qu, Moying; Chen, Yao; Zhou, Yaxiong; Wan, Zhi

    2016-01-01

    Objectives We performed a meta-analysis to explore the effects of adding statins to standard treatment on adult patients of pulmonary hypertension (PH). Methods A systematic search up to December, 2015 of Medline, EMBASE, Cochrane Database of Systematic reviews and Cochrane Central Register of Controlled Trials was performed to identify randomized controlled trials with PH patients treated with statins. Results Five studies involving 425 patients were included into this meta-analysis. The results of our analysis showed that the statins can’t significantly increase 6-minute walking distance (6MWD, mean difference [MD] = -0.33 [CI: -18.25 to 17.59]), decrease the BORG dyspnea score (MD = -0.72 [CI: -2.28 to 0.85]), the clinical worsening risk (11% in statins vs. 10.1% in controls, Risk ratio = 1.06 [CI: 0.61, 1.83]), or the systolic pulmonary arterial pressure (SPAP) (MD = -0.72 [CI: -2.28 to 0.85]). Subgroup analysis for PH due to COPD or non-COPD also showed no significance. Conclusions Statins have no additional beneficial effect on standard therapy for PH, but the results from subgroup of PH due to COPD seem intriguing and further study with larger sample size and longer follow-up is suggested. PMID:27992469

  17. Regression analysis of mixed recurrent-event and panel-count data with additive rate models.

    PubMed

    Zhu, Liang; Zhao, Hui; Sun, Jianguo; Leisenring, Wendy; Robison, Leslie L

    2015-03-01

    Event-history studies of recurrent events are often conducted in fields such as demography, epidemiology, medicine, and social sciences (Cook and Lawless, 2007, The Statistical Analysis of Recurrent Events. New York: Springer-Verlag; Zhao et al., 2011, Test 20, 1-42). For such analysis, two types of data have been extensively investigated: recurrent-event data and panel-count data. However, in practice, one may face a third type of data, mixed recurrent-event and panel-count data or mixed event-history data. Such data occur if some study subjects are monitored or observed continuously and thus provide recurrent-event data, while the others are observed only at discrete times and hence give only panel-count data. A more general situation is that each subject is observed continuously over certain time periods but only at discrete times over other time periods. There exists little literature on the analysis of such mixed data except that published by Zhu et al. (2013, Statistics in Medicine 32, 1954-1963). In this article, we consider the regression analysis of mixed data using the additive rate model and develop some estimating equation-based approaches to estimate the regression parameters of interest. Both finite sample and asymptotic properties of the resulting estimators are established, and the numerical studies suggest that the proposed methodology works well for practical situations. The approach is applied to a Childhood Cancer Survivor Study that motivated this study.

  18. 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

  19. A thermodynamic analysis of native point defect and dopant solubilities in zinc-blende III-V semiconductors

    NASA Astrophysics Data System (ADS)

    Hurle, D. T. J.

    2010-06-01

    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 GaSb antisite defect appears to be grown-in from the melt. This contrasts with the AsGa 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+ 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 InAs. Results for native

  20. 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.

  1. Development of a residential gas fired absorption heat pump. Physical and thermodynamic properties of R123A/ETFE system development and testing economic analysis. Final report

    SciTech Connect

    Murphy, K.; Simon, R.; Phillips, B.; Marsala, J.; Whitlow, E.

    1985-08-01

    This report covers the development work on the R123a/ETFE (ethyltetrahydro furfuryl ether) pair and an economic analysis of the system. Extensive thermodynamic and physical properties of the R123a/ETFE system were developed. Theoretical analysis of the data was made and showed very good performance. Subsequent testings on equipment not fully developed for R123a/ETFE confirmed this very good performance. The economic analysis showed the system competitive in most areas of the US if improved performance goals (COP = 1.5) can be met. The most important factors in determining the competitiveness are heating to cooling ratios and the relative cost of gas and electric.

  2. 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.

  3. Binding of the iminium and alkanolamine forms of sanguinarine to lysozyme: spectroscopic analysis, thermodynamics, and molecular modeling studies.

    PubMed

    Jash, Chandrima; Payghan, Pavan V; Ghoshal, Nanda; Suresh Kumar, Gopinatha

    2014-11-20

    Sanguinarine (SGR) exists in charged iminium (SGRI) and neutral alkanolamine (SGRA) forms. The binding of these two forms to the protein lysozyme (Lyz) was investigated by fluorescence, UV-vis absorbance and circular dichroism spectroscopy, and in silico molecular docking approaches. Binding thermodynamics were studied by microcalorimetry. Both forms of sanguinarine quenched the intrinsic fluorescence of Lyz, but the quenching efficiencies varied on the basis of binding that was derived after correction for an inner-filter effect. The equilibrium binding constants at 25 ± 1.0 °C for the iminium and alkanolamine forms were 1.17 × 10(5) and 3.32 × 10(5) M(-1), respectively, with approximately one binding site for both forms of the protein. Conformational changes of the protein in the presence of SGR were confirmed by absorbance, circular dichroism, three-dimensional fluorescence, and synchronous fluorescence spectroscopy. Microcalorimetry data revealed that SGRI binding is endothermic and predominantly involves electrostatic and hydrophobic interactions, whereas SGRA binding is exothermic and dominated by hydrogen-bonding interactions. The molecular distances (r) of 3.27 and 3.04 nm between the donor (Lyz) and the SGRI and SGRA acceptors, respectively, were calculated according to Förster's theory. These data suggested that both forms were bound near the Trp-62/63 residues of Lyz. Stronger binding of SGRA than SGRI was apparent from the results of both structural and thermodynamic experiments. Molecular docking studies revealed that the putative binding site for the SGR analogues resides at the catalytic site. The docking results are in accordance with the spectroscopic and thermodynamic data, further validating the stronger binding of SGRA over SGRI to Lyz. The binding site is situated near a deep crevice on the protein surface and is close to several crucial amino acid residues, including Asp-52, Glu-35, Trp-62, and Trp-63. This study advances our knowledge of

  4. Thermodynamic calculations and analysis of the deoxidation of special alloys by strong deoxidizers and carbon in vacuum

    NASA Astrophysics Data System (ADS)

    Sisev, A. A.; Paderin, S. N.; Troyanov, K. V.

    2015-06-01

    The thermodynamic calculations of the equilibrium activities of oxygen with deoxidizers Al, Ca, Mg, Ti, La, and Ce are performed from the compositions of metal samples taken during melting of special alloys in a vacuum induction furnace. The emf was measured simultaneously with sampling during the immersion of an oxygen sensor into a liquid metal. The results of calculations of the equilibrium oxygen activities with each deoxidizer are compared to the oxygen activities calculated by the measured values of emf and the temperature metal.

  5. 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

  6. Revisiting the thermodynamic theory of optimal ATP stoichiometries by analysis of various ATP-producing metabolic pathways.

    PubMed

    Werner, Sarah; Diekert, Gabriele; Schuster, Stefan

    2010-12-01

    The stoichiometry of ATP-producing metabolic pathways had been analysed theoretically by several authors by using evolutionary arguments and optimality principles. Waddell et al. (Biochem Educ 27:12-13, 1999) analysed (lactate-producing) glycolysis and used linear irreversible thermodynamics. The result was that half of the free-energy difference should be converted into free-energy of ATP and the remaining half should be used to drive the pathway. The calculated stoichiometry is in agreement with the observed yield of two moles of ATP per mole of glucose. Using the same approach, we here analyse eight other metabolic pathways. Although the deviation is not very large, the calculated values do not fit as nicely as for glycolysis as leading to lactate. For example, for O₂ respiration, the theoretical ATP yield equals 27.9. The real value varies among organisms between 26 and 38. For mixed-acid fermentation in Escherichia coli, the theoretical and experimental values are 2.24 and 2, respectively. For arginine degradation in M. pneumoniae, the calculated value is 2.43 mol of ATP, while in vivo only one mole is produced. During evolution, some pathways may not have reached their optimal ATP net production because energy yield is not their only function. Moreover, it should be acknowledged that the approach by linear irreversible thermodynamics is a rough approximation.

  7. Additional Keplerian Signals in the HARPS data for Gliese 667C: Further Analysis

    NASA Astrophysics Data System (ADS)

    Gregory, Philip C.; Lawler, Samantha M.; Gladman, Brett

    2014-01-01

    A re-analysis of Gliese 667C HARPS precision radial velocity data was carried out with a Bayesian multi-planet Kepler periodogram (from 0 to 7 planets) based on a fusion Markov chain Monte Carlo algorithm. The most probable number of signals detected is six with a Bayesian false alarm probability of 0.012. The residuals were shown to be consistent with white noise. The six signals detected include two previously reported with periods of 7.198 (b) and 28.14 (c) days, plus additional periods of 30.82, 38.82, 53.22, and 91.3 days. The existence of these Keplerian-like signals suggest the possibility of additional planets in the habitable zone of Gl 667C although some of the signals could be artifacts arising from the sampling or stellar surface activity. N-body orbital integrations are being undertaken to determine which of these signals are consistent with a stable planetary system. Preliminary results demonstrate that four of the signals, with periods of 7.2, 28.1, 38.8, & 91 d, are consistent with a stable 4 planet system on time scales of 107 yr. The M sin i values are ~5.5, 4.4, 1.9, and 4.7 M⊕, respectively.

  8. An analysis of candidates for addition to the Clean Air Act list of hazardous air pollutants.

    PubMed

    Lunder, Sonya; Woodruff, Tracey J; Axelrad, Daniel A

    2004-02-01

    There are 188 air toxics listed as hazardous air pollutants (HAPs) in the Clean Air Act (CAA), based on their potential to adversely impact public health. This paper presents several analyses performed to screen potential candidates for addition to the HAPs list. We analyzed 1086 HAPs and potential HAPs, including chemicals regulated by the state of California or with emissions reported to the Toxics Release Inventory (TRI). HAPs and potential HAPs were ranked by their emissions to air, and by toxicity-weighted (tox-wtd) emissions for cancer and noncancer, using emissions information from the TRI and toxicity information from state and federal agencies. Separate consideration was given for persistent, bioaccumulative toxins (PBTs), reproductive or developmental toxins, and chemicals under evaluation for regulation as toxic air contaminants in California. Forty-four pollutants were identified as candidate HAPs based on three ranking analyses and whether they were a PBT or a reproductive or developmental toxin. Of these, nine qualified in two or three different rankings (ammonia [NH3], copper [Cu], Cu compounds, nitric acid [HNO3], N-methyl-2-pyrrolidone, sulfuric acid [H2SO4], vanadium [V] compounds, zinc [Zn], and Zn compounds). This analysis suggests further evaluation of several pollutants for possible addition to the CAA list of HAPs.

  9. 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.

  10. 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.

  11. Thermodynamics of anisotropic branes

    NASA Astrophysics Data System (ADS)

    Ávila, Daniel; Fernández, Daniel; Patiño, Leonardo; Trancanelli, Diego

    2016-11-01

    We study the thermodynamics of flavor D7-branes embedded in an anisotropic black brane solution of type IIB supergravity. The flavor branes undergo a phase transition between a `Minkowski embedding', in which they lie outside of the horizon, and a `black hole embedding', in which they fall into the horizon. This transition depends on the black hole temperature, its degree of anisotropy, and the mass of the flavor degrees of freedom. It happens either at a critical temperature or at a critical anisotropy. A general lesson we learn from this analysis is that the anisotropy, in this particular realization, induces similar effects as the temperature. In particular, increasing the anisotropy bends the branes more and more into the horizon. Moreover, we observe that the transition becomes smoother for higher anisotropies.

  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. Thermodynamics of protein-ligand interactions as a reference for computational analysis: how to assess accuracy, reliability and relevance of experimental data

    NASA Astrophysics Data System (ADS)

    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.

  14. 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.

  15. 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.

  16. 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

    2013-09-06

    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.

  17. Thermodynamic geometry of supercooled water

    NASA Astrophysics Data System (ADS)

    May, Helge-Otmar; Mausbach, Peter; Ruppeiner, George

    2015-03-01

    The thermodynamic curvature scalar R is evaluated for supercooled water with a two-state equation of state correlated with the most recent available experimental data. This model assumes a liquid-liquid critical point. Our investigation extends the understanding of the thermodynamic behavior of R considerably. We show that R diverges to -∞ when approaching the assumed liquid-liquid critical point. This limit is consistent with all of the fluid critical point models known so far. In addition, we demonstrate a sign change of R along the liquid-liquid line from negative near the critical point to positive on moving away from the critical point in the low density "ice-like" liquid phase. We also trace out the Widom line in phase space. In addition, we investigate increasing correlation length in supercooled water and compare our results with recent published small angle x-ray scattering measurements.

  18. Thermodynamic theory of equilibrium fluctuations

    SciTech Connect

    Mishin, Y.

    2015-12-15

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

  19. 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

  20. An analysis of the quantum effect on the thermodynamic and transport properties of cryogenic hydrogen using molecular dynamics method

    NASA Astrophysics Data System (ADS)

    Nagashima, Hiroki; Tsuda, Shin-ichi; Tsuboi, Nobuyuki; Koshi, Mitsuo; Hayashi, A. Koichi; Tokumasu, Takashi

    2014-03-01

    In this paper, we have analysed an effect of quantum nature of the hydrogen molecule on its thermodynamic and transport properties using molecular dynamics (MD) method based on the path integral method. We performed NVE constant MD simulation and the quantum effect on the molecular mechanism was analysed. The simulation results were compared with experimental data. As a result, we clarified that the quantum nature makes the virial pressure larger than in classical mechanics and taking account the quantum nature makes smaller intermolecular interaction energy and larger repulsive force than classical representation. Besides, we have confirmed that the path-integral-based MD method well reproduces the thermal conductivity and quantum effect on the transport properties is also large.

  1. 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.

  2. Stochastic Thermodynamics of Learning

    NASA Astrophysics Data System (ADS)

    Goldt, Sebastian; Seifert, Udo

    2017-01-01

    Virtually every organism gathers information about its noisy environment and builds models from those data, mostly using neural networks. Here, we use stochastic thermodynamics to analyze the learning of a classification rule by a neural network. We show that the information acquired by the network is bounded by the thermodynamic cost of learning and introduce a learning efficiency η ≤1 . We discuss the conditions for optimal learning and analyze Hebbian learning in the thermodynamic limit.

  3. 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.

  4. 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.

  5. Analysis of additive metals in fuel and emission aerosols of diesel vehicles with and without particle traps.

    PubMed

    Ulrich, Andrea; Wichser, Adrian

    2003-09-01

    Fuel additives used in particle traps have to comply with environmental directives and should not support the formation of additional toxic substances. The emission of metal additives from diesel engines with downstream particle traps has been studied. Aspects of the optimisation of sampling procedure, sample preparation and analysis are described. Exemplary results in form of a mass balance calculation are presented. The results demonstrate the high retention rate of the studied filter system but also possible deposition of additive metals in the engine.

  6. High-temperature thermodynamics.

    NASA Technical Reports Server (NTRS)

    Margrave, J. L.

    1967-01-01

    High temperature thermodynamics requiring species and phases identification, crystal structures, molecular geometries and vibrational, rotational and electronic energy levels and equilibrium constants

  7. 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.

  8. 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

  9. Genome-wide transcript analysis of maize hybrids: allelic additive gene expression and yield heterosis.

    PubMed

    Guo, Mei; Rupe, Mary A; Yang, Xiaofeng; Crasta, Oswald; Zinselmeier, Christopher; Smith, Oscar S; Bowen, Ben

    2006-09-01

    Heterosis, or hybrid vigor, has been widely exploited in plant breeding for many decades, but the molecular mechanisms underlying the phenomenon remain unknown. In this study, we applied genome-wide transcript profiling to gain a global picture of the ways in which a large proportion of genes are expressed in the immature ear tissues of a series of 16 maize hybrids that vary in their degree of heterosis. Key observations include: (1) the proportion of allelic additively expressed genes is positively associated with hybrid yield and heterosis; (2) the proportion of genes that exhibit a bias towards the expression level of the paternal parent is negatively correlated with hybrid yield and heterosis; and (3) there is no correlation between the over- or under-expression of specific genes in maize hybrids with either yield or heterosis. The relationship of the expression patterns with hybrid performance is substantiated by analysis of a genetically improved modern hybrid (Pioneer hybrid 3394) versus a less improved older hybrid (Pioneer hybrid 3306) grown at different levels of plant density stress. The proportion of allelic additively expressed genes is positively associated with the modern high yielding hybrid, heterosis and high yielding environments, whereas the converse is true for the paternally biased gene expression. The dynamic changes of gene expression in hybrids responding to genotype and environment may result from differential regulation of the two parental alleles. Our findings suggest that differential allele regulation may play an important role in hybrid yield or heterosis, and provide a new insight to the molecular understanding of the underlying mechanisms of heterosis.

  10. 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.

  11. Integrated stoichiometric, thermodynamic and kinetic modelling of steady state metabolism

    PubMed Central

    Fleming, R.M.T.; Thiele, I.; Provan, G.; Nasheuer, H.P.

    2010-01-01

    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 E. coli and compare favourably with in silico prediction by flux balance analysis. PMID:20230840

  12. 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

  13. 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.

  14. Failure location prediction by finite element analysis for an additive manufactured mandible implant.

    PubMed

    Huo, Jinxing; Dérand, Per; Rännar, Lars-Erik; Hirsch, Jan-Michaél; Gamstedt, E Kristofer

    2015-09-01

    In order to reconstruct a patient with a bone defect in the mandible, a porous scaffold attached to a plate, both in a titanium alloy, was designed and manufactured using additive manufacturing. Regrettably, the implant fractured in vivo several months after surgery. The aim of this study was to investigate the failure of the implant and show a way of predicting the mechanical properties of the implant before surgery. All computed tomography data of the patient were preprocessed to remove metallic artefacts with metal deletion technique before mandible geometry reconstruction. The three-dimensional geometry of the patient's mandible was also reconstructed, and the implant was fixed to the bone model with screws in Mimics medical imaging software. A finite element model was established from the assembly of the mandible and the implant to study stresses developed during mastication. The stress distribution in the load-bearing plate was computed, and the location of main stress concentration in the plate was determined. Comparison between the fracture region and the location of the stress concentration shows that finite element analysis could serve as a tool for optimizing the design of mandible implants.

  15. 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.

  16. 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.

  17. 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

  18. 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.

  19. Thermodynamic evaluation of a microscale heat pump

    SciTech Connect

    Drost, M.K.; Beckette, M.; Wegeng, R.

    1994-11-01

    The development of microscale thermal components has reached a level of maturity that suggests that complete microthermal systems can be developed. This paper presents the results of a thermodynamic evaluation of a microscale heat pump for space heating and cooling applications. The concept involves fabricating individual unit processes on separate sheets of material and then combining the sheets to form complete systems. The sheet architecture allows a large number of microheat pumps to be fabricated and operated in parallel. Results of the thermodynamic analysis suggest that the microscale heat pump is theoretically feasible. Pressure drop in the evaporators and condensers was not significant, and performance requirements for the microscale compressor are challenging but not unattainable. Results also suggest that there is significant potential for improving heat pump performance by optimizing the integration of the heat pump with the microchannel evaporators and condensers. Sensitivity studies investigated the impact of working fluid selection, heat exchanger approach temperature, and compressor efficiency on cycle performance. Based on the results of this evaluation, additional research on microscale heat exchangers and compressors is suggested.

  20. 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.

  1. 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

  2. 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.

  3. Vibrational and electronic investigations, thermodynamic parameters, HOMO and LUMO analysis on crotonaldehyde by ab initio and DFT methods

    NASA Astrophysics Data System (ADS)

    Jayaprakash, A.; Arjunan, V.; Jose, Sujin P.; Mohan, S.

    2011-12-01

    The energy, geometrical parameters and vibrational wavenumbers of crotonaldehyde were calculated by using ab initio and B3LYP with 6-31G(d,p) and 6-311G(d,p) basis sets. The FT-IR and FT-Raman spectra for liquid state crotonaldehyde have been recorded in the region 3400-400 cm -1 and 3400-100 cm -1, respectively and compared with the theoretical spectrographs constructed from the scaled harmonic vibrational frequencies calculated at HF and DFT levels. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. Detailed interpretations on vibrational modes have been made on the observed and theoretical spectra and PED for each mode was also reported more precisely. HOMO and LUMO energy levels are constructed and the corresponding theoretical frontier energy gaps are calculated to realise the charge transfer occurring in the molecule. The thermodynamic properties of the title compound have been calculated at different temperatures and the results reveals the standard heat capacities ( C0p), standard entropies ( S0) and standard enthalpy changes (Δ H0) increases with rise in temperature.

  4. 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.

  5. Thermodynamic analysis of the W--F--Si--H and W--F--Si--H--Cl systems

    SciTech Connect

    Rode, E.J. ); Harshbarger, W.R. )

    1990-01-01

    Chemical vapor deposition of WSi{sub 2} was studied through thermodynamic equilibrium calculations for the W--F--Si--H and W--F--Si--H--Cl systems. The calculations were made with a computer program that minimizes the Gibbs free energy by Langrangian multiplier techniques. The parameter range for these system analyses were: temperature 473 to 1073 K, pressure from 50 to 500 mTorr, and Si/W ratios of 3 to 1000. 21 gas phase species and eight solid species were included in the calculations for the W--F--Si--H system and 39 gas phase species and 15 solid species were considered for the W--F--Si--H--Cl system. At the equilibrium condition, H{sub 2}, SiF{sub 4}, and SiF{sub 2}H{sub 2} are the most prominent gaseous species for the W--F--Si--H system while WSi{sub 2} and Si are formed in the solid phase. For the W--F--Si--H--Cl system, WSi{sub 2} and Si are formed in the solid phase, while H{sub 2}, SiCl{sub 4}, HCl, SiF{sub 4} and SiHCl{sub 3} are the most prominent gas phase species. The SiCl{sub 2} intermediate plays a key role in the surface activated reaction for this system.

  6. 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.

  7. 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

  8. Thermodynamic Stability of Topological Insulators

    NASA Astrophysics Data System (ADS)

    Usanmaz, Demet; Nath, Pinku; Plata, Jose J.; Hart, Gus L. W.; Nardelli, Marco B.; Curtarolo, Stefano; CenterMaterials Genomics Team; G. L. W. Hart Collaboration; M. B. Nardelli Collaboration

    2015-03-01

    Well known three-dimensional TIs such as Bi2Te3,Bi2Se3,Bi2Te2Se, Sb2Te2Se, have been the subject of research due to potential application for spintronic devices. TIs have large bulk band gap and metallic surface states at the special time-reversal-invariant momentum (TRIM) points of the Brillouin zone. These fascinating properties constitute the current carry along the surface and not conduct current through the bulk. Creating heterostructures of TIs has recently been demonstrated to be advantageous for controlling electronic properties. In addition to the importance of the electronic properties of materials, thermodynamic stability is the key for manufacturability of materials. Guided by cluster expansion, we have investigated the thermodynamic stability of TI interfaces.

  9. 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.

  10. Thermodynamic constraints for biochemical networks.

    PubMed

    Beard, Daniel A; Babson, Eric; Curtis, Edward; Qian, Hong

    2004-06-07

    The constraint-based approach to analysis of biochemical systems has emerged as a useful tool for rational metabolic engineering. Flux balance analysis (FBA) is based on the constraint of mass conservation; energy balance analysis (EBA) is based on non-equilibrium thermodynamics. The power of these approaches lies in the fact that the constraints are based on physical laws, and do not make use of unknown parameters. Here, we show that the network structure (i.e. the stoichiometric matrix) alone provides a system of constraints on the fluxes in a biochemical network which are feasible according to both mass balance and the laws of thermodynamics. A realistic example shows that these constraints can be sufficient for deriving unambiguous, biologically meaningful results. The thermodynamic constraints are obtained by comparing of the sign pattern of the flux vector to the sign patterns of the cycles of the internal cycle space via connection between stoichiometric network theory (SNT) and the mathematical theory of oriented matroids.

  11. Analysis of synthetic motor oils for additive elements by ICP-AES

    SciTech Connect

    Williams, M.C.; Salmon, S.G.

    1995-12-31

    Standard motor oils are made by blending paraffinic or naphthenic mineral oil base stocks with additive packages containing anti-wear agents, dispersants, corrosion inhibitors, and viscosity index improvers. The blender can monitor the correct addition of the additives by determining the additive elements in samples dissolved in a solvent by ICP-AES. Internal standardization is required to control sample transport interferences due to differences in viscosity between samples and standards. Synthetic motor oils, made with poly-alpha-olefins and trimethylol propane esters, instead of mineral oils, pose an additional challenge since these compounds affect the plasma as well as having sample transport interference considerations. The synthetic lubricant base stocks add significant oxygen to the sample matrix, which makes the samples behave differently than standards prepared in mineral oil. Determination of additive elements in synthetic motor oils will be discussed.

  12. 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.

  13. The role of thermodynamics in biochemical engineering

    NASA Astrophysics Data System (ADS)

    von Stockar, Urs

    2013-09-01

    This article is an adapted version of the introductory chapter of a book whose publication is imminent. It bears the title "Biothermodynamics - The role of thermodynamics in biochemical engineering." The aim of the paper is to give a very short overview of the state of biothermodynamics in an engineering context as reflected in this book. Seen from this perspective, biothermodynamics may be subdivided according to the scale used to formalize the description of the biological system into three large areas: (i) biomolecular thermodynamics (most fundamental scale), (ii) thermodynamics of metabolism (intermediary scale), and (iii) whole-cell thermodynamics ("black-box" description of living entities). In each of these subareas, the main available theoretical approaches and the current and the potential applications are discussed. Biomolecular thermodynamics (i) is especially well developed and is obviously highly pertinent for the development of downstream processing. Its use ought to be encouraged as much as possible. The subarea of thermodynamics of live cells (iii), although scarcely applied in practice, is also expected to enhance bioprocess research and development, particularly in predicting culture performances, for understanding the driving forces for cellular growth, and in developing, monitoring, and controlling cellular cultures. Finally, there is no question that thermodynamic analysis of cellular metabolism (ii) is a promising tool for systems biology and for many other applications, but quite a large research effort is still needed before it may be put to practical use.

  14. Micromechanical analysis of volumetric growth in the context of open systems thermodynamics and configurational mechanics. Application to tumor growth

    NASA Astrophysics Data System (ADS)

    Ganghoffer, J. F.; Boubaker, M. B.

    2017-03-01

    We adopt in this paper the physically and micromechanically motivated point of view that growth (resp. resorption) occurs as the expansion (resp. contraction) of initially small tissue elements distributed within a host surrounding matrix, due to the interfacial motion of their boundary. The interface motion is controlled by the availability of nutrients and mechanical driving forces resulting from the internal stresses that built in during the growth. A general extremum principle of the zero potential for open systems witnessing a change of their mass due to the diffusion of nutrients is constructed, considering the framework of open systems thermodynamics. We postulate that the shape of the tissue element evolves in such a way as to minimize the zero potential among all possible admissible shapes of the growing tissue elements. The resulting driving force for the motion of the interface sets a surface growth models at the scale of the growing tissue elements, and is conjugated to a driving force identified as the interfacial jump of the normal component of an energy momentum tensor, in line with Hadamard's structure theorem. The balance laws associated with volumetric growth at the mesoscopic level result as the averaging of surface growth mechanisms occurring at the microscopic scale of the growing tissue elements. The average kinematics has been formulated in terms of the effective growth velocity gradient and elastic rate of deformation tensor, both functions of time. This formalism is exemplified by the simulation of the avascular growth of multicell spheroids in the presence of diffusion of nutrients, showing the respective influence of mechanical and chemical driving forces in relation to generation of internal stresses.

  15. Micromechanical analysis of volumetric growth in the context of open systems thermodynamics and configurational mechanics. Application to tumor growth

    NASA Astrophysics Data System (ADS)

    Ganghoffer, J. F.; Boubaker, M. B.

    2016-11-01

    We adopt in this paper the physically and micromechanically motivated point of view that growth (resp. resorption) occurs as the expansion (resp. contraction) of initially small tissue elements distributed within a host surrounding matrix, due to the interfacial motion of their boundary. The interface motion is controlled by the availability of nutrients and mechanical driving forces resulting from the internal stresses that built in during the growth. A general extremum principle of the zero potential for open systems witnessing a change of their mass due to the diffusion of nutrients is constructed, considering the framework of open systems thermodynamics. We postulate that the shape of the tissue element evolves in such a way as to minimize the zero potential among all possible admissible shapes of the growing tissue elements. The resulting driving force for the motion of the interface sets a surface growth models at the scale of the growing tissue elements, and is conjugated to a driving force identified as the interfacial jump of the normal component of an energy momentum tensor, in line with Hadamard's structure theorem. The balance laws associated with volumetric growth at the mesoscopic level result as the averaging of surface growth mechanisms occurring at the microscopic scale of the growing tissue elements. The average kinematics has been formulated in terms of the effective growth velocity gradient and elastic rate of deformation tensor, both functions of time. This formalism is exemplified by the simulation of the avascular growth of multicell spheroids in the presence of diffusion of nutrients, showing the respective influence of mechanical and chemical driving forces in relation to generation of internal stresses.

  16. 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.

  17. Additive-subtractive phase-modulated electronic speckle interferometry: analysis of fringe visibility.

    PubMed

    Pouet, B F; Krishnaswamy, S

    1994-10-01

    Fringe-visibility issues of additive-subtractive phase-modulated (ASPM) electronic speckle pattern interferometry (ESPI) are explored. ASPM ESPI is a three-step method in which additive-speckle images are acquired rapidly in an analog fashion in every frame of a video sequence, a speckle phase modulation is intentionally introduced between frames, and a digital subtraction of consecutive pairs of additive-speckle images is performed. We show that this scheme has the good high-frequency noise immunity associated with additive-ESPI techniques as well as the good fringe visibility associated with subtractive-ESPI techniques. The method has better fringe visibility than can be obtained with purely additive ESPI and also does not suffer from the fringe distortions that can occur with subtractive ESPI in the presence of high-frequency noise. We show that even if full speckle decorrelation were to occur between the two additive speckle images that are to be subtracted, the visibility of ASPM ESPI fringes can be made to approach unity by suitable adjustment of the reference-to-object beam-intensity ratio.

  18. 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.

  19. Turbopump thermodynamic cooling

    NASA Technical Reports Server (NTRS)

    Patten, T. C.; Mckee, H. B.

    1972-01-01

    System for cooling turbopumps used in cryogenic fluid storage facilities is described. Technique uses thermodynamic propellant vent to intercept pump heat at desired conditions. Cooling system uses hydrogen from outside source or residual hydrogen from cryogenic storage tank.

  20. 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.

  1. 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)

  2. 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.

  3. Product versus additive threshold models for analysis of reproduction outcomes in animal genetics.

    PubMed

    David, I; Bodin, L; Gianola, D; Legarra, A; Manfredi, E; Robert-Granié, C

    2009-08-01

    The phenotypic observation of some reproduction traits (e.g., insemination success, interval from lambing to insemination) is the result of environmental and genetic factors acting on 2 individuals: the male and female involved in a mating couple. In animal genetics, the main approach (called additive model) proposed for studying such traits assumes that the phenotype is linked to a purely additive combination, either on the observed scale for continuous traits or on some underlying scale for discrete traits, of environmental and genetic effects affecting the 2 individuals. Statistical models proposed for studying human fecundability generally consider reproduction outcomes as the product of hypothetical unobservable variables. Taking inspiration from these works, we propose a model (product threshold model) for studying a binary reproduction trait that supposes that the observed phenotype is the product of 2 unobserved phenotypes, 1 for each individual. We developed a Gibbs sampling algorithm for fitting a Bayesian product threshold model including additive genetic effects and showed by simulation that it is feasible and that it provides good estimates of the parameters. We showed that fitting an additive threshold model to data that are simulated under a product threshold model provides biased estimates, especially for individuals with high breeding values. A main advantage of the product threshold model is that, in contrast to the additive model, it provides distinct estimates of fixed effects affecting each of the 2 unobserved phenotypes.

  4. Defense Health Care: Additional Analysis of Costs and Benefits of Potential Governance Structures Is Needed

    DTIC Science & Technology

    2012-09-01

    options, (2) a business case analysis and strategy for implementing its shared services concept, and (3) more complete analyses of the options’ strengths...and weaknesses. DoD concurred with developing a business case analysis for its shared services concept. DoD did not concur with the other two

  5. 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.

  6. Thermodynamic laws in isolated systems

    NASA Astrophysics Data System (ADS)

    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.

  7. 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.

  8. 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.

  9. Thermodynamics in Fractional Calculus

    NASA Astrophysics Data System (ADS)

    Meilanov, R. P.; Magomedov, R. A.

    2014-11-01

    A generalization of thermodynamics in the formalism of fractional-order derivatives is given. Results of the traditional thermodynamics of Carnot, Clausius, and Helmholtz are obtained in the particular case where the exponent of a fractional-order derivative is equal to unity. A one-parametric "fractal" equation of state is obtained with account of the second virial coefficient. The application of the resulting equation of state in the case of the gas argon is considered.

  10. 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.

  11. A Comparative Analysis of British and Taiwanese Students' Conceptual and Procedural Knowledge of Fraction Addition

    ERIC Educational Resources Information Center

    Li, Hui-Chuan

    2014-01-01

    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…

  12. Association analysis of historical bread wheat germplasm using additive genetic covariance of relatives and population structure.

    PubMed

    Crossa, José; Burgueño, Juan; Dreisigacker, Susanne; Vargas, Mateo; Herrera-Foessel, Sybil A; Lillemo, Morten; Singh, Ravi P; Trethowan, Richard; Warburton, Marilyn; Franco, Jorge; Reynolds, Matthew; Crouch, Jonathan H; Ortiz, Rodomiro

    2007-11-01

    Linkage disequilibrium can be used for identifying associations between traits of interest and genetic markers. This study used mapped diversity array technology (DArT) markers to find associations with resistance to stem rust, leaf rust, yellow rust, and powdery mildew, plus grain yield in five historical wheat international multienvironment trials from the International Maize and Wheat Improvement Center (CIMMYT). Two linear mixed models were used to assess marker-trait associations incorporating information on population structure and covariance between relatives. An integrated map containing 813 DArT markers and 831 other markers was constructed. Several linkage disequilibrium clusters bearing multiple host plant resistance genes were found. Most of the associated markers were found in genomic regions where previous reports had found genes or quantitative trait loci (QTL) influencing the same traits, providing an independent validation of this approach. In addition, many new chromosome regions for disease resistance and grain yield were identified in the wheat genome. Phenotyping across up to 60 environments and years allowed modeling of genotype x environment interaction, thereby making possible the identification of markers contributing to both additive and additive x additive interaction effects of traits.

  13. Consequence analysis of an unmitigated NaOH solution spray release during addition to waste tank

    SciTech Connect

    Himes, D.A., Westinghouse Hanford

    1996-08-21

    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.

  14. 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

  15. Synthesis of Submicron Silver Powder by the Hydrometallurgical Reduction of Silver Nitrate with Hydrazine Hydrate and a Thermodynamic Analysis of the System

    NASA Astrophysics Data System (ADS)

    Ghosh, Dinabandhu; Dasgupta, Samudra

    2008-02-01

    A silver powder of submicron size was produced from the aqueous solutions of its compounds. The silver compounds tried out were silver nitrate and silver oxide, and the reducing agents employed were dimethyl formamide (DMF), hydrazine hydrate, and sodium azide. The solvent mediums were distilled water for the reductions with DMF and sodium azide, and a 2:1 (by volume) mixture of distilled water and ethanol for the reductions with hydrazine hydrate. Of the three reductants, hydrazine hydrate (N2H4·H2O) alone was successful in reducing both the silver compounds to a submicron (<500 nm) metallic silver powder, as revealed by X-ray diffraction (XRD) studies and scanning electron microscopy (SEM) analyses. Additionally, the thermodynamic equilibrium of the system AgNO3-N2H4·H2O in the water ethanol mixture (2:1) was studied at 298 K; the equilibrium constant data so generated was found to compare very well with those derived from the established data of enthalpies and free energies of formation, and half-cell potentials. The following activity coefficient (Raoultian) composition relationship for hydrazine hydrate in its dilute solution in water (plus ethanol) at 298 K is proposed: ln (γ_{{{text{N}_2text{H}_4}}{text{.H}_2text{O}}} ) = 1862( ± 371) - 2055( ± 424)(1 - X_{{{text{N}_2text{H}_4 \\cdot text{H}_2text{O}}}} )2

  16. Thermodynamic and kinetic analysis of the interaction between hepatitis B surface antibody and antigen on a gold electrode modified with cysteamine and colloidal gold via electrochemistry.

    PubMed

    He, Yan Bin; Luo, Hong Qun; Li, Nian Bing

    2007-06-15

    Hepatitis B surface antibody (HBsAb) was immobilized to the surface of a gold electrode modified with cysteamine and colloidal gold as matrices to detect hepatitis B surface antigen (HBsAg). Differential pulse voltammetry (DPV) method was used for the investigation of the specific interaction between the immobilized HBsAb and HBsAg in solution, which was followed as a change of peak current in DPV with time. With the modified gold electrode, the differences in affinity of HBsAb with HBsAg at the temperatures of 37 and 40 degrees C were easily distinguished and the kinetic rate constants (k(ass) and k(diss)) and kinetic affinity constant K were determined from the curves of current versus time. In addition, the thermodynamic constants, DeltaG, DeltaH and DeltaS, of the interaction at 37 degrees C were calculated, which were -56.65, -64.54 and -25.45 kJ mol(-1), respectively.

  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.

  18. 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.

  19. Analysis of Additional CFT Support at Z=0 for the Silicon Half Trough

    SciTech Connect

    Cease, H.; Lee, A.; /Fermilab

    2000-03-20

    The D-Zero silicon trough is segmented into two half troughs. Loading to the Central Fiber Tracker Barrel 1 is at both ends and near Z = 0. The loading near Z = 0 is thought to be 4 lbs at 4 points. The point locations are at +/-45 degrees for each half trough on each side of Z = O. An additional support at Z = O is required to prevent beam sag and out of round distortions to the CFT Barrel 1. An additional joining washer will be attached between barrels 1 and 2 at Z = 0. Also a support ring will be attached to the inner diameter of barrel 1 to further help in out of round distortions. Details of the washer and loading are modeled using ANSYS.

  20. Analysis of the Potential Impact of Additive Manufacturing on Army Logistics

    DTIC Science & Technology

    2013-12-01

    highlighting the state of AM during the Leading Edge Forum titled 3D Printing and the Future of Additive Manufacturing. In the program, CSC highlighted...great success is Boeing. CSC (2012) described Boeing’s experience using AM as follows: Boeing, a pioneer in 3D printing , has printed 22,000...components that are used in a variety of aircraft. For example, Boeing has used 3D printing to produce environmental control ducting (ECD) for its new 787

  1. 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.

  2. 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).

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Thermodynamic equilibrium-air correlations for flowfield applications

    NASA Technical Reports Server (NTRS)

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

    1981-01-01

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

  8. 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.

  9. [Analysis of components in natural food additive "grapefruit seed extract" by HPLC and LC/MS].

    PubMed

    Sakamoto, S; Sato, K; Maitani, T; Yamada, T

    1996-01-01

    The components in a commercial natural food additive "Grapefruit seed extract" and the ethanol extract of grapefruit seeds were analyzed by HPLC and LC/MS. The HPLC chromatogram of the commercial grapefruit seed extract was quite different from that of the ethanol extract of grapefruit seeds. Three main peaks were observed in the chromatogram of the commercial grapefruit seed extract. By comparison of the retention times and the absorption spectra with those of authentic samples, two peaks were ascribed to methyl-p-hydroxybenzoate and 2,4,4'-trichloro-2'-hydroxydiphenylether (triclosan). Triclosan was also identified by LC/MS by using the negative electrospray ionization method.

  10. Determination of thermodynamic properties by supercritical fluid chromatography.

    PubMed

    Roth, Michal

    2004-05-28

    This survey attempts to summarise thermodynamic applications of supercritical fluid chromatography (SFC) with an emphasis on the results published during the last 10 years. In addition to a review of thermodynamic measurements by SFC, it contains brief sections on instrumental considerations and on the sources of auxiliary information needed when processing the retention data.

  11. Thermodynamic analysis of interactions between Ni-based solid oxide fuel cells (SOFC) anodes and trace species in a survey of coal syngas

    SciTech Connect

    Martinez, Andrew; Gerdes, Kirk; Gemmen, Randall; Postona, James

    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.

  12. 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.

  13. Proteomic analysis of salt tolerance in sugar beet monosomic addition line M14.

    PubMed

    Yang, Le; Zhang, Yanjun; Zhu, Ning; Koh, Jin; Ma, Chunquan; Pan, Yu; Yu, Bing; Chen, Sixue; Li, Haiying

    2013-11-01

    Understanding the mechanisms of plant salinity tolerance can facilitate plant engineering for enhanced salt stress tolerance. Sugar beet monosomic addition line M14 obtained from the intercross between Beta vulgaris L. and Beta corolliflora Zoss exhibits tolerance to salt stress. Here we report the salt-responsive characteristics of the M14 plants under 0, 200, and 400 mM NaCl conditions using quantitative proteomics approaches. Proteins from control and the salt treated M14 plants were separated using 2D-DIGE. Eighty-six protein spots representing 67 unique proteins in leaves and 22 protein spots representing 22 unique proteins in roots were identified. In addition, iTRAQ LC-MS/MS was employed to identify and quantify differentially expressed proteins under salt stress. Seventy-five differentially expressed proteins in leaves and 43 differentially expressed proteins in roots were identified. The proteins were mainly involved in photosynthesis, energy, metabolism, protein folding and degradation, and stress and defense. Moreover, gene transcription data obtained from the same samples were compared to the corresponding protein data. Thirteen proteins in leaves and 12 in roots showed significant correlation in gene expression and protein levels. These results suggest the important processes for the M14 tolerance to salt stress include enhancement of photosynthesis and energy metabolism, accumulation of osmolyte and antioxidant enzymes, and regulation of methionine metabolism and ion uptake/exclusion.

  14. Rates of False-Positive Classification Resulting From the Analysis of Additional Embedded Performance Validity Measures.

    PubMed

    Silk-Eglit, Graham M; Stenclik, Jessica H; Miele, Andrea S; Lynch, Julie K; McCaffrey, Robert J

    2015-01-01

    Several studies have documented improvements in the classification accuracy of performance validity tests (PVTs) when they are combined to form aggregated models. Fewer studies have evaluated the impact of aggregating additional PVTs and changing the classification threshold within these models. A recent Monte Carlo simulation demonstrated that to maintain a false-positive rate (FPR) of ≤.10, only 1, 4, 8, 10, and 15 PVTs should be analyzed at classification thresholds of failing at least 1, at least 2, at least 3, at least 4, and at least 5 PVTs, respectively. The current study sought to evaluate these findings with embedded PVTs in a sample of real-life litigants and to highlight a potential danger in analytic flexibility with embedded PVTs. Results demonstrated that to maintain an FPR of ≤.10, only 3, 7, 10, 14, and 15 PVTs should be analyzed at classification thresholds of failing at least 1, at least 2, at least 3, at least 4, and at least 5 PVTs, respectively. Analyzing more than these numbers of PVTs resulted in a dramatic increase in the FPR. In addition, in the most extreme case, flexibility in analyzing and reporting embedded PVTs increased the FPR by 67%. Given these findings, a more objective approach to analyzing and reporting embedded PVTs should be introduced.

  15. Thermodynamics and evolution.

    PubMed

    Demetrius, L

    2000-09-07

    The science of thermodynamics is concerned with understanding the properties of inanimate matter in so far as they are determined by changes in temperature. The Second Law asserts that in irreversible processes there is a uni-directional increase in thermodynamic entropy, a measure of the degree of uncertainty in the thermal energy state of a randomly chosen particle in the aggregate. The science of evolution is concerned with understanding the properties of populations of living matter in so far as they are regulated by changes in generation time. Directionality theory, a mathematical model of the evolutionary process, establishes that in populations subject to bounded growth constraints, there is a uni-directional increase in evolutionary entropy, a measure of the degree of uncertainty in the age of the immediate ancestor of a randomly chosen newborn. This article reviews the mathematical basis of directionality theory and analyses the relation between directionality theory and statistical thermodynamics. We exploit an analytic relation between temperature, and generation time, to show that the directionality principle for evolutionary entropy is a non-equilibrium extension of the principle of a uni-directional increase of thermodynamic entropy. The analytic relation between these directionality principles is consistent with the hypothesis of the equivalence of fundamental laws as one moves up the hierarchy, from a molecular ensemble where the thermodynamic laws apply, to a population of replicating entities (molecules, cells, higher organisms), where evolutionary principles prevail.

  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. Organocatalyzed asymmetric Michael addition by an efficient bifunctional carbohydrate-thiourea hybrid with mechanistic DFT analysis.

    PubMed

    Azad, Chandra S; Khan, Imran A; Narula, Anudeep K

    2016-12-28

    A series of thiourea based bifunctional organocatalysts having d-glucose as a core scaffold were synthesized and examined as catalysts for the asymmetric Michael addition reaction of aryl/alkyl trans-β-nitrostyrenes over cyclohexanone and other Michael donors having active methylene. Excellent enantioselectivities (<95%), diastereoselectivities (<99%), and yields (<99%) were attained under solvent free conditions using 10 mol% of 1d0. The obtained results were explained through DFT calculations using the B3LYP/6-311G(d,p)//B3LYP/6-31G(d) basic set. The QM/MM calculations revealed the role of cyclohexanone as a solvent as well as reactant in the rate determining step imparting 31.91 kcal mol(-1) of energy towards the product formation.

  19. Electron Backscatter Diffraction Analysis of Inconel 718 Parts Fabricated by Selective Laser Melting Additive Manufacturing

    NASA Astrophysics Data System (ADS)

    Wang, Xiaoqing; Chou, Kevin

    2016-11-01

    In this study, the crystallographic texture of an Inconel 718 part fabricated by selective laser melting was investigated. The front surface (X-Z plane) microstructure is characterized by the columnar grains growing along the build direction, and the width of columnar grains is in the range of about 75-150 µm, with the bottom layers having narrower grains as a result of a higher cooling rate. In addition to equiaxed grains, the top surface (X-Y plane) has a feature of patch patterns resulting from the laser scanning strategy. Based on the electron backscatter diffraction results, there appears only weak crystallographic texture in both the X-Z plane and the X-Y plane of the part. From the grain boundary map, the microstructures are composed of high-angle boundaries with a larger fraction of subgrain boundaries.

  20. Electron Backscatter Diffraction Analysis of Inconel 718 Parts Fabricated by Selective Laser Melting Additive Manufacturing

    NASA Astrophysics Data System (ADS)

    Wang, Xiaoqing; Chou, Kevin

    2017-02-01

    In this study, the crystallographic texture of an Inconel 718 part fabricated by selective laser melting was investigated. The front surface (X-Z plane) microstructure is characterized by the columnar grains growing along the build direction, and the width of columnar grains is in the range of about 75-150 µm, with the bottom layers having narrower grains as a result of a higher cooling rate. In addition to equiaxed grains, the top surface (X-Y plane) has a feature of patch patterns resulting from the laser scanning strategy. Based on the electron backscatter diffraction results, there appears only weak crystallographic texture in both the X-Z plane and the X-Y plane of the part. From the grain boundary map, the microstructures are composed of high-angle boundaries with a larger fraction of subgrain boundaries.

  1. 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.

  2. Patient-specific in vitro models for hemodynamic analysis of congenital heart disease - Additive manufacturing approach.

    PubMed

    Medero, Rafael; García-Rodríguez, Sylvana; François, Christopher J; Roldán-Alzate, Alejandro

    2017-03-21

    Non-invasive hemodynamic assessment of total cavopulmonary connection (TCPC) is challenging due to the complex anatomy. Additive manufacturing (AM) is a suitable alternative for creating patient-specific in vitro models for flow measurements using four-dimensional (4D) Flow MRI. These in vitro systems have the potential to serve as validation for computational fluid dynamics (CFD), simulating different physiological conditions. This study investigated three different AM technologies, stereolithography (SLA), selective laser sintering (SLS) and fused deposition modeling (FDM), to determine differences in hemodynamics when measuring flow using 4D Flow MRI. The models were created using patient-specific MRI data from an extracardiac TCPC. These models were connected to a perfusion pump circulating water at three different flow rates. Data was processed for visualization and quantification of velocity, flow distribution, vorticity and kinetic energy. These results were compared between each model. In addition, the flow distribution obtained in vitro was compared to in vivo. The results showed significant difference in velocities measured at the outlets of the models that required internal support material when printing. Furthermore, an ultrasound flow sensor was used to validate flow measurements at the inlets and outlets of the in vitro models. These results were highly correlated to those measured with 4D Flow MRI. This study showed that commercially available AM technologies can be used to create patient-specific vascular models for in vitro hemodynamic studies at reasonable costs. However, technologies that do not require internal supports during manufacturing allow smoother internal surfaces, which makes them better suited for flow analyses.

  3. 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

    2014-04-04

    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.

  4. 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

  5. Quantitative assessment of thermodynamic constraints on the solution space of genome-scale metabolic models.

    PubMed

    Hamilton, Joshua J; Dwivedi, Vivek; Reed, Jennifer L

    2013-07-16

    Constraint-based methods provide powerful computational techniques to allow understanding and prediction of cellular behavior. These methods rely on physiochemical constraints to eliminate infeasible behaviors from the space of available behaviors. One such constraint is thermodynamic feasibility, the requirement that intracellular flux distributions obey the laws of thermodynamics. The past decade has seen several constraint-based methods that interpret this constraint in different ways, including those that are limited to small networks, rely on predefined reaction directions, and/or neglect the relationship between reaction free energies and metabolite concentrations. In this work, we utilize one such approach, thermodynamics-based metabolic flux analysis (TMFA), to make genome-scale, quantitative predictions about metabolite concentrations and reaction free energies in the absence of prior knowledge of reaction directions, while accounting for uncertainties in thermodynamic estimates. We applied TMFA to a genome-scale network reconstruction of Escherichia coli and examined the effect of thermodynamic constraints on the flux space. We also assessed the predictive performance of TMFA against gene essentiality and quantitative metabolomics data, under both aerobic and anaerobic, and optimal and suboptimal growth conditions. Based on these results, we propose that TMFA is a useful tool for validating phenotypes and generating hypotheses, and that additional types of data and constraints can improve predictions of metabolite concentrations.

  6. 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

  7. 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.

  8. [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.

  9. University Students' Understanding of Chemical Thermodynamics

    ERIC Educational Resources Information Center

    Sreenivasulu, Bellam; Subramaniam, R.

    2013-01-01

    This study explored undergraduate students' understanding of the chemistry topic of thermodynamics using a 4-tier diagnostic instrument, comprising 30 questions, and follow-up interviews. An additional objective of the study was to assess the utility of the 4-tier instrument for use in studies on alternative conceptions (ACs) as there has been no…

  10. Submonolayer Ag films on Fe(100): A first-principles analysis of energetics controlling adlayer thermodynamics and kinetics

    DOE PAGES

    Li, Wei; Huang, Li; Evans, James W.; ...

    2016-04-11

    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 bentmore » 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. Furthermore, energy barriers for diffusion along island edges can be determined with the aid of both conventional and unconventional interactions.« less

  11. 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.

  12. Submonolayer Ag films on Fe(100): A first-principles analysis of energetics controlling adlayer thermodynamics and kinetics

    SciTech Connect

    Li, Wei; Huang, Li; Evans, James W.; Han, Yong

    2016-04-11

    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. Furthermore, energy barriers for diffusion along island edges can be determined with the aid of both conventional and unconventional interactions.

  13. 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.

  14. Thermodynamics and evolutionary genetics

    NASA Astrophysics Data System (ADS)

    Müller, Ingo

    2010-03-01

    Thermodynamics and evolutionary genetics have something in common. Thus, the randomness of mutation of cells may be likened to the random thermal fluctuations in a gas. And the probabilistic nature of entropy in statistical thermodynamics can be carried over to a population of haploid and diploid cells without any conceptual change. The energetic potential wells in which the atoms of a liquid are caught correspond to selective advantages for some phenotype over others. Thus, the eventual stable state in a population comes about as a compromise in the universal competition between entropy and energy.

  15. 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.

  16. Blood pressure goal achievement with olmesartan medoxomil-based treatment: additional analysis of the OLMEBEST study

    PubMed Central

    Barrios, Vivencio; Escobar, Carlos; Calderon, Alberto; Böhm, Michael

    2009-01-01

    Aims Guidelines recommend blood pressure (BP) in hypertensive patients should be <140 systolic BP (SBP) and <90 diastolic BP (DBP) mmHg. This analysis assessed goal rate achievement in hypertensive patients receiving olmesartan-based treatment in the OLMEBEST study. Methods Patients with essential hypertension (DBP ≥ 90 mmHg and <110 mmHg) received open-label olmesartan medoxomil 20 mg/day (n = 2306). After 8 weeks, patients with DBP ≥ 90 mmHg (n = 627) were randomized to 4 weeks’ double-blind treatment with olmesartan 40 mg/day monotherapy or olmesartan 20 mg/day plus hydrochlorothiazide (HCTZ) 12.5 mg/day. For this analysis, the numbers and proportions of patients who achieved SBP < 140 mmHg and/or DBP < 90 mmHg at the end of the 4 weeks were calculated. Results In patients who achieved DBP normalization (<90 mmHg) at week 8 (n = 1546) and continued open-label olmesartan 20 mg/day, 66.7% achieved SBP/DBP < 140/90 mmHg at Week 12. In patients who did not achieve DBP normalization at Week 8, 26.8% of those randomized to olmesartan 40 mg/day and 42.5% of those randomized to olmesartan 20 mg/day plus HCTZ 12.5 mg/day achieved a SBP/DBP < 140/90 mmHg at Week 12. Conclusion Olmesartan 40 mg/day and olmesartan 20 mg/day plus HCTZ 12.5 mg/day allow substantial proportions of patients to achieve BP goals. PMID:19756164

  17. 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.

  18. Systematic vibration thermodynamic properties of bromine

    NASA Astrophysics Data System (ADS)

    Liu, G. Y.; Sun, W. G.; Liao, B. T.

    2015-11-01

    Based on the analysis of the maturity and finiteness of vibrational levels of bromine molecule in ground state and evaluating the effect on statistical computation, according to the elementary principles of quantum statistical theorem, using the full set of bromine molecular vibrational levels determined with algebra method, the statistical contribution for bromine systematical macroscopic thermodynamic properties is discussed. Thermodynamic state functions Helmholtz free energy, entropy and observable vibration heat capacity are calculated. The results show that the determination of full set of vibrational levels and maximum vibrational quantum number is the key in the correct statistical analysis of bromine systematical thermodynamic property. Algebra method results are clearly different from data of simple harmonic oscillator and the related algebra method results are no longer analytical but numerical and are superior to simple harmonic oscillator results. Compared with simple harmonic oscillator's heat capacities, the algebra method's heat capacities are more consistent with the experimental data in the given temperature range of 600-2100 K.

  19. Building Loads Analysis and System Thermodynamics (BLAST) program users manual. Volume 1: Supplement (version 3.0)

    NASA Astrophysics Data System (ADS)

    Herron, D.; Walton, G.; Lawrie, L.

    1981-03-01

    BLAST Version 3.0 can be used to model passive solar applications and to analyze large-scale industrial facilities. Parameters, users can study with BLAST Version 3.0 (in addition to BLAST 2.0 capabilities) include (1) interzone heat transfer and ventilation, (2) movable insulation, (3) daylighting, (4) exact internal solar distribution, (5) radiant temperature control, (6) exterior radiant interchange, (7) mechanical ventilation, (8) process heat as heat source, (9) latent air-to-air heat recovery, (10) water-cooled packaged systems, (11) induction unit systems, (12) direct-drive chillers, and (13) purchased steam from utilities. BLAST version 3.0 also offers the user a generalized report writer and several new output report options not available from BLAST Version 2.0. Although the simulation capabilities of BLAST Version 3.0 are expanded over BLAST Version 2.0, users familiar with BLAST Version 2.0 can use Version 3.0 without modifying their approach or their BLAST input.

  20. 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.