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Sample records for separations thermodynamic spectroscopic

  1. Quest for Environmentally-Benign Ligands for Actinide Separations: Thermodynamic, Spectroscopic, and Structural Characterization of U(VI) Complexes with Oxa-Diamide and Related Ligands

    Energy Technology Data Exchange (ETDEWEB)

    Advanced Light Source; Tian, Guoxin; Rao, Linfeng; Teat, Simon J.; Liu, Guokui

    2009-01-05

    Complexation of U(VI) with N,N,N{prime},N{prime}-tetramethyl-3-oxa-glutaramide (TMOGA) and N,N-dimethyl-3-oxa-glutaramic acid (DMOGA) was studied in comparison with their dicarboxylate analog, oxydiacetic acid (ODA). Thermodynamic parameters, including stability constants, enthalpy and entropy of complexation, were determined by spectrophotometry, potentiometry and calorimetry. Single-crystal X-ray diffractometry, EXAFS spectroscopy, FT-IR absorption and laser-induced luminescence spectroscopy were used to obtain structural information on the U(VI) complexes. Like ODA, TMOGA and DMOGA form tridentate U(VI) complexes, with three oxygen atoms (the amide, ether and/or carboxylate oxygen) coordinating to the linear UO{sub 2}{sup 2+} cation via the equatorial plane. The stability constants, enthalpy and entropy of complexation all decrease in the order ODA > DMOGA > TMOGA, showing that the complexation is entropy driven and the substitution of a carboxylate group with an amide group reduces the strength of complexation with U(VI) due to the decrease in the entropy of complexation. The trend in the thermodynamic stability of the complexes correlates very well with the structural and spectroscopic data obtained by single crystal XRD, FT-IR and laser-induced luminescence spectroscopy.

  2. Thermodynamics for separation-process technology

    Energy Technology Data Exchange (ETDEWEB)

    Prausnitz, J.M.

    1995-10-01

    When contemplating or designing a separation process, every chemical engineer at once recognizes the thermodynamic boundary conditions that must be satisfied: when a mixture is continuously processed to yield at least partially purified products, energy and mass must be conserved and work must be done. In his daily tasks, a chemical engineer uses thermodynamic concepts as tacit, almost subconscious, knowledge. Thus, qualitative thermodynamics significantly informs process conception at its most fundamental level. However, quantitative design requires detailed knowledge of thermodynamic relations and physical chemistry. Most process engineers, concerned with flow sheets and economics, cannot easily command that detailed knowledge and therefore it is advantageous for them to maintain close contact with those specialists who do. Quantitative chemical thermodynamics provides an opportunity to evaluate possible separation processes not only because it may give support to the process engineer`s bold imagination but also because, when coupled with molecular models, it can significantly reduce the experimental effort required to determine an optimum choice of process alternatives. Six examples are presented to indicate the application of thermodynamics for conventional and possible future separation processes.

  3. Quantitative Thermodynamic Analyses of Spectroscopic Titration Curves§

    Science.gov (United States)

    Bujalowski, Wlodzimierz; Jezewska, Maria J.

    2014-01-01

    Elucidation of ligand - macromolecule interactions requires detailed knowledge of energetics of the formed complexes. Spectroscopic methods are most commonly used in characterizing molecular interactions in solution. The methods do not require large quantities of material and most importantly, do not perturb the studied reactions. However, spectroscopic methods absolutely require the determination of the relationship between the observed signal and the degree of binding in order to obtain meaningful interaction parameters. In other words, the meaningful, thermodynamic interaction parameters can be only determined if the relationship between the observed signal and the degree of binding is determined and not assumed, based on an ad hoc model of the relationship. The approaches discussed here allow an experimenter to quantitatively determine the degree of binding and the free ligand concentration, i.e., they enable to construct thermodynamic binding isotherms in a model-independent fashion. PMID:25284889

  4. Thermodynamic considerations in renal separation processes

    National Research Council Canada - National Science Library

    Robert H Louw; David M Rubin; David Glasser; Robyn F R Letts; Diane Hildebrandt

    2017-01-01

    .... This study uses a thermodynamic analysis to evaluate the minimum work requirements for urine production in the human kidney and provide a new perspective on the energy costs of urine production...

  5. Calculation of the thermodynamic properties of fuel-vapor species from spectroscopic data

    Energy Technology Data Exchange (ETDEWEB)

    Green, D.W.

    1980-09-01

    Measured spectroscopic data, estimated molecular parameters, and a densty-of-states model for electronic structure have been used to calculate thermodynamic functions for gaseous ThO, ThO/sub 2/, UO, UO/sub 2/, UO/sub 3/, PuO, and PuO/sub 2/. Various methods for estimating parameters have been considered and numerically evaluated. The sensitivity of the calculated thermodynamic functions to molecular parameters has been examined quantitatively. New values of the standard enthalpies of formation at 298.15/sup 0/K have been derived from the best available ..delta..G/sup 0//sub f/ equations and the calculated thermodynamic functions. Estimates of the uncertainties have been made for measured and estimated data as well as for various mathematical and physical approximations. Tables of the thermodynamic functions to 6000/sup 0/K are recommended for gaseous thorium, uranium, and plutonium oxides.

  6. Biochemical activity of a fluorescent dye rhodamine 6G: Molecular modeling, electrochemical, spectroscopic and thermodynamic studies.

    Science.gov (United States)

    Al Masum, Abdulla; Chakraborty, Maharudra; Ghosh, Soumen; Laha, Dipranjan; Karmakar, Parimal; Islam, Md Maidul; Mukhopadhyay, Subrata

    2016-11-01

    Interaction of CT DNA with Rhodamine 6G (R6G) has been studied using molecular docking, electrochemical, spectroscopic and thermodynamic methods. From the study, it was illustrated that Rhodamine 6G binds to the minor groove of CT DNA. The binding was cooperative in nature. Circular voltametric study showed significant change in peak current and peak potential due to complexation. All the studies showed that the binding constant was in the order of 106M-1. Circular dichroic spectra showed significant conformational change on binding and DNA unwind during binding. Thermodynamic study showed that binding was favored by negative enthalpy and positive entropy change. From thermodynamic study it was also observed that several positive and negative free energies played significant role during binding and the unfavorable conformational free energy change was overcame by highly negative hydrophobic and salt dependent free energy changes. The experimental results were further validated using molecular docking study and the effect of structure on binding has been studied theoretically. From docking study it was found that the hydrophobic interaction and hydrogen bonds played a significant role during binding. The dye was absorbed by cell and this phenomenon was studied using fluorescent microscope. Cell survivability test showed that the dye active against Human Breast Cancer cells MDA-MB 468. ROS study showed that the activity is due to the production of reactive oxygen. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Thermodynamic Theory with Mixing Entropy Coupled to Mixing Energy for Phase Separation and Solubility Transition

    Science.gov (United States)

    Sasaki, Shigeo

    2017-10-01

    Thermodynamic theory is developed by introducing the concept of intermolecular interaction surface areas in the evaluation of the mixing free energy, which can quantitatively explain the phase separation with the lower critical solution temperature (LCST) and the solubility transition.

  8. Thermodynamic Studies to Support Actinide/Lanthanide Separations

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    Rao, Linfeng [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2016-09-04

    Thermodynamic data on the complexation of Np(V) with HEDTA in a wide pH region were re-modeled by including a dimeric complex species, (NpO2)2(OH)2L26- where L3- stands for the fully deprotonated HEDTA ligand and better fits were achieved for the spectrophotometric data. The presence of the dimeric complex species in high pH region was verified for the first time by the EXAFS experiments at Stanford Synchrotron Radiation Laboratory (SSRL).

  9. Uranium(VI) Binding Forms in Selected Human Body Fluids: Thermodynamic Calculations versus Spectroscopic Measurements.

    Science.gov (United States)

    Osman, Alfatih A A; Geipel, Gerhard; Barkleit, Astrid; Bernhard, Gert

    2015-02-16

    Human exposure to uranium increasingly becomes a subject of interest in many scientific disciplines such as environmental medicine, toxicology, and radiation protection. Knowledge about uranium chemical binding forms(speciation) in human body fluids can be of great importance to understand not only its biokinetics but also its relevance in risk assessment and in designing decorporation therapy in the case of accidental overexposure. In this study, thermodynamic calculations of uranium speciation in relevant simulated and original body fluids were compared with spectroscopic data after ex-situ uranium addition. For the first time, experimental data on U(VI) speciation in body fluids (saliva, sweat, urine) was obtained by means of cryogenic time-resolved laser-induced fluorescence spectroscopy (cryo-TRLFS) at 153 K. By using the time dependency of fluorescence decay and the band positions of the emission spectra, various uranyl complexes were demonstrated in the studied samples. The variations of the body fluids in terms of chemical composition, pH, and ionic strength resulted in different binding forms of U(VI). The speciation of U(VI) in saliva and in urine was affected by the presence of bioorganic ligands, whereas in sweat, the distribution depends mainly on inorganic ligands. We also elucidated the role of biological buffers, i.e., phosphate (H(2)PO(4−)/HPO(4)(2−)) on U(VI) distribution, and the system Ca(2+)/UO(2)(2+)/PO(4)(3−) was discussed in detail in both saliva and urine. The theoretical speciation calculations of the main U(VI) species in the investigated body fluids were significantly consistent with the spectroscopic data. Laser fluorescence spectroscopy showed success and reliability for direct determination of U(VI) in such biological matrices with the possibility for further improvement.

  10. Thermodynamic Studies to Support Actinide/Lanthanide Separations

    Energy Technology Data Exchange (ETDEWEB)

    Rao, Linfeng [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2015-09-01

    This milestone report summarizes the data obtained in FY15 on the complexation of HEDTA with Np(V) and U(VI) in a temperature range from 25 to 70°C. The results show the effect of temperature on the chemical speciation of Np(V) and U(VI) in the modified TALSPEAK Process, and help to evaluate the effectiveness of the process when the operation envelope (e.g., temperature) varies. Eventually, the results from this study will help to achieve a better control of the separation process based on the HEDTA/HEH[EHP] combination.

  11. Thermodynamics of polyamide separation membrane in contact with aqueous solutions

    Science.gov (United States)

    Zhang, Xijing

    Composite reverse osmosis (RO) membranes, which are typically comprised of a polyamide active-layer that is formed by interfacial polymerization on a porous polysulfone support, are widely used in technologies for desalination and water purification. The water permeation and the rejection of salts or other contaminants are mainly determined by the transport properties of the polyamide active layer. Both the permeabilities of water and salt are described using solution-diffusion model and the mechanism of salt distribution in polyamide is distinguished into ion-exchange and ion partitioning. The ion partition coefficient κ in the active layer is a key thermodynamic parameter that partially controls the ability of the membrane to desalinate water. FT30 membranes are soaked in aqueous solutions of CsCl, KBr, or Na 2WO4, freeze-dried to remove water without disturbing ion distribution, and analyzed by Rutherford backscattering spectrometry. κ is calculated as ˜ 6 from the ion concentration in active layer measured using RBS and porosity in the polysulfone support layer is also derived as 40--50% from RBS data. Stress change induced by salt distribution is investigated with an optical system. Stress goes up to 9 MPa for transferred polyamide active layer from commercial RO membrane FT30 and 8 MPa for lab-synthesized polyamide film. The saturation in stress change is due to the pre-occupation of ions onto all the stress-related sites. The absorption of water in reverse osmosis membranes FT30 and LF10 is investigated by a combination of measurements of water mass uptake and biaxial stress as a function of relative humidity. Water solubility in polyamide active layer is 12 wt% at a relative humidity of 95%. The slope of a water concentration versus humidity curve can be used to calculate inter-diffusivity of water in polyamide active layers. By combining the measurements of water mass uptake and biaxial stress, we estimate the specific volume of water in the active

  12. Binding of phenazinium dye safranin T to polyriboadenylic acid: spectroscopic and thermodynamic study.

    Directory of Open Access Journals (Sweden)

    Ankur Bikash Pradhan

    Full Text Available Here, we report results from experiments designed to explore the association of the phenazinium dye safranin T (ST, 3,7-diamino-2,8-dimethyl-5-phenylphenazinium chloride with single and double stranded form of polyriboadenylic acid (hereafter poly-A using several spectroscopic techniques. We demonstrate that the dye binds to single stranded polyriboadenylic acid (hereafter ss poly-A with high affinity while it does not interact at all with the double stranded (ds form of the polynucleotide. Fluorescence and absorption spectral studies reveal the molecular aspects of binding of ST to single stranded form of the polynucleotide. This observation is also supported by the circular dichroism study. Thermodynamic data obtained from temperature dependence of binding constant reveals that association is driven by negative enthalpy change and opposed by negative entropy change. Ferrocyanide quenching studies have shown intercalative binding of ST to ss poly-A. Experiments on viscosity measurements confirm the binding mode of the dye to be intercalative. The effect of [Na⁺] ion concentration on the binding process suggests the role of electrostatic forces in the complexation. Present studies reveal the utility of the dye in probing nucleic acid structure.

  13. Spectroscopic and thermodynamic studies on ferulic acid - Alpha-2-macroglobulin interaction

    Science.gov (United States)

    Rehman, Ahmed Abdur; Sarwar, Tarique; Arif, Hussain; Ali, Syed Saqib; Ahsan, Haseeb; Tabish, Mohammad; Khan, Fahim Halim

    2017-09-01

    Ferulic acid is a major phenolic acid found in numerous plant species in conjugated form. It binds to enzymes and oligomeric proteins and modifies their structure and function. This study was designed to examine the interaction of ferulic acid, an active ingredient of some important medicines, with α2M, a key serum proteinase, under physiological conditions. The mechanism of interaction was studied by spectroscopic techniques such as, UV-visible absorption, fluorescence spectroscopy, circular dichroism along with isothermal titration calorimetry. Fluorescence quenching of α2M by ferulic acid demonstrated the formation of α2M-ferulic acid complex by static quenching mechanism. Binding parameters calculated by Stern-Volmer method showed that ferulic acid binds to α2M with moderate affinity of the order of ∼104 M-1. The thermodynamic signatures reveal that binding was enthalpy driven and hydrogen bonding played a major role in ferulic acid-α2M binding. CD spectra analysis suggests very little conformational changes in α2M on ferulic acid binding.

  14. Spectroscopic investigation of species separation in opening switch plasmas

    Science.gov (United States)

    Jackson, S. L.; Phipps, D. G.; Richardson, A. S.; Commisso, R. J.; Hinshelwood, D. D.; Murphy, D. P.; Schumer, J. W.; Weber, B. V.; Boyer, C. N.; Doron, R.; Biswas, S.; Maron, Y.

    2015-11-01

    Interactions between magnetic fields and current-carrying plasmas that lead to the separation of plasma species in multi-species plasmas are being studied in a plasma opening switch geometry. Several Marshall guns are used to inject single or multi-species plasmas between coaxial conductors connected to the output of the Naval Research Laboratory's Hawk pulsed-power generator. Following injection of the plasma, the generator is used at roughly half power to apply an electrical pulse with a peak current of 450 kA, a peak voltage of 400 kV, and a rise time of 1.2 μs. The resulting magnetic field interacts with the plasma through a combination of field penetration and magnetohydrodynamic (MHD) pushing that is not well understood but can lead to the separation of plasma species in multi-species plasmas. An ICCD-coupled spectrometer has been used in combination with magnetic probes, a ribbon-beam interferometer, and particle-in-cell (PIC) modeling to diagnose and understand conditions in the plasma from the time it is injected until the end of the conduction phase of the opening switch. This work supported by the Naval Research Laboratory Base Program and the Office of Naval Research.

  15. Study on the interaction between amphiphilic drug and bovine serum albumin: A thermodynamic and spectroscopic description

    Energy Technology Data Exchange (ETDEWEB)

    Rub, Malik Abdul, E-mail: malikrub@gmail.com [Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah-21589 (Saudi Arabia); Khan, Javed Masood [Interdisciplinary Biotechnology Unit, Aligarh Muslim University, Aligarh 202002 (India); Asiri, Abdullah M. [Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah-21589 (Saudi Arabia); Center of Excellence for Advanced Materials Research, King Abdulaziz University, Jeddah-21589 (Saudi Arabia); Khan, Rizwan Hasan, E-mail: rizwanhkhan1@gmail.com [Interdisciplinary Biotechnology Unit, Aligarh Muslim University, Aligarh 202002 (India); Kabir-ud-Din [Department of Applied Chemistry, Aligarh Muslim University, Aligarh-202002 (India)

    2014-11-15

    Herein we report the interaction of amphiphilic drug clomipramine hydrochloride (CLP—a tricyclic antidepressant) with bovine serum albumin (BSA) studied by fluorescence, UV–vis, and circular dichroism (CD) spectroscopic techniques. Clomipramine hydrochloride is used to treat a variety of mental health problems. The quenching rate constant (k{sub q}) values, calculated according to the fluorescence data, decrease with increase in temperature indicating the static quenching procedure for the CLP–BSA interaction. The association binding constants (K{sub A}), evaluated at different conditions, and the thermodynamic parameters (free energy, enthalpy and entropy changes) indicate that the hydrophobic forces play a major role in the binding interaction of drug. The interaction of BSA with CLP was further confirmed by UV absorption spectra. Blue shift of position was detected due to the complex formation between the BSA–CLP. The molecular distance, r{sub 0}, between donor (BSA) and acceptor (CLP) was estimated by fluorescence resonance energy transfer (FRET) whose value (4.47 nm) suggests high probability of static quenching interaction. The CD results prove the conformational changes in the BSA on binding with the drug. Thus, the results supply qualitative and quantitative understanding of the binding of BSA to CLP, which is important in understanding their effect as therapeutic agents. - Highlights: • BSA can be considered as a good carrier for transportation of CLP in vivo. • The fluorescence results indicated the presence of static quenching mechanism in the binding process. • CD spectra showed the change in molecular conformation of BSA in the presence of CLP. • The results have applicability in model drug delivery.

  16. Spectroscopic and thermodynamic properties of molecular hydrogen dissolved in water at pressures up to 200 MPa.

    Science.gov (United States)

    Borysow, Jacek; del Rosso, Leonardo; Celli, Milva; Moraldi, Massimo; Ulivi, Lorenzo

    2014-04-28

    We have measured the Raman Q-branch of hydrogen in a solution with water at a temperature of about 280 K and at pressures from 20 to 200 MPa. From a least-mean-square fitting analysis of the broad Raman Q-branch, we isolated the contributions from the four lowest individual roto-vibrational lines. The vibrational lines were narrower than the pure rotational Raman lines of hydrogen dissolved in water measured previously, but significantly larger than in the gas. The separations between these lines were found to be significantly smaller than in gaseous hydrogen and their widths were slightly increasing with pressure. The lines were narrowing with increasing rotational quantum number. The Raman frequencies of all roto-vibrational lines were approaching the values of gas phase hydrogen with increasing pressure. Additionally, from the comparison of the integrated intensity signal of Q-branch of hydrogen to the integrated Raman signal of the water bending mode, we have obtained the concentration of hydrogen in a solution with water along the 280 K isotherm. Hydrogen solubility increases slowly with pressure, and no deviation from a smooth behaviour was observed, even reaching thermodynamic conditions very close to the transition to the stable hydrogen hydrate. The analysis of the relative hydrogen concentration in solution on the basis of a simple thermodynamic model has allowed us to obtain the molar volume for the hydrogen gas/water solution. Interestingly, the volume relative to one hydrogen molecule in solution does not decrease with pressure and, at high pressure, is larger than the volume pertinent to one molecule of water. This is in favour of the theory of hydrophobic solvation, for which a larger and more stable structure of the water molecules is expected around a solute molecule.

  17. Spectroscopic and thermodynamic properties of molecular hydrogen dissolved in water at pressures up to 200 MPa

    Energy Technology Data Exchange (ETDEWEB)

    Borysow, Jacek, E-mail: jborysow@mtu.edu; Rosso, Leonardo del; Celli, Milva; Ulivi, Lorenzo, E-mail: lorenzo.ulivi@isc.cnr.it [Consiglio Nazionale delle Ricerche, Istituto dei Sistemi Complessi, Via Madonna del piano 10, I-50019 Sesto Fiorentino (Italy); Moraldi, Massimo [Dipartimento di Fisica e Astronomia, Università degli Studi di Firenze, Via Sansone 1, I-50019 Sesto Fiorentino (Italy)

    2014-04-28

    We have measured the Raman Q-branch of hydrogen in a solution with water at a temperature of about 280 K and at pressures from 20 to 200 MPa. From a least-mean-square fitting analysis of the broad Raman Q-branch, we isolated the contributions from the four lowest individual roto-vibrational lines. The vibrational lines were narrower than the pure rotational Raman lines of hydrogen dissolved in water measured previously, but significantly larger than in the gas. The separations between these lines were found to be significantly smaller than in gaseous hydrogen and their widths were slightly increasing with pressure. The lines were narrowing with increasing rotational quantum number. The Raman frequencies of all roto-vibrational lines were approaching the values of gas phase hydrogen with increasing pressure. Additionally, from the comparison of the integrated intensity signal of Q-branch of hydrogen to the integrated Raman signal of the water bending mode, we have obtained the concentration of hydrogen in a solution with water along the 280 K isotherm. Hydrogen solubility increases slowly with pressure, and no deviation from a smooth behaviour was observed, even reaching thermodynamic conditions very close to the transition to the stable hydrogen hydrate. The analysis of the relative hydrogen concentration in solution on the basis of a simple thermodynamic model has allowed us to obtain the molar volume for the hydrogen gas/water solution. Interestingly, the volume relative to one hydrogen molecule in solution does not decrease with pressure and, at high pressure, is larger than the volume pertinent to one molecule of water. This is in favour of the theory of hydrophobic solvation, for which a larger and more stable structure of the water molecules is expected around a solute molecule.

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

    Energy Technology Data Exchange (ETDEWEB)

    Leigh R. Martin; Peter R. Zalupski

    2010-09-01

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

  19. Quantum chemical calculations and spectroscopic measurements of spectroscopic and thermodynamic properties of given uranyl complexes in aqueous solutions with possible environmental and industrial applications

    Directory of Open Access Journals (Sweden)

    Višňak Jakub

    2016-01-01

    Full Text Available A brief introduction into computational methodology and preliminary results for spectroscopic (excitation energies, vibrational frequencies in ground and excited electronic states and thermodynamic (stability constants, standard enthalpies and entropies of complexation reactions properties of some 1:1, 1:2 and 1:3 uranyl sulphato- and selenato- complexes in aqueos solutions will be given. The relativistic effects are included via Effective Core Potential (ECP, electron correlation via (TDDFT/B3LYP (dispersion interaction corrected and solvation is described via explicit inclusion of one hydration sphere beyond the coordinated water molecules. We acknowledge limits of this approximate description – more accurate calculations (ranging from semi-phenomenological two-component spin-orbit coupling up to four-component Dirac-Coulomb-Breit hamiltonian and Molecular Dynamics simulations are in preparation. The computational results are compared with the experimental results from Time-resolved Laser-induced Fluorescence Spectroscopy (TRLFS and UV-VIS spectroscopic studies (including our original experimental research on this topic. In case of the TRLFS and UV-VIS speciation studies, the problem of complex solution spectra decomposition into individual components is ill-conditioned and hints from theoretical chemistry could be very important. Qualitative agreement between our quantum chemical calculations of the spectroscopic properties and experimental data was achieved. Possible applications for geochemical modelling (e.g. safety studies of nuclear waste repositories, modelling of a future mining site and analytical chemical studies (including natural samples are discussed.

  20. Comparative thermodynamic and spectroscopic properties of water interaction with human stratum corneum.

    Science.gov (United States)

    Yadav, Santosh; Wickett, R Randall; Pinto, Neville G; Kasting, Gerald B; Thiel, Stephen W

    2009-05-01

    The water content of skin has a significant impact on skin properties; sufficient hydration is necessary to keep the skin supple, flexible, and smooth. To understand more completely the water retention properties of the human skin barrier, physical macroscopic properties must be related to the structural organization of the stratum corneum (SC). Water, lipids, and natural moisturizing factor (NMF) influence the molecular structures that affect the properties of SC, including water sorption and binding enthalpy. In the research reported here, isothermal microcalorimetry was used to study the interaction of water vapor with isolated human SC in intact, delipidized, and water-washed delipidized forms to identify the influences of the principal components of SC on water sorption. The calorimetric data are interpreted in conjunction with spectroscopic results to identify the conformational changes in keratins induced by lipid and NMF removal and to assess the influence of these changes on water binding in SC. Isothermal calorimetry was used to measure the integral heat of water vapor sorption on intact, delipidized, and water-washed delipidized human SC at 32 degrees C as a function of relative humidity using back and thigh skin from three donors. Calorimetric measurements were combined with water vapor sorption measurements to determine the differential thermodynamic properties of these systems. Attenuated total reflection-Fourier transform infrared spectroscopy was used to investigate effects of extraction on protein secondary structure. The magnitudes of the differential enthalpy, entropy, and free energy were greatest for intact SC and least for water-washed delipidized SC. Water sorption followed a similar trend. Delipidization led to a significantly reduced binding enthalpy at low water content; water washing the delipidized SC had only a small additional effect on binding enthalpy. Delipidization converts a fraction of keratin alpha-helixes to turns and random

  1. Thermodynamics

    CERN Document Server

    Fermi, Enrico

    1956-01-01

    Indisputably, this is a modern classic of science. Based on a course of lectures delivered by the author at Columbia University, the text is elementary in treatment and remarkable for its clarity and organization. Although it is assumed that the reader is familiar with the fundamental facts of thermometry and calorimetry, no advanced mathematics beyond calculus is assumed.Partial contents: thermodynamic systems, the first law of thermodynamics (application, adiabatic transformations), the second law of thermodynamics (Carnot cycle, absolute thermodynamic temperature, thermal engines), the entr

  2. Mechanism of Arsenic Adsorption on Magnetite Nanoparticles from Water: Thermodynamic and Spectroscopic Studies.

    Science.gov (United States)

    Liu, Cheng-Hua; Chuang, Ya-Hui; Chen, Tsan-Yao; Tian, Yuan; Li, Hui; Wang, Ming-Kuang; Zhang, Wei

    2015-07-07

    Removal of arsenic (As) from water supplies is needed to reduce As exposure through drinking water and food consumption in many regions of the world. Magnetite nanoparticles (MNPs) are promising and novel adsorbents for As removal because of their great adsorption capacity for As and easy separation. This study aimed to investigate the adsorption mechanism of arsenate, As(V), and arsenite, As(III), on MNPs by macroscopic adsorption experiments in combination with thermodynamic calculation and microspectroscopic characterization using synchrotron-radiation-based X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS). Adsorption reactions are favorable endothermic processes as evidenced by increased adsorption with increasing temperatures, and high positive enthalpy change. EXAFS spectra suggested predominant formation of bidentate binuclear corner-sharing complexes ((2)C) for As(V), and tridentate hexanuclear corner-sharing ((3)C) complexes for As(III) on MNP surfaces. The macroscopic and microscopic data conclusively identified the formation of inner-sphere complexes between As and MNP surfaces. More intriguingly, XANES and XPS results revealed complex redox transformation of the adsorbed As on MNPs exposed to air: Concomitant with the oxidation of MNPs, the oxidation of As(III) and MNPs was expected, but the observed As(V) reduction was surprising because of the role played by the reactive Fe(II).

  3. An efficient and rigorous thermodynamic library and optimal-control of a cryogenic air separation unit

    DEFF Research Database (Denmark)

    Gaspar, Jozsef; Ritschel, Tobias Kasper Skovborg; Jørgensen, John Bagterp

    2017-01-01

    Cryogenic air separation (CAS) is the leading technology for large scale production of pure N2, O2 and Ar. This process is very electric-energy intensive; thus it is a likely candidate for load balancing of power stations in a smart grid. This type of intermittent operation of CAS, requires a non...... objective is to reduce the cost of compression in a volatile electricity market while meeting the production requirements, i.e. product flow rate and purity. This model is implemented in Matlab and uses the ThermoLib rigorous thermodynamic library. The present work represents a first step towards plant...

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

    OpenAIRE

    Kotowicz Janusz; Bartela Łukasz; Mikosz Dorota

    2014-01-01

    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...

  5. Liquid Chromatographic Separation and Thermodynamic Investigation of Mirabegron Enantiomers on a Chiralpak AY-H Column.

    Science.gov (United States)

    Zhou, Fan; Zhou, Yuxia; Zou, Qiaogen; Sun, Lili; Wei, Ping

    2015-09-01

    Liquid chromatographic separation of mirabegron enantiomers on Chiralpak AY-H, a column coated with amylose tris-(5-chloro-2-methylphenylcarbamate) as a chiral stationary phase, was studied under normal phase conditions. The influence of ethanol content (30-45%) and column temperature (20-40°C) on retention, resolution and separation were evaluated. Apparent thermodynamic parameters deduced from Van't Hoff plots were used to understand chiral separation mechanisms, and the chiral separation was enthalpy driven. The optimized chromatographic conditions were using a mixture solution of n-hexane, ethanol and diethyl amine (55 : 45 : 0.1, v/v/v) as a mobile phase at a flow rate of 1.0 mL/min. The column temperature and UV detector were set at 35°C and 254 nm, respectively. The method was validated to be simple, accuracy, sensitive and robust according to the ICH guidelines, and it was suitable for the routine quality control of mirabegron enantiomers for pharmaceutical industries. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

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

    Directory of Open Access Journals (Sweden)

    Kotowicz Janusz

    2014-12-01

    Full Text Available 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.

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

    Science.gov (United States)

    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.

  8. Porous materials with optimal adsorption thermodynamics and kinetics for CO2 separation.

    Science.gov (United States)

    Nugent, Patrick; Belmabkhout, Youssef; Burd, Stephen D; Cairns, Amy J; Luebke, Ryan; Forrest, Katherine; Pham, Tony; Ma, Shengqian; Space, Brian; Wojtas, Lukasz; Eddaoudi, Mohamed; Zaworotko, Michael J

    2013-03-07

    The energy costs associated with the separation and purification of industrial commodities, such as gases, fine chemicals and fresh water, currently represent around 15 per cent of global energy production, and the demand for such commodities is projected to triple by 2050 (ref. 1). The challenge of developing effective separation and purification technologies that have much smaller energy footprints is greater for carbon dioxide (CO2) than for other gases; in addition to its involvement in climate change, CO2 is an impurity in natural gas, biogas (natural gas produced from biomass), syngas (CO/H2, the main source of hydrogen in refineries) and many other gas streams. In the context of porous crystalline materials that can exploit both equilibrium and kinetic selectivity, size selectivity and targeted molecular recognition are attractive characteristics for CO2 separation and capture, as exemplified by zeolites 5A and 13X (ref. 2), as well as metal-organic materials (MOMs). Here we report that a crystal engineering or reticular chemistry strategy that controls pore functionality and size in a series of MOMs with coordinately saturated metal centres and periodically arrayed hexafluorosilicate (SiF(2-)(6)) anions enables a 'sweet spot' of kinetics and thermodynamics that offers high volumetric uptake at low CO2 partial pressure (less than 0.15 bar). Most importantly, such MOMs offer an unprecedented CO2 sorption selectivity over N2, H2 and CH4, even in the presence of moisture. These MOMs are therefore relevant to CO2 separation in the context of post-combustion (flue gas, CO2/N2), pre-combustion (shifted synthesis gas stream, CO2/H2) and natural gas upgrading (natural gas clean-up, CO2/CH4).

  9. Porous materials with optimal adsorption thermodynamics and kinetics for CO2 separation

    KAUST Repository

    Nugent, Patrick S.

    2013-02-27

    The energy costs associated with the separation and purification of industrial commodities, such as gases, fine chemicals and fresh water, currently represent around 15 per cent of global energy production, and the demand for such commodities is projected to triple by 2050 (ref. 1). The challenge of developing effective separation and purification technologies that have much smaller energy footprints is greater for carbon dioxide (CO2) than for other gases; in addition to its involvement in climate change, CO 2 is an impurity in natural gas, biogas (natural gas produced from biomass), syngas (CO/H 2, the main source of hydrogen in refineries) and many other gas streams. In the context of porous crystalline materials that can exploit both equilibrium and kinetic selectivity, size selectivity and targeted molecular recognition are attractive characteristics for CO 2 separation and capture, as exemplified by zeolites 5A and 13X (ref. 2), as well as metal-organic materials (MOMs). Here we report that a crystal engineering or reticular chemistry strategy that controls pore functionality and size in a series of MOMs with coordinately saturated metal centres and periodically arrayed hexafluorosilicate (SiF 6 2-) anions enables a \\'sweet spot\\' of kinetics and thermodynamics that offers high volumetric uptake at low CO2 partial pressure (less than 0.15 bar). Most importantly, such MOMs offer an unprecedented CO 2 sorption selectivity over N2, H 2 and CH 4, even in the presence of moisture. These MOMs are therefore relevant to CO2 separation in the context of post-combustion (flue gas, CO2/N2), pre-combustion (shifted synthesis gas stream, CO 2/H 2) and natural gas upgrading (natural gas clean-up, CO2/CH 4). © 2013 Macmillan Publishers Limited. All rights reserved.

  10. Macromolecular Competition Titration Method: Accessing Thermodynamics of the Unmodified Macromolecule–Ligand Interactions Through Spectroscopic Titrations of Fluorescent Analogs

    Science.gov (United States)

    Bujalowski, Wlodzimierz; Jezewska, Maria J.

    2011-01-01

    Analysis of thermodynamically rigorous binding isotherms provides fundamental information about the energetics of the ligand–macromolecule interactions and often an invaluable insight about the structure of the formed complexes. The Macromolecular Competition Titration (MCT) method enables one to quantitatively obtain interaction parameters of protein–nucleic acid interactions, which may not be available by other methods, particularly for the unmodified long polymer lattices and specific nucleic acid substrates, if the binding is not accompanied by adequate spectroscopic signal changes. The method can be applied using different fluorescent nucleic acids or fluorophores, although the etheno-derivatives of nucleic acid are especially suitable as they are relatively easy to prepare, have significant blue fluorescence, their excitation band lies far from the protein absorption spectrum, and the modification eliminates the possibility of base pairing with other nucleic acids. The MCT method is not limited to the specific size of the reference nucleic acid. Particularly, a simple analysis of the competition titration experiments is described in which the fluorescent, short fragment of nucleic acid, spanning the exact site-size of the protein–nucleic acid complex, and binding with only a 1:1 stoichiometry to the protein, is used as a reference macromolecule. Although the MCT method is predominantly discussed as applied to studying protein–nucleic acid interactions, it can generally be applied to any ligand–macromolecule system by monitoring the association reaction using the spectroscopic signal originating from the reference macromolecule in the presence of the competing macromolecule, whose interaction parameters with the ligand are to be determined. PMID:21195223

  11. Thermodynamic and spectroscopic study of Al3+interaction with glycine, l-cysteine and tranexamic acid in aqueous solution.

    Science.gov (United States)

    Cardiano, Paola; Giacobello, Fausta; Giuffrè, Ottavia; Sammartano, Silvio

    2017-11-01

    In this paper a thermodynamic and spectroscopic study on the interaction between Al 3+ and glycine (Gly), l-cysteine (Cys), tranexamic acid (Tranex) is reported. Speciation models have been obtained by processing potentiometric titration data to determine stability constants of the species formed in aqueous solution at T=298.15K, 0.15≤I/molL -1 ≤1 in NaCl. Thermodynamic formation parameters have been obtained from calorimetric titration data, at T=298.15K, I=0.15molL -1 using NaCl as ionic medium. Al 3+ -Cys system was also investigated by spectrophotometric and 1 H NMR measurements. 1 H NMR experiments were performed on Al 3+ -Tranex system as well. Different speciation models have been observed for the three systems. The results showed the formation of MLH, ML and M 2 L 2 (OH) 2 species for Gly, ML, M 2 L and MLOH for Cys, MLH and MLOH for Tranex. The formed species are quite stable, i.e. for ML, logβ=7.18, 11.91 for Gly and Cys, respectively, at I=0.15molL -1 and T=298.15K. For all the systems the dependence of formation constants on ionic strength over the range 0.1-1molL -1 is reported. The sequestering ability of the ligands under study was also evaluated by pL 0.5 empiric parameter. For Gly, Cys and Tranex, pL 0.5 =2.51, 3.74, 3.91 respectively, at pH=5, I=0.15molL -1 and T=298.15K. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. FY-2011 Status Report for Thermodynamics and Kinetics of Advanced Separations Systems

    Energy Technology Data Exchange (ETDEWEB)

    Leigh R. Martin; Peter R. Zalupski; Travis S. Grimes

    2011-09-01

    This report presents a summary of the work performed in the area of thermodynamics and kinetics of advanced separations systems under the Fuel Cycle Research and Development (FCR&D) program during FY 2011 at the INL. On the thermodynamic front, investigations of liquid-liquid distribution of lanthanides at TALSPEAK-related conditions continued in FY11. It has been determined that a classical ion-exchanging phase transfer mechanism, where three HDEHP dimers solvate the metal ion in the organic phase, dominates metal extraction for systems that contain up to 0.1 M free lactate in solution. The correct graphical interpretation of the observed data in those regions relied on incorporating corrections for non-ideal behavior of HDEHP dimer in aliphatic diluents as well as sodium extraction equilibria. When aqueous conditions enter the complex regions of high lactate concentrations, slope analysis is no longer possible. When normalized metal distribution ratios were studied along the increasing concentration of free lactate, a slope of -1 was apparent. Such dependency either indicates aqueous complexing competition from lactate, or, a more likely scenario, a participation of lactate in the extracted metal complex. This finding agrees with our initial assessment of postulated changes in the extraction mechanism as a source of the lactate-mediated loss of extraction efficiency. The observed shape in the lanthanide distribution curve in our studies of TALSPEAK systems was the same for solutions containing no lactate or 2.3 M lactate. As such we may conclude that the mechanism of phase transfer is not altered dramatically and remains similarly sensitive to effective charge density of the metal ion. In addition to these thermodynamics studies, this report also summarizes the first calorimetric determination of heat of extraction of 248Cm in a bi-phasic system. The heat of extraction measured by isothermal titration calorimetry is compared to that determined using van

  13. Thermodynamic and Spectroscopic Investigation of Interactions between Reactive Red 223 and Reactive Orange 122 Anionic Dyes and Cetyltrimethyl Ammonium Bromide (CTAB Cationic Surfactant in Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Muhammad Irfan

    2014-01-01

    Full Text Available The present study describes the conductometric and spectroscopic study of the interaction of reactive anionic dyes, namely, reactive red 223 and reactive orange 122 with the cationic surfactant cetyltrimethyl ammonium bromide (CTAB. In a systematic investigation, the electrical conductivity data was used to calculate various thermodynamic parameters such as free energy (ΔG, enthalpy (ΔH, and the entropy (ΔS of solubilization. The trend of change in these thermodynamic quantities indicates toward the entropy driven solubilization process. Moreover, the results from spectroscopic data reveal high degree of solubilization, with strong interactions observed in the cases of both dyes and the CTAB. The spontaneous nature of solubilization and binding was evident from the observed negative values of free energies (ΔGp and ΔGb.

  14. Molecular spectroscopic and thermodynamic studies on the interaction of anti-platelet drug ticlopidine with calf thymus DNA

    Science.gov (United States)

    Afrin, Shumaila; Rahman, Yusra; Sarwar, Tarique; Husain, Mohammed Amir; Ali, Abad; Shamsuzzaman; Tabish, Mohammad

    2017-11-01

    Ticlopidine is an anti-platelet drug which belongs to the thienopyridine structural family and exerts its effect by functioning as an ADP receptor inhibitor. Ticlopidine inhibits the expression of TarO gene in S. aureus and may provide protection against MRSA. Groove binding agents are known to disrupt the transcription factor DNA complex and consequently inhibit gene expression. Understanding the mechanism of interaction of ticlopidine with DNA can prove useful in the development of a rational drug designing system. At present, there is no such study on the interaction of anti-platelet drugs with nucleic acids. A series of biophysical experiments were performed to ascertain the binding mode between ticlopidine and calf thymus DNA. UV-visible and fluorescence spectroscopic experiments confirmed the formation of a complex between ticlopidine and calf thymus DNA. Moreover, the values of binding constant were found to be in the range of 103 M- 1, which is indicative of groove binding between ticlopidine and calf thymus DNA. These results were further confirmed by studying the effect of denaturation on double stranded DNA, iodide quenching, viscometric studies, thermal melting profile as well as CD spectral analysis. The thermodynamic profile of the interaction was also determined using isothermal titration calorimetric studies. The reaction was found to be endothermic and the parameters obtained were found to be consistent with those of known groove binders. In silico molecular docking studies further corroborated well with the experimental results.

  15. Hydrogen adsorption on the faujasite-type zeolite Mg-X: An IR spectroscopic and thermodynamic study

    Energy Technology Data Exchange (ETDEWEB)

    Turnes Palomino, G., E-mail: g.turnes@uib.es [Departamento de Quimica, Universidad de las Islas Baleares, Palma de Mallorca (Spain); Otero Arean, C.; Llop Carayol, M.R. [Departamento de Quimica, Universidad de las Islas Baleares, Palma de Mallorca (Spain)

    2010-06-15

    Hydrogen adsorption (physisorption) on the faujasite-type zeolite Mg-X was studied by means of variable-temperature (80-140 K) FT-IR spectroscopy. Perturbation of the adsorbed H{sub 2} molecules by the cationic adsorbing centres of the zeolite renders the H-H stretching mode IR active, at 4065 cm{sup -1}. Simultaneous measurement of IR absorbance and hydrogen equilibrium pressure, for a series of spectra recorded at the increasing temperature, allowed standard adsorption enthalpy and entropy to be determined. They resulted to be {Delta}H{sup 0} = -13 kJ mol{sup -1} and {Delta}S{sup 0} = -114 J mol{sup -1} K{sup -1}, respectively. Both, spectroscopic and thermodynamic results are discussed in the broader context of corresponding data for hydrogen adsorption on other alkali and alkaline-earth cation exchanged zeolites, showing that, while an approximate correlation exists between {Delta}H{sup 0} and H-H stretching frequency, deviations can be expected for the case of zeolites containing small metal cations.

  16. Thermodynamic and spectroscopic studies of alanine and phenylalanine in aqueous β-cyclodextrin solutions

    Directory of Open Access Journals (Sweden)

    Anwar Ali

    2017-01-01

    Full Text Available Ultrasonic speed, u and density, ρ have been measured for dl-alanine (Ala and l-phenylalanine (Phe in aqueous β-cyclodextrin (β-CD at 298.15, 303.15, 308.15, and 313.15 K. The complexation of Ala and Phe with β-CD has been studied by means of UV–vis and thermodynamic (ultrasonic speed and density studies. Using the measured ultrasonic speed and density data the apparent molar compressibility (κS,φ, apparent molar volume (Vφ, limiting apparent molar compressibility (κS,φ0, limiting apparent molar volume (Vφ0, their constants (SK and Sv, and hydration number (nH have been obtained. The positive values of transfer properties at infinite dilution for Ala and Phe in β-CD is the outcome of the balance between released water molecules from β-CD cavity and hydrophobic groups of Ala and Phe that enter into the macrocycle β-CD cavity. The experimental results have also been discussed on the basis of UV–vis absorbance. The results indicate the formation of a more stable host–guest complex between Phe-β-CD than between Ala-β-CD.

  17. Phase Behavior and Thermodynamic Model Parameters in Simulations of Extractive Distillation for Azeotrope Separation.

    Science.gov (United States)

    Li, Min; Xu, Xicai; Li, Xin; Ma, Kang; Qin, Bin; Zhu, Zhaoyou; Wang, Yinglong

    2017-08-25

    Extractive distillation (ED) processes for separating ternary mixtures of benzene-cyclohexane-toluene with dimethyl formamide (DMF) and N-methyl-2-pyrrolidone (NMP) were studied using Aspen Plus and PRO/II simulators. The Aspen Plus built-in binary interaction parameters for the toluene-DMF, benzene-NMP and cyclohexane-NMP systems resulted in inaccurate phase behavior calculations. The vapor-liquid equilibrium (VLE) for the three binary systems was regressed to illustrate the importance of using accurate model parameters. The obtained binary interaction parameters described the phase behavior more accurately compared with the built-in binary interaction parameters in Aspen Plus. In this study, the effects of the regressed and built-in binary interaction parameters on the ED process design are presented. The total annual cost (TAC) was calculated to further illustrate the importance of the regressed binary interaction parameters. The results show that phase behavior and thermodynamic model parameters should receive more attention during the research and development of ED processes.

  18. Human serum albumin unfolding pathway upon drug binding: A thermodynamic and spectroscopic description

    Energy Technology Data Exchange (ETDEWEB)

    Cheema, Mohammad Arif [Grupo de Fisica de Coloides y Polimeros, Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Santiago de Compostela, E-15782, Santiago de Compostela (Spain); Department of Chemistry, Quaid-i-Azam University, Islamabad 45320 (Pakistan); Taboada, Pablo [Grupo de Fisica de Coloides y Polimeros, Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Santiago de Compostela, E-15782, Santiago de Compostela (Spain); Department of Chemistry, Quaid-i-Azam University, Islamabad 45320 (Pakistan)], E-mail: pablo.taboada@usc.es; Barbosa, Silvia; Juarez, Josue; Gutierrez-Pichel, Manuel [Grupo de Fisica de Coloides y Polimeros, Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Santiago de Compostela, E-15782, Santiago de Compostela (Spain); Department of Chemistry, Quaid-i-Azam University, Islamabad 45320 (Pakistan); Siddiq, Mohammad [Department of Chemistry, Quaid-i-Azam University, Islamabad 45320 (Pakistan); Mosquera, Victor [Grupo de Fisica de Coloides y Polimeros, Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Santiago de Compostela, E-15782, Santiago de Compostela (Spain); Department of Chemistry, Quaid-i-Azam University, Islamabad 45320 (Pakistan)

    2009-04-15

    The interest on phenothiazine drugs has been increased during last years due to their proved utility in the treatment of several diseases and biomolecular processes. In the present work, the binding of the amphiphilic phenothiazines promazine and thioridazine hydrochlorides to the carrier protein human serum albumin (HSA) has been examined by {zeta}-potential, isothermal titration calorimetry (ITC), fluorescence and circular dichorism (CD) spectroscopies, and dynamic light scattering (DLS) at physiological pH with the aim of analyzing the role of the different interactions in the drug complexation process with this protein. The {zeta}-potential results were used to check the existence of complexation. This is confirmed by a progressive screening of the protein charge up to a reversal point as a consequence of drug binding. On the other hand, binding causes alterations on the tertiary and secondary structures of the protein, which were observed by fluorescence and CD spectroscopies, involving a two-step, three-state transition. The thermodynamics of the binding process was derived from ITC results. The binding enthalpies were negative, which reveal the existence of electrostatic interactions between protein and drug molecules. In addition, increases in entropy are consistent with the predominance of hydrophobic interactions. Two different classes of binding sites were detected, viz. Binding to the first class of binding sites is dominated by an enthalpic contribution due to electrostatic interactions whereas binding to a second class of binding sites is dominated by hydrophobic bonding. In the light of these results, protein conformational change resembles the acid-induced denaturation of HSA with accumulation of an intermediate state. Binding isotherms were derived from microcalorimetric results by using a theoretical model based on the Langmuir isotherm. On the other hand, the population distribution of the different species in solution and their sizes were

  19. Spectroscopic and thermodynamic studies of light harvesting perylenediimide derivative - zinc porphyrin complex in aqueous media

    Science.gov (United States)

    El-Refaey, Ahmed; Shaban, Shaban Y.; El-Kemary, Maged; El-Khouly, Mohamed E.

    2017-11-01

    Self-assembly of perylene derivative such as N,N‧-bis(2(trimethylammonium iodide) ethylene)perylene-3,4,9,10-tetracarboxyldiimide (TAIPDI) can produce one-dimensional form (1D) in an aqueous media. The ability of one-dimensional TAIPDI to form light harvesting complex with water-soluble zinc porphyrin (ZnTPPS4) via the π-π and electrostatic interactions has been described. Owing to electronic interactions between the π-systems, the complex formation is accompanied by pronounced absorption spectral changes in the UV/Vis absorption bands. The formation constant of the ZnTPPS4-TAIPDI complex has been determined as 2.60 × 104 M- 1 suggests a moderately stable complex. The steady-state fluorescence measurements exhibited fluorescence quenching of both the singlet TAIPDI and ZnTPPS4 because of the electron transfer process from the electron-donating ZnTPPS4 to the electron-accepting TAIPDI. Based on the picosecond time-resolved fluorescence, the rate and quantum yield of the electron transfer were found to be 2.47 × 1010 s- 1 and 0.99, respectively, indicating fast and efficient electron transfer. The thermodynamic parameters of the complex formation have been determined from the stopped-flow measurements. The interaction between ZnTPPS4 and TAIPDI occurs in two steps, a fast and reversible step followed by a slow and irreversible one. The activation parameters for the complex formation (ΔH# = 22 ± 5 kJ mol- 1 and ΔS# = - 123 ± 18 J K- 1 mol- 1), (ΔH# = 133 ± 4 kJ mol- 1 and ΔS# = 167 ± 13 J mol- 1 K- 1) were determined from variable temperature studies for the ;on; and the ;off; of the first step and ΔS# = 246 ± 37.89 J mol- 1 K- 1 and ΔH# = 130 ± 11 kJ mol- 1 for the second step. The negative and positive ΔS# values found for the interaction reactions are consistent with an associative interaction for the first step followed by dissociative mechanism for both the ;off; and the second step.

  20. Thermodynamic evaluation of supercritical oxy-type power plant with high-temperature three-end membrane for air separation

    Directory of Open Access Journals (Sweden)

    Kotowicz Janusz

    2014-09-01

    Full Text Available Among the technologies which allow to reduce greenhouse gas emissions, mainly of carbon dioxide, special attention deserves the idea of ‘zero-emission’ technology based on boilers working in oxy-combustion technology. In the paper a thermodynamic analysis of supercritical power plant fed by lignite was made. Power plant consists of: 600 MW steam power unit with live steam parameters of 650 °C/30 MPa and reheated steam parameters of 670 °C/6 MPa; circulating fluidized bed boiler working in oxy-combustion technology; air separation unit and installation of the carbon dioxide compression. Air separation unit is based on high temperature membrane working in three-end technology. Models of steam cycle, circulation fluidized bed boiler, air separation unit and carbon capture installation were made using commercial software. After integration of these models the net electricity generation efficiency as a function of the degree of oxygen recovery in high temperature membrane was analyzed.

  1. Recent advances in chromatographic separation and spectroscopic characterization of the higher fullerenes C76 and C84.

    Science.gov (United States)

    Jovanovic, T; Koruga, Dj

    2014-01-01

    The basic and the higher fullerenes were chromatographically isolated from the obtained series of carbon soot extracts, in increased yields, by the new, advanced methods, on Al2O3 columns. The elution was performed continuously, in one phase of each process, at ambient conditions, with the several different original hexane-toluene gradients. Various separation systems were used previously. The unique and the main, dominant absorption maxima of the purified higher fullerenes were registered in the spectral regions where they intensively absorb, applying the IR and UV/VIS techniques. All the observed absorption bands are in excellent agreement with theoretical calculations, indicating the achieved advancement in chromatographic separation and spectroscopic characterization. The isolated fullerenes are important for investigation of their remarkable optical and electronic properties, as well as for the numerous possible applications in chemistry, physics, biomedicine, diagnostic and therapeutic agents, sensors, polymers, nanophotonic materials, special lenses, optical limiting, organic field effect transistors, solar cells etc.

  2. Separating and stabilizing phosphate from high-level radioactive waste: process development and spectroscopic monitoring.

    Science.gov (United States)

    Lumetta, Gregg J; Braley, Jenifer C; Peterson, James M; Bryan, Samuel A; Levitskaia, Tatiana G

    2012-06-05

    Removing phosphate from alkaline high-level waste sludges at the Department of Energy's Hanford Site in Washington State is necessary to increase the waste loading in the borosilicate glass waste form that will be used to immobilize the highly radioactive fraction of these wastes. We are developing a process which first leaches phosphate from the high-level waste solids with aqueous sodium hydroxide, and then isolates the phosphate by precipitation with calcium oxide. Tests with actual tank waste confirmed that this process is an effective method of phosphate removal from the sludge and offers an additional option for managing the phosphorus in the Hanford tank waste solids. The presence of vibrationally active species, such as nitrate and phosphate ions, in the tank waste processing streams makes the phosphate removal process an ideal candidate for monitoring by Raman or infrared spectroscopic means. As a proof-of-principle demonstration, Raman and Fourier transform infrared (FTIR) spectra were acquired for all phases during a test of the process with actual tank waste. Quantitative determination of phosphate, nitrate, and sulfate in the liquid phases was achieved by Raman spectroscopy, demonstrating the applicability of Raman spectroscopy for the monitoring of these species in the tank waste process streams.

  3. Simplified thermodynamic functions for vapor-liquid phase separation and fountain effect pumps

    Science.gov (United States)

    Yuan, S. W. K.; Hepler, W. A.; Frederking, T. H. K.

    1984-01-01

    He-4 fluid handling devices near 2 K require novel components for non-Newtonian fluid transport in He II. Related sizing of devices has to be based on appropriate thermophysical property functions. The present paper presents simplified equilibrium state functions for porous media components which serve as vapor-liquid phase separators and fountain effect pumps.

  4. Thermodynamic Study of Racemic Ibuprofen Separation by Liquid Chromatography Using Cellulose-Based Stationary Phase

    Directory of Open Access Journals (Sweden)

    Wilson M. Ferrari

    2016-01-01

    Full Text Available Ibuprofen is a nonsteroidal anti-inflammatory drug (NSAID, also known for its significant antipyretic and analgesic properties. This chiral drug is commercialized in racemic form; however, only S-(+-ibuprofen has clinical activities. In this paper the effect of temperature change (from 288.15 to 308.15 K on the ibuprofen resolution was studied. A column (250×4.6 mm packed with tris(3,5-dimethylphenylcarbamate was used to obtain the thermodynamic parameters, such as enthalpy change (ΔH, entropy change (ΔS, variation enthalpy change (ΔΔH, variation entropy change (ΔΔS, and isoenantioselective temperature (Tiso. The mobile phase was a combination of hexane (99%, isopropyl alcohol (1%, and TFA (0.1%, as an additive. The conditions led to a selectivity of 1.20 and resolution of 4.55. The first peak, R-(−-ibuprofen, presented an enthalpy change of 7.21 kJ/mol and entropy change of 42.88 kJ/K·mol; the last peak, S-(+-ibuprofen, has an enthalpy change of 8.76 kJ/mol and 49.40 kJ/K·mol of entropy change.

  5. Double stars with wide separations in the AGK3 - I. Components that are themselves spectroscopic binaries

    OpenAIRE

    Halbwachs, J.-L; Mayor, M.; Udry, S.

    2017-01-01

    Wide binaries are tracers of the gravity field of the Galaxy, but their study requires some caution. A large list of common proper motion stars selected from the third Astronomischen Gesellschaft Katalog (AGK3) was monitored with the CORAVEL (for COrrelation RAdial VELocities) spectrovelocimeter, in order to prepare a sample of physical binaries with very wide separations. 66 stars received special attention, since their radial velocities (RV) seemed to be variable. These stars were monitored...

  6. Theory of multiple phase separations in binary mixtures: Phase diagrams, thermodynamic properties, and comparisons with experiments

    Science.gov (United States)

    Goldstein, Raymond E.; Walker, James S.

    1983-02-01

    The lattice-gas models of phase separating binary liquid mixtures, introduced by Walker and Vause, are studied in detail and generalized within a high-temperature series expansion. This approximation allows for a straightforward study of rather complex, orientationally specific pair interactions, like those found in real systems. These theories can predict much of the complex miscibility phenomena often found in these mixtures, which are characterized by hydrogen-bonding interactions. Such phenomena include up to five critical solution points as a function of temperature. By comparisons with experiments, we determine the model parameters, thus mapping these experiments onto the global phase diagrams. These experiments include studies of the dependence of liquid/liquid miscibility on temperature, pressure, concentration of electrolytes, and addition of a dilute third component. Specifically, we make direct comparison with various experiments on the binary systems 2-butanol+H2O, 3-methyl pyridine+H2O(D2O), gylcerol +o- methoxy phenol and ethanol+H2O+electrolytes. Very simple and often easily interpreted trends in the parameters are found and quantitative agreement with experiments is possible with minimum parametric freedom. Explicit predictions of critical exponent renormalization in several systems are made. In addition, suggestions are made for a number of light scattering and specific heat experiments, some of which may demonstrate incipient critical behavior, such as the onset of long range correlations, in systems not undergoing phase separation.

  7. Spectroscopic and conformational properties of size-fractions acid separated from a lignite humic

    Energy Technology Data Exchange (ETDEWEB)

    Conte, P.; Spaccini, R.; Smejkalova, D.; Nebbioso, A.; Piccolo, A. [University of Naples Federico 2, Portici (Italy)

    2007-10-15

    A lignite humic acid (HA) was fractionated by preparative high performance size-exclusion chromatography (HPSEC) in seven different size-fractions. The size-fractions were characterized by cross polarization (CP) magic angle spinning (MAS) {sup 13}C NMR spectroscopy and a further analytical HPSEC elution under UV and fluorescence detection. The alkyl hydrophobic components mainly distributed in the largest molecular-size-fraction, whereas the amount of oxidized carbons increased with decreasing size of fractions. Cross polarization time (T{sub CH}) and proton spin-lattice relaxation time in the rotating frame (T{sub 1p}(H)) were measured from variable contact time (VCT) experiments. The bulk HA was characterized by the shortest T{sub CH} values and the longest T{sub 1p}(H) values which suggested, respectively, one, an aggregation of components in a large conformation that favored a fast H-C cross polarization, and, two, consequent steric hindrances that prevented fast local molecular motions and decreased proton relaxation rates. Conversely, the separated size-fractions showed longer T{sub CH} values and shorter T{sub 1p}(H) values than the bulk HA, thereby indicating that they were constituted by a larger number of mobile molecular conformations. The UV and fluorescence absorptions were both low in the large size-fractions that mainly contained alkyl carbons, whereas they increased in the olephinic- and aromatic-rich fractions with intermediate molecular-size, and decreased again in the smaller fractions which were predominantly composed by oxidized carbons. These results support the supramolecular structure of humic Substances and indicate that the observed variation in conformational distribution in humic association may be used to explain environmental processes with additional precision.

  8. Bifunctional cyclam-based ligands with phosphorus acid pendant moieties for radiocopper separation: thermodynamic and kinetic studies.

    Science.gov (United States)

    Paúrová, Monika; Havlíčková, Jana; Pospíšilová, Aneta; Vetrík, Miroslav; Císařová, Ivana; Stephan, Holger; Pietzsch, Hans-Jürgen; Hrubý, Martin; Hermann, Petr; Kotek, Jan

    2015-03-16

    Two macrocyclic ligands based on cyclam with trans-disposed N-methyl and N-(4-aminobenzyl) substituents as well as two methylphosphinic (H2L1) or methylphosphonic (H4L2) acid pendant arms were synthesised and investigated in solution. The ligands form stable complexes with transition metal ions. Both ligands show high thermodynamic selectivity for divalent copper over nickel(II) and zinc(II)-K(CuL) is larger than K(Ni/ZnL) by about seven orders of magnitude. Complexation is significantly faster for the phosphonate ligand H4L2, probably due to the stronger coordination ability of the more basic phosphonate groups, which efficiently bind the metal ion in an "out-of-cage" complex and thus accelerate its "in-cage" binding. The rate of Cu(II) complexation by the phosphinate ligand H2L1 is comparable to that of cyclam itself and its derivatives with non-coordinating substituents. Acid-assisted decomplexation of the copper(II) complexes is relatively fast (τ1/2 = 44 and 42 s in 1 M aq. HClO4 at 25 °C for H2L1 and H4L2, respectively). This combination of properties is convenient for selective copper removal/purification. Thus, the title ligands were employed in the preparation of ion-selective resins for radiocopper(II) separation. Glycidyl methacrylate copolymer beads were modified with the ligands through a diazotisation reaction. The separation ability of the modified polymers was tested with cold copper(II) and non-carrier-added (64)Cu in the presence of a large excess of both nickel(II) and zinc(II). The experiments exhibited high overall separation efficiency leading to 60-70% recovery of radiocopper with high selectivity over the other metal ions, which were originally present in 900-fold molar excess. The results showed that chelating resins with properly tuned selectivity of their complexing moieties can be employed for radiocopper separation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Exploring molecular and thermodynamic properties of zwitterions vs ionic liquids: A comprehensive computational analysis to develop advanced separation processes.

    Science.gov (United States)

    Moreno, Daniel; Gonzalez-Miquel, Maria; Ferro, Victor R; Palomar, Jose

    2018-01-07

    Zwitterions ionic liquids (ZIs) are compounds in which both counterions are covalently tethered, conferring them with unique characteristics; however, most of their properties are still unknown, remaining a bottleneck to exploit practical applications. Herein, molecular and fluid properties of ZIs and their mixtures are explored by means of quantum chemical analysis based on density functional theory (DFT) and COSMO-RS method, and compared against homologous ILs, to provide a comprehensive overview on the effect of the distinct structures on their physicochemical and thermodynamic behavior. Overall, ZIs were revealed as compounds with higher polarity and stronger hydrogen bonding capacity, implying higher density, viscosity and melting point, and even lower volatility than structurally similar ILs. Phase equilibrium of binary and ternary systems support stronger attractive interactions between ZIs and polar compounds, whereas higher liquid-liquid immiscibility with non-polar compounds may be expected. Ultimately, the performance of ZIs in the wider context of separation processes is illustrated, while providing molecular insights to allow their selection and design for relevant applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Thermodynamic and kinetic study of chiral separations of coumarin-based anticoagulants on derivatized amylose stationary phase.

    Science.gov (United States)

    Gebreyohannes, Kahsay G; McGuffin, Victoria L

    2010-09-17

    Thermodynamic and kinetic studies are performed on amylose derivatized with tris-(3,5-dimethylphenyl carbamate) stationary phase for the chiral separation of coumarin-based anticoagulants. Polar-organic eluents that contain acetonitrile as bulk solvent with modifiers such as methanol, i-butanol, t-butanol, and tetrahydrofuran are used in the study. Temperature is varied from 5 to 45 degrees C at constant pressure of 1500psi. In general, both retention and enantioselectivity decrease as the temperature increases and as hydrogen bond donating ability of the modifiers increases. The van't Hoff plots are found to show both linear and non-linear behavior. The non-linear plots are believed to be the result of conformational changes in the derivatized amylose phase and are observed around room temperature. The retention behavior in acetonitrile mobile phase provides a linear enthalpy-entropy compensation plot, indicating that all coumarins may have a similar retention mechanism. In contrast, enthalpy-entropy compensation is not observed for warfarin and coumatetralyl enantiomers when separated with different organic modifiers in the mobile phase. The kinetic data indicate that the rate of sorption is always greater than the rate of desorption. An increase in the concentration of alcohol modifiers causes an increase in the desorption rate constant. In contrast, an increase in the concentration of tetrahydrofuran causes a decrease in the desorption rate constant. This effect is most significant for the second eluted enantiomer of coumatetralyl, for which the desorption rate is 36 times slower than the first eluted enantiomer. 2010 Elsevier B.V. All rights reserved.

  11. Influence of galloyl moiety in interaction of epicatechin with bovine serum albumin: a spectroscopic and thermodynamic characterization.

    Directory of Open Access Journals (Sweden)

    Sandip Pal

    Full Text Available The health benefits stemming from green tea are well known, but the exact mechanism of its biological activity is not elucidated. Epicatechin (EC and epicatechin gallate (ECG are two dietary catechins ubiquitously present in green tea. Serum albumins functionally carry these catechins through the circulatory system and eliminate reactive oxygen species (ROS induced injury. In the present study ECG is observed to have higher antioxidant activity; which is attributed to the presence of galloyl moiety. The binding affinity of these catechins to bovine serum albumin (BSA will govern the efficacy of their biological activity. EC and ECG bind with BSA with binding constants 1.0 × 10(6 M(-1 and 6.6 × 10(7 M(-1, respectively. Changes in secondary structure of BSA on interaction with EC and ECG have been identified by circular dichroism (CD and Fourier transform infrared (FT-IR spectroscopy. Thermodynamic characterization reveals the binding process to be exothermic, spontaneous and entropy driven. Mixed binding forces (hydrophobic, electrostatic and hydrogen bonding exist between ECG and BSA. Binding site for EC is primarily site-II in sub-domain IIIA of BSA and for ECG; it is site-I in sub-domain IIA. ECG with its high antioxidant activity accompanied by high affinity for BSA could be a model in drug designing.

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

    Science.gov (United States)

    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±0.20×104M-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. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Influence of galloyl moiety in interaction of epicatechin with bovine serum albumin: a spectroscopic and thermodynamic characterization.

    Science.gov (United States)

    Pal, Sandip; Saha, Chabita; Hossain, Maidul; Dey, Subrata Kumar; Kumar, Gopinatha Suresh

    2012-01-01

    The health benefits stemming from green tea are well known, but the exact mechanism of its biological activity is not elucidated. Epicatechin (EC) and epicatechin gallate (ECG) are two dietary catechins ubiquitously present in green tea. Serum albumins functionally carry these catechins through the circulatory system and eliminate reactive oxygen species (ROS) induced injury. In the present study ECG is observed to have higher antioxidant activity; which is attributed to the presence of galloyl moiety. The binding affinity of these catechins to bovine serum albumin (BSA) will govern the efficacy of their biological activity. EC and ECG bind with BSA with binding constants 1.0 × 10(6) M(-1) and 6.6 × 10(7) M(-1), respectively. Changes in secondary structure of BSA on interaction with EC and ECG have been identified by circular dichroism (CD) and Fourier transform infrared (FT-IR) spectroscopy. Thermodynamic characterization reveals the binding process to be exothermic, spontaneous and entropy driven. Mixed binding forces (hydrophobic, electrostatic and hydrogen bonding) exist between ECG and BSA. Binding site for EC is primarily site-II in sub-domain IIIA of BSA and for ECG; it is site-I in sub-domain IIA. ECG with its high antioxidant activity accompanied by high affinity for BSA could be a model in drug designing.

  14. Separating climate change signals into thermodynamic, lapse-rate and circulation effects: theory and application to the European summer climate

    Science.gov (United States)

    Kröner, Nico; Kotlarski, Sven; Fischer, Erich; Lüthi, Daniel; Zubler, Elias; Schär, Christoph

    2017-05-01

    Climate models robustly project a strong overall summer warming across Europe showing a characteristic north-south gradient with enhanced warming and drying in southern Europe. However, the processes that are responsible for this pattern are not fully understood. We here employ an extended surrogate or pseudo-warming approach to disentangle the contribution of different mechanisms to this response pattern. The basic idea of the surrogate technique is to use a regional climate model and apply a large-scale warming to the lateral boundary conditions of a present-day reference simulation, while maintaining the relative humidity (and thus implicitly increasing the specific moisture content). In comparison to previous studies, our approach includes two important extensions: first, different vertical warming profiles are applied in order to separate the effects of a mean warming from lapse-rate effects. Second, a twin-design is used, in which the climate change signals are not only added to present-day conditions, but also subtracted from a scenario experiment. We demonstrate that these extensions provide an elegant way to separate the full climate change signal into contributions from large-scale thermodynamic (TD), lapse-rate (LR), and circulation and other remaining effects (CO). The latter in particular include changes in land-ocean contrast and spatial variations of the SST warming patterns. We find that the TD effect yields a large-scale warming across Europe with no distinct latitudinal gradient. The LR effect, which is quantified for the first time in our study, leads to a stronger warming and some drying in southern Europe. It explains about 50 % of the warming amplification over the Iberian Peninsula, thus demonstrating the important role of lapse-rate changes. The effect is linked to an extending Hadley circulation. The CO effect as inherited from the driving GCM is shown to further amplify the north-south temperature change gradient. In terms of mean summer

  15. Thermodynamic tables to accompany Modern engineering thermodynamics

    CERN Document Server

    Balmer, Robert T

    2011-01-01

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

  16. FT-IR spectroscopic and thermodynamic study on the adsorption of carbon dioxide and dinitrogen in the alkaline zeolite K-L

    Energy Technology Data Exchange (ETDEWEB)

    Arean, C.O.; Bibiloni, G.F. [Department of Chemistry, University of the Balearic Islands, E-07122 Palma de Mallorca (Spain); Delgado, M.R., E-mail: montserrat.rodriguez@uib.es [Department of Chemistry, University of the Balearic Islands, E-07122 Palma de Mallorca (Spain)

    2012-10-15

    Highlights: Black-Right-Pointing-Pointer Variable temperature IR spectroscopy is used to study adsorption of CO{sub 2} and N{sub 2} in the alkaline zeolite K-L. Black-Right-Pointing-Pointer By simultaneously recording IR absorbance, temperature and equilibrium pressure, standard adsorption enthalpy and entropy for each gas was determined. Black-Right-Pointing-Pointer The results are discussed in the broader context of gas separation using zeolites; focusing on carbon dioxide capture. - Abstract: The thermodynamics of carbon dioxide and dinitrogen adsorption on the zeolite K-L was investigated by means of variable temperature IR spectroscopy, a technique that affords determination of standard adsorption enthalpy ({Delta}H Degree-Sign ) and entropy ({Delta}S Degree-Sign ) from analysis of IR spectra recorded over a temperature range while simultaneously measuring equilibrium pressure inside a closed IR cell. {Delta}H Degree-Sign resulted to be -42.5 and -20.6 kJ mol{sup -1} for CO{sub 2} and N{sub 2}, respectively. Corresponding values of {Delta}S Degree-Sign were found to be -182 and -151 J mol{sup -1} K{sup -1}. The obtained adsorption enthalpy values are discussed in the context of carbon dioxide capture and sequestration.

  17. 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.

    Science.gov (United States)

    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. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. Thermodynamic study of phase equilibria in petroleum separation plants; Estudo termodinamico do equilibrio de fases em plantas de separacao de petroleo

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Ciro Rodolfo Santos; Duarte, Lindemberg de Jesus Nogueira [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil); Santos, Luiz Carlos Lobato [Universidade Federal da Bahia (UFBA), BA (Brazil)

    2012-07-01

    Through a thermodynamic approach of liquid-vapor separation it is possible to provide for a given load, of known composition and given temperature and pressure conditions, which are the volumes and the compositions of liquid and vapor phases in equilibrium. In this sense, the aim of this work is to analyze the separation conditions of the fluids produced in the well 1-FMO-001-BA, belonging to the Field School Project (ANP / UFBA), through a thermodynamic approach of phase equilibrium. This Well is characterized by being in an advanced stage of exploration with low oil and high gas production. Initially, the overall composition of the gas produced from the 1-FMO-001-BA was quantified by gas chromatography and its composition was similar to a typical natural gas found in the Reconcavo's basin. Then, the equilibrium constants were determined by Wilson empirical correlation, which could enable the determination of the dead oil composition. This oil showed low concentration of light hydrocarbons (e.g., methane, etc.) and moderate concentrations of heavy components (e.g., C{sub 10} {sub +}). Moreover, the original composition of the fluid that reaches the separator vessel had a similar chemical composition to the outlet gaseous stream of the separator vessel, proving that the Fazenda Mamoeiro's reservoir is classified as a gas reservoir. Finally, it was determined the relative density of the gas ({gamma} g = 0.8264), the specific gravity of the dead oil ({gamma} {sub o} = 0.7542), the API gravity (56.13) and gas-oil ratio (GOR 950.98 m{sup 3}std / m{sup 3}std), which are consistent with the data provided by PETROBRAS. (author)

  19. In vivo measurement of non-keratinized squamous epithelium using a spectroscopic microendoscope with multiple source-detector separations

    Science.gov (United States)

    Greening, Gage J.; Rajaram, Narasimhan; Muldoon, Timothy J.

    2016-03-01

    In the non-keratinized epithelia, dysplasia typically arises near the basement membrane and proliferates into the upper epithelial layers over time. We present a non-invasive, multimodal technique combining high-resolution fluorescence imaging and broadband sub-diffuse reflectance spectroscopy (sDRS) to monitor health at various tissue layers. This manuscript focuses on characterization of the sDRS modality, which contains two source-detector separations (SDSs) of 374 μm and 730 μm, so that it can be used to extract in vivo optical parameters from human oral mucosa at two tissue thicknesses. First, we present empirical lookup tables (LUTs) describing the relationship between reduced scattering (μs') and absorption coefficients (μa) and absolute reflectance. LUTS were shown to extract μs' and μa with accuracies of approximately 4% and 8%, respectively. We then present LUTs describing the relationship between μs', μa and sampling depth. Sampling depths range between 210-480 and 260-620 μm for the 374 and 730 μm SDSs, respectively. We then demonstrate the ability to extract in vivo μs', μa, hemoglobin concentration, bulk tissue oxygen saturation, scattering exponent, and sampling depth from the inner lip of thirteen healthy volunteers to elucidate the differences in the extracted optical parameters from each SDS (374 and 730 μm) within non-keratinized squamous epithelia.

  20. Thermodynamic and spectroscopic speciation to explain the blackening process of hematite formed by atmospheric SO2 impact: the case of Marcus Lucretius House (Pompeii).

    Science.gov (United States)

    Maguregui, Maite; Knuutinen, Ulla; Martínez-Arkarazo, Irantzu; Castro, Kepa; Madariaga, Juan M

    2011-05-01

    After many decades exposed to a polluted environment, in some areas of Marcus Lucretius House, there are clear signs that plasters and hematite pigments are suffering deterioration. In the exhaustive analysis of the black layer covering the red pigment hematite it was possible to identify magnetite (Fe(3)O(4)) as responsible for the black colour, which always appears in combination with gypsum. Thermodynamic modelling stated that the presence of gypsum as well as the transformation of hematite into magnetite is a consequence of the attack of atmospheric SO(2).

  1. Interactions fulvate-metal (Zn²⁺, Cu²⁺ and Fe²⁺): theoretical investigation of thermodynamic, structural and spectroscopic properties.

    Science.gov (United States)

    Bertoli, Alexandre C; Garcia, Jerusa S; Trevisan, Marcello G; Ramalho, Teodorico C; Freitas, Matheus P

    2016-04-01

    The use of theoretical calculation to determine structural properties of fulvate-metal complex (zinc, copper and iron) is here related. The species were proposed in the ratio 1:1 and 2:1 for which the molecular structure was obtained through the semi-empirical method PM6. The calculation of thermodynamic stability ([Formula: see text]) predicted that the iron complex were more exo-energetic. Metallic ions were coordinated to the phtalate groups of the model-structure of fulvic acid Suwannee River and the calculations of vibrational frequencies suggested that hydrogen bonds may help on the stability of the complex formation.

  2. Spectroscopic investigation (FTIR spectrum), NBO, HOMO-LUMO energies, NLO and thermodynamic properties of 8-Methyl-N-vanillyl-6-nonenamideby DFT methods

    Science.gov (United States)

    Sherin Percy Prema Leela, J.; Hemamalini, R.; Muthu, S.; Al-Saadi, Abdulaziz A.

    2015-07-01

    Capsicum a hill grown vegetable is also known as red pepper or chili pepper. Capsaicin(8-Methyl-N-vanillyl-6-nonenamide) is the active component in chili peppers, which is currently used in the treatment of osteoarthritis, psoriasis and cancer. Fourier transform infrared (FT-IR) spectrum of Capsaicin in the solid phase were recorded in the region 4000-400 cm-1 and analyzed. The vibrational frequencies of the title compound were obtained theoretically by DFT/B3LYP calculations employing the standard 6-311++G(d,p) basis set and were compared with Fourier transform infrared spectrum. Complete vibrational assignment analysis and correlation of the fundamental modes for the title compound were carried out. The vibrational harmonic frequencies were scaled using scale factor, yielding a good agreement between the experimentally recorded and the theoretically calculated values. Stability of the molecule arising from hyper conjugative interactions, charge delocalization and intra molecular hydrogen bond-like weak interaction has been analyzed using Natural bond orbital (NBO) analysis by using B3LYP/6-311++G(d,p) method. The results show that electron density (ED) in the σ∗ and π∗ antibonding orbitals and second-order delocalization energies E (2) confirm the occurrence of intra molecular charge transfer (ICT) within the molecule. The dipole moment (μ), polarizability (α) and the hyperpolarizability (β) values of the molecule has been computed. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures were calculated.

  3. Spectroscopic investigation (FTIR spectrum), NBO, HOMO-LUMO energies, NLO and thermodynamic properties of 8-Methyl-N-vanillyl-6-nonenamideby DFT methods.

    Science.gov (United States)

    Leela, J Sherin Percy Prema; Hemamalini, R; Muthu, S; Al-Saadi, Abdulaziz A

    2015-07-05

    Capsicum a hill grown vegetable is also known as red pepper or chili pepper. Capsaicin(8-Methyl-N-vanillyl-6-nonenamide) is the active component in chili peppers, which is currently used in the treatment of osteoarthritis, psoriasis and cancer. Fourier transform infrared (FT-IR) spectrum of Capsaicin in the solid phase were recorded in the region 4000-400 cm(-1) and analyzed. The vibrational frequencies of the title compound were obtained theoretically by DFT/B3LYP calculations employing the standard 6-311++G(d,p) basis set and were compared with Fourier transform infrared spectrum. Complete vibrational assignment analysis and correlation of the fundamental modes for the title compound were carried out. The vibrational harmonic frequencies were scaled using scale factor, yielding a good agreement between the experimentally recorded and the theoretically calculated values. Stability of the molecule arising from hyper conjugative interactions, charge delocalization and intra molecular hydrogen bond-like weak interaction has been analyzed using Natural bond orbital (NBO) analysis by using B3LYP/6-311++G(d,p) method. The results show that electron density (ED) in the σ∗ and π∗ antibonding orbitals and second-order delocalization energies E (2) confirm the occurrence of intra molecular charge transfer (ICT) within the molecule. The dipole moment (μ), polarizability (α) and the hyperpolarizability (β) values of the molecule has been computed. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures were calculated. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Thermodynamic and spectroscopic investigations of TMPyP4 association with guanine- and cytosine-rich DNA and RNA repeats of C9orf72.

    Science.gov (United States)

    Alniss, Hasan; Zamiri, Bita; Khalaj, Melisa; Pearson, Christopher E; Macgregor, Robert B

    2018-01-22

    An expansion of the hexanucleotide repeat (GGGGCC)n·(GGCCCC)n in the C9orf72 promoter has been shown to be the cause of Amyotrophic lateral sclerosis and frontotemporal dementia (ALS-FTD). The C9orf72 repeat can form four-stranded structures; the cationic porphyrin (TMPyP4) binds and distorts these structures. Isothermal titration calorimetry (ITC), and circular dichroism (CD) were used to study the binding of TMPyP4 to the C-rich and G-rich DNA and RNA oligos containing the hexanucleotide repeat at pH 7.5 and 0.1 M K + . The CD spectra of G-rich DNA and RNA TMPyP4 complexes showed features of antiparallel and parallel G-quadruplexes, respectively. The shoulder at 260 nm in the CD spectrum becomes more intense upon formation of complexes between TMPyP4 and the C-rich DNA. The peak at 290 nm becomes more intense in the c-rich RNA molecules, suggesting induction of an i-motif structure. The ITC data showed that TMPyP4 binds at two independent sites for all DNA and RNA molecules. For DNA, the data are consistent with TMPyP4 stacking on the terminal tetrads and intercalation. For RNA, the thermodynamics of the two binding modes are consistent with groove binding and intercalation. In both cases, intercalation is the weaker binding mode. These findings are considered with respect to the structural differences of the folded DNA and RNA molecules and the energetics of the processes that drive site-specific recognition by TMPyP4; these data will be helpful in efforts to optimize the specificity and affinity of the binding of porphyrin-like molecules. Copyright © 2018 Elsevier Inc. All rights reserved.

  5. Spectroscopic and thermodynamic studies on the complexation of trivalent curium with inorganic ligands at increased temperatures; Spektroskopische und thermodynamische Untersuchungen zur Komplexierung von trivalentem Curium mit anorganischen Liganden bei erhoehten Temperaturen

    Energy Technology Data Exchange (ETDEWEB)

    Skerencak, Andrej

    2010-05-11

    The subject of the present investigation is the complexation of trivalent actinides at elevated temperatures. The objective of this work is to broaden the comprehension of the geochemical processes relevant for the migration of radionuclides in the near-field of a nuclear waste repository. Depending on the disposed nuclear waste, the temperature in the direct vicinity of a nuclear waste repository may reach up to 200 C. The result is a distinct change of the geochemistry of the actinides. Many of these processes have already been studied in detail at room temperature. Yet, data at elevated temperature are rare. However, a comprehensive long term safety analysis of a nuclear waste repository requires the precise thermodynamic description of the relevant geochemical processes at room as well as at elevated temperatures. The present work is focused on the investigation of the complexation of trivalent curium (Cm(III)) with different inorganic ligands at elevated temperatures. Due to its outstanding spectroscopic properties, Cm(III) is chosen as a representative for trivalent actinides. The studied ligand systems are nitrate (NO{sub 3}{sup -}), fluoride (F{sup -}), sulphate (SO{sub 4}{sup 2-}) and chloride (Cl{sup -}). The main analytical method employed is the ''time resolved laser fluorescence spectroscopy'' (TRLFS). The experiments with nitrate, sulphate and chloride were carried out in a custom-built high temperature cell, enabling spectroscopic studies at temperatures up to 200 C. The Cm(III)-fluoride-system was studied in a cuvette (quartz glass) in the temperature range from 20 to 90 C. Supplementary structural studies were performed using EXAFS (Extended X-Ray Absorption Fine Structure) spectroscopy and supported by quantum chemical calculations at DFT (Density Functional Theory) level. The results of the TRLFS studies show a general shift of the chemical equilibrium towards the complexed species with increasing temperature. For instance

  6. Extended thermodynamics

    CERN Document Server

    Müller, Ingo

    1993-01-01

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

  7. Factors Controlling Redox Speciation of Plutonium and Neptunium in Extraction Separation Processes

    Energy Technology Data Exchange (ETDEWEB)

    Paulenova, Alena [Principal Investigator; Vandegrift, III, George F. [Collaborator

    2013-09-24

    The objective of the project was to examine the factors controlling redox speciation of plutonium and neptunium in UREX+ extraction in terms of redox potentials, redox mechanism, kinetics and thermodynamics. Researchers employed redox-speciation extractions schemes in parallel to the spectroscopic experiments. The resulting distribution of redox species w studied uring spectroscopic, electrochemical, and spectro-electrochemical methods. This work reulted in collection of data on redox stability and distribution of redox couples in the nitric acid/nitrate electrolyte and the development of redox buffers to stabilize the desired oxidation state of separated radionuclides. The effects of temperature and concentrations on the redox behavior of neptunium were evaluated.

  8. General thermodynamics

    CERN Document Server

    Olander, Donald

    2007-01-01

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

  9. Atmospheric thermodynamics

    CERN Document Server

    Iribarne, J V

    1973-01-01

    The thermodynamics of the atmosphere is the subject of several chapters in most textbooks on dynamic meteorology, but there is no work in English to give the subject a specific and more extensive treatment. In writing the present textbook, we have tried to fill this rather remarkable gap in the literature related to atmospheric sciences. Our aim has been to provide students of meteorology with a book that can playa role similar to the textbooks on chemical thermodynamics for the chemists. This implies a previous knowledge of general thermodynamics, such as students acquire in general physics courses; therefore, although the basic principles are reviewed (in the first four chapters), they are only briefly discussed, and emphasis is laid on those topics that will be useful in later chapters, through their application to atmospheric problems. No attempt has been made to introduce the thermodynamics of irreversible processes; on the other hand, consideration of heterogeneous and open homogeneous systems permits a...

  10. Green thermodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Cengel, Y.A. [Nevada Univ., Reno, NV (United States). Dept. of Mechanical Engineering

    2006-07-01

    Green components of thermodynamics were identified and general aspects of green practices associated with thermodynamics were assessed. Energy uses associated with fossil fuels were reviewed. Green energy sources such as solar, wind, geothermal and hydropower were discussed, as well as biomass plantations. Ethanol production practices were reviewed. Conservation practices in the United States were outlined. Energy efficiency and exergy analyses were discussed. Energy intensity measurements and insulation products for houses were also reviewed. Five case studies were presented to illustrate aspects of green thermodynamics: (1) light in a classroom; (2) fuel saved by low-resistance tires; and (3) savings with high-efficiency motors; (4) renewable energy; and (5) replacing a valve with a turbine at a cryogenic manufacturing facility. It was concluded that the main principles of green thermodynamics are to ensure that all material and energy inputs minimize the depletion of energy resources; prevent waste; and improve or innovate technologies that achieve sustainability. 17 refs., 2 tabs., 9 figs.

  11. Stochastic thermodynamics

    Science.gov (United States)

    Eichhorn, Ralf; Aurell, Erik

    2014-04-01

    'Stochastic thermodynamics as a conceptual framework combines the stochastic energetics approach introduced a decade ago by Sekimoto [1] with the idea that entropy can consistently be assigned to a single fluctuating trajectory [2]'. This quote, taken from Udo Seifert's [3] 2008 review, nicely summarizes the basic ideas behind stochastic thermodynamics: for small systems, driven by external forces and in contact with a heat bath at a well-defined temperature, stochastic energetics [4] defines the exchanged work and heat along a single fluctuating trajectory and connects them to changes in the internal (system) energy by an energy balance analogous to the first law of thermodynamics. Additionally, providing a consistent definition of trajectory-wise entropy production gives rise to second-law-like relations and forms the basis for a 'stochastic thermodynamics' along individual fluctuating trajectories. In order to construct meaningful concepts of work, heat and entropy production for single trajectories, their definitions are based on the stochastic equations of motion modeling the physical system of interest. Because of this, they are valid even for systems that are prevented from equilibrating with the thermal environment by external driving forces (or other sources of non-equilibrium). In that way, the central notions of equilibrium thermodynamics, such as heat, work and entropy, are consistently extended to the non-equilibrium realm. In the (non-equilibrium) ensemble, the trajectory-wise quantities acquire distributions. General statements derived within stochastic thermodynamics typically refer to properties of these distributions, and are valid in the non-equilibrium regime even beyond the linear response. The extension of statistical mechanics and of exact thermodynamic statements to the non-equilibrium realm has been discussed from the early days of statistical mechanics more than 100 years ago. This debate culminated in the development of linear response

  12. Modern thermodynamics

    CERN Document Server

    Ben-Naim, Arieh

    2017-01-01

    This textbook introduces thermodynamics with a modern approach, starting from four fundamental physical facts (the atomic nature of matter, the indistinguishability of atoms and molecules of the same species, the uncertainty principle, and the existence of equilibrium states) and analyzing the behavior of complex systems with the tools of information theory, in particular with Shannon's measure of information (or SMI), which can be defined on any probability distribution. SMI is defined and its properties and time evolution are illustrated, and it is shown that the entropy is a particular type of SMI, i.e. the SMI related to the phase-space distribution for a macroscopic system at equilibrium. The connection to SMI allows the reader to understand what entropy is and why isolated systems follow the Second Law of Thermodynamics. The Second Llaw is also formulated for other systems, not thermally isolated and even open with respect to the transfer of particles. All the fundamental aspects of thermodynamics are d...

  13. Extraction of 2-Phenylethanol (PEA) from Aqueous Solution Using Ionic Liquids: Synthesis, Phase Equilibrium Investigation, Selectivity in Separation, and Thermodynamic Models.

    Science.gov (United States)

    Domańska, Urszula; Okuniewska, Patrycja; Paduszyński, Kamil; Królikowska, Marta; Zawadzki, Maciej; Więckowski, Mikołaj

    2017-08-17

    This study assessed the effect of ionic liquids (ILs) on extraction of 2-phenylethanol (PEA) from aqueous phase. It consists the synthesis of four new ILs, their physicochemical properties, and experimental solubility measurements in water as well as liquid-liquid phase equilibrium in ternary systems. ILs are an important new media for imaging and sensing applications because of their solvation property, thermal stability, and negligible vapor pressure. However, complex procedures and nonmiscibility with water are often required in PEA extraction. Herein, a facile and general strategy using four ILs as extraction media including the synthesis of new bis(fluorosulfonyl)imide-based ILs, 1-hexyl-methylmorpholinium bis(fluorosulfonyl)imide, [HMMOR][FSI], N-octylisoquinolinium bis(fluorosulfonyl)imide, [OiQuin][FSI], 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide, [BMPYR][FSI], and N-triethyl-N-octylammonium bis(fluorosulfonyl)imide, [N 2228 ][FSI], were investigated. The thermal properties, density, viscosity, and surface tension of new ILs were measured. Calorimetric measurements (DSC) were used to determine the melting point and the enthalpy of melting as well as the glass transition temperature and heat capacity at glass transition of the ILs. The phase equilibrium in binary systems (IL + PEA, or water) and in ternary systems {IL (1) + PEA (2) + water (3)} at temperature T = 308.15 K and ambient pressure are reported. All systems present liquid-liquid equilibrium with the upper critical solution temperature (UCST). All ILs revealed complete miscibility with PEA. In all ternary systems immiscibility gap was observed, which classified measured systems as Treybal's type II. The two partially miscible binaries (IL + water) and (PEA + water) exist in these systems. The discussion contains the specific selectivity and the solute distribution ratio of separation for the used ILs. The commonly used NRTL model was used for the correlation of the experimental binary

  14. Extragalactic background light: a measurement at 400 nm using dark cloud shadow - II. Spectroscopic separation of the dark cloud's light, and results★

    Science.gov (United States)

    Mattila, K.; Väisänen, P.; Lehtinen, K.; von Appen-Schnur, G.; Leinert, Ch.

    2017-09-01

    In a project aimed at measuring the optical extragalactic background light (EBL), we are using the shadow of a dark cloud. We have performed, with the ESO VLT/FORS, spectrophotometry of the surface brightness towards the high-galactic-latitude dark cloud Lynds 1642. A spectrum representing the difference between the opaque core of the cloud and several unobscured positions around the cloud was presented in Paper I. The topic of this paper is the separation of the scattered starlight from the dark cloud itself which is the only remaining foreground component in this difference. While the scattered starlight spectrum has the characteristic Fraunhofer lines and the discontinuity at 400 nm, typical of integrated light of galaxies, the EBL spectrum is a smooth one without these features. As template for the scattered starlight, we make use of the spectra at two semitransparent positions. The resulting EBL intensity at 400 nm is IEBL = 2.9 ± 1.1 10-9 erg cm-2 s-1 sr-1 Å-1 or 11.6 ± 4.4 nW m-2sr-1, which represents a 2.6σ detection; the scaling uncertainty is +20 per cent/-16 per cent. At 520 nm, we have set a 2σ upper limit of IEBL ≤4.5 10-9 erg cm-2 s-1 sr-1 Å-1 or ≤ 23.4 nW m-2sr-1 +20 per cent/-16 per cent. Our EBL value at 400 nm is ≳ 2 times as high as the integrated light of galaxies. No known diffuse light sources, such as light from Milky Way halo, intra-cluster or intra-group stars appear capable of explaining the observed EBL excess over the integrated light of galaxies.

  15. Using the Antenna Effect as a Spectroscopic Tool; Photophysics and Solution Thermodynamics of the Model Luminescent Hydroxypyridonate Complex [EuIII(3,4,3-LI(1,2-HOPO))]-

    Energy Technology Data Exchange (ETDEWEB)

    Abergel, Rebecca J.; D' Aleo, Anthony; Ng Pak Leung, Clara; Shuh, David; Raymond, Kenneth

    2009-11-20

    While widely used in bioassays, the spectrofluorimetric method described here uses the antenna effect as a tool to probe the thermodynamic parameters of ligands that sensitize lanthanide luminescence. The Eu3+ coordination chemistry, solution thermodynamic stability and photophysical properties of the spermine-based hydroxypyridonate octadentate chelator 3,4,3-LI(1,2-HOPO) are reported. The complex [EuIII(3,4,3-LI(1,2-HOPO))]- luminesces with a long lifetime (805 mu s) and a quantum yield of 7.0percent in aqueous solution, at pH 7.4. These remarkable optical properties were exploited to determine the high (and proton-independent) stability of the complex (log beta 110 = 20.2(2)) and to define the influence of the ligand scaffold on the stability and photophysical properties.

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

    Science.gov (United States)

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

    1996-09-01

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

  17. Solvation thermodynamics

    CERN Document Server

    Ben-Naim, Arieh

    1987-01-01

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

  18. Spectroscopic data

    CERN Document Server

    Melzer, J

    1976-01-01

    During the preparation of this compilation, many people contributed; the compilers wish to thank all of them. In particular they appreciate the efforts of V. Gilbertson, the manuscript typist, and those of K. C. Bregand, J. A. Kiley, and W. H. McPherson, who gave editorial assistance. They would like to thank Dr. J. R. Schwartz for his cooperation and encouragement. In addition, they extend their grati­ tude to Dr. L. Wilson of the Air Force Weapons Laboratory, who gave the initial impetus to this project. v Contents I. I ntroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 . . . . . . . . . . . . . . . . 11. Organization ofthe Spectroscopic Table. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Methods of Production and Experimental Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Band Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2...

  19. Quantum quenches in the thermodynamic limit.

    Science.gov (United States)

    Rigol, M

    2014-05-02

    We introduce a linked-cluster based computational approach that allows one to study quantum quenches in lattice systems in the thermodynamic limit. This approach is used to study quenches in one-dimensional lattices. We provide evidence that, in the thermodynamic limit, thermalization occurs in the nonintegrable regime but fails at integrability. A phase transitionlike behavior separates the two regimes.

  20. Thermodynamics of Fluid Polyamorphism

    Science.gov (United States)

    Anisimov, Mikhail A.; Duška, Michal; Caupin, Frédéric; Amrhein, Lauren E.; Rosenbaum, Amanda; Sadus, Richard J.

    2018-01-01

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

  1. Phantom thermodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez-Diaz, Pedro F. [Colina de los Chopos, Centro de Fisica ' Miguel A. Catalan' , Instituto de Matematicas y Fisica Fundamental, Consejo Superior de Investigaciones Cientificas, Serrano 121, 28006 Madrid (Spain)]. E-mail: p.gonzalezdiaz@imaff.cfmac.csic.es; Sigueenza, Carmen L. [Colina de los Chopos, Centro de Fisica ' Miguel A. Catalan' , Instituto de Matematicas y Fisica Fundamental, Consejo Superior de Investigaciones Cientificas, Serrano 121, 28006 Madrid (Spain)

    2004-10-04

    This paper deals with the thermodynamic properties of a phantom field in a flat Friedmann-Robertson-Walker universe. General expressions for the temperature and entropy of a general dark-energy field with equation of state p={omega}{rho} are derived from which we have deduced that, whereas the temperature of a cosmic phantom fluid ({omega}-1) is definite negative, its entropy is always positive. We interpret that result in terms of the intrinsic quantum nature of the phantom field and apply it to (i) attain a consistent explanation for some recent results concerning the evolution of black holes which,induced by accreting phantom energy, gradually loss their mass to finally vanish exactly at the big rip, and (ii) introduce the concept of cosmological information and its relation with life and the anthropic principle. Some quantum statistical-thermodynamic properties of the quantum field are also considered that include a generalized Wien law and the prediction of some novel phenomena such as the stimulated absorption of phantom energy and the anti-laser effect.

  2. Equilibrium thermodynamics

    CERN Document Server

    Oliveira, Mário J

    2013-01-01

    This textbook provides an exposition of equilibrium thermodynamics and its applications to several areas of physics with particular attention to phase transitions and critical phenomena. The applications include several areas of condensed matter physics and include also a chapter on thermochemistry. Phase transitions and critical phenomena are treated according to the modern development of the field, based on the ideas of universality and on the Widom scaling theory. For each topic, a mean-field or Landau theory is presented to describe qualitatively the phase transitions.  These theories include the van der Waals theory of the liquid-vapor transition, the Hildebrand-Heitler theory of regular mixtures, the Griffiths-Landau theory for multicritical points in multicomponent systems, the Bragg-Williams theory of order-disorder in alloys, the Weiss theory of ferromagnetism, the Néel theory of antiferromagnetism, the Devonshire theory for ferroelectrics and Landau-de Gennes theory of liquid crystals. This textbo...

  3. Equilibrium thermodynamics

    CERN Document Server

    de Oliveira, Mário J

    2017-01-01

    This textbook provides an exposition of equilibrium thermodynamics and its applications to several areas of physics with particular attention to phase transitions and critical phenomena. The applications include several areas of condensed matter physics and include also a chapter on thermochemistry. Phase transitions and critical phenomena are treated according to the modern development of the field, based on the ideas of universality and on the Widom scaling theory. For each topic, a mean-field or Landau theory is presented to describe qualitatively the phase transitions. These theories include the van der Waals theory of the liquid-vapor transition, the Hildebrand-Heitler theory of regular mixtures, the Griffiths-Landau theory for multicritical points in multicomponent systems, the Bragg-Williams theory of order-disorder in alloys, the Weiss theory of ferromagnetism, the Néel theory of antiferromagnetism, the Devonshire theory for ferroelectrics and Landau-de Gennes theory of liquid crystals. This new edit...

  4. Metal complexes of triazine - Schiff bases: Spectroscopic and thermodynamic studies of complexation of some divalent metal ions with 3-(a-acetylethylidenehydrazino-5,6-diphenyl-1,2,4-triazine

    Directory of Open Access Journals (Sweden)

    A. TAHA

    1999-10-01

    Full Text Available Metal complexes of some divalent metal ions (Co, Ni, Cu and Zn with 3-(a-acetylethylidenehydrazino-5,6-diphenyl-1,2,4-triazine (AHDT as a Schiff-base have been investigated potentiometrically and spectrophotometrically and found to have the stoichiometric formulae 1:1 and 1:2 (M:L. The formation constants of the proton-ligand and metal-ligand complexes have been determined potentiometrically at different temperatures (10, 20, 30, 40 and 50°C at an ionic strength of 0.1 M KNO3 in 75% (v/v dioxane-water solution. The standard thermodynamic parameters, viz. DG°, DH°, and DS°, for the proton-ligand and the stepwise metal-ligand complexes have been evaluated.

  5. Thermodynamics of Radiation Modes

    Science.gov (United States)

    Pina, Eduardo; de la Selva, Sara Maria Teresa

    2010-01-01

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

  6. Thermodynamics of Fluid Polyamorphism

    Directory of Open Access Journals (Sweden)

    Mikhail A. Anisimov

    2018-01-01

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

  7. Mathematical foundations of thermodynamics

    CERN Document Server

    Giles, R; Stark, M; Ulam, S

    2013-01-01

    Mathematical Foundations of Thermodynamics details the core concepts of the mathematical principles employed in thermodynamics. The book discusses the topics in a way that physical meanings are assigned to the theoretical terms. The coverage of the text includes the mechanical systems and adiabatic processes; topological considerations; and equilibrium states and potentials. The book also covers Galilean thermodynamics; symmetry in thermodynamics; and special relativistic thermodynamics. The book will be of great interest to practitioners and researchers of disciplines that deal with thermodyn

  8. Thermodynamics and energy conversion

    CERN Document Server

    Struchtrup, Henning

    2014-01-01

    This textbook gives a thorough treatment of engineering thermodynamics with applications to classical and modern energy conversion devices.   Some emphasis lies on the description of irreversible processes, such as friction, heat transfer and mixing, and the evaluation of the related work losses. Better use of resources requires high efficiencies, therefore the reduction of irreversible losses should be seen as one of the main goals of a thermal engineer. This book provides the necessary tools.   Topics include: car and aircraft engines,  including Otto, Diesel and Atkinson cycles, by-pass turbofan engines, ramjet and scramjet;  steam and gas power plants, including advanced regenerative systems, solar tower, and compressed air energy storage; mixing and separation, including reverse osmosis, osmotic powerplants, and carbon sequestration; phase equilibrium and chemical equilibrium, distillation, chemical reactors, combustion processes, and fuel cells; the microscopic definition of entropy.    The book i...

  9. Classical and statistical thermodynamics

    CERN Document Server

    Rizk, Hanna A

    2016-01-01

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

  10. Thermodynamics of molecular recognitions between antineoplastic drug taxol and phosphatidylcholine

    Directory of Open Access Journals (Sweden)

    Erhan Süleymanoglu

    2010-12-01

    Full Text Available The aim of this study was to study the basic features of Taxol recognition with phospholipids by applying the thermodynamic and spectroscopic measurements. The obtained information could be used further for deductions on its precise cellular and pharmacological mechanisms of action, on improvements of its solubility properties by phospholipids, as well as for designing the novel lipidic carriers for drug delivery.

  11. Treatise on thermodynamics

    CERN Document Server

    Planck, Max Karl Ernst Ludwig

    Great classic, still one of the best introductions to thermodynamics. Fundamentals, first and second principles of thermodynamics, applications to special states of equilibrium, more. Numerous worked examples. 1917 edition.

  12. Twenty lectures on thermodynamics

    CERN Document Server

    Buchdahl, H A

    2013-01-01

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

  13. Introduction to applied thermodynamics

    CERN Document Server

    Helsdon, R M; Walker, G E

    1965-01-01

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

  14. Separate Colors, Separate Minds.

    Science.gov (United States)

    Meyers, Michael; Nidiry, John P.

    2002-01-01

    Explains that racial separation causes cultural separation, and the way to improve race relations is to continue to move toward integration. Discusses the need to debunk race, examining racial issues in education. Highlights the importance of actively supporting integration and opposing separatism, explaining that for there to be social progress,…

  15. Rational extended thermodynamics

    CERN Document Server

    Müller, Ingo

    1998-01-01

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

  16. An introduction to equilibrium thermodynamics

    CERN Document Server

    Morrill, Bernard; Hartnett, James P; Hughes, William F

    1973-01-01

    An Introduction to Equilibrium Thermodynamics discusses classical thermodynamics and irreversible thermodynamics. It introduces the laws of thermodynamics and the connection between statistical concepts and observable macroscopic properties of a thermodynamic system. Chapter 1 discusses the first law of thermodynamics while Chapters 2 through 4 deal with statistical concepts. The succeeding chapters describe the link between entropy and the reversible heat process concept of entropy; the second law of thermodynamics; Legendre transformations and Jacobian algebra. Finally, Chapter 10 provides a

  17. Planar chromatography coupled with spectroscopic techniques.

    NARCIS (Netherlands)

    Somsen, G.W.; Wilson, I.D.; Morden, W.

    1995-01-01

    Recent progress in the combination of planar, or thin-layer chromatography (TLC) with a variety of modern spectroscopic techniques is reviewed. The utility of TLC for separation followed by mass spectrometry, with a variety of ionisation techniques, is illustrated with reference to a wide range of

  18. DERIVED THERMODYNAMIC PROPERTIES OF [o-XYLENE OR p ...

    African Journals Online (AJOL)

    Preferred Customer

    This paper is a continuation of our earlier work related to the study of thermodynamic properties of binary and ternary mixtures [1-6]. Reliable data on phase behavior and thermodynamic excess properties of multi component fluid mixtures are necessary for the proper design of synthesis and separation processes of the ...

  19. Thermodynamics of Bioreactions.

    Science.gov (United States)

    Held, Christoph; Sadowski, Gabriele

    2016-06-07

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

  20. On thermodynamics and gravity

    Science.gov (United States)

    Nagle, Ian

    2017-09-01

    A new entropic gravity inspired derivation of general relativity from thermodynamics is presented. This generalizes the "Thermodynamics of Spacetime" approach by T. Jacobson, which relies on the null Raychaudhuri evolution equation. Here the rest of the first law of thermodynamics is incorporated by using the null Damour-Navier-Stokes equation, known from the membrane paradigm for describing the tangential flow of deformations along a horizon.

  1. Stochastic Thermodynamics of Learning

    Science.gov (United States)

    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.

  2. Thermodynamic modelling of the extraction of nitrates of lanthanides by CMPO and by CMPO-like calixarene in concentrated nitric acid medium. Application in the optimization of the separation of lanthanides and actinides/lanthanides; Modelisation thermodynamique de l'extraction de nitrates de lanthanides par le CMPO et par un calixarene-CMPO en milieu acide nitrique concentre. Application a l'optimisation de la separation des lanthanides et des actinides/lanthanides

    Energy Technology Data Exchange (ETDEWEB)

    Belair, S

    2003-07-01

    The separation minor actinides / lanthanides in nitric acid medium is as one of problems of separative chemistry the most delicate within the framework of the processes allowing the recovery of long life radioelements present in the solutions of fission products. Previous studies showed that CMPO-substituted calix[4]arenes presents a better affinity for actinides than for lanthanides. To optimize the operating conditions of separation and to take into account the degree of non-ideality for the concentrated nitric solutions, we adopted a thermodynamic approach. The methodology taken to determine the number and the stoichiometry of the complexes formed in organic phase base on MIKULIN-SERGIEVSKII's model used through a software of data processing of experimental extraction isotherms. These tools are exploited at first on an extraction system engaging the CMPO, extractant reagent of actinides and lanthanides in concentrated nitric medium. The modelling of the system Ln(NO{sub 3}){sub 3}-HNO{sub 3}-H{sub 2}O/CMPO comes to confirm the results of several studies. At the same time, they allow to establish working hypotheses aiming at limiting the investigations of our researches towards the most stable complexes formed between lanthanides and CMPO-like calixarene to which the same method is then applied. An analytical expression of the selectivity of separation by the calixarene is established to determine the parameters and physico-chemical variables on which it depends. So, the ratio of the constants of extraction and the value of the activity of water of the system fixes the selectivity of separation of 2 elements. The exploitation of this relation allows to preview the influence of a variation of the concentration of nitric acid. Experiments of extraction confirm these forecasts and inform about the affinity of the calixarene with respect to lanthanides elements and to the americium. (author)

  3. Methods of thermodynamics

    CERN Document Server

    Reiss, Howard

    1997-01-01

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

  4. Thermodynamic modeling to analyse composition of carbonaceous ...

    Indian Academy of Sciences (India)

    Equilibrium thermodynamic analysis has been applied to the low-pressure MOCVD process using manganese acetylacetonate as the precursor. ``CVD phase stability diagrams” have been constructed separately for the processes carried out in argon and oxygen ambient, depicting the compositions of the resulting films as ...

  5. Thermodynamic parameters of elasticity and electrical conductivity ...

    African Journals Online (AJOL)

    The thermodynamic parameters (change in free energy of elasticity, DGe; change in enthalpy of elasticity, DHe; and change in entropy of elasticity, DSe) and the electrical conductivity of natural rubber composites reinforced separately with some agricultural wastes have been determined. Results show that the reinforced ...

  6. Thermodynamic cycle analysis for capacitive deionization

    NARCIS (Netherlands)

    Biesheuvel, P.M.

    2009-01-01

    Capacitive deionization (CDI) is an ion removal technology based on temporarily storing ions in the polarization layers of two oppositely positioned electrodes. Here we present a thermodynamic model for the minimum work required for ion separation in the fully reversible case by describing the ionic

  7. Spectroscopic analysis and control

    Science.gov (United States)

    Tate; , James D.; Reed, Christopher J.; Domke, Christopher H.; Le, Linh; Seasholtz, Mary Beth; Weber, Andy; Lipp, Charles

    2017-04-18

    Apparatus for spectroscopic analysis which includes a tunable diode laser spectrometer having a digital output signal and a digital computer for receiving the digital output signal from the spectrometer, the digital computer programmed to process the digital output signal using a multivariate regression algorithm. In addition, a spectroscopic method of analysis using such apparatus. Finally, a method for controlling an ethylene cracker hydrogenator.

  8. Thermodynamic and Quantum Thermodynamic Analyses of Brownian Movement

    OpenAIRE

    Gyftopoulos, Elias P.

    2006-01-01

    Thermodynamic and quantum thermodynamic analyses of Brownian movement of a solvent and a colloid passing through neutral thermodynamic equilibrium states only. It is shown that Brownian motors and E. coli do not represent Brownian movement.

  9. Thermodynamics and heat power

    CERN Document Server

    Granet, Irving

    2014-01-01

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

  10. Equilibrium thermodynamics - Callen's postulational approach

    NARCIS (Netherlands)

    Jongschaap, R.J.J.; Öttinger, Hans Christian

    2001-01-01

    In order to provide the background for nonequilibrium thermodynamics, we outline the fundamentals of equilibrium thermodynamics. Equilibrium thermodynamics must not only be obtained as a special case of any acceptable nonequilibrium generalization but, through its shining example, it also elucidates

  11. Thermodynamics an engineering approach

    CERN Document Server

    Cengel, Yunus A

    2014-01-01

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

  12. Thermodynamics of complexity

    DEFF Research Database (Denmark)

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

    1998-01-01

    Thermodynamics has always been a remarkable science in that it studies macroscopic properties that are only partially determined by the properties of individual molecules. Entropy and free energy only exist in constellations of more than a single molecule (degree of freedom). They are the so...... understanding of this BioComplexity, modem thermodynamic concepts and methods (nonequilibrium thermodynamics, metabolic and hierarchical control analysis) will be needed. We shall propose to redefine nonequilibrium thermodynamics as: The science that aims at understanding the behaviour of nonequilibrium systems...... by taking into account both the molecular properties and the emergent properties that are due to (dys)organisation. This redefinition will free nonequilibrium thermodynamics from the limitations imposed by earlier near-equilibrium assumptions, resolve the duality with kinetics, and bridge the apparent gap...

  13. A thermodynamic approach to choosing pervaporatives membranes

    Directory of Open Access Journals (Sweden)

    Mahacine Amrani

    2006-09-01

    Full Text Available This work describes separating a mixture of several components obtained as a product of methyl polymethyl metha- crylate (PMMA thermo-degradation. It was aimed at purifying methyl methacrylate monomer (MMA obtained by 95% mass thermal degradation to reach 99.5% maximum pervaporation concentration. This work studied the theory of pervaporation and applying the main thermodynamic criteria for choosing suitable polymer membranes for separating the MMA/PRP/ISB mixture. Such thermodynamic criteria were based on monomer interaction with and solubility on the membrane. The advantage of using this separation technique lies mainly in the fact that this method has low energy consumption compared to other processes, such as distillation or crystallisation.

  14. A thermodynamic approach to choosing pervaporatives membranes

    Directory of Open Access Journals (Sweden)

    Mahacine Amrani

    2010-04-01

    Full Text Available This work describes separating a mixture of several components obtained as a product of methyl polymethyl metha- crylate (PMMA thermo-degradation. It was aimed at purifying methyl methacrylate monomer (MMA obtained by 95% mass thermal degradation to reach 99.5% maximum pervaporation concentration. This work studied the theory of pervaporation and applying the main thermodynamic criteria for choosing suitable polymer membranes for separating the MMA/PRP/ISB mixture. Such thermodynamic criteria were based on monomer interaction with and solubility on the membrane. The advantage of using this separation technique lies mainly in the fact that this method has low energy consumption compared to other processes, such as distillation or crystallisation.

  15. Modern engineering thermodynamics

    CERN Document Server

    Balmer, Robert T

    2010-01-01

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

  16. Thermodynamics I essentials

    CERN Document Server

    REA, The Editors of

    2012-01-01

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

  17. Advanced thermodynamics engineering

    CERN Document Server

    Annamalai, Kalyan; Jog, Milind A

    2011-01-01

    Thermolab Excel-Based Software for Thermodynamic Properties and Flame Temperatures of Fuels IntroductionImportance, Significance and LimitationsReview of ThermodynamicsMathematical BackgroundOverview of Microscopic/NanothermodynamicsSummaryAppendix: Stokes and Gauss Theorems First Law of ThermodynamicsZeroth LawFirst Law for a Closed SystemQuasi Equilibrium (QE) and Nonquasi-equilibrium (NQE) ProcessesEnthalpy and First LawAdiabatic Reversible Process for Ideal Gas with Constant Specific HeatsFirst Law for an Open SystemApplications of First Law for an Open SystemIntegral and Differential Form

  18. Selected problems in thermodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Andrianova, T.N.; Dzampov, B.V.; Remizov, S.A.; Zubarev, V.N.

    1981-01-01

    This collection of problems is designed for a course in engineering thermodynamics for engineering and thermophysical disciplines in energy institutes. The problems contain the following fundamentals: first and second laws of thermodynamics, physical state and change of state processes in ideal and real gases, water, steam and moist air; efflux and choking of gases and steam, internal combustion cycles, gas and steam turbines, refrigerators, compressors, as well as problems in chemical thermodynamics. Answers to all problems are given, examples include solutions. The SI system of units is used.

  19. Non-equilibrium thermodynamics

    CERN Document Server

    De Groot, Sybren Ruurds

    1984-01-01

    The study of thermodynamics is especially timely today, as its concepts are being applied to problems in biology, biochemistry, electrochemistry, and engineering. This book treats irreversible processes and phenomena - non-equilibrium thermodynamics.S. R. de Groot and P. Mazur, Professors of Theoretical Physics, present a comprehensive and insightful survey of the foundations of the field, providing the only complete discussion of the fluctuating linear theory of irreversible thermodynamics. The application covers a wide range of topics: the theory of diffusion and heat conduction, fluid dyn

  20. Spectroscopic Dosimeter Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Analysis of Phase I test data demonstrates that the Photogenics Spectroscopic Dosimeter will detect neutron energies from 0.8 up to 600 MeV. The detector...

  1. Workshop on Teaching Thermodynamics

    CERN Document Server

    1985-01-01

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

  2. Elements of chemical thermodynamics

    CERN Document Server

    Nash, Leonard K

    2005-01-01

    This survey of purely thermal data in calculating the position of equilibrium in a chemical reaction highlights the physical content of thermodynamics, as distinct from purely mathematical aspects. 1970 edition.

  3. Theoretical physics 5 thermodynamics

    CERN Document Server

    Nolting, Wolfgang

    2017-01-01

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

  4. Elementary chemical thermodynamics

    CERN Document Server

    Mahan, Bruce H

    1963-01-01

    This text introduces thermodynamic principles in a straightforward manner. Suitable for advanced undergraduates and graduate students, it emphasizes chemical applications and physical interpretations and simplifies mathematical development. 1964 edition.

  5. Electrochemical thermodynamic measurement system

    Science.gov (United States)

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

    2009-09-29

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

  6. Chemical engineering thermodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Newman, S.A. (ed.)

    1983-01-01

    This book contains most of the papers presented at the thermodynamics sessions of the Second World Congress of Chemical Engineering held October 4-9, 1981 in Montreal, Canada. The chapters of the book have been categorized into the following areas: (1) Phase Equilibria, (2) Equations of State, (3) Electrolytes, and (4) Other Thermodynamic Topics. Topics presented in the chapters include: thermophysical data banks; group contribution methods applied to phase equilibrai; equations of state for vapor-liquid and liquid-liquid equilibria with applications to design; vapor-liquid equilibria in systems including bitumen, heavy oil and coal-derived liquids; thermodynamics of polar substances; coal char thermochemical data; chemical equilibria; petroleum fraction thermodynamics and sour water vapor-liquid equilibria. (DP)

  7. Polyelectrolytes thermodynamics and rheology

    CERN Document Server

    P M, Visakh; Picó, Guillermo Alfredo

    2014-01-01

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

  8. General and Statistical Thermodynamics

    CERN Document Server

    Tahir-Kheli, Raza

    2012-01-01

    This textbook explains completely the general and statistical thermodynamics. It begins with an introductory statistical mechanics course, deriving all the important formulae meticulously and explicitly, without mathematical short cuts. The main part of the book deals with the careful discussion of the concepts and laws of thermodynamics, van der Waals, Kelvin and Claudius theories, ideal and real gases, thermodynamic potentials, phonons and all the related aspects. To elucidate the concepts introduced and to provide practical problem solving support, numerous carefully worked examples are of great value for students. The text is clearly written and punctuated with many interesting anecdotes. This book is written as main textbook for upper undergraduate students attending a course on thermodynamics.

  9. Elements of statistical thermodynamics

    CERN Document Server

    Nash, Leonard K

    2006-01-01

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

  10. A New Perspective on Thermodynamics

    CERN Document Server

    Lavenda, Bernard H

    2010-01-01

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

  11. Unitary Thermodynamics from Thermodynamic Geometry II: Fit to a Local-Density Approximation

    Science.gov (United States)

    Ruppeiner, George

    2015-10-01

    Strongly interacting Fermi gasses at low density possess universal thermodynamic properties that have recently seen very precise PVT measurements by a group at MIT. This group determined local thermodynamic properties of a system of ultracold atoms tuned to Feshbach resonance. In this paper, I analyze the MIT data with a thermodynamic theory of unitary thermodynamics based on ideas from critical phenomena. This theory was introduced in the first paper of this sequence and characterizes the scaled thermodynamics by the entropy per particle and the energy per particle Y( z), in units of the Fermi energy. Y( z) is in two segments, separated by a second-order phase transition at : a "superfluid" segment for and a "normal" segment for . For small z, the theory obeys a series where is a constant exponent and () are constant series coefficients. For large z, the theory obeys a perturbation of the ideal gas , where is a constant exponent and () are constant series coefficients. This limiting form for large z differs from the series used in the first paper and was necessary to fit the MIT data. I fit the MIT data by adjusting four free independent theory parameters: . This fit process was augmented by trap integration and comparison with earlier thermal data taken at Duke University. The overall match to both the data sets was good and had , , , scaled critical temperature , where is the Fermi temperature, and Bertsch parameter . I also discuss the virial expansion in the context of this thermodynamic geometric theory.

  12. Thermodynamics of Crystalline States

    CERN Document Server

    Fujimoto, Minoru

    2010-01-01

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

  13. Statistical thermodynamics of alloys

    CERN Document Server

    Gokcen, N A

    1986-01-01

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

  14. Extended Irreversible Thermodynamics

    CERN Document Server

    Jou, David

    2010-01-01

    This is the 4th edition of the highly acclaimed monograph on Extended Irreversible Thermodynamics, a theory that goes beyond the classical theory of irreversible processes. In contrast to the classical approach, the basic variables describing the system are complemented by non-equilibrium quantities. The claims made for extended thermodynamics are confirmed by the kinetic theory of gases and statistical mechanics. The book covers a wide spectrum of applications, and also contains a thorough discussion of the foundations and the scope of the current theories on non-equilibrium thermodynamics. For this new edition, the authors critically revised existing material while taking into account the most recent developments in fast moving fields such as heat transport in micro- and nanosystems or fast solidification fronts in materials sciences. Several fundamental chapters have been revisited emphasizing physics and applications over mathematical derivations. Also, fundamental questions on the definition of non-equil...

  15. Thermodynamics II essentials

    CERN Document Server

    REA, The Editors of

    2013-01-01

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

  16. Thermodynamics for engineers

    CERN Document Server

    Wong, Kaufui Vincent

    2011-01-01

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

  17. Concise chemical thermodynamics

    CERN Document Server

    Peters, APH

    2010-01-01

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

  18. Mechanics, Waves and Thermodynamics

    Science.gov (United States)

    Ranjan Jain, Sudhir

    2016-05-01

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

  19. Beyond Equilibrium Thermodynamics

    Science.gov (United States)

    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.

  20. Low-temperature thermodynamics in the context of dissipative diamagnetism.

    Science.gov (United States)

    Kumar, Jishad; Sreeram, P A; Dattagupta, Sushanta

    2009-02-01

    We revisit here the effect of quantum dissipation on the much studied problem of Landau diamagnetism and analyze the results in the light of the third law of thermodynamics. The case of an additional parabolic potential is separately assessed. We find that dissipation arising from strong coupling of the system to its environment qualitatively alters the low-temperature thermodynamic attributes such as the entropy and the specific heat.

  1. Experimental thermodynamics experimental thermodynamics of non-reacting fluids

    CERN Document Server

    Neindre, B Le

    2013-01-01

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

  2. Separated Shoulder

    Science.gov (United States)

    ... an injury to the ligaments that hold your collarbone (clavicle) to your shoulder blade. In a mild separated ... tenderness or pain near the end of your collarbone. Causes The most common cause of a separated ...

  3. The Thermodynamics of Black Holes

    National Research Council Canada - National Science Library

    Emparan, Roberto; Tinto, Massimo; Barbero G, J Fernando; Heusler, Markus; Rendall, Alan D; Adamo, Timothy M; Liebling, Steven L; Sasaki, Misao; Poisson, Eric; Wald, Robert M; Postnov, Konstantin A; Amendola, Luca; Shibata, Masaru; Tagoshi, Hideyuki; Reall, Harvey S; Kozameh, Carlos; Palenzuela, Carlos; Yungelson, Lev R; Villaseñor, Eduardo J. S; Appleby, Stephen; Taniguchi, Keisuke; Dhurandhar, Sanjeev V; Bacon, David; Newman, Ezra T; Baker, Tessa; Baldi, Marco; Bartolo, Nicola; Blanchard, Alain; Bonvin, Camille; Borgani, Stefano; Branchini, Enzo; Burrage, Clare; Camera, Stefano; Carbone, Carmelita; Casarini, Luciano; Cropper, Mark; de Rham, Claudia; Di Porto, Cinzia; Ealet, Anne; Ferreira, Pedro G; Finelli, Fabio; García-Bellido, Juan; Giannantonio, Tommaso; Guzzo, Luigi; Heavens, Alan; Heisenberg, Lavinia; Heymans, Catherine; Hoekstra, Henk; Hollenstein, Lukas; Holmes, Rory; Horst, Ole; Jahnke, Knud; Kitching, Thomas D; Koivisto, Tomi; Kunz, Martin; La Vacca, Giuseppe; March, Marisa; Majerotto, Elisabetta; Markovic, Katarina; Marsh, David; Marulli, Federico; Massey, Richard; Mellier, Yannick; Mota, David F; Nunes, Nelson J; Percival, Will; Pettorino, Valeria; Porciani, Cristiano; Quercellini, Claudia; Read, Justin; Rinaldi, Massimiliano; Sapone, Domenico; Scaramella, Roberto; Skordis, Constantinos; Simpson, Fergus; Taylor, Andy; Thomas, Shaun; Trotta, Roberto; Verde, Licia; Vernizzi, Filippo; Vollmer, Adrian; Wang, Yun; Weller, Jochen; Zlosnik, Tom

    ...We review the present status of black hole thermodynamics. Our review includes discussion of classical black hole thermodynamics, Hawking radiation from black holes, the generalized second law, and the issue of entropy bounds...

  4. Chemical thermodynamics. An introduction

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-07-01

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

  5. Thermodynamics with Design Problems.

    Science.gov (United States)

    Cilento, E. V.; Sears, J. T.

    1983-01-01

    Discusses how basic thermodynamics concepts are integrated with design problems. Includes course goals, instructional strategies, and major advantages/disadvantages of the integrated design approach. Advantages include making subject more concrete, emphasizing interrelation of variables, and reinforcing concepts by use in design analysis; whereas…

  6. Thermodynamics of meat proteins

    NARCIS (Netherlands)

    Sman, van der R.G.M.

    2012-01-01

    We describe the water activity of meat, being a mixture of proteins, salts and water, by the Free-Volume-Flory–Huggins (FVFH) theory augmented with the equation. Earlier, the FVFH theory is successfully applied to describe the thermodynamics to glucose homopolymers like starch, dextrans and

  7. Thermodynamics and statistical mechanics

    CERN Document Server

    Landsberg, Peter T

    1990-01-01

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

  8. Nonequilibrium thermodynamics of nucleation

    NARCIS (Netherlands)

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

    2014-01-01

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

  9. Thermodynamic stabilization of colloids

    NARCIS (Netherlands)

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

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

  10. The thermodynamics of portfolios

    OpenAIRE

    Piotrowski, Edward W.; Jan Sladkowski

    2000-01-01

    We propose a new method of valuation of portfolios and their respective investing strategies. To this end we define a canonical ensemble of portfolios that allows to use the formalism of thermodynamics. (final version published in Acta Phys.Pol.B,32(2001)597-604)

  11. On Teaching Thermodynamics

    Science.gov (United States)

    Debbasch, F.

    2011-01-01

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

  12. Thermodynamical Arguments against Evolution

    Science.gov (United States)

    Rosenhouse, Jason

    2017-01-01

    The argument that the second law of thermodynamics contradicts the theory of evolution has recently been revived by anti-evolutionists. In its basic form, the argument asserts that whereas evolution implies that there has been an increase in biological complexity over time, the second law, a fundamental principle of physics, shows this to be…

  13. Thermodynamics Far from the Thermodynamic Limit.

    Science.gov (United States)

    de Miguel, Rodrigo; Rubí, J Miguel

    2017-11-16

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

  14. Thermodynamics for the practicing engineer

    CERN Document Server

    Theodore, Louis; Vanvliet, Timothy

    2009-01-01

    This book concentrates specifically on the applications of thermodynamics, rather than the theory. It addresses both technical and pragmatic problems in the field, and covers such topics as enthalpy effects, equilibrium thermodynamics, non-ideal thermodynamics and energy conversion applications. Providing the reader with a working knowledge of the principles of thermodynamics, as well as experience in their application, it stands alone as an easy-to-follow self-teaching aid to practical applications and contains worked examples.

  15. Separate and simultaneous binding effects of aspirin and amlodipine to human serum albumin based on fluorescence spectroscopic and molecular modeling characterizations: A mechanistic insight for determining usage drugs doses

    Energy Technology Data Exchange (ETDEWEB)

    Abdollahpour, Nooshin [Department of Biology, Faculty of Sciences, Mashhad Branch, Islamic Azad University, Mashhad (Iran, Islamic Republic of); Asoodeh, Ahmad [Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad (Iran, Islamic Republic of); Saberi, Mohammad Reza [Department of Medical Chemistry, School of Pharmacy, Mashhad University of Medical Sciences, Mashhad (Iran, Islamic Republic of); Chamani, JamshidKhan, E-mail: chamani@ibb.ut.ac.ir [Department of Biology, Faculty of Sciences, Mashhad Branch, Islamic Azad University, Mashhad (Iran, Islamic Republic of)

    2011-09-15

    effects. Molecular dynamic studies showed that the affinity of each of the drugs to HSA was reduced in the presence of significant amounts of the other. In the interaction of HSA with both drugs, the zeta potential of the ternary system is more negative than its binary counterpart. The zeta-potential results suggested induced conformational changes on HSA that confirmed the experimental and theoretical results. - Highlights: > We studied the simultaneous interaction of amlodipine and aspirin with HSA. > They may compete in binding to HSA and increase uncontrolled toxic effects. > We determined the critical induced aggregation concentration of both drugs on HSA. > The binding mechanism of drugs as separate and simultaneous to HSA has been compared. > The binding site of both drugs as simultaneous effects on HSA has been determined.

  16. The Thermodynamic Scale of Inorganic Crystalline Metastability

    Science.gov (United States)

    Sun, Wenhao; Dacek, Stephen; Ong, Shyue Ping; Hautier, Geoffroy; Jain, Anubhav; Richards, William; Gamst, Anthony; Persson, Kristin; Ceder, Gerbrand; Materials Project Team

    The space of metastable materials offers promising new design opportunities for next-generation technological materials such as complex oxides, semiconductors, pharmaceuticals, steels and beyond. Although metastable phases are ubiquitous in both nature and technology, only a heuristic understanding of their underlying thermodynamics exists. Here we report a large-scale data-mining study of the Materials Project, a high-throughput database of DFT-calculated energetics of ICSD structures, to explicitly quantify the thermodynamic scale of metastability for 29,902 observed inorganic crystalline phases. We reveal the influence of chemistry and composition on the accessible thermodynamic range of crystalline metastability for polymorphic and phase-separating compounds, yielding new physical insights that can guide the design of novel metastable materials. We further assert that not all low-energy metastable compounds can necessarily be synthesized, and propose a principle of ``remnant metastability'' - that observable metastable crystalline phases are generally remnants of thermodynamic conditions where they were once the lowest free-energy phase. DOE Contract DE-AC02-05CH11231 and Contract no. UGA-0-41029-16/ER392000.

  17. The thermodynamic scale of inorganic crystalline metastability.

    Science.gov (United States)

    Sun, Wenhao; Dacek, Stephen T; Ong, Shyue Ping; Hautier, Geoffroy; Jain, Anubhav; Richards, William D; Gamst, Anthony C; Persson, Kristin A; Ceder, Gerbrand

    2016-11-01

    The space of metastable materials offers promising new design opportunities for next-generation technological materials, such as complex oxides, semiconductors, pharmaceuticals, steels, and beyond. Although metastable phases are ubiquitous in both nature and technology, only a heuristic understanding of their underlying thermodynamics exists. We report a large-scale data-mining study of the Materials Project, a high-throughput database of density functional theory-calculated energetics of Inorganic Crystal Structure Database structures, to explicitly quantify the thermodynamic scale of metastability for 29,902 observed inorganic crystalline phases. We reveal the influence of chemistry and composition on the accessible thermodynamic range of crystalline metastability for polymorphic and phase-separating compounds, yielding new physical insights that can guide the design of novel metastable materials. We further assert that not all low-energy metastable compounds can necessarily be synthesized, and propose a principle of 'remnant metastability'-that observable metastable crystalline phases are generally remnants of thermodynamic conditions where they were once the lowest free-energy phase.

  18. New water soluble phosphonate and polycarboxylate complexants for enhanced f element separations

    Energy Technology Data Exchange (ETDEWEB)

    Nash, K.L.; Rickert, P.G.; Lessmann, E.P.; Mendoza, M.D.; Feil, J.F.; Sullivan, J.C.

    1994-08-01

    While lipophilic extractant molecules and ion exchange polymeric materials are clearly essential to efficient separation of metal ions by solvent extraction or ion exchange, the most difficult separations often could not be accomplished without the use of water soluble complexants. This report focuses on recent developments in design, synthesis and characterization of phosphonic acid and polycarboxylic acid ligands for enhanced f element separations. Emphasis is on the basic solution chemistry and crystal structures of complexes of the f elements with selected amino-derivatives of methanediphosphonic acid and with tetrahydrofuran-2,3,4,5-tetracarboxylic acid. The former series of compounds exhibit high affinity for lanthanides and actinides in acidic solutions. The latter ligand exhibits an unusual (and very useful) ``anti-selectivity`` for uranyl ion in a solvent extraction process, which permits efficient separation of uranyl from more radioactive components of nuclear wastes. Most of the observed effects can be explained through examination of the structure of the ligand, and comparison of the spectroscopic and thermodynamic parameters for complexation of various metal ions.

  19. Thermodynamics of Crystalline States

    CERN Document Server

    Fujimoto, Minoru

    2013-01-01

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

  20. Mechanics and thermodynamics

    CERN Document Server

    Demtröder, Wolfgang

    2017-01-01

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

  1. Thermodynamics and emergent universe

    OpenAIRE

    Ghosh, Saumya; Gangopadhyay, Sunandan

    2016-01-01

    We show that in the isentropic scenario the first order thermodynamical particle creation model gives an emergent universe solution even when the chemical potential is non-zero. However there exists no emergent universe scenario in the second order non-equilibrium theory for the particle creation model. We then point out a correspondence between the particle creation model with barotropic equation of state and the equation of state giving rise to an emergent universe without particle creation...

  2. The discovery of thermodynamics

    Science.gov (United States)

    Weinberger, Peter

    2013-07-01

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

  3. PARAFFIN SEPARATION VACUUM DISTILLATION

    Directory of Open Access Journals (Sweden)

    Zaid A. Abdulrahman

    2013-05-01

    Full Text Available Simulated column performance curves were constructed for existing paraffin separation vacuum distillation column in LAB plant (Arab Detergent Company/Baiji-Iraq. The variables considered in this study are the thermodynamic model option, top vacuum pressure, top and bottom temperatures, feed temperature, feed composition & reflux ratio. Also simulated columns profiles for the temperature, vapor & liquid flow rates composition were constructed. Four different thermodynamic model options (SRK, TSRK, PR, and ESSO were used, affecting the results within 1-25% variation for the most cases.The simulated results show that about 2% to 8 % of paraffin (C10, C11, C12, & C13 present at the bottom stream which may cause a problem in the LAB plant. The major variations were noticed for the top temperature & the  paraffin weight fractions at bottom section with top vacuum pressure. The bottom temperature above 240 oC is not recommended because the total bottom flow rate decreases sharply, where as  the weight fraction of paraffins decrease slightly. The study gives evidence about a successful simulation with CHEMCAD

  4. CENTRIFUGAL SEPARATORS

    Science.gov (United States)

    Skarstrom, C.

    1959-03-10

    A centrifugal separator is described for separating gaseous mixtures where the temperature gradients both longitudinally and radially of the centrifuge may be controlled effectively to produce a maximum separation of the process gases flowing through. Tbe invention provides for the balancing of increases and decreases in temperature in various zones of the centrifuge chamber as the result of compression and expansions respectively, of process gases and may be employed effectively both to neutralize harmful temperature gradients and to utilize beneficial temperaturc gradients within the centrifuge.

  5. Extraction, Purification, and Spectroscopic Characterization of a Mixture of Capsaicinoids

    Science.gov (United States)

    Wagner, Carl E.; Cahill, Thomas M.; Marshall, Pamela A.

    2011-01-01

    This laboratory experiment provides a safe and effective way to instruct undergraduate organic chemistry students about natural-product extraction, purification, and NMR spectroscopic characterization. On the first day, students extract dried habanero peppers with toluene, perform a pipet silica gel column to separate carotenoids from…

  6. Spectroscopic imaging: basic principles.

    Science.gov (United States)

    Skoch, Antonin; Jiru, Filip; Bunke, Jürgen

    2008-08-01

    Spectroscopic imaging (SI) is a method that enables the measurement of the spatial distribution of metabolite concentrations in tissue. In this paper, an overview of measurement and processing techniques for SI is given. First, the basic structure of SI pulse sequences is introduced and the concepts of k-space, point spread function and spatial resolution are described. Then, special techniques are presented for the purpose of eliminating spurious signals and reducing measurement time. Finally, basic post-processing of SI data and the methods for viewing the results of SI measurement are summarized.

  7. A review of the thermodynamics of protein association to ligands, protein adsorption, and adsorption isotherms

    DEFF Research Database (Denmark)

    Mollerup, Jørgen

    2008-01-01

    The application of thermodynamic models in the development of chromatographic separation processes is discussed. The paper analyses the thermodynamic principles of protein adsorption. It can be modeled either as a reversible association between the adsorbate and the ligands or as a steady...... of adsorption is discussed. Hydrophobic and reversed phase chromatography are useful techniques for measuring solute activity coefficients at infinite dilution....

  8. Thermodynamics: The Unique Universal Science

    Directory of Open Access Journals (Sweden)

    Wassim M. Haddad

    2017-11-01

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

  9. Thermodynamics of adaptive molecular resolution.

    Science.gov (United States)

    Delgado-Buscalioni, R

    2016-11-13

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

  10. RNA Thermodynamic Structural Entropy.

    Science.gov (United States)

    Garcia-Martin, Juan Antonio; Clote, Peter

    2015-01-01

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

  11. RNA Thermodynamic Structural Entropy.

    Directory of Open Access Journals (Sweden)

    Juan Antonio Garcia-Martin

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

  12. Time and Thermodynamics

    CERN Document Server

    Kirkland, Kyle

    2007-01-01

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

  13. Molecular thermodynamics of nonideal fluids

    CERN Document Server

    Lee, Lloyd L

    2013-01-01

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

  14. Thermodynamics of Accelerating Black Holes.

    Science.gov (United States)

    Appels, Michael; Gregory, Ruth; Kubizňák, David

    2016-09-23

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

  15. Thermodynamics of geothermal fluids

    Energy Technology Data Exchange (ETDEWEB)

    Rogers, P.S.Z.

    1981-03-01

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

  16. Thermodynamics of liquid 3He−4He mixtures

    NARCIS (Netherlands)

    de Waele, A.Th.A.M.; Kuerten, Johannes G.M.

    1989-01-01

    The osmotic pressure of 3He−4He solutions is shown to follow in a natural way from the separation of the specific heat in a quasiparticle contribution and a 4He-contribution. Expressions for important thermodynamic properties such as the chemical potentials, the internal energy, the entropy,

  17. Biochemical Thermodynamics under near Physiological Conditions

    Science.gov (United States)

    Mendez, Eduardo

    2008-01-01

    The recommendations for nomenclature and tables in Biochemical Thermodynamics approved by IUBMB and IUPAC in 1994 can be easily introduced after the chemical thermodynamic formalism. Substitution of the usual standard thermodynamic properties by the transformed ones in the thermodynamic equations, and the use of appropriate thermodynamic tables…

  18. Spectroscopic characterization of cardiovascular tissue.

    Science.gov (United States)

    Clarke, R H; Isner, J M; Gauthier, T; Nakagawa, K; Cerio, F; Hanlon, E; Gaffney, E; Rouse, E; DeJesus, S

    1988-01-01

    We present results of a series of laser spectroscopic measurements on in vitro samples of cardiovascular tissue. These include laser Raman scattering, Fourier transform infrared, plasma emission and fluorescence, and electron paramagnetic resonance spectroscopy. The results of these spectroscopic measurements are discussed in terms of their implications for the field of laser angioplasty.

  19. Thermodynamics of cosmological matter creation

    Science.gov (United States)

    Prigogine, I.; Geheniau, J.; Gunzig, E.; Nardone, P.

    1988-01-01

    A type of cosmological history that includes large-scale entropy production is proposed. These cosmologies are based on reinterpretation of the matter-energy stress tensor in Einstein's equations. This modifies the usual adiabatic energy conservation laws, thereby including irreversible matter creation. This creation corresponds to an irreversible energy flow from the gravitational field to the created matter constituents. This point of view results from consideration of the thermodynamics of open systems in the framework of cosmology. It is shown that the second law of thermodynamics requires that space-time transforms into matter, while the inverse transformation is forbidden. It appears that the usual initial singularity associated with the big bang is structurally unstable with respect to irreversible matter creation. The corresponding cosmological history therefore starts from an instability of the vacuum rather than from a singularity. This is exemplified in the framework of a simple phenomenological model that leads to a three-stage cosmology: the first drives the cosmological system from the initial instability to a de Sitter regime, and the last connects with the usual matter-radiation Robertson-Walker universe. Matter as well as entropy creation occurs during the first two stages, while the third involves the traditional cosmological evolution. A remarkable fact is that the de Sitter stage appears to be an attractor independent of the initial fluctuation. This is also the case for all the physical predictions involving the present Robertson-Walker universe. Most results obtained previously, in the framework of quantum field theory, can now be obtained on a macroscopic basis. It is shown that this description leads quite naturally to the introduction of primeval black holes as the intermediate stage between the Minkowski vacuum and the present matter-radiation universe. The instability at the origin of the universe is the result of fluctuations of the

  20. Thermodynamics of cosmological matter creation.

    Science.gov (United States)

    Prigogine, I; Geheniau, J; Gunzig, E; Nardone, P

    1988-10-01

    A type of cosmological history that includes large-scale entropy production is proposed. These cosmologies are based on reinterpretation of the matter-energy stress tensor in Einstein's equations. This modifies the usual adiabatic energy conservation laws, thereby including irreversible matter creation. This creation corresponds to an irreversible energy flow from the gravitational field to the created matter constituents. This point of view results from consideration of the thermodynamics of open systems in the framework of cosmology. It is shown that the second law of thermodynamics requires that space-time transforms into matter, while the inverse transformation is forbidden. It appears that the usual initial singularity associated with the big bang is structurally unstable with respect to irreversible matter creation. The corresponding cosmological history therefore starts from an instability of the vacuum rather than from a singularity. This is exemplified in the framework of a simple phenomenological model that leads to a three-stage cosmology: the first drives the cosmological system from the initial instability to a de Sitter regime, and the last connects with the usual matter-radiation Robertson-Walker universe. Matter as well as entropy creation occurs during the first two stages, while the third involves the traditional cosmological evolution. A remarkable fact is that the de Sitter stage appears to be an attractor independent of the initial fluctuation. This is also the case for all the physical predictions involving the present Robertson-Walker universe. Most results obtained previously, in the framework of quantum field theory, can now be obtained on a macroscopic basis. It is shown that this description leads quite naturally to the introduction of primeval black holes as the intermediate stage between the Minkowski vacuum and the present matter-radiation universe. The instability at the origin of the universe is the result of fluctuations of the

  1. Isotope separation

    Science.gov (United States)

    Bartlett, Rodney J.; Morrey, John R.

    1978-01-01

    A method and apparatus is described for separating gas molecules containing one isotope of an element from gas molecules containing other isotopes of the same element in which all of the molecules of the gas are at the same electronic state in their ground state. Gas molecules in a gas stream containing one of the isotopes are selectively excited to a different electronic state while leaving the other gas molecules in their original ground state. Gas molecules containing one of the isotopes are then deflected from the other gas molecules in the stream and thus physically separated.

  2. ISOTOPE SEPARATORS

    Science.gov (United States)

    Bacon, C.G.

    1958-08-26

    An improvement is presented in the structure of an isotope separation apparatus and, in particular, is concerned with a magnetically operated shutter associated with a window which is provided for the purpose of enabling the operator to view the processes going on within the interior of the apparatus. The shutier is mounted to close under the force of gravity in the absence of any other force. By closing an electrical circuit to a coil mouated on the shutter the magnetic field of the isotope separating apparatus coacts with the magnetic field of the coil to force the shutter to the open position.

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

    Science.gov (United States)

    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'0can 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. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Thermodynamics of disordered Heisenberg model

    Science.gov (United States)

    Mulanix, Michael; Khatami, Ehsan

    Using numerical linked-cluster expansions, we study the thermodynamic properties of the disordered Heisenberg model on the square lattice. We implement a new technique for treating continuous disorder within the NLCE and obtain results for the energy, entropy, specific heat, and spin correlations in the thermodynamic limit.

  5. Thermodynamic aspects of energy conservation

    NARCIS (Netherlands)

    Gool, W. van

    1980-01-01

    Thermodynamics deals with processes in a time independent approach. Industrial productions and many other activities are bound to perform a certain production per unit of time. It will be demonstrated that the stationary process model is a useful tool in relating thermodynamic functions to the

  6. Thermodynamics from Car to Kitchen

    Science.gov (United States)

    Auty, Geoff

    2014-01-01

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

  7. The Thermodynamics of Black Holes

    Directory of Open Access Journals (Sweden)

    Wald Robert M.

    2001-01-01

    Full Text Available We review the present status of black hole thermodynamics. Our review includes discussion of classical black hole thermodynamics, Hawking radiation from black holes, the generalized second law, and the issue of entropy bounds. A brief survey also is given of approaches to the calculation of black hole entropy. We conclude with a discussion of some unresolved open issues.

  8. Applied thermodynamics: A new frontier for biotechnology

    DEFF Research Database (Denmark)

    Mollerup, Jørgen

    2006-01-01

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

  9. Thermodynamic properties of cryogenic fluids

    CERN Document Server

    Leachman, Jacob; Lemmon, Eric; Penoncello, Steven

    2017-01-01

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

  10. Thermodynamics of anisotropic branes

    Energy Technology Data Exchange (ETDEWEB)

    Ávila, Daniel [Departamento de Física, Facultad de Ciencias, Universidad Nacional Autónoma de México, A.P. 70-542, México D.F. 04510 (Mexico); Fernández, Daniel [Max-Planck-Institut für Physik,Föhringer Ring 6, 80805 München (Germany); Patiño, Leonardo [Departamento de Física, Facultad de Ciencias, Universidad Nacional Autónoma de México, A.P. 70-542, México D.F. 04510 (Mexico); Trancanelli, Diego [Institute of Physics, University of São Paulo,05314-970 São Paulo (Brazil)

    2016-11-22

    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.

  11. Thermodynamics of Protein Aggregation

    Science.gov (United States)

    Osborne, Kenneth L.; Barz, Bogdan; Bachmann, Michael; Strodel, Birgit

    Amyloid protein aggregation characterizes many neurodegenerative disorders, including Alzheimer's, Parkinson's, and Creutz- feldt-Jakob disease. Evidence suggests that amyloid aggregates may share similar aggregation pathways, implying simulation of full-length amyloid proteins is not necessary for understanding amyloid formation. In this study we simulate GNNQQNY, the N-terminal prion-determining domain of the yeast protein Sup35 to investigate the thermodynamics of structural transitions during aggregation. We use a coarse-grained model with replica-exchange molecular dynamics to investigate the association of 3-, 6-, and 12-chain GNNQQNY systems and we determine the aggregation pathway by studying aggregation states of GN- NQQNY. We find that the aggregation of the hydrophilic GNNQQNY sequence is mainly driven by H-bond formation, leading to the formation of /3-sheets from the very beginning of the assembly process. Condensation (aggregation) and ordering take place simultaneously, which is underpinned by the occurrence of a single heat capacity peak only.

  12. Differences between gas separation cascade work and the work of isobaric-isothermal mixing

    Science.gov (United States)

    Chizhkov, V. P.; Boitsov, V. N.

    2017-11-01

    The change in entropy at the nodes of the a separation cascade during the processing of a multicomponent mixture is calculated. A thermodynamic interpretation of the nature of the difference between the work of the cascade, determined from the separation potential and the thermodynamically estimated work of the isobaric-isothermal mixing of the fractions released at its ends, is presented.

  13. Ecofriendly gold nanoparticles - Lysozyme interaction: Thermodynamical perspectives.

    Science.gov (United States)

    Roy, Swarup; Saxena, Shailendra K; Mishra, Suryakant; Yogi, Priyanka; Sagdeo, P R; Kumar, Rajesh

    2017-09-01

    In the featured work interaction between biosynthesized gold nanoparticles (GNP) and lysozyme (Lys) has been studied using multi-spectroscopic approach. A moderate association constant (Kapp) of 2.66×104L/mol has been observed indicative of interactive nature. The binding constant (Kb) was 1.99, 6.30 and 31.6×104L/mol at 291, 298 and 305K respectively and the number of binding sites (n) was found to be approximately one. Estimated values of thermodynamic parameters (Enthalpy change, ΔH=141.99kJ/mol, entropy change, ΔS=570J/mol/K, Gibbs free energy change, ΔG=-27.86kJ/mol at 298K) suggest hydrophobic force as the main responsible factor for the Lys-GNP interaction and also the process of interaction is spontaneous. The average binding distance (r=3.06nm) and the critical energy transfer distance (Ro=1.84nm) between GNP and Lys was also evaluated using Förster's non-radiative energy transfer (FRET) theory and results clearly indicate that non-radiative type energy transfer is possible. Moreover, the addition of GNP does not show any significant change in the secondary structure of Lys as confirmed from circular dichroism (CD) spectra. Furthermore, NMR spectroscopy also indicates interaction between Lys and GNP. The resulting insight is important for the better understanding of structural nature and thermodynamic aspects of binding between the Lys and GNP. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. THERMODYNAMICS OF PROTEIN-LIGAND INTERACTIONS AND THEIR ANALYSIS

    Directory of Open Access Journals (Sweden)

    Rummi Devi Saini

    2017-11-01

    Full Text Available Physiological processes are controlled mainly by intermolecular recognition mechanisms which involve protein–protein and protein–ligand interactions with a high specificity and affinity to form a specific complex. Proteins being an important class of macromolecules in biological systems, it is important to understand their actions through binding to other molecules of proteins or ligands. In fact, the binding of low molecular weight ligands to proteins plays a significant role in regulating biological processes such as cellular metabolism and signal transmission. Therefore knowledge of the protein–ligand interactions and the knowledge of the mechanisms involved in the protein-ligand recognition and binding are key in understanding biology at molecular level which will facilitate the discovery, design, and development of drugs. In this review, the mechanisms involved in protein–ligand binding, the binding kinetics, thermodynamic concepts and binding driving forces are discussed. Thermodynamic mechanisms involved in a few important protein-ligand binding are described. Various spectroscopic, non-spectroscopic and computational method for analysis of protein–ligand binding are also discussed.

  15. Thermodynamics of Van der Waals Fluids with quantum statistics

    CERN Document Server

    Redlich, Krzysztof

    2016-01-01

    We consider thermodynamics of the van der Waals fluid of quantum systems. We derive general relations of thermodynamic functions and parameters of any ideal gas and the corresponding van der Waals fluid. This provides unambiguous generalization of the classical van der Waals theory to quantum statistical systems. As an example, we apply the van der Waals fluid with fermi statistics to characterize the liquid-gas critical point in nuclear matter. We also introduce the Bose-Einstein condensation in the relativistic van der Waals boson gas, and argue, that it exhibits two-phase structure separated in space.

  16. HRS Separator

    CERN Multimedia

    2016-01-01

    Footage of the 90 and 60 degree ISOLDE HRS separator magnets in the HRS separator zone. In the two vacuum sectors HRS20 and HRS30 equipment such as the HRS slits SL240, the HRS faraday cup FC300 and wiregrid WG210 can be spotted. Vacuum valves, turbo pumps, beamlines, quadrupoles, water and compressed air connections, DC and signal cabling can be seen throughout the video. The HRS main and user beamgate in the beamline between MAG90 and MAG60 and its switchboxes as well as all vacuum bellows and flanges are shown. Instrumentation such as the HRS scanner unit 482 / 483, the HRS WG470 wiregrid and slits piston can be seen. The different quadrupoles and supports are shown as well as the RILIS guidance tubes and installation at the magnets and the different radiation monitors.

  17. GPS Separator

    CERN Multimedia

    2016-01-01

    Footage of the 70 degree ISOLDE GPS separator magnet MAG70 as well as the switchyard for the Central Mass and GLM (GPS Low Mass) and GHM (GPS High Mass) beamlines in the GPS separator zone. In the GPS20 vacuum sector equipment such as the long GPS scanner 482 / 483 unit, faraday cup FC 490, vacuum valves and wiregrid piston WG210 and WG475 and radiation monitors can also be seen. Also the RILIS laser guidance and trajectory can be seen, the GPS main beamgate switch box and the actual GLM, GHM and Central Beamline beamgates in the beamlines as well as the first electrostatic quadrupoles for the GPS lines. Close up of the GHM deflector plates motor and connections and the inspection glass at the GHM side of the switchyard.

  18. Separation system

    Science.gov (United States)

    Rubin, Leslie S.

    1986-01-01

    A separation system for dewatering radioactive waste materials includes a disposal container, drive structure for receiving the container, and means for releasably attaching the container to the drive structure. Separation structure disposed in the container adjacent the inner surface of the side wall structure retains solids while allowing passage of liquids. Inlet port structure in the container top wall is normally closed by first valve structure that is centrifugally actuated to open the inlet port and discharge port structure at the container periphery receives liquid that passes through the separation structure and is normally closed by second valve structure that is centrifugally actuated to open the discharge ports. The container also includes coupling structure for releasable engagement with the centrifugal drive structure. Centrifugal force produced when the container is driven in rotation by the drive structure opens the valve structures, and radioactive waste material introduced into the container through the open inlet port is dewatered, and the waste is compacted. The ports are automatically closed by the valves when the container drum is not subjected to centrifugal force such that containment effectiveness is enhanced and exposure of personnel to radioactive materials is minimized.

  19. Thermodynamic Constraints Improve Metabolic Networks.

    Science.gov (United States)

    Krumholz, Elias W; Libourel, Igor G L

    2017-08-08

    In pursuit of establishing a realistic metabolic phenotypic space, the reversibility of reactions is thermodynamically constrained in modern metabolic networks. The reversibility constraints follow from heuristic thermodynamic poise approximations that take anticipated cellular metabolite concentration ranges into account. Because constraints reduce the feasible space, draft metabolic network reconstructions may need more extensive reconciliation, and a larger number of genes may become essential. Notwithstanding ubiquitous application, the effect of reversibility constraints on the predictive capabilities of metabolic networks has not been investigated in detail. Instead, work has focused on the implementation and validation of the thermodynamic poise calculation itself. With the advance of fast linear programming-based network reconciliation, the effects of reversibility constraints on network reconciliation and gene essentiality predictions have become feasible and are the subject of this study. Networks with thermodynamically informed reversibility constraints outperformed gene essentiality predictions compared to networks that were constrained with randomly shuffled constraints. Unconstrained networks predicted gene essentiality as accurately as thermodynamically constrained networks, but predicted substantially fewer essential genes. Networks that were reconciled with sequence similarity data and strongly enforced reversibility constraints outperformed all other networks. We conclude that metabolic network analysis confirmed the validity of the thermodynamic constraints, and that thermodynamic poise information is actionable during network reconciliation. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  20. Thermodynamic Metrics and Optimal Paths

    Energy Technology Data Exchange (ETDEWEB)

    Sivak, David; Crooks, Gavin

    2012-05-08

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

  1. Statistical Thermodynamics of Disperse Systems

    DEFF Research Database (Denmark)

    Shapiro, Alexander

    1996-01-01

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

  2. The Thermodynamic Properties of Cubanite

    Science.gov (United States)

    Berger, E. L.; Lauretta, D. S.; Keller, L. P.

    2012-01-01

    CuFe2S3 exists in two polymorphs, a low-temperature orthorhombic form (cubanite) and a high-temperature cubic form (isocubanite). Cubanite has been identified in the CI-chondrite and Stardust collections. However, the thermodynamic properties of cubanite have neither been measured nor estimated. Our derivation of a thermodynamic model for cubanite allows constraints to be placed on the formation conditions. This data, along with the temperature constraint afforded by the crystal structure, can be used to assess the environments in which cubanite formation is (or is not) thermodynamically favored.

  3. Gas separating

    Science.gov (United States)

    Gollan, A.

    1988-03-29

    Feed gas is directed tangentially along the non-skin surface of gas separation membrane modules comprising a cylindrical bundle of parallel contiguous hollow fibers supported to allow feed gas to flow from an inlet at one end of a cylindrical housing through the bores of the bundled fibers to an outlet at the other end while a component of the feed gas permeates through the fibers, each having the skin side on the outside, through a permeate outlet in the cylindrical casing. 3 figs.

  4. Flow Separation

    Science.gov (United States)

    1975-11-01

    perfomanoas que oette oirconstance peut entrainer, soit encore, d’un point de vue plus fondamental par la recherche dM phenomknas qui caracterisent 1M...dtfoolleoent, dont le m^canlsme de formation eat en tout point sen- blable h celui qui a etc döcrit § 2.2. XL se caracterise par la presence d’une onde...during orbital maneuvers with the Reaction Control System (RCS) and later plume induced separation leading to aerodynamic heating and control problems

  5. Thermodynamical string fragmentation

    Science.gov (United States)

    Fischer, Nadine; Sjöstrand, Torbjörn

    2017-01-01

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

  6. Association theories for complex thermodynamics

    DEFF Research Database (Denmark)

    Kontogeorgis, Georgios; Rafiqul Gani

    2013-01-01

    Thermodynamics of complex systems (e.g. with associating molecules, multicomponent mixtures, multiphase equilibria, wide ranges of conditions, estimation of many different properties simultaneously) is a topic of great importance in chemical engineering and for a wide range of industrial...... promising direction for a general and useful for engineering purposes modeling of complex thermodynamics is via the use of association theories e.g. those based on chemical theory (like APACT), or on the lattice theory (like NRHB) or those based on perturbation theory (like SAFT and CPA). The purpose...... applications. While specialized models can handle different cases, even complex ones, with the advent of powerful theories and computers there is the hope that a single or a few models could be suitable for a general modeling of complex thermodynamics. After more than 100 years with active use of thermodynamic...

  7. Experimental approaches to membrane thermodynamics

    DEFF Research Database (Denmark)

    Westh, Peter

    2009-01-01

    Thermodynamics describes a system on the macroscopic scale, yet it is becoming an important tool for the elucidation of many specific molecular aspects of membrane properties. In this note we discuss this application of thermodynamics, and give a number of examples on how thermodynamic measuremen...... have contributed to the understanding of specific membrane phenomena. We mainly focus on non-specific interactions of bilayers and small molecules (water and solutes) in the surrounding solvent, and the changes in membrane properties they bring about. Differences between thermodynamic...... and stoichiometric (structural) definitions of non-specific binding or partitioning are emphasized, and it is concluded that this distinction is important for weak, but not for strong, interactions....

  8. Spectrophotometric Determination and Thermodynamic Parameters ...

    African Journals Online (AJOL)

    Erah

    Spectrophotometric Determination and Thermodynamic. Parameters of Charge Transfer Complexation Between. Stavudine and Chloranilic Acid. Wilfred O Obonga, Edwin O Omeje*, Philip F Uzor and Malachy O Ugwu. Department of Pharmaceutical and Medicinal Chemistry, Faculty of Pharmaceutical Sciences, University ...

  9. Shock Thermodynamic Applied Research Facility

    Data.gov (United States)

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

  10. Thermodynamics from concepts to applications

    CERN Document Server

    Shavit, Arthur

    2008-01-01

    The book presents a logical methodology for solving problems in the context of conservation laws and property tables or equations. The authors elucidate the terms around which thermodynamics has historically developed, such as work, heat, temperature, energy, and entropy. Using a pedagogical approach that builds from basic principles to laws and eventually corollaries of the laws, the text enables students to think in clear and correct thermodynamic terms as well as solve real engineering problems.

  11. Thermodynamics of Asymptotically Conical Geometries.

    Science.gov (United States)

    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.

  12. THERRP: a thermodynamic properties program

    Energy Technology Data Exchange (ETDEWEB)

    Deeds, R.S.

    1977-05-01

    The computer program THERPP, a program that calculates the thermodynamic properties of light hydrocarbons and mixtures of light hydrocarbons is documented. A specific pressure--temperature or pressure--enthalpy grid is input to obtain properties in the desired region. THERPP is a modification of the program HSGC. Thermodynamic properties are calculated using Starling's modification to the Benedict-Webb-Rubin equation of state.

  13. Thermodynamics of nonsingular bouncing universes

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Pedro C. [Universidade Federal do Rio Grande do Norte, Escola de Ciencias e Tecnologia, Natal, Rio Grande do Norte (Brazil); Pavon, Diego [Universidad Autonoma de Barcelona, Departamento de Fisica, Bellaterra, Barcelona (Spain)

    2016-01-15

    Homogeneous and isotropic, nonsingular, bouncing world models are designed to evade the initial singularity at the beginning of the cosmic expansion. Here, we study the thermodynamics of the subset of these models governed by general relativity. Considering the entropy of matter and radiation and considering the entropy of the apparent horizon to be proportional to its area, we argue that these models do not respect the generalized second law of thermodynamics, also away from the bounce. (orig.)

  14. Generalization of Gibbs Entropy and Thermodynamic Relation

    OpenAIRE

    Park, Jun Chul

    2010-01-01

    In this paper, we extend Gibbs's approach of quasi-equilibrium thermodynamic processes, and calculate the microscopic expression of entropy for general non-equilibrium thermodynamic processes. Also, we analyze the formal structure of thermodynamic relation in non-equilibrium thermodynamic processes.

  15. [Progress in Raman spectroscopic measurement of methane hydrate].

    Science.gov (United States)

    Xu, Feng; Zhu, Li-hua; Wu, Qiang; Xu, Long-jun

    2009-09-01

    Complex thermodynamics and kinetics problems are involved in the methane hydrate formation and decomposition, and these problems are crucial to understanding the mechanisms of hydrate formation and hydrate decomposition. However, it was difficult to accurately obtain such information due to the difficulty of measurement since methane hydrate is only stable under low temperature and high pressure condition, and until recent years, methane hydrate has been measured in situ using Raman spectroscopy. Raman spectroscopy, a non-destructive and non-invasive technique, is used to study vibrational modes of molecules. Studies of methane hydrate using Raman spectroscopy have been developed over the last decade. The Raman spectra of CH4 in vapor phase and in hydrate phase are presented in this paper. The progress in the research on methane hydrate formation thermodynamics, formation kinetics, decomposition kinetics and decomposition mechanism based on Raman spectroscopic measurements in the laboratory and deep sea are reviewed. Formation thermodynamic studies, including in situ observation of formation condition of methane hydrate, analysis of structure, and determination of hydrate cage occupancy and hydration numbers by using Raman spectroscopy, are emphasized. In the aspect of formation kinetics, research on variation in hydrate cage amount and methane concentration in water during the growth of hydrate using Raman spectroscopy is also introduced. For the methane hydrate decomposition, the investigation associated with decomposition mechanism, the mutative law of cage occupancy ratio and the formulation of decomposition rate in porous media are described. The important aspects for future hydrate research based on Raman spectroscopy are discussed.

  16. HPLC retention thermodynamics of grape and wine tannins.

    Science.gov (United States)

    Barak, Jennifer A; Kennedy, James A

    2013-05-08

    The effect of grape and wine tannin structure on retention thermodynamics under reversed-phase high-performance liquid chromatography conditions on a polystyrene divinylbenzene column was investigated. On the basis of retention response to temperature, an alternative retention factor was developed to approximate the combined temperature response of the complex, unresolvable tannin mixture. This alternative retention factor was based upon relative tannin peak areas separated by an abrupt change in solvent gradient. Using this alternative retention factor, retention thermodynamics were calculated. Van't Hoff relationships of the natural log of the alternative retention factor against temperature followed Kirchoff's relationship. An inverse quadratic equation was fit to the data, and from this the thermodynamic parameters for tannin retention were calculated. All tannin fractions exhibited exothermic, spontaneous interaction, with enthalpy-entropy compensation observed. Normalizing for tannin size, distinct tannin compositional effects on thermodynamic parameters were observed. The results of this study indicate that HPLC can be valuable for measuring the thermodynamics of tannin interaction with a hydrophobic surface and provides a potentially valuable alternative to calorimetry. Furthermore, the information gathered may provide insight into understanding red wine astringency quality.

  17. Thermodynamics of firms' growth

    Science.gov (United States)

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

    2015-01-01

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

  18. Condensation: Passenger Not Driver in Atmospheric Thermodynamics

    OpenAIRE

    Jack Denur

    2016-01-01

    The second law of thermodynamics states that processes yielding work or at least capable of yielding work are thermodynamically spontaneous, and that those costing work are thermodynamically nonspontaneous. Whether a process yields or costs heat is irrelevant. Condensation of water vapor yields work and hence is thermodynamically spontaneous only in a supersaturated atmosphere; in an unsaturated atmosphere it costs work and hence is thermodynamically nonspontaneous. Far more of Earth’s atmosp...

  19. Kinetic vs. Thermodynamic Control of Bacteriorhodopsin Pumping

    Science.gov (United States)

    Gunner, Marilyn

    2011-03-01

    Bacteriorhodopsin is a transmembrane proton pump that converts light energy to a transmembrane electrochemical gradient. Retinal, bound in the center of the protein, absorbs light and isomerizes from the all-trans to 13-cis configuration. A series of conformational changes and proton transfers then restores the structure to the all-trans ground state while pumping one proton from the high pH cell interior to the low pH exterior, saving energy in an electrochemical gradient. Poorly understood gating elements control key steps where incorrect proton transfer would return the protein to the ground state without pumping. The gate's barrier height determines how much the pump leaks. Analysis of high-resolution structures trapped in different intermediates has produced ideas for how bacteriorhodopsin ensures pumping. There are two contrasting strategies, one primarily thermodynamic and the other relying on kinetic control to ensure that protons are moved uphill. With thermodynamic control, residue protonation states always remain in quasi-equilibrium. Relatively slow conformational changes shift the energy landscape modifying site pKas. Residues then change ionization remaining in equilibrium in each metastable intermediate. The sequence of intermediates imparts the directionality to the transfers. Alternatively, the direction of transfer is determined by the accessibility of low energy pathways so is thus is under kinetic control. We will discuss which steps in the bacteriorhodopsin photocycle are under thermodynamic or under kinetic control. The role of three specific conformational changes (retinal isomerization, Arg82 reorientation and Glu194 and 204 separations) on the degree of proton transfer will be described. Supported by NFS MCB 1022208. Carried out with Yifan Song now at the University of Washington Department of Biochemistry.

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

    Science.gov (United States)

    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. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Thermodynamics of weight loss diets

    Directory of Open Access Journals (Sweden)

    Fine Eugene J

    2004-12-01

    Full Text Available Abstract 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.

  2. Selective spectroscopic methods for water analysis

    Energy Technology Data Exchange (ETDEWEB)

    Vaidya, Bikas [Iowa State Univ., Ames, IA (United States)

    1997-06-24

    This dissertation explores in large part the development of a few types of spectroscopic methods in the analysis of water. Methods for the determination of some of the most important properties of water like pH, metal ion content, and chemical oxygen demand are investigated in detail. This report contains a general introduction to the subject and the conclusions. Four chapters and an appendix have been processed separately. They are: chromogenic and fluorogenic crown ether compounds for the selective extraction and determination of Hg(II); selective determination of cadmium in water using a chromogenic crown ether in a mixed micellar solution; reduction of chloride interference in chemical oxygen demand determination without using mercury salts; structural orientation patterns for a series of anthraquinone sulfonates adsorbed at an aminophenol thiolate monolayer chemisorbed at gold; and the role of chemically modified surfaces in the construction of miniaturized analytical instrumentation.

  3. Membrane manufacture for peptide separations

    KAUST Repository

    Kim, Dooli

    2016-06-07

    Nanostructured polymeric membranes are key tools in biomedical applications such as hemodialysis, protein separations, in the food industry, and drinking water supply from seawater. Despite of the success in different separation processes, membrane manufacture itself is at risk, since the most used solvents are about to be banned in many countries due to environmental and health issues. We propose for the first time the preparation of polyethersulfone membranes based on dissolution in the ionic liquid 1-ethyl-3-methylimidazolium dimethylphosphate ([EMIM]DEP). We obtained a series of membranes tailored for separation of solutes with molecular weight of 30, 5, 1.3, and 1.25 kg mol-1 with respective water permeances of 140, 65, 30 and 20 Lm-2h-1bar-1. We demonstrate their superior efficiency in the separation of complex mixtures of peptides with molecular weights in the range of 800 to 3500 gmol-1. Furthermore, the thermodynamics and kinetics of phase separation leading to the pore formation in the membranes were investigated. The rheology of the solutions and the morphology of the prepared membranes were examed and compared to those of polyethersulfone in organic solvents currently used for membrane manufacture.

  4. Spectroscopic analysis of optoelectronic semiconductors

    CERN Document Server

    Jimenez, Juan

    2016-01-01

    This book deals with standard spectroscopic techniques which can be used to analyze semiconductor samples or devices, in both, bulk, micrometer and submicrometer scale. The book aims helping experimental physicists and engineers to choose the right analytical spectroscopic technique in order to get specific information about their specific demands. For this purpose, the techniques including technical details such as apparatus and probed sample region are described. More important, also the expected outcome from experiments is provided. This involves also the link to theory, that is not subject of this book, and the link to current experimental results in the literature which are presented in a review-like style. Many special spectroscopic techniques are introduced and their relationship to the standard techniques is revealed. Thus the book works also as a type of guide or reference book for people researching in optical spectroscopy of semiconductors.

  5. Eigenstate Thermalization Hypothesis and Quantum Thermodynamics

    Science.gov (United States)

    Olshanii, Maxim

    2009-03-01

    One of the open questions in quantum thermodynamics reads: how can linear quantum dynamics provide chaos necessary for thermalization of an isolated quantum system? To this end, we perform an ab initio numerical analysis of a system of hard-core bosons on a lattice and show [Marcos Rigol, Vanja Dunjko & Maxim Olshanii, Nature 452, 854 (2008)] that the above controversy can be resolved via the Eigenstate Thermalization Hypothesis suggested independently by Deutsch [J. M. Deutsch, Phys. Rev. A 43, 2046 (1991)] and Srednicki [M. Srednicki, Phys. Rev. E 50, 888 (1994)]. According to this hypothesis, in quantum systems thermalization happens in each individual eigenstate of the system separately, but it is hidden initially by coherences between them. In course of the time evolution the thermal properties become revealed through (linear) decoherence that needs not to be chaotic.

  6. Quenching Phase Separation by Vapor Deposition Polymerization

    Science.gov (United States)

    Tao, Ran; Anthamatten, Mitchell

    2015-03-01

    Initiated chemical vapor deposition (iCVD) is a solventless, free radical technique predominately used to deposit homogeneous films of linear and crosslinked polymers directly from gas phase feeds. We report a template-free method to fabricate continuous-phase porous polymer films by simultaneous phase separation during iCVD. Phase separation during film growth is achieved by condensing an inert porogen, along with initiator, monomer, and crosslinker. When the vapor mixture transports to the cooled substrate, phase separation occurs along with polymerization and crosslinking, which quench the state of phase separation. The kinetics of spontaneously phase separation can be qualitatively understood on the basis of Cahn-Hilliard theory. A series of films were grown by varying monomer and porogen's degree of saturation. Deposited films were studied by electron microscopy and spectroscopic techniques.

  7. Thermodynamics of quantum information scrambling.

    Science.gov (United States)

    Campisi, Michele; Goold, John

    2017-06-01

    Scrambling of quantum information can conveniently be quantified by so-called out-of-time-order correlators (OTOCs), i.e., correlators of the type 〈[W_{τ},V]^{†}[W_{τ},V]〉, whose measurements present a formidable experimental challenge. Here we report on a method for the measurement of OTOCs based on the so-called two-point measurement scheme developed in the field of nonequilibrium quantum thermodynamics. The scheme is of broader applicability than methods employed in current experiments and provides a clear-cut interpretation of quantum information scrambling in terms of nonequilibrium fluctuations of thermodynamic quantities, such as work and heat. Furthermore, we provide a numerical example on a spin chain which highlights the utility of our thermodynamic approach when understanding the differences between integrable and ergodic behaviors. We also discuss how the method can be used to extend the reach of current experiments.

  8. Nanofluidics thermodynamic and transport properties

    CERN Document Server

    Michaelides, Efstathios E (Stathis)

    2014-01-01

    This volume offers a comprehensive examination of the subject of heat and mass transfer with nanofluids as well as a critical review of the past and recent research projects in this area. Emphasis is placed on the fundamentals of the transport processes using particle-fluid suspensions, such as nanofluids. The nanofluid research is examined and presented in a holistic way using a great deal of our experience with the subjects of continuum mechanics, statistical thermodynamics, and non-equilibrium thermodynamics of transport processes. Using a thorough database, the experimental, analytical, and numerical advances of recent research in nanofluids are critically examined and connected to past research with medium and fine particles as well as to functional engineering systems. Promising applications and technological issues of heat/mass transfer system design with nanofluids are also discussed. This book also: Provides a deep scientific analysis of nanofluids using classical thermodynamics and statistical therm...

  9. Thermodynamics a complete undergraduate course

    CERN Document Server

    Steane, Andrew M

    2016-01-01

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

  10. The Thermodynamic Machinery of Life

    CERN Document Server

    Kurzynski, Michal

    2006-01-01

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

  11. Statistical thermodynamics of clustered populations.

    Science.gov (United States)

    Matsoukas, Themis

    2014-08-01

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

  12. An introduction to endoreversible thermodynamics

    Directory of Open Access Journals (Sweden)

    Hoffmann, Karl Heinz

    2008-02-01

    Full Text Available Reversible thermodynamic processes are convenient abstractions of real processes, which are always irreversible. Approaching the reversible regime means to become more and more quasistatic, letting behind processes which achieve any kind of finite transformation rate for the quantities studied. On the other hand studying processes with finite transformation rates means to deal with irreversibilities and in many cases these irreversibilities must be included in a realistic description of such processes. Endoreversible thermodynamics is a non-equilibrium approach in this direction by viewing a system as a network of internally reversible (endoreversible subsystems exchanging energy in an irreversible fashion. This material provides an introduction to the subject.

  13. Irreversible Thermodynamic Bound for the Efficiency of Light-Emitting Diodes

    Science.gov (United States)

    Xue, Jin; Li, Zheng; Ram, Rajeev J.

    2017-07-01

    A thermodynamic model for light-emitting diodes (LEDs) is developed by considering energy and entropy flows in the system. Thermodynamic constraints have previously been considered separately for the reversible process of electroluminescence in LEDs and for light extraction and collimation in other optical systems. By considering both processes in the LED model, an irreversible upper bound for the conversion of electrical energy to optical energy is derived and shown to be higher than unity, but tighter and more realistic than the reversible case. We also model a LED as an endoreversible heat engine where the carrier-transport processes can be directly connected to the elements of a thermodynamic cycle.

  14. Spectroscopic Classification of Two Supernovae

    Science.gov (United States)

    Gomez, S.; Blanchard, P.; Nicholl, M.; Berger, E.

    2018-02-01

    We obtained optical spectroscopic observations of 2 transients reported to the Transient Name Server by the ATLAS survey (Tonry et al. 2011, PASP, 123, 58; Tonry et al., ATel #8680) and the Pan-STARRS Survey for Transients (PSST; Huber et al., ATel #7153; http://star.pst.qub.ac.uk/ps1threepi/).

  15. Thermodynamic properties for polycyclic systems by non-calorimetric methods

    Energy Technology Data Exchange (ETDEWEB)

    Steele, W.V.; Chirico, R.D.; Klots, T.D.

    1993-03-01

    A detailed vibrational spectroscopic study of furan, pyrrole, and thiophene has been completed. These compounds form part of the base of five-membered ring systems on which the rest of the research program will be built Several methyl-substituted derivatives were also studied. The results will be used to confirm the model for alkyl- substitution in the ring systems. Gas-phase spectra and fundamental- frequency assignments were completed for 2,3- and 2,5-dihydrofuran. Those compounds initiate work on ring-puckering within the research program. A paper describing the need for third virial estimation, when using the virial equation of state to derive thermodynamic properties at pressures greater than 1 bar was completed.

  16. On thermodynamic limits of entropy densities

    NARCIS (Netherlands)

    Moriya, H; Van Enter, A

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

  17. Thermodynamics of asymptotically safe theories

    DEFF Research Database (Denmark)

    Rischke, Dirk H.; Sannino, Francesco

    2015-01-01

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

  18. Thermodynamics of random number generation

    Science.gov (United States)

    Aghamohammadi, Cina; Crutchfield, James P.

    2017-06-01

    We analyze the thermodynamic costs of the three main approaches to generating random numbers via the recently introduced Information Processing Second Law. Given access to a specified source of randomness, a random number generator (RNG) produces samples from a desired target probability distribution. This differs from pseudorandom number generators (PRNGs) that use wholly deterministic algorithms and from true random number generators (TRNGs) in which the randomness source is a physical system. For each class, we analyze the thermodynamics of generators based on algorithms implemented as finite-state machines, as these allow for direct bounds on the required physical resources. This establishes bounds on heat dissipation and work consumption during the operation of three main classes of RNG algorithms—including those of von Neumann, Knuth, and Yao and Roche and Hoshi—and for PRNG methods. We introduce a general TRNG and determine its thermodynamic costs exactly for arbitrary target distributions. The results highlight the significant differences between the three main approaches to random number generation: One is work producing, one is work consuming, and the other is potentially dissipation neutral. Notably, TRNGs can both generate random numbers and convert thermal energy to stored work. These thermodynamic costs on information creation complement Landauer's limit on the irreducible costs of information destruction.

  19. Some Considerations about Thermodynamic Cycles

    Science.gov (United States)

    da Silva, M. F. Ferreira

    2012-01-01

    After completing their introductory studies on thermodynamics at the university level, typically in a second-year university course, most students show a number of misconceptions. In this work, we identify some of those erroneous ideas and try to explain their origins. We also give a suggestion to attack the problem through a systematic and…

  20. Thermodynamics on the Molality Scale

    Science.gov (United States)

    Canagaratna, Sebastian G.; Maheswaran, M.

    2013-01-01

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

  1. One Antimatter— Two Possible Thermodynamics

    Directory of Open Access Journals (Sweden)

    Alexander Y. Klimenko

    2014-02-01

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

  2. Conformal Gauge Transformations in Thermodynamics

    Directory of Open Access Journals (Sweden)

    Alessandro Bravetti

    2015-09-01

    Full Text Available In this work, we show that the thermodynamic phase space is naturally endowed with a non-integrable connection, defined by all of those processes that annihilate the Gibbs one-form, i.e., reversible processes. We argue that such a connection is invariant under re-scalings of the connection one-form, whilst, as a consequence of the non-integrability of the connection, its curvature is not and, therefore, neither is the associated pseudo-Riemannian geometry. We claim that this is not surprising, since these two objects are associated with irreversible processes. Moreover, we provide the explicit form in which all of the elements of the geometric structure of the thermodynamic phase space change under a re-scaling of the connection one-form. We call this transformation of the geometric structure a conformal gauge transformation. As an example, we revisit the change of the thermodynamic representation and consider the resulting change between the two metrics on the thermodynamic phase space, which induce Weinhold’s energy metric and Ruppeiner’s entropy metric. As a by-product, we obtain a proof of the well-known conformal relation between Weinhold’s and Ruppeiner’s metrics along the equilibrium directions. Finally, we find interesting properties of the almost para-contact structure and of its eigenvectors, which may be of physical interest.

  3. Thermodynamic basis for cluster kinetics

    DEFF Research Database (Denmark)

    Hu, Lina; Bian, Xiufang; Qin, Xubo

    2006-01-01

    Due to the inaccessibility of the supercooled region of marginal metallic glasses (MMGs) within the experimental time window, we study the cluster kinetics above the liquidus temperature, Tl, to acquire information on the fragility of the MMG systems. Thermodynamic basis for the stability...

  4. THERMODYNAMICS USED IN ENVIRONMENTAL ENGINEERING

    Science.gov (United States)

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

  5. A Simple Statistical Thermodynamics Experiment

    Science.gov (United States)

    LoPresto, Michael C.

    2010-01-01

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

  6. Simulating Metabolism with Statistical Thermodynamics

    Science.gov (United States)

    Cannon, William R.

    2014-01-01

    New methods are needed for large scale modeling of metabolism that predict metabolite levels and characterize the thermodynamics of individual reactions and pathways. Current approaches use either kinetic simulations, which are difficult to extend to large networks of reactions because of the need for rate constants, or flux-based methods, which have a large number of feasible solutions because they are unconstrained by the law of mass action. This report presents an alternative modeling approach based on statistical thermodynamics. The principles of this approach are demonstrated using a simple set of coupled reactions, and then the system is characterized with respect to the changes in energy, entropy, free energy, and entropy production. Finally, the physical and biochemical insights that this approach can provide for metabolism are demonstrated by application to the tricarboxylic acid (TCA) cycle of Escherichia coli. The reaction and pathway thermodynamics are evaluated and predictions are made regarding changes in concentration of TCA cycle intermediates due to 10- and 100-fold changes in the ratio of NAD+:NADH concentrations. Finally, the assumptions and caveats regarding the use of statistical thermodynamics to model non-equilibrium reactions are discussed. PMID:25089525

  7. Simulating metabolism with statistical thermodynamics.

    Science.gov (United States)

    Cannon, William R

    2014-01-01

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

  8. The ISOLDE experimental hall, wth the isotope separator in the upper left corner.

    CERN Multimedia

    CERN PhotoLab

    1969-01-01

    Beam tubes branch out from a switchyard, which by electrostatic deflectors direct beams of short-lived isotopes to various spectroscopic equipment. From left to right, Rudi Stoeckli at the separator control panel, Gilbert Droz and Henri Bersinger.

  9. Chemical Thermodynamics and Information Theory with Applications

    CERN Document Server

    Graham, Daniel J

    2011-01-01

    Thermodynamics and information touch theory every facet of chemistry. However, the physical chemistry curriculum digested by students worldwide is still heavily skewed toward heat/work principles established more than a century ago. Rectifying this situation, Chemical Thermodynamics and Information Theory with Applications explores applications drawn from the intersection of thermodynamics and information theory--two mature and far-reaching fields. In an approach that intertwines information science and chemistry, this book covers: The informational aspects of thermodynamic state equations The

  10. Thermodynamics of statistical inference by cells.

    Science.gov (United States)

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

    2014-10-03

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

  11. Some Trends in Quantum Thermodynamics

    Directory of Open Access Journals (Sweden)

    Michael R. von Spakovsky

    2014-06-01

    Full Text Available Traditional answers to what the 2nd Law is are well known. Some are based on the microstate of a system wandering rapidly through all accessible phase space, while others are based on the idea of a system occupying an initial multitude of states due to the inevitable imperfections of measurements that then effectively, in a coarse grained manner, grow in time (mixing. What has emerged are two somewhat less traditional approaches from which it is said that the 2nd Law emerges, namely, that of the theory of quantum open systems and that of the theory of typicality. These are the two principal approaches, which form the basis of what today has come to be called quantum thermodynamics. However, their dynamics remains strictly linear and unitary, and, as a number of recent publications have emphasized, “testing the unitary propagation of pure states alone cannot rule out a nonlinear propagation of mixtures”. Thus, a non-traditional approach to capturing such a propagation would be one which complements the postulates of QM by the 2nd Law of thermodynamics, resulting in a possibly meaningful, nonlinear dynamics. An unorthodox approach, which does just that, is intrinsic quantum thermodynamics and its mathematical framework, steepest-entropy-ascent quantum thermodynamics. The latter has evolved into an effective tool for modeling the dynamics of reactive and non-reactive systems at atomistic scales. It is the usefulness of this framework in the context of quantum thermodynamics as well as the theory of typicality which are discussed here in some detail. A brief discussion of some other trends such as those related to work, work extraction, and fluctuation theorems is also presented.

  12. The thermodynamic cube: A mnemonic and learning device for students of classical thermodynamics

    Science.gov (United States)

    Pate, Stephen F.

    1999-12-01

    The "thermodynamic cube," a mnemonic device for learning and recalling thermodynamic relations, is introduced. The cube is an extension of the familiar "thermodynamic square" seen in many textbooks. The cube reproduces the functions of the usual thermodynamic squares and incorporates the Euler relations which are not as well known.

  13. Thermodynamic magnon recoil for domain wall motion

    NARCIS (Netherlands)

    Yan, P.; Cao, Y.; Sinova, J.

    2015-01-01

    We predict a thermodynamic magnon recoil effect for domain wall motions in the presence of temperature gradients. All current thermodynamic theories assert that a magnetic domain wall must move toward the hotter side, based on equilibrium thermodynamic arguments. Microscopic calculations, on the

  14. Bioengineering Thermodynamics: An Engineering Science for Thermodynamics of Biosystems

    OpenAIRE

    Lucia, Umberto

    2015-01-01

    Cells are open complex thermodynamic systems. Energy transformations, thermo-electro-chemical processes and transports occur across the cells membranes. Different thermo-electro-biochemical behaviours occur between health and disease states. Moreover, living systems waste heat, the result of the internal irreversibility. This heat is dissipated into the environment. But, this wasted heat represent a sort of information, which outflows from the cell toward its environment, completely accessibl...

  15. Nano-spectroscopic imaging of intermolecular structure, coupling and dynamics

    CERN Document Server

    Pollard, Benjamin; Hinrichs, Karsten; Raschke, Markus B

    2013-01-01

    Molecular self-assembly, the function of biomembranes, and the performance of organic solar cells rely on molecular interactions on the nanoscale. The understanding and design of such intrinsic or engineered heterogeneous functional soft matter has long been impeded by a lack of spectroscopic tools with sufficient nanometer spatial resolution, attomolar sensitivity, and intermolecular spectroscopic specificity. We implement vibrational scattering-scanning near-field optical microscopy ($s$-SNOM) in a multi-spectral modality with unprecedented spectral precision to investigate the structure-function relationship in nano-phase separated block-copolymers. We use a vibrational resonance as a sensitive reporter of the local chemical environment and resolve, with few nanometer spatial resolution and 0.2 cm$^{-1}$ spectral precision, spectral Stark shifts and line broadening correlated with molecular-scale morphologies. By creating images of solvatochromic vibrational shifts we discriminate local variations in elect...

  16. The 1997 spectroscopic GEISA databank.

    Science.gov (United States)

    Jacquinet-Husson, N.; Arie, E.; Ballard, J.; Barbe, A.; Bjoraker, G.; Bonnet, B.; Brown, L. R.; Camy-Peyret, C.; Champion, J. P.; Chedin, A.; Chursin, A.; Clerbaux, C.; Duxbury, G.; Flaud, J.-M.; Fourrie, N.; Fayt, A.; Graner, G.; Gamache, R.; Goldman, A.; Golovko, V.; Guelachvili, G.; Hartmann, J. M.; Hilico, J. C.; Hillman, J.; Lefevre, G.; Lellouch, E.; Mikhailenko, S. N.; Naumenko, O. V.; Nemtchinov, V.; Newnham, D. A.; Nikitin, A.; Orphal, J.; Perrin, A.; Reuter, D. C.; Rinsland, C. P.; Rosenmann, L.; Rothman, L. S.; Scott, N. A.; Selby, J.; Sinitsa, L. N.; Sirota, J. M.; Smith, A. M.; Smith, K. M.; Tyuterev, V. G.; Tipping, R. H.; Urban, S.; Varanasi, P.; Weber, M.

    1999-05-01

    The current version GEISA-97 of the computer-accessible database system GEISA (Gestion et Etude des Informations Spectroscopiques Atmospheriques: Management and Study of Atmospheric Spectroscopic Information) is described. This catalogue contains 1,346,266 entries. These are the spectroscopic parameters required to describe adequately the individual spectral lines belonging to 42 molecules (96 isotopic species) and located between 0 and 22656 cm-1. The featured molecules are of interest in studies of the terrestrial as well as the other planetary atmospheres, especially those of the giant planets. GEISA-97 contains also a catalog of absorption cross-sections of molecules such as chlorofluorocarbons which exhibit unresolvable spectra. The modifications and improvements made to the earlier edition (GEISA-92) and the data management software are described.

  17. Classical thermodynamics of non-electrolyte solutions

    CERN Document Server

    Van Ness, H C

    1964-01-01

    Classical Thermodynamics of Non-Electrolyte Solutions covers the historical development of classical thermodynamics that concerns the properties of vapor and liquid solutions of non-electrolytes. Classical thermodynamics is a network of equations, developed through the formal logic of mathematics from a very few fundamental postulates and leading to a great variety of useful deductions. This book is composed of seven chapters and begins with discussions on the fundamentals of thermodynamics and the thermodynamic properties of fluids. The succeeding chapter presents the equations of state for

  18. Thermodynamic Fluid Equations-of-State

    Directory of Open Access Journals (Sweden)

    Leslie V. Woodcock

    2018-01-01

    Full Text Available As experimental measurements of thermodynamic properties have improved in accuracy, to five or six figures, over the decades, cubic equations that are widely used for modern thermodynamic fluid property data banks require ever-increasing numbers of terms with more fitted parameters. Functional forms with continuity for Gibbs density surface ρ(p,T which accommodate a critical-point singularity are fundamentally inappropriate in the vicinity of the critical temperature (Tc and pressure (pc and in the supercritical density mid-range between gas- and liquid-like states. A mesophase, confined within percolation transition loci that bound the gas- and liquid-state by third-order discontinuities in derivatives of the Gibbs energy, has been identified. There is no critical-point singularity at Tc on Gibbs density surface and no continuity of gas and liquid. When appropriate functional forms are used for each state separately, we find that the mesophase pressure functions are linear. The negative and positive deviations, for both gas and liquid states, on either side of the mesophase, are accurately represented by three or four-term virial expansions. All gaseous states require only known virial coefficients, and physical constants belonging to the fluid, i.e., Boyle temperature (TB, critical temperature (Tc, critical pressure (pc and coexisting densities of gas (ρcG and liquid (ρcL along the critical isotherm. A notable finding for simple fluids is that for all gaseous states below TB, the contribution of the fourth virial term is negligible within experimental uncertainty. Use may be made of a symmetry between gas and liquid states in the state function rigidity (dp/dρT to specify lower-order liquid-state coefficients. Preliminary results for selected isotherms and isochores are presented for the exemplary fluids, CO2, argon, water and SF6, with focus on the supercritical mesophase and critical region.

  19. Quantum Chemical Methods for the Prediction of Energetic, Physical, and Spectroscopic Properties of Ionic Liquids.

    Science.gov (United States)

    Izgorodina, Ekaterina I; Seeger, Zoe L; Scarborough, David L A; Tan, Samuel Y S

    2017-05-24

    The accurate prediction of physicochemical properties of condensed systems is a longstanding goal of theoretical (quantum) chemistry. Ionic liquids comprising entirely of ions provide a unique challenge in this respect due to the diverse chemical nature of available ions and the complex interplay of intermolecular interactions among them, thus resulting in the wide variability of physicochemical properties, such as thermodynamic, transport, and spectroscopic properties. It is well understood that intermolecular forces are directly linked to physicochemical properties of condensed systems, and therefore, an understanding of this relationship would greatly aid in the design and synthesis of functionalized materials with tailored properties for an application at hand. This review aims to give an overview of how electronic structure properties obtained from quantum chemical methods such as interaction/binding energy and its fundamental components, dipole moment, polarizability, and orbital energies, can help shed light on the energetic, physical, and spectroscopic properties of semi-Coulomb systems such as ionic liquids. Particular emphasis is given to the prediction of their thermodynamic, transport, spectroscopic, and solubilizing properties.

  20. Single nanoparticle tracking spectroscopic microscope

    Science.gov (United States)

    Yang, Haw [Moraga, CA; Cang, Hu [Berkeley, CA; Xu, Cangshan [Berkeley, CA; Wong, Chung M [San Gabriel, CA

    2011-07-19

    A system that can maintain and track the position of a single nanoparticle in three dimensions for a prolonged period has been disclosed. The system allows for continuously imaging the particle to observe any interactions it may have. The system also enables the acquisition of real-time sequential spectroscopic information from the particle. The apparatus holds great promise in performing single molecule spectroscopy and imaging on a non-stationary target.

  1. Spectroscopic Classification of Seven Supernovae

    Science.gov (United States)

    Blanchard, P.; Gomez, S.; Nicholl, M.; Berger, E.

    2018-01-01

    We obtained optical spectroscopic observations of 7 transients reported to the Transient Name Server by the ATLAS survey (Tonry et al. 2011, PASP, 123, 58; Tonry et al., ATel #8680), the Pan-STARRS Survey for Transients (PSST; Huber et al., ATel #7153; http://star.pst.qub.ac.uk/ps1threepi/), DPAC and the ESA Gaia Photometric Science Alerts Team (http://gsaweb.ast.cam.ac.uk/alerts), and the Tsinghua University-National Astronomical Observatories of China Transient Survey (TNTS).

  2. Multi-pass spectroscopic ellipsometry

    Energy Technology Data Exchange (ETDEWEB)

    Stehle, Jean-Louis [Sopralab, 7 rue du Moulin des Bruyeres, 92400 Courbevoie (France); Samartzis, Peter C., E-mail: sama@iesl.forth.gr [Institute of Electronic Structure and Laser, Foundation of Research and Technology-Hellas, Vassilika Vouton 71110, Heraklion Crete (Greece); Stamataki, Katerina [Institute of Electronic Structure and Laser, Foundation of Research and Technology-Hellas, Vassilika Vouton 71110, Heraklion Crete (Greece); Department of Chemistry, University of Crete, Voutes, 71003, Heraklion (Greece); Piel, Jean-Philippe [Sopralab, 7 rue du Moulin des Bruyeres, 92400 Courbevoie (France); Katsoprinakis, George E.; Papadakis, Vassilis [Institute of Electronic Structure and Laser, Foundation of Research and Technology-Hellas, Vassilika Vouton 71110, Heraklion Crete (Greece); Schimowski, Xavier [Sopralab, 7 rue du Moulin des Bruyeres, 92400 Courbevoie (France); Rakitzis, T. Peter [Institute of Electronic Structure and Laser, Foundation of Research and Technology-Hellas, Vassilika Vouton 71110, Heraklion Crete (Greece); Department of Physics, University of Crete, Voutes, 71003, Heraklion (Greece); Loppinet, Benoit [Institute of Electronic Structure and Laser, Foundation of Research and Technology-Hellas, Vassilika Vouton 71110, Heraklion Crete (Greece)

    2014-03-31

    Spectroscopic ellipsometry is an established technique, particularly useful for thickness measurements of thin films. It measures polarization rotation after a single reflection of a beam of light on the measured substrate at a given incidence angle. In this paper, we report the development of multi-pass spectroscopic ellipsometry where the light beam reflects multiple times on the sample. We have investigated both theoretically and experimentally the effect of sample reflectivity, number of reflections (passes), angles of incidence and detector dynamic range on ellipsometric observables tanΨ and cosΔ. The multiple pass approach provides increased sensitivity to small changes in Ψ and Δ, opening the way for single measurement determination of optical thickness T, refractive index n and absorption coefficient k of thin films, a significant improvement over the existing techniques. Based on our results, we discuss the strengths, the weaknesses and possible applications of this technique. - Highlights: • We present multi-pass spectroscopic ellipsometry (MPSE), a multi-pass approach to ellipsometry. • Different detectors, samples, angles of incidence and number of passes were tested. • N passes improve polarization ratio sensitivity to the power of N. • N reflections improve phase shift sensitivity by a factor of N. • MPSE can significantly improve thickness measurements in thin films.

  3. Thermodynamic constraints on fluctuation phenomena

    Science.gov (United States)

    Maroney, O. J. E.

    2009-12-01

    The relationships among reversible Carnot cycles, the absence of perpetual motion machines, and the existence of a nondecreasing globally unique entropy function form the starting point of many textbook presentations of the foundations of thermodynamics. However, the thermal fluctuation phenomena associated with statistical mechanics has been argued to restrict the domain of validity of this basis of the second law of thermodynamics. Here we demonstrate that fluctuation phenomena can be incorporated into the traditional presentation, extending rather than restricting the domain of validity of the phenomenologically motivated second law. Consistency conditions lead to constraints upon the possible spectrum of thermal fluctuations. In a special case this uniquely selects the Gibbs canonical distribution and more generally incorporates the Tsallis distributions. No particular model of microscopic dynamics need be assumed.

  4. Gravity and/is Thermodynamics

    CERN Document Server

    Padmanabhan, T

    2015-01-01

    The equations of motion describing all physical systems, except gravity, remain invariant if a constant is added to the Lagrangian. In the conventional approach, gravitational theories break this symmetry exhibited by all other physical systems. Restoring this symmetry to gravity and demanding that gravitational field equations should also remain invariant under the addition of a constant to a Lagrangian, leads to the interpretation of gravity as the thermodynamic limit of the kinetic theory of atoms of space. This approach selects, in a very natural fashion, Einstein's general relativity in $d=4$. Developing this paradigm at a deeper level, one can obtain the distribution function for the atoms of space and connect it up with the thermodynamic description of spacetime. This extension relies on a curious fact that the quantum spacetime endows each event with a finite area but zero volume. This approach allows us determine the numerical value of the cosmological constant and suggests a new perspective on cosmo...

  5. Thermodynamic Measure for Nonequilibrium Processes

    Directory of Open Access Journals (Sweden)

    Attila Grandpierre

    2007-07-01

    Full Text Available One of the most fundamental laws of Nature is formulated by the Second Law of Thermodynamics. At present, in its usual formulation the central concept is entropy characterized in terms of equilibrium state variables. We point out that because thermodynamic changes arise when systems are out of equilibrium and because entropy is not a natural state variable characterizing non-equilibrium states, a new formulation of the Second Law is required. In this paper, we introduce a new, more general, but still entropic measure that is suitable in non-equilibrium conditions as well. This new entropic measure has given a name extropy. The introduction of extropy allows us to formulate the Second Law in a more suitable and precise form, and it resolves some conceptual difficulties related to the interpretation of entropy. We point out that extropy has a fundamental significance in physics, in biology, and in our scientific worldview.

  6. Thermodynamic Model of Spatial Memory

    Science.gov (United States)

    Kaufman, Miron; Allen, P.

    1998-03-01

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

  7. Thermodynamic Calculations for Systems Biocatalysis

    DEFF Research Database (Denmark)

    Abu, Rohana; Gundersen, Maria T.; Woodley, John M.

    2015-01-01

    ‘Systems Biocatalysis’ is a term describing multi-enzyme processes in vitro for the synthesis of chemical products. Unlike in-vivo systems, such an artificial metabolism can be controlled in a highly efficient way in order to achieve a sufficiently favourable conversion for a given target product...... the transamination of a pro-chiral ketone into a chiral amine (interesting in many pharmaceutical applications). Here, the products are often less energetically stable than the reactants, meaning that the reaction may be thermodynamically unfavourable. As in nature, such thermodynamically-challenged reactions can...... energy change, View the MathML source ΔGro′, of the overall cascade. The findings show that unfavourable reactions in the cascade can be improved by coupling to a favourable reaction giving more energetically stable products....

  8. Statistical Thermodynamics of Economic Systems

    Directory of Open Access Journals (Sweden)

    Hernando Quevedo

    2011-01-01

    Full Text Available We formulate the thermodynamics of economic systems in terms of an arbitrary probability distribution for a conserved economic quantity. As in statistical physics, thermodynamic macroeconomic variables emerge as the mean value of microeconomic variables, and their determination is reduced to the computation of the partition function, starting from an arbitrary function. Explicit hypothetical examples are given which include linear and nonlinear economic systems as well as multiplicative systems such as those dominated by a Pareto law distribution. It is shown that the macroeconomic variables can be drastically changed by choosing the microeconomic variables in an appropriate manner. We propose to use the formalism of phase transitions to study severe changes of macroeconomic variables.

  9. Statistical thermodynamics of nonequilibrium processes

    CERN Document Server

    Keizer, Joel

    1987-01-01

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

  10. Fundamentals of Nano-Thermodynamics

    OpenAIRE

    Hartmann, M.; Mahler, G.; Hess, O.

    2004-01-01

    Recent progress in the synthesis and processing of nano-structured materials and systems calls for an improved understanding of thermal properties on small length scales. In this context, the question whether thermodynamics and, in particular, the concept of temperature can apply on the nanoscale is of central interest. Here we consider a quantum system consisting of a regular chain of elementary subsystems with nearest neighbour interactions and assume that the total system is in a canonical...

  11. Thermodynamics of freezing and melting

    OpenAIRE

    Pedersen, Ulf Rørbæk; Costigliola, Lorenzo; Bailey, Nicholas; Schrøder, Thomas; Dyre, Jeppe C.

    2016-01-01

    Although the freezing of liquids and melting of crystals are fundamental for many areas of the sciences, even simple properties like the temperature?pressure relation along the melting line cannot be predicted today. Here we present a theory in which properties of the coexisting crystal and liquid phases at a single thermodynamic state point provide the basis for calculating the pressure, density and entropy of fusion as functions of temperature along the melting line, as well as the variatio...

  12. Thermodynamic properties of sea air

    Directory of Open Access Journals (Sweden)

    R. Feistel

    2010-02-01

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

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

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

  13. Chiral thermodynamics of nuclear matter

    Energy Technology Data Exchange (ETDEWEB)

    Fiorilla, Salvatore

    2012-10-23

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

  14. Thermodynamic aspects of therapeutic hypothermia.

    Science.gov (United States)

    Vanlandingham, Sean C; Kurz, Michael C; Wang, Henry E

    2015-01-01

    Therapeutic hypothermia (TH) is an important treatment for post-cardiac arrest syndrome. Despite its widespread practice, only limited data describe the thermodynamic aspects of heat transfer during TH. This paper reviews the principles of human body heat balance and provides a conceptual model for characterizing heat exchange during TH. The model may provide a framework for computer simulation for improving training in or clinical methods of TH. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

  15. The Thermodynamics of Exercise Science

    OpenAIRE

    Simeoni, R. J.

    2014-01-01

    This article describes the “human body engine” via a thermodynamics-based model that considers the work associated with gas pressure, volume and temperature changes for the glucose-based equation of respiration. The efficacy of the model is supported by prior studies that: accurately predict the slow component of oxygen uptake kinetics; quantitatively explain observed race splitting strategies within endurance events; and accurately predict maximum velocities in endurance swimming. These pr...

  16. Thermodynamic functions of arsenic selenides

    Science.gov (United States)

    Babanly, D. M.; Velieva, G. M.; Imamaliyeva, S. Z.; Babanly, M. B.

    2017-07-01

    The solid-phase equilibria and thermodynamic properties of an As-Se system are studied using the electromotive force (EMF). The existence of compounds As2Se3, AsSe, and As4Se3 in a system with near constant composition is confirmed. The relative partial molar functions, standard Gibbs free energies, enthalpies of formation, and standard entropies of As in the alloys are calculated using EMF measurements.

  17. Hadron melting and QCD thermodynamics

    OpenAIRE

    Jakovac, A.

    2013-01-01

    We study in this paper mechanisms of hadron melting based on the spectral representation of hadronic quantum channels, and examine the hadron width dependence of the pressure. The findings are applied to a statistical hadron model of QCD thermodynamics, where hadron masses are distributed by the Hagedorn model and a uniform mechanism for producing hadron widths is assumed. According to this model the hadron - quark gluon plasma transition occurs at $T\\approx 200$-250 MeV, the numerically obse...

  18. Thermodynamical journey in plant biology

    Directory of Open Access Journals (Sweden)

    Adelin eBarbacci

    2015-06-01

    Full Text Available 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 process is modeled as an avalanche of dissipative structures. Each dissipative structure, corresponds to an unitary 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.

  19. Predicting RNA pseudoknot folding thermodynamics

    Science.gov (United States)

    Cao, Song; Chen, Shi-Jie

    2006-01-01

    Based on the experimentally determined atomic coordinates for RNA helices and the self-avoiding walks of the P (phosphate) and C4 (carbon) atoms in the diamond lattice for the polynucleotide loop conformations, we derive a set of conformational entropy parameters for RNA pseudoknots. Based on the entropy parameters, we develop a folding thermodynamics model that enables us to compute the sequence-specific RNA pseudoknot folding free energy landscape and thermodynamics. The model is validated through extensive experimental tests both for the native structures and for the folding thermodynamics. The model predicts strong sequence-dependent helix-loop competitions in the pseudoknot stability and the resultant conformational switches between different hairpin and pseudoknot structures. For instance, for the pseudoknot domain of human telomerase RNA, a native-like and a misfolded hairpin intermediates are found to coexist on the (equilibrium) folding pathways, and the interplay between the stabilities of these intermediates causes the conformational switch that may underlie a human telomerase disease. PMID:16709732

  20. Thermodynamic studies for drug design and screening.

    Science.gov (United States)

    Garbett, Nichola C; Chaires, Jonathan B

    2012-04-01

    A key part of drug design and development is the optimization of molecular interactions between an engineered drug candidate and its binding target. Thermodynamic characterization provides information about the balance of energetic forces driving binding interactions and is essential for understanding and optimizing molecular interactions. This review discusses the information that can be obtained from thermodynamic measurements and how this can be applied to the drug development process. Current approaches for the measurement and optimization of thermodynamic parameters are presented, specifically higher throughput and calorimetric methods. Relevant literature for this review was identified in part by bibliographic searches for the period 2004 - 2011 using the Science Citation Index and PUBMED and the keywords listed below. The most effective drug design and development platform comes from an integrated process utilizing all available information from structural, thermodynamic and biological studies. Continuing evolution in our understanding of the energetic basis of molecular interactions and advances in thermodynamic methods for widespread application are essential to realize the goal of thermodynamically driven drug design. Comprehensive thermodynamic evaluation is vital early in the drug development process to speed drug development toward an optimal energetic interaction profile while retaining good pharmacological properties. Practical thermodynamic approaches, such as enthalpic optimization, thermodynamic optimization plots and the enthalpic efficiency index, have now matured to provide proven utility in the design process. Improved throughput in calorimetric methods remains essential for even greater integration of thermodynamics into drug design. © 2012 Informa UK, Ltd.

  1. Thermodynamic Studies for Drug Design and Screening

    Science.gov (United States)

    Garbett, Nichola C.; Chaires, Jonathan B.

    2012-01-01

    Introduction A key part of drug design and development is the optimization of molecular interactions between an engineered drug candidate and its binding target. Thermodynamic characterization provides information about the balance of energetic forces driving binding interactions and is essential for understanding and optimizing molecular interactions. Areas covered This review discusses the information that can be obtained from thermodynamic measurements and how this can be applied to the drug development process. Current approaches for the measurement and optimization of thermodynamic parameters are presented, specifically higher throughput and calorimetric methods. Relevant literature for this review was identified in part by bibliographic searches for the period 2004 – 2011 using the Science Citation Index and PUBMED and the keywords listed below. Expert opinion The most effective drug design and development platform comes from an integrated process utilizing all available information from structural, thermodynamic and biological studies. Continuing evolution in our understanding of the energetic basis of molecular interactions and advances in thermodynamic methods for widespread application are essential to realize the goal of thermodynamically-driven drug design. Comprehensive thermodynamic evaluation is vital early in the drug development process to speed drug development towards an optimal energetic interaction profile while retaining good pharmacological properties. Practical thermodynamic approaches, such as enthalpic optimization, thermodynamic optimization plots and the enthalpic efficiency index, have now matured to provide proven utility in design process. Improved throughput in calorimetric methods remains essential for even greater integration of thermodynamics into drug design. PMID:22458502

  2. Study of interaction of butyl p-hydroxybenzoate with human serum albumin by molecular modeling and multi-spectroscopic method

    Energy Technology Data Exchange (ETDEWEB)

    Wang Qin, E-mail: wqing07@lzu.c [Department of Chemistry, Lanzhou University, Lanzhou 730000 (China); Zhang Yaheng, E-mail: zhangyah04@lzu.c [Department of Chemistry, Lanzhou University, Lanzhou 730000 (China); Sun Huijun, E-mail: sun.hui.jun-04@163.co [Department of Chemistry, Lanzhou University, Lanzhou 730000 (China); Chen Hongli, E-mail: hlchen@lzu.edu.c [Department of Chemistry, Lanzhou University, Lanzhou 730000 (China); Chen Xingguo, E-mail: chenxg@lzu.edu.c [Department of Chemistry, Lanzhou University, Lanzhou 730000 (China)

    2011-02-15

    Study of the interaction between butyl p-hydroxybenzoate (butoben) and human serum albumin (HSA) has been performed by molecular modeling and multi-spectroscopic method. The interaction mechanism was predicted through molecular modeling first, then the binding parameters were confirmed using a series of spectroscopic methods, including fluorescence spectroscopy, UV-visible absorbance spectroscopy, circular dichroism (CD) spectroscopy and Fourier transform infrared (FT-IR) spectroscopy. The thermodynamic parameters of the reaction, standard enthalpy {Delta}H{sup 0} and entropy {Delta}S{sup 0}, have been calculated to be -29.52 kJ mol{sup -1} and -24.23 J mol{sup -1} K{sup -1}, respectively, according to the Van't Hoff equation, which suggests the van der Waals force and hydrogen bonds are the predominant intermolecular forces in stabilizing the butoben-HSA complex. Results obtained by spectroscopic methods are consistent with that of the molecular modeling study. In addition, alteration of secondary structure of HSA in the presence of butoben was evaluated using the data obtained from UV-visible absorbance, CD and FT-IR spectroscopies. - Research highlights: The interaction between butyl p-hydroxybenzoate with HSA has been investigated for the first time. Molecular modeling study can provide theoretical direction for experimental design. Multi-spectroscopic method can provide the binding parameters and thermodynamic parameters. These results are important for food safety and human health when using parabens as a preservative.

  3. Spectroscopic Tools Applied to Element Z = 115 Decay Chains

    Directory of Open Access Journals (Sweden)

    Forsberg U.

    2014-03-01

    Full Text Available Nuclides that are considered to be isotopes of element Z = 115 were produced in the reaction 48Ca + 243Am at the GSI Helmholtzzentrum für Schwerionenforschung Darmstadt. The detector setup TASISpec was used. It was mounted behind the gas-filled separator TASCA. Thirty correlated α-decay chains were found, and the energies of the particles were determined with high precision. Two important spectroscopic aspects of the offline data analysis are discussed in detail: the handling of digitized preamplified signals from the silicon strip detectors, and the energy reconstruction of particles escaping to upstream detectors relying on pixel-by-pixel dead-layer thicknesses.

  4. Simulation models for food separation by adsorption process | Aoyi ...

    African Journals Online (AJOL)

    Separation of simulated industrial food products, by method of adsorption, has been studied. A thermodynamic approach has been applied to study the liquid adsorption where benzene and cyclohexane have been used to simulate edible oils in a system that employs silica gel as the adsorbent. Different models suggested ...

  5. Thermodynamics of Complexation between Thiourea-based Receptor and Acetate in Water/Acetonitrile Mixture.

    Science.gov (United States)

    Suzuki, Takaya; Shibuya, Yuuta; Sato, Takaya; Nishizawa, Seiichi; Sato, Itaru; Yamaguchi, Akira

    2016-01-01

    A thiourea-based receptor has been extensively studied for selective anion recognition for reasons of its strong hydrogen bond donor ability. In the present study, the thermodynamics of complexation between a thiourea-based receptor and acetate was examined in a water/acetonitrile mixture. The receptor used in this study was N,N'-bis(p-nitrophenyl)thiourea (BNPTU). UV/vis spectroscopic titration and isothermal titration calorimetry (ITC) experiments clearly revealed endothermic and entropy-driven complexation of BNPTU with acetate in water/acetonitrile mixtures. Since the endothermic peaks found in water/acetonitrile mixtures were about three times greater than those in acetonitrile, it appears that preferential hydration of both receptor and acetate was responsible for the endothermic and entropy-driven complexation reaction. The thermodynamic properties found in this study have the potential to contribute to the design of a thiourea-based anion receptor.

  6. Thermodynamics for Chemists, Physicists and Engineers

    CERN Document Server

    Hołyst, Robert

    2012-01-01

    Thermodynamics is an essential part of chemical physics and is of fundamental importance in physics, chemistry and engineering courses. This textbook takes an interdisciplinary approach to the subject and is therefore suitable for undergraduates in all those courses. The book is an introduction to phenomenological thermodynamics and its applications to phase transitions and chemical reactions, with some references to statistical mechanics. It strikes the balance between the rigorousness of the Callen text and phenomenological approach of the Atkins text. The book is divided in three parts. The first introduces the postulates and laws of thermodynamics and complements these initial explanations with practical examples. The second part is devoted to applications of thermodynamics to phase transitions in pure substances and mixtures. The third part covers thermodynamic systems in which chemical reactions take place. There are some sections on more advanced topics such as thermodynamic potentials, natural variabl...

  7. Spectroscopic and thermodynamic study of charge transfer complexes of cloxacillin sodium in aqueous ethanol medium

    Science.gov (United States)

    Roy, Dalim Kumar; Saha, Avijit; Mukherjee, Asok K.

    2005-07-01

    Cloxacillin sodium has been shown to form charge transfer (CT) complexes of 1:1 stoichiometry with a number of electron acceptors in 50% (v/v) aqueous ethanol medium. From the trends in the CT absorption bands, the vertical ionization potential of the drug molecule (cloxacillin sodium) has been estimated to be 7.89 eV. The enthalpies and entropies of formation of two such complexes have been determined by estimating the formation constants spectrophotometrically at five different temperatures. The oscillator strengths and transition dipole moments of these complexes have been determined. It has further been noted that the reduction of o-chloranil by aqueous ethanol is completely inhibited by cloxacillin sodium, a phenomenon that makes the present study of formation equilibrium possible.

  8. Thermodynamic studies on the recognition of flexible peptides by transition-metal complexes.

    Science.gov (United States)

    Sun, Shuguang; Fazal, Md Abul; Roy, Bidhan C; Chandra, Binita; Mallik, Sanku

    2002-03-25

    Strong and selective binding to a trihistidine peptide has been achieved employing Cu(2+)-histidine interactions in aqueous medium (25 mM HEPES buffer, pH 7.0). When the pattern of cupric ions on a complex matched with the pattern of histidines on the peptide, a strong and selective binding was observed. UV-vis spectroscopic studies show that the cupric ions coordinate to the histidines of the peptides. Thermodynamic studies reveal that the binding process is enthalpy driven over the entire range of working temperature (25-40 degrees C). An enthalpy-entropy compensation effect was also observed.

  9. Thermodynamics of random reaction networks.

    Directory of Open Access Journals (Sweden)

    Jakob Fischer

    Full Text Available Reaction networks are useful for analyzing reaction systems occurring in chemistry, systems biology, or Earth system science. Despite the importance of thermodynamic disequilibrium for many of those systems, the general thermodynamic properties of reaction networks are poorly understood. To circumvent the problem of sparse thermodynamic data, we generate artificial reaction networks and investigate their non-equilibrium steady state for various boundary fluxes. We generate linear and nonlinear networks using four different complex network models (Erdős-Rényi, Barabási-Albert, Watts-Strogatz, Pan-Sinha and compare their topological properties with real reaction networks. For similar boundary conditions the steady state flow through the linear networks is about one order of magnitude higher than the flow through comparable nonlinear networks. In all networks, the flow decreases with the distance between the inflow and outflow boundary species, with Watts-Strogatz networks showing a significantly smaller slope compared to the three other network types. The distribution of entropy production of the individual reactions inside the network follows a power law in the intermediate region with an exponent of circa -1.5 for linear and -1.66 for nonlinear networks. An elevated entropy production rate is found in reactions associated with weakly connected species. This effect is stronger in nonlinear networks than in the linear ones. Increasing the flow through the nonlinear networks also increases the number of cycles and leads to a narrower distribution of chemical potentials. We conclude that the relation between distribution of dissipation, network topology and strength of disequilibrium is nontrivial and can be studied systematically by artificial reaction networks.

  10. Thermodynamics of Random Reaction Networks

    Science.gov (United States)

    Fischer, Jakob; Kleidon, Axel; Dittrich, Peter

    2015-01-01

    Reaction networks are useful for analyzing reaction systems occurring in chemistry, systems biology, or Earth system science. Despite the importance of thermodynamic disequilibrium for many of those systems, the general thermodynamic properties of reaction networks are poorly understood. To circumvent the problem of sparse thermodynamic data, we generate artificial reaction networks and investigate their non-equilibrium steady state for various boundary fluxes. We generate linear and nonlinear networks using four different complex network models (Erdős-Rényi, Barabási-Albert, Watts-Strogatz, Pan-Sinha) and compare their topological properties with real reaction networks. For similar boundary conditions the steady state flow through the linear networks is about one order of magnitude higher than the flow through comparable nonlinear networks. In all networks, the flow decreases with the distance between the inflow and outflow boundary species, with Watts-Strogatz networks showing a significantly smaller slope compared to the three other network types. The distribution of entropy production of the individual reactions inside the network follows a power law in the intermediate region with an exponent of circa −1.5 for linear and −1.66 for nonlinear networks. An elevated entropy production rate is found in reactions associated with weakly connected species. This effect is stronger in nonlinear networks than in the linear ones. Increasing the flow through the nonlinear networks also increases the number of cycles and leads to a narrower distribution of chemical potentials. We conclude that the relation between distribution of dissipation, network topology and strength of disequilibrium is nontrivial and can be studied systematically by artificial reaction networks. PMID:25723751

  11. Interaction of methotrexate with trypsin analyzed by spectroscopic and molecular modeling methods

    Science.gov (United States)

    Wang, Yanqing; Zhang, Hongmei; Cao, Jian; Zhou, Qiuhua

    2013-11-01

    Trypsin is one of important digestive enzymes that have intimate correlation with human health and illness. In this work, the interaction of trypsin with methotrexate was investigated by spectroscopic and molecular modeling methods. The results revealed that methotrexate could interact with trypsin with about one binding site. Methotrexate molecule could enter into the primary substrate-binding pocket, resulting in inhibition of trypsin activity. Furthermore, the thermodynamic analysis implied that electrostatic force, hydrogen bonding, van der Waals and hydrophobic interactions were the main interactions for stabilizing the trypsin-methotrexate system, which agreed well with the results from the molecular modeling study.

  12. Thermodynamics of freezing and melting

    DEFF Research Database (Denmark)

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

    2016-01-01

    Although the freezing of liquids and melting of crystals are fundamental for many areas of the sciences, even simple properties like the temperature–pressure relation along the melting line cannot be predicted today. Here we present a theory in which properties of the coexisting crystal and liquid...... phases at a single thermodynamic state point provide the basis for calculating the pressure, density and entropy of fusion as functions of temperature along the melting line, as well as the variation along this line of the reduced crystalline vibrational mean-square displacement (the Lindemann ratio...

  13. Thermodynamics of the hot BIon

    DEFF Research Database (Denmark)

    Grignani, Gianluca; Harmark, Troels; Marini, Andrea

    2011-01-01

    We investigate the thermodynamics of the recently obtained nite temperature BIon solution of arXiv:1012.1494, focusing on two aspects. The first concerns comparison of the free energy of the three available phases for the finite temperature brane-antibrane wormhole configuration. Based on this we...... propose a heuristic picture for the dynamics of the phases that involves a critical temperature below which a stable phase exists. This stable phase is the finite temperature analogue of the thin throat branch of the extremal brane anti-brane wormhole configuration. The second aspect that we consider...

  14. An introduction to statistical thermodynamics

    CERN Document Server

    Hill, Terrell L

    1987-01-01

    ""A large number of exercises of a broad range of difficulty make this book even more useful…a good addition to the literature on thermodynamics at the undergraduate level."" - Philosophical MagazineAlthough written on an introductory level, this wide-ranging text provides extensive coverage of topics of current interest in equilibrium statistical mechanics. Indeed, certain traditional topics are given somewhat condensed treatment to allow room for a survey of more recent advances.The book is divided into four major sections. Part I deals with the principles of quantum statistical mechanics a

  15. Thermal physics kinetic theory and thermodynamics

    CERN Document Server

    Singh, Devraj; Yadav, Raja Ram

    2016-01-01

    THERMAL PHYSICS: Kinetic Theory and Thermodynamics is designed for undergraduate course in Thermal Physics and Thermodynamics. The book provides thorough understanding of the fundamental principles of the concepts in Thermal Physics. The book begins with kinetic theory, then moves on liquefaction, transport phenomena, the zeroth, first, second and third laws, thermodynamics relations and thermal conduction. The book concluded with radiation phenomenon. KEY FEATURES: * Include exercises * Short Answer Type Questions * Long Answer Type Questions * Numerical Problems * Multiple Choice Questions

  16. Quantum Thermodynamics with Degenerate Eigenstate Coherences

    Directory of Open Access Journals (Sweden)

    Gregory Bulnes Cuetara

    2016-12-01

    Full Text Available We establish quantum thermodynamics for open quantum systems weakly coupled to their reservoirs when the system exhibits degeneracies. The first and second law of thermodynamics are derived, as well as a finite-time fluctuation theorem for mechanical work and energy and matter currents. Using a double quantum dot junction model, local eigenbasis coherences are shown to play a crucial role on thermodynamics and on the electron counting statistics.

  17. Quantum thermodynamics: a nonequilibrium Green's function approach.

    Science.gov (United States)

    Esposito, Massimiliano; Ochoa, Maicol A; Galperin, Michael

    2015-02-27

    We establish the foundations of a nonequilibrium theory of quantum thermodynamics for noninteracting open quantum systems strongly coupled to their reservoirs within the framework of the nonequilibrium Green's functions. The energy of the system and its coupling to the reservoirs are controlled by a slow external time-dependent force treated to first order beyond the quasistatic limit. We derive the four basic laws of thermodynamics and characterize reversible transformations. Stochastic thermodynamics is recovered in the weak coupling limit.

  18. Thermodynamically consistent model calibration in chemical kinetics

    Directory of Open Access Journals (Sweden)

    Goutsias John

    2011-05-01

    Full Text Available Abstract Background The dynamics of biochemical reaction systems are constrained by the fundamental laws of thermodynamics, which impose well-defined relationships among the reaction rate constants characterizing these systems. Constructing biochemical reaction systems from experimental observations often leads to parameter values that do not satisfy the necessary thermodynamic constraints. This can result in models that are not physically realizable and may lead to inaccurate, or even erroneous, descriptions of cellular function. Results We introduce a thermodynamically consistent model calibration (TCMC method that can be effectively used to provide thermodynamically feasible values for the parameters of an open biochemical reaction system. The proposed method formulates the model calibration problem as a constrained optimization problem that takes thermodynamic constraints (and, if desired, additional non-thermodynamic constraints into account. By calculating thermodynamically feasible values for the kinetic parameters of a well-known model of the EGF/ERK signaling cascade, we demonstrate the qualitative and quantitative significance of imposing thermodynamic constraints on these parameters and the effectiveness of our method for accomplishing this important task. MATLAB software, using the Systems Biology Toolbox 2.1, can be accessed from http://www.cis.jhu.edu/~goutsias/CSS lab/software.html. An SBML file containing the thermodynamically feasible EGF/ERK signaling cascade model can be found in the BioModels database. Conclusions TCMC is a simple and flexible method for obtaining physically plausible values for the kinetic parameters of open biochemical reaction systems. It can be effectively used to recalculate a thermodynamically consistent set of parameter values for existing thermodynamically infeasible biochemical reaction models of cellular function as well as to estimate thermodynamically feasible values for the parameters of new

  19. Thermodynamics of Enzyme-Catalyzed Reactions Database

    Science.gov (United States)

    SRD 74 Thermodynamics of Enzyme-Catalyzed Reactions Database (Web, free access)   The Thermodynamics of Enzyme-Catalyzed Reactions Database contains thermodynamic data on enzyme-catalyzed reactions that have been recently published in the Journal of Physical and Chemical Reference Data (JPCRD). For each reaction the following information is provided: the reference for the data, the reaction studied, the name of the enzyme used and its Enzyme Commission number, the method of measurement, the data and an evaluation thereof.

  20. Treatise on irreversible and statistical thermodynamics an introduction to nonclassical thermodynamics

    CERN Document Server

    Yourgrau, Wolfgang; Raw, Gough

    2002-01-01

    Extensively revised edition of a much-respected work examines thermodynamics of irreversible processes, general principles of statistical thermodynamics, assemblies of noninteracting structureless particles, and statistical theory. 1966 edition.

  1. Black hole thermodynamics with conical defects

    Science.gov (United States)

    Appels, Michael; Gregory, Ruth; Kubizňák, David

    2017-05-01

    Recently we have shown [1] how to formulate a thermodynamic first law for a single (charged) accelerated black hole in AdS space by fixing the conical deficit angles present in the spacetime. Here we show how to generalise this result, formulating thermodynamics for black holes with varying conical deficits. We derive a new potential for the varying tension defects: the thermodynamic length, both for accelerating and static black holes. We discuss possible physical processes in which the tension of a string ending on a black hole might vary, and also map out the thermodynamic phase space of accelerating black holes and explore their critical phenomena.

  2. Coherence and measurement in quantum thermodynamics

    Science.gov (United States)

    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

  3. Spectroscopic insight for tablet compression.

    Science.gov (United States)

    Lakio, S; Ylinärä, H; Antikainen, O; Räikkönen, H; Yliruusi, J

    2015-02-01

    Tablet compression process has been studied over the years from various perspectives. However what exactly happens to material during compression is still unknown. In this study a novel compression die which enables real-time spectroscopic measurements during the compression of material is represented. Both near infrared and Raman spectroscope probes can be attached to the die. In this study the usage of the die is demonstrated by using Raman spectroscopy. Eicosane, d-glucose anhydrate, α-lactose monohydrate and xylitol were used in the study because their compression behavior and bonding properties during compression were assumed to be different. The intensity of the Raman signal changed during compression with all of the materials. However, the intensity changes were different within the materials. The biggest differences were within the xylitol spectra. It was noticed that some peaks disappeared with higher compression pressures indicating that the pressure affected variously on different bonds in xylitol structure. These reversible changes were supposed to relate the changes in conformation and crystal structure. As a conclusion, the die was found to be a significant addition for studying compression process in real-time. It can help to reveal Process induced transformations (PITs) occurring during powder compaction. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Phase Separation in Solutions of Monoclonal Antibodies

    Science.gov (United States)

    Benedek, George; Wang, Ying; Lomakin, Aleksey; Latypov, Ramil

    2012-02-01

    We report the observation of liquid-liquid phase separation (LLPS) in a solution of humanized monoclonal antibodies, IgG2, and the effects of human serum albumin, a major blood protein, on this phase separation. We find a significant reduction of phase separation temperature in the presence of albumin, and a preferential partitioning of the albumin into the antibody-rich phase. We provide a general thermodynamic analysis of the antibody-albumin mixture phase diagram and relate its features to the magnitude of the effective inter-protein interactions. Our analysis suggests that additives (HSA in this report), which have moderate attraction with antibody molecules, may be used to forestall undesirable protein condensation in antibody solutions. Our findings are relevant to understanding the stability of pharmaceutical solutions of antibodies and the mechanisms of cryoglobulinemia.

  5. Thermodynamic optimization of a Penrose process: an engineers' approach to black hole thermodynamics

    OpenAIRE

    Bravetti, Alessandro; Gruber, Christine; Lopez-Monsalvo, Cesar S.

    2015-01-01

    In this work we present a new view on the thermodynamics of black holes introducing effects of irreversibility by employing thermodynamic optimization and finite-time thermodynamics. These questions are of importance both in physics and in engineering, combining standard thermodynamics with optimal control theory in order to find optimal protocols and bounds for realistic processes without assuming anything about the microphysics involved. We find general bounds on the maximum work and the ef...

  6. Thermodynamic features of dioxins’ adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Prisciandaro, Marina [Department of Industrial and Information Engineering and of Economics, University of L’Aquila, Viale Giovanni Gronchi 18, L’Aquila 67100 (Italy); Piemonte, Vincenzo, E-mail: v.piemonte@unicampus.it [Faculty of Engineering, University Campus Biomedico of Rome, Via Alvaro del Portillo 21, Rome 00128 (Italy); Mazziotti di Celso, Giuseppe [Faculty of Bioscience, University of Teramo, Via R. Balzarini, 1, 64100 Teramo (Italy); Ronconi, Silvia [Arta Abruzzo, Department of L’Aquila, Bazzano (AQ), 67100 L’Aquila (Italy); Capocelli, Mauro [Faculty of Engineering, University Campus Biomedico of Rome, Via Alvaro del Portillo 21, Rome 00128 (Italy)

    2017-02-15

    Highlights: • We develop the P-T diagram for six PCDD. • We derive theoretical adsorption isotherms according to the Langmuir’s model. • We calculate K and w{sub max} values for several temperatures. • We estimate the adsorption heat with a good agreement with literature data. - Abstract: In this paper, the six more poisonous species among all congeners of dioxin group are taken into account, and the P-T diagram for each of them is developed. Starting from the knowledge of vapour tensions and thermodynamic parameters, the theoretical adsorption isotherms are calculated according to the Langmuir’s model. In particular, the Langmuir isotherm parameters (K and w{sub max}) have been validated through the estimation of the adsorption heat (ΔH{sub ads}), which varies in the range 20–24 kJ/mol, in agreement with literature values. This result will allow to put the thermodynamical basis for a rational design of different process units devoted to dioxins removal.

  7. Bioengineering thermodynamics of biological cells.

    Science.gov (United States)

    Lucia, Umberto

    2015-12-01

    Cells are open complex thermodynamic systems. They can be also regarded as complex engines that execute a series of chemical reactions. Energy transformations, thermo-electro-chemical processes and transports phenomena can occur across the cells membranes. Moreover, cells can also actively modify their behaviours in relation to changes in their environment. Different thermo-electro-biochemical behaviours occur between health and disease states. But, all the living systems waste heat, which is no more than the result of their internal irreversibility. This heat is dissipated into the environment. But, this wasted heat represent also a sort of information, which outflows from the cell toward its environment, completely accessible to any observer. The analysis of irreversibility related to this wasted heat can represent a new approach to study the behaviour of the cells themselves and to control their behaviours. So, this approach allows us to consider the living systems as black boxes and analyze only the inflows and outflows and their changes in relation to the modification of the environment. Therefore, information on the systems can be obtained by analyzing the changes in the cell heat wasted in relation to external perturbations. The bioengineering thermodynamics bases are summarized and used to analyse possible controls of the calls behaviours based on the control of the ions fluxes across the cells membranes.

  8. Thermodynamic indicators for environmental certification.

    Science.gov (United States)

    Panzieri, Margherita; Porcelli, Marcello; Pulselli, Federico Maria

    2002-09-01

    The Earth is an open thermodynamic system, that remains in a steady state far from the equilibrium, through energy and matter exchanges with the surrounding environment. These natural constraints, which prevent the system from maximizing its entropy, are threatened by human action and our ecosystem needs urgent protection. In this viewpoint the environmental certification was born, according to international standards ISO 14001, ISO 14040, and European Regulation EMAS. These are voluntary adhesions to a program of environmental protection by companies, administrations and organizations which, starting from the respect of the existing environmental laws and regulations, decide to further improve their environmental performance. To obtain and maintain certification of a system is necessary to apply some indicators to evaluate its environmental performance and to demonstrate its progressive improvement. Here we propose to use for this purpose the thermodynamic indicators produced from energy analysis by Odum. The case study is Montalcino city (Italy) and energy indicators are used to evaluate environmental performance of this system where exist different activities, from agricultural productions, to tourism. Results show that energy analysis could become a valid standard monitoring method for environmental certification, especially in consideration of its wide application field.

  9. Fictional Separation Logic

    DEFF Research Database (Denmark)

    Jensen, Jonas Buhrkal; Birkedal, Lars

    2012-01-01

    , separation means physical separation. In this paper, we introduce \\emph{fictional separation logic}, which includes more general forms of fictional separating conjunctions P * Q, where "*" does not require physical separation, but may also be used in situations where the memory resources described by P and Q...... overlap. We demonstrate, via a range of examples, how fictional separation logic can be used to reason locally and modularly about mutable abstract data types, possibly implemented using sophisticated sharing. Fictional separation logic is defined on top of standard separation logic, and both the meta...

  10. Separating biological cells

    Science.gov (United States)

    Brooks, D. E.

    1979-01-01

    Technique utilizing electric field to promote biological cell separation from suspending medium in zero gravity increases speed, reduces sedimentation, and improves efficiency of separation in normal gravity.

  11. Raman Spectroscopic Studies of Methane Gas Hydrates

    DEFF Research Database (Denmark)

    Hansen, Susanne Brunsgaard; Berg, Rolf W.

    2009-01-01

    A brief review of the Raman spectroscopic studies of methane gas hydrates is given, supported by some new measurements done in our laboratory.......A brief review of the Raman spectroscopic studies of methane gas hydrates is given, supported by some new measurements done in our laboratory....

  12. CHROMATOGRAPHIC SEPARATION AND SPECTRO ...

    African Journals Online (AJOL)

    contain aromatic nucleus based on IR and UV-VIS spectroscopic data. Other functional groups ... There are two types of dyes: natural and synthetic dyes; natural dyes include plant dyes, animal dyes and mineral ... direction that depend on the crystal structure of the sample and the resulting X-ray diffraction pattern is unique ...

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

    CERN Document Server

    Mitra, Saugata; Chakraborty, Subenoy

    2016-01-01

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

  14. Balanced Biochemical Reactions: A New Approach to Unify Chemical and Biochemical Thermodynamics

    Science.gov (United States)

    Sabatini, Antonio; Vacca, Alberto; Iotti, Stefano

    2012-01-01

    A novel procedure is presented which, by balancing elements and electric charge of biochemical reactions which occur at constant pH and pMg, allows assessing the thermodynamics properties of reaction ΔrG′0, ΔrH′0, ΔrS′0 and the change in binding of hydrogen and magnesium ions of these reactions. This procedure of general applicability avoids the complex calculations required by the use of the Legendre transformed thermodynamic properties of formation ΔfG′0, ΔfH′0 and ΔfS′0 hitherto considered an obligatory prerequisite to deal with the thermodynamics of biochemical reactions. As a consequence, the term “conditional” is proposed in substitution of “Legendre transformed” to indicate these thermodynamics properties. It is also shown that the thermodynamic potential G is fully adequate to give a criterion of spontaneous chemical change for all biochemical reactions and then that the use of the Legendre transformed G′ is unnecessary. The procedure proposed can be applied to any biochemical reaction, making possible to re-unify the two worlds of chemical and biochemical thermodynamics, which so far have been treated separately. PMID:22247780

  15. Balanced biochemical reactions: a new approach to unify chemical and biochemical thermodynamics.

    Science.gov (United States)

    Sabatini, Antonio; Vacca, Alberto; Iotti, Stefano

    2012-01-01

    A novel procedure is presented which, by balancing elements and electric charge of biochemical reactions which occur at constant pH and pMg, allows assessing the thermodynamics properties of reaction Δ(r)G'⁰, Δ(r)H'⁰, Δ(r)S'⁰ and the change in binding of hydrogen and magnesium ions of these reactions. This procedure of general applicability avoids the complex calculations required by the use of the Legendre transformed thermodynamic properties of formation Δ(f)G'⁰, Δ(f)H'⁰ and Δ(f)S'⁰ hitherto considered an obligatory prerequisite to deal with the thermodynamics of biochemical reactions. As a consequence, the term "conditional" is proposed in substitution of "Legendre transformed" to indicate these thermodynamics properties. It is also shown that the thermodynamic potential G is fully adequate to give a criterion of spontaneous chemical change for all biochemical reactions and then that the use of the Legendre transformed G' is unnecessary. The procedure proposed can be applied to any biochemical reaction, making possible to re-unify the two worlds of chemical and biochemical thermodynamics, which so far have been treated separately.

  16. Balanced biochemical reactions: a new approach to unify chemical and biochemical thermodynamics.

    Directory of Open Access Journals (Sweden)

    Antonio Sabatini

    Full Text Available A novel procedure is presented which, by balancing elements and electric charge of biochemical reactions which occur at constant pH and pMg, allows assessing the thermodynamics properties of reaction Δ(rG'⁰, Δ(rH'⁰, Δ(rS'⁰ and the change in binding of hydrogen and magnesium ions of these reactions. This procedure of general applicability avoids the complex calculations required by the use of the Legendre transformed thermodynamic properties of formation Δ(fG'⁰, Δ(fH'⁰ and Δ(fS'⁰ hitherto considered an obligatory prerequisite to deal with the thermodynamics of biochemical reactions. As a consequence, the term "conditional" is proposed in substitution of "Legendre transformed" to indicate these thermodynamics properties. It is also shown that the thermodynamic potential G is fully adequate to give a criterion of spontaneous chemical change for all biochemical reactions and then that the use of the Legendre transformed G' is unnecessary. The procedure proposed can be applied to any biochemical reaction, making possible to re-unify the two worlds of chemical and biochemical thermodynamics, which so far have been treated separately.

  17. Thermodynamic activity-based intrinsic enzyme kinetic sheds light on enzyme-solvent interactions.

    Science.gov (United States)

    Grosch, Jan-Hendrik; Wagner, David; Nistelkas, Vasilios; Spieß, Antje C

    2017-01-01

    The reaction medium has major impact on biocatalytic reaction systems and on their economic significance. To allow for tailored medium engineering, thermodynamic phenomena, intrinsic enzyme kinetics, and enzyme-solvent interactions have to be discriminated. To this end, enzyme reaction kinetic modeling was coupled with thermodynamic calculations based on investigations of the alcohol dehydrogenase from Lactobacillus brevis (LbADH) in monophasic water/methyl tert-butyl ether (MTBE) mixtures as a model solvent. Substrate concentrations and substrate thermodynamic activities were varied separately to identify the individual thermodynamic and kinetic effects on the enzyme activity. Microkinetic parameters based on concentration and thermodynamic activity were derived to successfully identify a positive effect of MTBE on the availability of the substrate to the enzyme, but a negative effect on the enzyme performance. In conclusion, thermodynamic activity-based kinetic modeling might be a suitable tool to initially curtail the type of enzyme-solvent interactions and thus, a powerful first step to potentially understand the phenomena that occur in nonconventional media in more detail. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 33:96-103, 2017. © 2016 American Institute of Chemical Engineers.

  18. Thermodynamic equilibrium at heterogeneous pressure

    Science.gov (United States)

    Vrijmoed, Johannes C.; Podladchikov, Yuri Y.

    2014-05-01

    Recent advances in metamorphic petrology point out the importance of grain-scale pressure variations in high-temperature metamorphic rocks. Pressures derived from chemical zonation using unconventional geobarometry based on equal chemical potentials fit mechanically feasible pressure variations. Here a thermodynamic equilibrium method is presented that predicts chemical zoning as a result of pressure variations by Gibbs energy minimization. Equilibrium thermodynamic prediction of the chemical zoning in the case of pressure heterogeneity is done by constraint Gibbs minimization using linear programming techniques. Compositions of phases considered in the calculation are discretized into 'pseudo-compounds' spanning the entire compositional space. Gibbs energies of these discrete compounds are generated for a given range and resolution of pressures for example derived by barometry or from mechanical model predictions. Gibbs energy minimization is subsequently performed considering all compounds of different composition and pressure. In addition to constraining the system composition a certain proportion of the system is constraint at a specified pressure. Input pressure variations need to be discretized and each discrete pressure defines an additional constraint for the minimization. The proportion of the system at each different pressure is equally distributed over the number of input pressures. For example if two input pressures P1 and P2 are specified, two constraints are added: 50 percent of the system is constraint at P1 while the remaining 50 percent is constraint at P2. The method has been tested for a set of 10 input pressures obtained by Tajčmanová et al. (2014) using their unconventional geobarometry method in a plagioclase rim around kyanite. Each input pressure is added as constraint to the minimization (1/10 percent of the system for each discrete pressure). Constraining the system composition to the average composition of the plagioclase rim

  19. Impact of Thermodynamic Principles in Systems Biology

    NARCIS (Netherlands)

    Heijnen, J.J.

    2010-01-01

    It is shown that properties of biological systems which are relevant for systems biology motivated mathematical modelling are strongly shaped by general thermodynamic principles such as osmotic limit, Gibbs energy dissipation, near equilibria and thermodynamic driving force. Each of these aspects

  20. Simple, Chemoselective Hydrogenation with Thermodynamic Stereocontrol

    OpenAIRE

    Iwasaki, Kotaro; Wan, Kanny K.; Oppedisano, Alberto; Crossley, Steven W. M.; Shenvi, Ryan A.

    2014-01-01

    Few methods permit the hydrogenation of alkenes to a thermodynamically favored configuration when steric effects dictate the alternative trajectory of hydrogen delivery. Dissolving metal reduction achieves this control, but with extremely low functional group tolerance. Here we demonstrate a catalytic hydrogenation of alkenes that affords the thermodynamic alkane products with remarkably broad functional group compatibility and rapid reaction rates at standard temperature and pressure.

  1. Simple, chemoselective hydrogenation with thermodynamic stereocontrol.

    Science.gov (United States)

    Iwasaki, Kotaro; Wan, Kanny K; Oppedisano, Alberto; Crossley, Steven W M; Shenvi, Ryan A

    2014-01-29

    Few methods permit the hydrogenation of alkenes to a thermodynamically favored configuration when steric effects dictate the alternative trajectory of hydrogen delivery. Dissolving metal reduction achieves this control, but with extremely low functional group tolerance. Here we demonstrate a catalytic hydrogenation of alkenes that affords the thermodynamic alkane products with remarkably broad functional group compatibility and rapid reaction rates at standard temperature and pressure.

  2. Warming to ecocide a thermodynamic diagnosis

    CERN Document Server

    Sangster, Alan J

    2011-01-01

    Suggests a route to avoiding runaway climate change by reinstating the greenhouse thermostat to its full operational capacity Addresses mankind's contribution to climate change from a thermodynamic perspective Describes and illustrates the power of thermodynamics to furnish insights into the thermal behaviour of complex physical systems

  3. Thermodynamic Ground States of Complex Oxide Heterointerfaces

    DEFF Research Database (Denmark)

    Gunkel, F.; Hoffmann-Eifert, S.; Heinen, R. A.

    2017-01-01

    The formation mechanism of 2-dimensional electron gases (2DEGs) at heterointerfaces between nominally insulating oxides is addressed with a thermodynamical approach. We provide a comprehensive analysis of the thermodynamic ground states of various 2DEG systems directly probed in high temperature...

  4. An Experimental Determination of Thermodynamic Values

    Science.gov (United States)

    Antony, Erling; Muccianti, Christine; Vogel, Tracy

    2012-01-01

    Measurements have been added to an old demonstration of chemical equilibria allowing the determination of thermodynamic constants. The experiment allows the students an opportunity to merge qualitative observations associated with Le Chatelier's principle and thermodynamic calculations using graphical techniques. (Contains 4 figures.)

  5. Detonation Jet Engine. Part 1--Thermodynamic Cycle

    Science.gov (United States)

    Bulat, Pavel V.; Volkov, Konstantin N.

    2016-01-01

    We present the most relevant works on jet engine design that utilize thermodynamic cycle of detonative combustion. The efficiency advantages of thermodynamic detonative combustion cycle over Humphrey combustion cycle at constant volume and Brayton combustion cycle at constant pressure were demonstrated. An ideal Ficket-Jacobs detonation cycle, and…

  6. Thermodynamic Property Needs for the Oleochemical Industry

    DEFF Research Database (Denmark)

    Ana Perederic, Olivia; Kalakul, Sawitree; Sarup, Bent

    and/or reliable thermodynamic models for the chemicals involved. Limited availability ofconsistent physical and thermodynamic properties of lipids compounds and their mixtures lead to difficulties with the use of process simulators for process synthesis and design, since all themodels to be used...

  7. Thermodynamics of charged and rotating black strings

    Science.gov (United States)

    Fatima, Aeeman; Saifullah, K.

    2012-10-01

    We study thermodynamics of cylindrically symmetric black holes. Uncharged as well as charged and rotating objects have been discussed. We derive surface gravity and hence the Hawking temperature and entropy for all these cases. We correct some results in the literature and present new ones. It is seen that thermodynamically these black configurations behave differently from spherically symmetric objects.

  8. Thermodynamics and heat transfer in fire fighting

    Science.gov (United States)

    Romanenko, P. N.; Koshmarov, Y. A.; Bashkirtsev, M. P.

    1985-05-01

    The book presents the fundamental principles of thermodynamics and heat transfer with particular reference to their application in problems related to fire prevention. Special attention is given to the study of unsteady heat transfer, radiant heat transfer (including radiation from flames to the surrounding), thermodynamic analysis of the growth of fires and theoretical modeling of fires in building.

  9. The thermodynamic solar energy; Le solaire thermodynamique

    Energy Technology Data Exchange (ETDEWEB)

    Rivoire, B. [Centre National de la Recherche Scientifique (CNRS-IMP), 66 - Perpignan (France)

    2002-04-01

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

  10. Understanding the Thermodynamics of Biological Order

    Science.gov (United States)

    Peterson, Jacob

    2012-01-01

    By growth in size and complexity (i.e., changing from more probable to less probable states), plants and animals appear to defy the second law of thermodynamics. The usual explanation describes the input of nutrient and sunlight energy into open thermodynamic systems. However, energy input alone does not address the ability to organize and create…

  11. Friction Force: From Mechanics to Thermodynamics

    Science.gov (United States)

    Ferrari, Christian; Gruber, Christian

    2010-01-01

    We study some mechanical problems in which a friction force is acting on a system. Using the fundamental concepts of state, time evolution and energy conservation, we explain how to extend Newtonian mechanics to thermodynamics. We arrive at the two laws of thermodynamics and then apply them to investigate the time evolution and heat transfer of…

  12. Teaching Differentials in Thermodynamics Using Spatial Visualization

    Science.gov (United States)

    Wang, Chih-Yueh; Hou, Ching-Han

    2012-01-01

    The greatest difficulty that is encountered by students in thermodynamics classes is to find relationships between variables and to solve a total differential equation that relates one thermodynamic state variable to two mutually independent state variables. Rules of differentiation, including the total differential and the cyclic rule, are…

  13. Controlling Separation in Turbomachines

    Science.gov (United States)

    Evans, Simon; Himmel, Christoph; Power, Bronwyn; Wakelam, Christian; Xu, Liping; Hynes, Tom; Hodson, Howard

    2010-01-01

    Four examples of flow control: 1) Passive control of LP turbine blades (Laminar separation control). 2) Aspiration of a conventional axial compressor blade (Turbulent separation control). 3) Compressor blade designed for aspiration (Turbulent separation control). 4.Control of intakes in crosswinds (Turbulent separation control).

  14. Composite heat damage spectroscopic analysis

    Energy Technology Data Exchange (ETDEWEB)

    Janke, C.J.; Muhs, J.D.; Wachter, E.A.; Ziegler, R.E. (Oak Ridge National Lab., TN (USA)); Powell, G.L.; Smyrl, N.R. (Oak Ridge Y-12 Plant, TN (USA)); Philpot, H.E. (Oak Ridge Gaseous Diffusion Plant, TN (USA))

    1990-09-01

    The Oak Ridge National Laboratory/Applied Technology Division (ORNL/ATD) has successfully demonstrated the unique applicability of two spectroscopic techniques that possess the capability of detecting heat damage in IM6/3501-6 laminates and correlation of this damage with the residual mechanical-strength properties. The results on the diffuse reflectance infrared fourier transform (DRIFT) and laser-pumped fluorescence (LPF) spectroscopic techniques, which are capable of rapid, in-service, non-destructive detection and quantitation of heat damage in IM6/3501-6 laminates, is presented. Both of these techniques have been shown to be quite effective at probing the elusive and complex molecular changes that take place in IM6/3501-6 laminates subjected to varying degrees of thermal degradation. Using LPF or DRIFT techniques, it has been shown that laminates having different thermal histories can be readily differentiated from one another due to their characteristic fingerprint'' spectral features. The effects of short-term, elevated temperature heating on the room- temperature compressive interlaminar-shear, and flexural strengths and room-temperature shore-D hardness properties of dry'' and wet'' preconditioned IM6/3501-6 laminates are discussed. Additionally, the geometrical changes and percent-weight-loss measurements of IM6/3501-6 laminates that accompany heat damage are also examined. It was found that below a certain temperature/time exposure threshold, these laminates visually and microscopically appeared to be undamaged but, in fact, may have lost a significant percentage of their original strength. In addition, laminates that were exposed above the temperature/time exposure threshold suffered dramatic geometrical changes and large amounts of weight loss. 32 refs., 39 figs., 10 tabs.

  15. An introduction to thermodynamics and statistical mechanics

    CERN Document Server

    Saxena, A K

    2016-01-01

    An Introduction to Thermodynamics and Statistical Mechanics aims to serve as a text book for undergraduate hons.and postgraduate students of physics. The book covers First Law of Thermodynamics, Entropy and Second Law ofThermodynamics, Thermodynamic Relations, The Statistical Basis of Thermodynamics, Microcanonical Ensemble,Classical Statistical and Canonical Distribution, Grand Canonical Ensemble, Quantum Statistical Mechanics, PhaseTransitions, Fluctuations, Irreversible Processes and Transport Phenomena (Diffusion).SALIENT FEATURES:iC* Offers students a conceptual development of the subjectiC* Review questions at the end of chapters.NEW TO THE SECOND EDITIONiC* PVT SurfacesiC* Real Heat EnginesiC* Van der Waals Models (Qualitative Considerations)iC* Cluster ExpansioniC* Brownian Motion (Einstein's Theory)

  16. Nonequilibrium thermodynamics of restricted Boltzmann machines

    Science.gov (United States)

    Salazar, Domingos S. P.

    2017-08-01

    In this work, we analyze the nonequilibrium thermodynamics of a class of neural networks known as restricted Boltzmann machines (RBMs) in the context of unsupervised learning. We show how the network is described as a discrete Markov process and how the detailed balance condition and the Maxwell-Boltzmann equilibrium distribution are sufficient conditions for a complete thermodynamics description, including nonequilibrium fluctuation theorems. Numerical simulations in a fully trained RBM are performed and the heat exchange fluctuation theorem is verified with excellent agreement to the theory. We observe how the contrastive divergence functional, mostly used in unsupervised learning of RBMs, is closely related to nonequilibrium thermodynamic quantities. We also use the framework to interpret the estimation of the partition function of RBMs with the annealed importance sampling method from a thermodynamics standpoint. Finally, we argue that unsupervised learning of RBMs is equivalent to a work protocol in a system driven by the laws of thermodynamics in the absence of labeled data.

  17. eQuilibrator—the biochemical thermodynamics calculator

    Science.gov (United States)

    Flamholz, Avi; Noor, Elad; Bar-Even, Arren; Milo, Ron

    2012-01-01

    The laws of thermodynamics constrain the action of biochemical systems. However, thermodynamic data on biochemical compounds can be difficult to find and is cumbersome to perform calculations with manually. Even simple thermodynamic questions like ‘how much Gibbs energy is released by ATP hydrolysis at pH 5?’ are complicated excessively by the search for accurate data. To address this problem, eQuilibrator couples a comprehensive and accurate database of thermodynamic properties of biochemical compounds and reactions with a simple and powerful online search and calculation interface. The web interface to eQuilibrator (http://equilibrator.weizmann.ac.il) enables easy calculation of Gibbs energies of compounds and reactions given arbitrary pH, ionic strength and metabolite concentrations. The eQuilibrator code is open-source and all thermodynamic source data are freely downloadable in standard formats. Here we describe the database characteristics and implementation and demonstrate its use. PMID:22064852

  18. Horizon thermodynamics in fourth-order gravity

    Directory of Open Access Journals (Sweden)

    Meng-Sen Ma

    2017-03-01

    Full Text Available In the framework of horizon thermodynamics, the field equations of Einstein gravity and some other second-order gravities can be rewritten as the thermodynamic identity: dE=TdS−PdV. However, in order to construct the horizon thermodynamics in higher-order gravity, we have to simplify the field equations firstly. In this paper, we study the fourth-order gravity and convert it to second-order gravity via a so-called “Legendre transformation” at the cost of introducing two other fields besides the metric field. With this simplified theory, we implement the conventional procedure in the construction of the horizon thermodynamics in 3 and 4 dimensional spacetime. We find that the field equations in the fourth-order gravity can also be written as the thermodynamic identity. Moreover, we can use this approach to derive the same black hole mass as that by other methods.

  19. Separation and determination of some carboxylic acids by capillary electrophoresis

    Energy Technology Data Exchange (ETDEWEB)

    Sladkov, V.; Fourest, B

    2006-07-01

    Separation and determination of some organic acids, mono-carboxylic (formic and acetic), dicarboxylic (oxalic and tartaric), tricarboxylic (citric) acids and aromatic acids (phtalic, benzoic, mellitic and trimellitic), by capillary electrophoresis are reviewed. The method development parameters, such as separation and injection mode, are discussed. Special attention is paid to the comparison of different detection types (spectroscopic and electrochemical). The optimisation of the carrier electrolyte composition (choice of carrier electrolyte, effect of pH, ionic strength, electro-osmotic flow modifier) is treated. Different additives (alkali-earth and transition metal ions, cyclodextrins and alcohol), which are often used for improving organic acid separation, are also considered. (authors)

  20. Advanced working fluids: Thermodynamic properties

    Science.gov (United States)

    Lee, Lloyd L.; Gering, Kevin L.

    1990-10-01

    Electrolytes are used as working fluids in gas fired heat pump chiller engine cycles. To find out which molecular parameters of the electrolytes impact on cycle performance, a molecular theory is developed for calculating solution properties, enthalpies, vapor-liquid equilibria, and engine cycle performance. Aqueous and ammoniac single and mixed salt solutions in single and multisolvent systems are investigated. An accurate correlation is developed to evaluate properties for concentrated electrolyte solutions. Sensitivity analysis is used to determine the impact of molecular parameters on the thermodynamic properties and cycle performance. The preferred electrolytes are of 1-1 valence type, small ion size, high molecular weight, and in strongly colligative cosolvent. The operating windows are determined for a number of absorption fluids of industrial importance.

  1. Thermodynamic cost of external control

    Science.gov (United States)

    Barato, Andre C.; Seifert, Udo

    2017-07-01

    Artificial molecular machines are often driven by the periodic variation of an external parameter. This external control exerts work on the system of which a part can be extracted as output if the system runs against an applied load. Usually, the thermodynamic cost of the process that generates the external control is ignored. Here, we derive a refined second law for such small machines that include this cost, which is, for example, generated by free energy consumption of a chemical reaction that modifies the energy landscape for such a machine. In the limit of irreversible control, this refined second law becomes the standard one. Beyond this ideal limiting case, our analysis shows that due to a new entropic term unexpected regimes can occur: the control work can be smaller than the extracted work and the work required to generate the control can be smaller than this control work. Our general inequalities are illustrated by a paradigmatic three-state system.

  2. Quantum cosmic models and thermodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez-Diaz, Pedro F; Rozas-Fernandez, Alberto [Colina de los Chopos, Centro de Fisica ' Miguel A Catalan' , Instituto de Fisica Fundamental, Consejo Superior de Investigaciones CientIficas, Serrano 121, 28006 Madrid (Spain)], E-mail: p.gonzalezdiaz@imaff.cfmac.csic.es, E-mail: a.rozas@cfmac.csic.es

    2008-09-07

    The current accelerating phase of the evolution of the universe is considered by constructing the most economical cosmic models that use just general relativity and some dominating quantum effects associated with the probabilistic description of quantum physics. Two such models are explicitly analyzed. They are based on the existence of a sub-quantum potential and correspond to a generalization of the spatially flat exponential model of de Sitter space. The thermodynamics of these two cosmic solutions is discussed, using the second principle as a guide to choose which among the two is more feasible. The paper also discusses the relativistic physics on which the models are based, their holographic description, some implications from the classical energy conditions and an interpretation of dark energy in terms of the entangled energy of the universe.

  3. Thermodynamic modeling of complex systems

    DEFF Research Database (Denmark)

    Liang, Xiaodong

    been developed, which has avoided the numerical pitfalls of having more than three volume roots in the real application range. It has been shown that it is possible to directly use the original PC-SAFT parameters with the new universal constants for the systems considered in this thesis. Finally...... after an oil spill. Engineering thermodynamics could be applied in the state-of-the-art sonar products through advanced artificial technology, if the speed of sound, solubility and density of oil-seawater systems could be satisfactorily modelled. The addition of methanol or glycols into unprocessed well...... streams during subsea pipelines is necessary to inhibit gas hydrate formation, and the offshore reservoirs often mean complicated temperature and pressure conditions. Accurate description of the phase behavior and thermalphysical properties of complex systems containing petroleum fluids and polar...

  4. Thermodynamic properties of Dynes superconductors

    Science.gov (United States)

    Herman, František; Hlubina, Richard

    2018-01-01

    The tunneling density of states in dirty s -wave superconductors is often well described by the phenomenological Dynes formula. Recently we have shown that this formula can be derived, within the coherent potential approximation, for superconductors with simultaneously present pair-conserving and pair-breaking impurity scattering. Here we demonstrate that the theory of such so-called Dynes superconductors is thermodynamically consistent. We calculate the specific heat and critical field of the Dynes superconductors, and we show that their gap parameter, specific heat, critical field, and penetration depth exhibit power-law scaling with temperature in the low-temperature limit. We also show that in the vicinity of a coupling-constant-controlled superconductor to normal metal transition, the Homes law is replaced by a different, pair-breaking-dominated scaling law.

  5. Compatibilized Immiscible Polymer Blends for Gas Separations

    Science.gov (United States)

    Panapitiya, Nimanka; Wijenayake, Sumudu; Nguyen, Do; Karunaweera, Chamaal; Huang, Yu; Balkus, Kenneth; Musselman, Inga; Ferraris, John

    2016-01-01

    Membrane-based gas separation has attracted a great deal of attention recently due to the requirement for high purity gasses in industrial applications like fuel cells, and because of environment concerns, such as global warming. The current methods of cryogenic distillation and pressure swing adsorption are energy intensive and costly. Therefore, polymer membranes have emerged as a less energy intensive and cost effective candidate to separate gas mixtures. However, the use of polymeric membranes has a drawback known as the permeability-selectivity tradeoff. Many approaches have been used to overcome this limitation including the use of polymer blends. Polymer blending technology synergistically combines the favorable properties of different polymers like high gas permeability and high selectivity, which are difficult to attain with a single polymer. During polymer mixing, polymers tend to uncontrollably phase separate due to unfavorable thermodynamics, which limits the number of completely miscible polymer combinations for gas separations. Therefore, compatibilizers are used to control the phase separation and to obtain stable membrane morphologies, while improving the mechanical properties. In this review, we focus on immiscible polymer blends and the use of compatibilizers for gas separation applications. PMID:28773766

  6. Modeling the thermodynamics of QCD

    Energy Technology Data Exchange (ETDEWEB)

    Hell, Thomas

    2010-07-26

    Strongly interacting (QCD) matter is expected to exhibit a multifaceted phase structure: a hadron gas at low temperatures, a quark-gluon plasma at very high temperatures, nuclear matter in the low-temperature and high-density region, color superconductors at asymptotically high densities. Most of the conjectured phases cannot yet be scrutinized by experiments. Much of the present picture - particularly concerning the intermediate temperature and density area of the phase diagram of QCD matter - is based on model calculations. Further insights come from Lattice-QCD computations. The present thesis elaborates a nonlocal covariant extension of the Nambu and Jona-Lasinio (NJL) model with built-in constraints from the running coupling of QCD at high-momentum and instanton physics at low-momentum scales. We present this model for two and three quark flavors (in the latter case paying particular attention to the axial anomaly). At finite temperatures and densities, gluon dynamics is incorporated through a gluonic background field, expressed in terms of the Polyakov loop (P). The thermodynamics of this nonlocal PNJL model accounts for both chiral and deconfinement transitions. We obtain results in mean-field approximation and beyond, including additional pionic and kaonic contributions to the chiral condensate, the pressure and other thermodynamic quantities. Finally, the nonlocal PNJL model is applied to the finite-density region of the QCD phase diagram; for three quark flavors we investigate, in particular, the dependence of the critical point appearing in the models on the axial anomaly. The thesis closes with a derivation of the nonlocal PNJL model from first principles of QCD. (orig.)

  7. Thermodynamics of TMPC/PSd/Fullerene Nanocomposites: SANS Study

    KAUST Repository

    Chua, Yang-Choo

    2010-11-23

    Wereport a small angle neutron scattering study of the thermodynamics of a polymer mixture in the presence of nanoparticles, both in equilibrium and during phase separation. Neutron cloud point measurements and random phase approximation (RPA) analysis demonstrate that 1-2 mass % of C60 fullerenes destabilizes a highly interacting mixture of poly(tetramethyl bisphenol A polycarbonate) and deuterated polystyrene (TMPC/PSd). We unequivocally corroborate these findings with time-resolved temperature jump experiments that, in identical conditions, result in phase separation for the nanocomposite and stability for the neat polymer mixture. At lower C 60 loadings (viz. 0.2-0.5 mass %), stabilization of the mixture is observed. The nonmonotonic variation of the spinodal temperature with fullerene addition suggests a competitive interplay of asymmetric component interactions and nanoparticle dispersion. The stability line shift depends critically on particle dispersion and vanishes upon nanoparticle agglomeration. © 2010 American Chemical Society.

  8. Thermodynamic analysis of the advanced zero emission power plant

    Directory of Open Access Journals (Sweden)

    Kotowicz Janusz

    2016-03-01

    Full Text Available 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.

  9. Thermodynamic analysis of the advanced zero emission power plant

    Science.gov (United States)

    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.

  10. Glycosylation and thermodynamic versus kinetic stability of horseradish peroxidase

    DEFF Research Database (Denmark)

    Tams, J.W.; Welinder, Karen G.

    1998-01-01

    Glycoprotein stability, glycoprotein unfolding, horseradish peroxidase, thermodynamic stability, kinetik stability......Glycoprotein stability, glycoprotein unfolding, horseradish peroxidase, thermodynamic stability, kinetik stability...

  11. Raman Spectroscopic Investigation of Dyes in Spices

    Science.gov (United States)

    Uhlemann, Ute; Ramoji, Anuradha; Rösch, Petra; Da Costa Filho, Paulo Augusto; Robert, Fabien; Popp, Jürgen

    2010-08-01

    In this study, a number of synthetic colorants for spices have been investigated by means of Raman spectroscopy, resonance Raman spectroscopy, and surface enhanced (resonance) Raman spectroscopy (SER(S)). The aim of the study was the determination of limits of detection for each dye separately and in binary mixtures of dyes in spiked samples of the spices. Most of the investigated dyes have been azo dyes, some being water-soluble, the other being fat-soluble. Investigating the composition of food preparations is an ongoing and important branch of analytical sciences. On one hand, new ingredients have to be analyzed with regard to their contents, on the other hand, raw materials that have been tampered have to be eliminated from food production processes. In the last decades, the various Raman spectroscopic methods have proven to be successful in many areas of life and materials sciences. The ability of Raman spectroscopy to distinguish even structural very similar analytes by means of their vibrational fingerprint will also be important in this study. Nevertheless, Raman scattering is a very weak process that is oftentimes overlaid by matrix interferences or fluorescence. In order to achieve limits of detection in the nanomolar range, the signal intensity has to be increased. According to the well-known equations, there are several ways of achieving this increase: •increasing sample concentration •increasing laser power •decreasing the laser wavelength •using electronic resonance •increasing the local electromagnetic field In this study, nearly all of the above-mentioned principles were applied. In a first step, all dyes were investigated in solution at different concentrations to determine a limit of detection. In the second step, spiked spice samples have been extracted with a variety of solvents and process parameters tested. To lower the limit of detection even further, SERS spectroscopy has been used as well in as out of electronic resonance.

  12. Structure and thermodynamic insights on acetylaminofluorene-modified deletion DNA duplexes as models for frameshift mutagenesis.

    Science.gov (United States)

    Sandineni, Anusha; Lin, Bin; MacKerell, Alexander D; Cho, Bongsup P

    2013-06-17

    2-Acetylaminofluorene (AAF) is a prototype arylamine carcinogen that forms C8-substituted dG-AAF and dG-AF as the major DNA lesions. The bulky N-acetylated dG-AAF lesion can induce various frameshift mutations depending on the base sequence around the lesion. We hypothesized that the thermodynamic stability of bulged-out slipped mutagenic intermediates (SMIs) is directly related to deletion mutations. The objective of the present study was to probe the structural/conformational basis of various dG-AAF-induced SMIs formed during translesion synthesis. We performed spectroscopic, thermodynamic, and molecular dynamics studies of several AAF-modified 16-mer model DNA duplexes, including fully paired and -1, -2, and -3 deletion duplexes of the 5'-CTCTCGATG[FAAF]CCATCAC-3' sequence and an additional -1 deletion duplex of the 5'-CTCTCGGCG[FAAF]CCATCAC-3' NarI sequence. Modified deletion duplexes existed in a mixture of external B and stacked S conformers, with the population of the S conformer being 'GC'-1 (73%) > 'AT'-1 (72%) > full (60%) > -2 (55%) > -3 (37%). Thermodynamic stability was in the order of -1 deletion > -2 deletion > fully paired > -3 deletion duplexes. These results indicate that the stacked S-type conformer of SMIs is thermodynamically more stable than the conformationally flexible external B conformer. Results from the molecular dynamics simulations indicate that perturbation of base stacking dominates the relative stability along with contributions from bending, duplex dynamics, and solvation effects that are important in specific cases. Taken together, these results support a hypothesis that the conformational and thermodynamic stabilities of the SMIs are critical determinants for the induction of frameshift mutations.

  13. Thermodynamic properties of uranium--mercury system

    Energy Technology Data Exchange (ETDEWEB)

    Lee, T.S.

    1979-01-01

    The EMF values in the fused salt cells of the type U(..cap alpha..)/KCl--LiCl--BaCl/sub 2/ eutectic, UCl/sub 3//U--Hg alloy, for the different two-phase alloys in the uranium--mercury system have been measured and the thermodynamic properties of this system have been calculated. These calculated values are in good agreement with values based on mercury vapor pressure measurements made by previous investigators. The inconsistency of the thermodynamic properties with the phase diagram determined by Frost are also confirmed. A tentative phase diagram based on the thermodynamic properties measured in this work was constructed.

  14. Introduction to physics mechanics, hydrodynamics thermodynamics

    CERN Document Server

    Frauenfelder, P

    2013-01-01

    Introduction of Physics: Mechanics , Hydrodynamics, Thermodynamics covers the principles of matter and its motion through space and time, as well as the related concepts of energy and force. This book is composed of eleven chapters, and begins with an introduction to the basic principles of mechanics, hydrodynamics, and thermodynamics. The subsequent chapters deal with the statics of rigid bodies and the dynamics of particles and rigid bodies. These topics are followed by discussions on elasticity, mechanics of fluids, the basic concept of thermodynamic, kinetic theory, and crystal structure o

  15. Thermodynamic Formalism and Applications to Dimension Theory

    CERN Document Server

    Barreira, Luis

    2011-01-01

    This self-contained monograph presents a unified exposition of the thermodynamic formalism and some of its main extensions, with emphasis on the relation to dimension theory and multifractal analysis of dynamical systems. In particular, the book considers three different flavors of the thermodynamic formalism, namely nonadditive, subadditive, and almost additive, and provides a detailed discussion of some of the most significant results in the area, some of them quite recent. It also includes a discussion of the most substantial applications of these flavors of the thermodynamic formalism to d

  16. Thermodynamic Volume in AdS/CFT

    Science.gov (United States)

    Kim, Kyung Kiu; Ahn, Byoungjoon

    2018-01-01

    In this note, we study on extended thermodynamics of AdS black holes by varying cosmological constant. We found and discussed pressure and volume of both bulk and boundary physics through AdS/CFT correspondence. In particular, we derive the relation between thermodynamic volume and a chemical potential for M2 brane dual to four dimensional AdS space. In addition, we show that thermodynamic volume of hyperbolic black hole is related to `entanglement pressure' coming from a generalized first law of entanglement entropy.

  17. Magnetic separation of algae

    Science.gov (United States)

    Nath, Pulak; Twary, Scott N.

    2016-04-26

    Described herein are methods and systems for harvesting, collecting, separating and/or dewatering algae using iron based salts combined with a magnetic field gradient to separate algae from an aqueous solution.

  18. Separation anxiety in children

    Science.gov (United States)

    ... page: //medlineplus.gov/ency/article/001542.htm Separation anxiety in children To use the sharing features on this page, please enable JavaScript. Separation anxiety in children is a developmental stage in which ...

  19. Separators for electrochemical cells

    Energy Technology Data Exchange (ETDEWEB)

    Carlson, Steven Allen; Anakor, Ifenna Kingsley; Farrell, Greg Robert

    2018-01-16

    Provided are separators for use in an electrochemical cell comprising (a) an inorganic oxide and (b) an organic polymer, wherein the inorganic oxide comprises organic substituents. Also provided are electrochemical cells comprising such separators.

  20. Significant structure theory applied to phase separation.

    Science.gov (United States)

    Lee, S H; Jhon, M S; Eyring, H

    1977-01-01

    The significant structure theory of liquids has been applied to the partially miscible system of the O(3)-O(2) mixture, which exhibits partial miscibility in the temperature range from -195.5 degrees C to -179.9 degrees C. The thermodynamic condition for phase separation is given by the following inequality: [Formula: see text] A partition function for the binary liquid mixture is developed using significant liquid structure theory. Here X(i) is the mole fraction of either of the two components. We obtain the coexistence curve of the O(3)-O(2) system by varying the mole fractions of the components to find the temperature at which the two liquids separate. The agreement between theory and experiment is satisfactory.

  1. Synthesis, Spectroscopic and Pharmacological Studies of Bivalent ...

    African Journals Online (AJOL)

    Synthesis, Spectroscopic and Pharmacological Studies of Bivalent Copper, Zinc and Mercury Complexes of Thiourea. ... All the metal complexes were characterized by elemental chemical analysis, molar conductance, magnetic susceptibility measurements and IR spectroscopy. Cu(II) complexes were additionally ...

  2. Structural, thermal and spectroscopic properties of supramolecular ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 118; Issue 6. Structural, thermal and spectroscopic properties of supramolecular coordination solids. Birinchi Kumar Das Sanchay Jyoti Bora Monideepa Chakrabortty Laksheswar Kalita Rajesh Chakrabarty Ramakanta Barman. Volume 118 Issue 6 November 2006 ...

  3. Synthesis, spectroscopic and structural characterization of new ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 125; Issue 3. Synthesis, spectroscopic and structural characterization of new linear mononuclear silver(I) complexes containing -keto phosphorus ylides as ambidentate ligands. Seyed Javad Sabounchei Mohsen Ahmadi Fatemeh Akhlaghi Hamid Reza Khavasi.

  4. Photometric and spectroscopic investigation of TW Draconis

    OpenAIRE

    Zejda, M.; Wolf, M.; Slechta, M.; Mikulasek, Z.; Zverko, J.; Svoboda, P.; Krticka, J.; Janik, J.; Bozic, H.

    2010-01-01

    Context. TW Draconis is one of the best studied Algol-type eclipsing binaries. There is significant evidence for miscellaneous physical processes between interacting binary components manifesting themselves by period and light curve changes. Aims. Obtaining new set of photometric and spectroscopic observations, we analysed them together with the older spectroscopic and photometric data to build model of this eclipsing system with respect to observed changes of O-C diagram and light curve. Met...

  5. Structural, conformational and thermodynamic aspects of groove-directed-intercalation of flavopiridol into DNA.

    Science.gov (United States)

    Ray, Bhumika; Agarwal, Shweta; Lohani, Neelam; Rajeswari, Moganty R; Mehrotra, Ranjana

    2016-11-01

    Certain plant-derived alkaloids and flavonoids have shown propitious cytotoxic acitvity against different types of cancer, having deoxyribose nucleic acid (DNA) as their main cellular target. Flavopiridol, a semi-synthetic derivative of rohitukine (a natural compound isolated from Dysoxylum binectariferum plant), has attained much attention owing to its anticancer potential against various haematological malignancies and solid tumours. This work focuses on investigating interaction between flavopiridol and DNA at molecular level in order to decipher its underlying mechanism of action, which is not well understood. To define direct influence of flavopiridol on the structural, conformational and thermodynamic aspects of DNA, various spectroscopic and calorimetric techniques have been used. ATR-FTIR and SERS spectral outcomes indicate a novel insight into groove-directed-intercalation of flavopiridol into DNA via direct binding with nitrogenous bases guanine (C6=O6) and thymine (C2=O2) in DNA groove together with slight external binding to its sugar-phosphate backbone. Circular dichroism spectral analysis of flavopiridol-DNA complexes suggests perturbation in native B-conformation of DNA and its transition into C-form, which may be localized up to a few base pairs of DNA. UV-visible spectroscopic results illustrate dual binding mode of flavopiridol when interacts with DNA having association constant, Ka = 1.18 × 10(4) M(-1). This suggests moderate type of interaction between flavopiridol and DNA. Further, UV melting analysis also supports spectroscopic outcomes. Thermodynamically, flavopiridol-DNA complexation is an enthalpy-driven exothermic process. These conclusions drawn from this study could be helpful in unveiling mechanism of cytoxicity induced by flavopiridol that can be further applied in the development of flavonoid-based new chemotherapeutics with more specificity and better efficacy.

  6. Vibrational spectroscopic characterization of fluoroquinolones

    Science.gov (United States)

    Neugebauer, U.; Szeghalmi, A.; Schmitt, M.; Kiefer, W.; Popp, J.; Holzgrabe, U.

    2005-05-01

    Quinolones are important gyrase inhibitors. Even though they are used as active agents in many antibiotics, the detailed mechanism of action on a molecular level is so far not known. It is of greatest interest to shed light on this drug-target interaction to provide useful information in the fight against growing resistances and obtain new insights for the development of new powerful drugs. To reach this goal, on a first step it is essential to understand the structural characteristics of the drugs and the effects that are caused by the environment in detail. In this work we report on Raman spectroscopical investigations of a variety of gyrase inhibitors (nalidixic acid, oxolinic acid, cinoxacin, flumequine, norfloxacin, ciprofloxacin, lomefloxacin, ofloxacin, enoxacin, sarafloxacin and moxifloxacin) by means of micro-Raman spectroscopy excited with various excitation wavelengths, both in the off-resonance region (532, 633, 830 and 1064 nm) and in the resonance region (resonance Raman spectroscopy at 244, 257 and 275 nm). Furthermore DFT calculations were performed to assign the vibrational modes, as well as for an identification of intramolecular hydrogen bonding motifs. The effect of small changes in the drug environment was studied by adding successively small amounts of water until physiological low concentrations of the drugs in aqueous solution were obtained. At these low concentrations resonance Raman spectroscopy proved to be a useful and sensitive technique. Supplementary information was obtained from IR and UV/vis spectroscopy.

  7. Spectroscopic Detection of Caries Lesions

    Directory of Open Access Journals (Sweden)

    Mika Ruohonen

    2013-01-01

    Full Text Available Background. A caries lesion causes changes in the optical properties of the affected tissue. Currently a caries lesion can be detected only at a relatively late stage of development. Caries diagnosis also suffers from high interobserver variance. Methods. This is a pilot study to test the suitability of an optical diffuse reflectance spectroscopy for caries diagnosis. Reflectance visible/near-infrared spectroscopy (VIS/NIRS was used to measure caries lesions and healthy enamel on extracted human teeth. The results were analysed with a computational algorithm in order to find a rule-based classification method to detect caries lesions. Results. The classification indicated that the measured points of enamel could be assigned to one of three classes: healthy enamel, a caries lesion, and stained healthy enamel. The features that enabled this were consistent with theory. Conclusions. It seems that spectroscopic measurements can help to reduce false positives at in vitro setting. However, further research is required to evaluate the strength of the evidence for the method’s performance.

  8. Meniscus Membranes For Separation

    Science.gov (United States)

    Dye, Robert C.; Jorgensen, Betty; Pesiri, David R.

    2005-09-20

    Gas separation membranes, especially meniscus-shaped membranes for gas separations are disclosed together with the use of such meniscus-shaped membranes for applications such as thermal gas valves, pre-concentration of a gas stream, and selective pre-screening of a gas stream. In addition, a rapid screening system for simultaneously screening polymer materials for effectiveness in gas separation is provided.

  9. Thermodynamics of quantum spacetime histories

    Science.gov (United States)

    Smolin, Lee

    2017-11-01

    We show that the simplicity constraints, which define the dynamics of spin foam models, imply, and are implied by, the first law of thermodynamics, when the latter is applied to causal diamonds in the quantum spacetime. This result reveals an intimate connection between the holographic nature of gravity, as reflected by the Bekenstein entropy, and the fact that general relativity and other gravitational theories can be understood as constrained topological field theories. To state and derive this correspondence we describe causal diamonds in the causal structure of spin foam histories and generalize arguments given for the near horizon region of black holes by Frodden, Gosh and Perez [Phys. Rev. D 87, 121503 (2013); , 10.1103/PhysRevD.87.121503Phys. Rev. D 89, 084069 (2014); , 10.1103/PhysRevD.89.084069Phys. Rev. Lett. 107, 241301 (2011); , 10.1103/PhysRevLett.107.241301Phys. Rev. Lett.108, 169901(E) (2012)., 10.1103/PhysRevLett.108.169901] and Bianchi [arXiv:1204.5122.]. This allows us to apply a recent argument of Jacobson [Phys. Rev. Lett. 116, 201101 (2016).10.1103/PhysRevLett.116.201101] to show that if a spin foam history has a semiclassical limit described in terms of a smooth metric geometry, that geometry satisfies the Einstein equations. These results suggest also a proposal for a quantum equivalence principle.

  10. Thermodynamics of Quantum Feedback Cooling

    Directory of Open Access Journals (Sweden)

    Pietro Liuzzo-Scorpo

    2016-02-01

    Full Text Available The ability to initialize quantum registers in pure states lies at the core of many applications of quantum technologies, from sensing to quantum information processing and computation. In this paper, we tackle the problem of increasing the polarization bias of an ensemble of two-level register spins by means of joint coherent manipulations, involving a second ensemble of ancillary spins and energy dissipation into an external heat bath. We formulate this spin refrigeration protocol, akin to algorithmic cooling, in the general language of quantum feedback control, and identify the relevant thermodynamic variables involved. Our analysis is two-fold: on the one hand, we assess the optimality of the protocol by means of suitable figures of merit, accounting for both its work cost and effectiveness; on the other hand, we characterise the nature of correlations built up between the register and the ancilla. In particular, we observe that neither the amount of classical correlations nor the quantum entanglement seem to be key ingredients fuelling our spin refrigeration protocol. We report instead that a more general indicator of quantumness beyond entanglement, the so-called quantum discord, is closely related to the cooling performance.

  11. Thermodynamics of superconducting quantum metamaterials

    Energy Technology Data Exchange (ETDEWEB)

    Dallaire-Demers, Pierre-Luc; Wilhelm-Mauch, Frank [Universitaet des Saarlandes (Germany)

    2015-07-01

    Left-handed matematerials are capacitively coupled layers of inductive pieces of conductors. These systems are well studied in the context of microwave metamaterials but their full quantum description or their embedding in highly correlated materials like superconductors are still an open problem. Notably, they are known to have a Van Hove singularity in the density of states at low energy and high pseudo-momentum that could effectively couple and condense Cooper pairs. The goal of this research is to analyze the thermodynamical properties of the order parameter of stacked layers of superconductors with a small repulsive Coulomb interaction. A 3D toy model of such a material is mapped to a Fermi-Hubbard lattice. The temperature dependent anomalous correlation functions are computed variationally from a self-energy functional of a small cluster where inter-cluster tunneling is treated perturbatively. The effect of the repulsive interaction on the Cooper pairs binding can then be seen from the momentum distribution of the condensation amplitude. Such a material could potentially be realized with optical lattices or nanoscaled superconductors.

  12. Computational studies of the electronic, conductivities, and spectroscopic properties of hydrolysed Ru(II) anticancer complexes.

    Science.gov (United States)

    Adeniyi, Adebayo A; Ajibade, Peter A

    2013-11-01

    The mechanism of activation of metal-based anticancer agents was reported to be through hydrolysis. In this study, computational method was used to gain insight to the correlation between the chemistry of the hydrolysis and the anticancer activities of selected Ru(II)-based complexes. Interestingly, we observed that the mechanism of activation by hydrolysis and their consequential anticancer activities is associated with favourable thermodynamic changes, higher hyperpolarizability (β), lower band-gap and higher first-order net current. The Fermi contact (FC) and spin dipole (SD) are found to be the two most significant Ramsey terms that determine the spin-spin couplings (J(HZ)) of most of the existing bonds in the complexes. Many of the computed properties give insights into the change in the chemistry of the complexes due to hydrolysis. Besides strong correlations of the computed properties to the anticancer activities of the complexes, using the quantum theory of atoms in a molecule (QTAIM) to analyse the spectroscopic properties shows a stronger correlation between the spectroscopic properties of Ru atom to the reported anticancer activities than the sum over of the spectroscopic properties of all atoms in the complexes. Copyright © 2013 Elsevier B.V. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1997-08-01

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

  14. ProTherm, version 4.0: thermodynamic database for proteins and mutants.

    Science.gov (United States)

    Bava, K Abdulla; Gromiha, M Michael; Uedaira, Hatsuho; Kitajima, Koji; Sarai, Akinori

    2004-01-01

    Release 4.0 of ProTherm, thermodynamic database for proteins and mutants, contains approximately 14,500 numerical data (approximately 450% of the first version) of several thermodynamic parameters along with experimental methods and conditions, and structural, functional and literature information. The sequence and structural information of proteins is connected with thermodynamic data through links between entries in Protein Data Bank, Protein Information Resource and SWISS-PROT and the data in ProTherm. We have separated the Gibbs free energy change obtained at extrapolated temperature from the data on denaturation temperature measured by the thermal denaturation method. We have added the statistics of amino acid replacements and links to homologous structures to each protein. Further, we have improved the search and display options to enhance search capability through the web interface. ProTherm is freely available at http://gibk26. bse.kyutech.ac.jp/jouhou/Protherm/protherm.html.

  15. [Thermodynamics of life from the point of view of technical thermodynamics and exergy].

    Science.gov (United States)

    Grassmann, P

    1984-07-01

    All living beings are, from the thermodynamic point of view, open, well regulated, and optimized systems with considerable internal irreversibilities. However scientific research is mainly based on closed systems. The theory of open systems is very well developed in engineering thermodynamics. Here the concept of "exergy"--the thermodynamic potential related to given surroundings--clearly distinguishes between the two concepts of the word "energy".

  16. Universalities of thermodynamic signatures in topological phases

    NARCIS (Netherlands)

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

    2016-01-01

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

  17. Thermodynamic Products in the Extended Phase Space

    CERN Document Server

    Pradhan, Parthapratim

    2016-01-01

    We have examined the thermodynamic properties of spherically symmetric charged-AdS black hole, charged AdS BH surrounded by quintessence and charged AdS BH in $f(R)$ gravity in the extended phase-space. Where the cosmological constant should be treated as thermodynamic pressure and its conjugate parameter as thermodynamic volume. Then they should behave as a analog of Van der Waal like systems. In the extended phase space we have calculated the \\emph{entropy product} and \\emph{thermodynamic volume product} of all horizons. The mass(or enthalpy) independent nature of the said products signals they are "universal" quantities. Various types of pictorial diagram of the specific heat is given. The divergence of the specific heat indicates that the second order phase transition occurs under certain condition.

  18. Metrics and Energy Landscapes in Irreversible Thermodynamics

    Directory of Open Access Journals (Sweden)

    Bjarne Andresen

    2015-09-01

    Full Text Available We describe how several metrics are possible in thermodynamic state space but that only one, Weinhold’s, has achieved widespread use. Lengths calculated based on this metric have been used to bound dissipation in finite-time (irreversible processes be they continuous or discrete, and described in the energy picture or the entropy picture. Examples are provided from thermodynamics of heat conversion processes as well as chemical reactions. Even losses in economics can be bounded using a thermodynamic type metric. An essential foundation for the metric is a complete equation of state including all extensive variables of the system; examples are given. Finally, the second law of thermodynamics imposes convexity on any equation of state, be it analytical or empirical.

  19. Quantum thermodynamics of general quantum processes.

    Science.gov (United States)

    Binder, Felix; Vinjanampathy, Sai; Modi, Kavan; Goold, John

    2015-03-01

    Accurately describing work extraction from a quantum system is a central objective for the extension of thermodynamics to individual quantum systems. The concepts of work and heat are surprisingly subtle when generalizations are made to arbitrary quantum states. We formulate an operational thermodynamics suitable for application to an open quantum system undergoing quantum evolution under a general quantum process by which we mean a completely positive and trace-preserving map. We derive an operational first law of thermodynamics for such processes and show consistency with the second law. We show that heat, from the first law, is positive when the input state of the map majorizes the output state. Moreover, the change in entropy is also positive for the same majorization condition. This makes a strong connection between the two operational laws of thermodynamics.

  20. Non-Equilibrium Thermodynamics in Multiphase Flows

    CERN Document Server

    Mauri, Roberto

    2013-01-01

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

  1. Thermodynamics of sedimentation in paucidisperse systems

    NARCIS (Netherlands)

    Hooyman, G.J.

    1956-01-01

    The previously given treatment of sedimentation phenomena in monodisperse uncharged systems with the help of thermodynamics of irreversible processes is extended to paucidisperse systems. The sedimentation rates of the components are derived by neglecting transverse effects and by introducing the

  2. Fluctuations of Intensive Quantities in Statistical Thermodynamics

    Directory of Open Access Journals (Sweden)

    Artur E. Ruuge

    2013-11-01

    Full Text Available In phenomenological thermodynamics, the canonical coordinates of a physical system split in pairs, with each pair consisting of an extensive quantity and an intensive one. In the present paper, the quasithermodynamic fluctuation theory of a model system of a large number of oscillators is extended to statistical thermodynamics based on the idea of perceiving the fluctuations of intensive variables as the fluctuations of specific extensive ones in a “thermodynamically dual” system. The extension is motivated by the symmetry of the problem in the context of an analogy with quantum mechanics, which is stated in terms of a generalized Pauli problem for the thermodynamic fluctuations. The doubled Boltzmann constant divided by the number of particles plays a similar role as the Planck constant.

  3. The entropy principle thermodynamics for the unsatisfied

    CERN Document Server

    Thess, André

    2011-01-01

    Entropy is the most important and the most difficult to understand term of thermodynamics. This book helps make this key concept understandable. It includes seven illustrative examples of applications of entropy, which are presented step by step.

  4. Thermodynamics of Computational Copying in Biochemical Systems

    Science.gov (United States)

    Ouldridge, Thomas E.; Govern, Christopher C.; ten Wolde, Pieter Rein

    2017-04-01

    Living cells use readout molecules to record the state of receptor proteins, similar to measurements or copies in typical computational devices. But is this analogy rigorous? Can cells be optimally efficient, and if not, why? We show that, as in computation, a canonical biochemical readout network generates correlations; extracting no work from these correlations sets a lower bound on dissipation. For general input, the biochemical network cannot reach this bound, even with arbitrarily slow reactions or weak thermodynamic driving. It faces an accuracy-dissipation trade-off that is qualitatively distinct from and worse than implied by the bound, and more complex steady-state copy processes cannot perform better. Nonetheless, the cost remains close to the thermodynamic bound unless accuracy is extremely high. Additionally, we show that biomolecular reactions could be used in thermodynamically optimal devices under exogenous manipulation of chemical fuels, suggesting an experimental system for testing computational thermodynamics.

  5. Safety shutdown separators

    Science.gov (United States)

    Carlson, Steven Allen; Anakor, Ifenna Kingsley; Farrell, Greg Robert

    2015-06-30

    The present invention pertains to electrochemical cells which comprise (a) an anode; (b) a cathode; (c) a solid porous separator, such as a polyolefin, xerogel, or inorganic oxide separator; and (d) a nonaqueous electrolyte, wherein the separator comprises a porous membrane having a microporous coating comprising polymer particles which have not coalesced to form a continuous film. This microporous coating on the separator acts as a safety shutdown layer that rapidly increases the internal resistivity and shuts the cell down upon heating to an elevated temperature, such as 110.degree. C. Also provided are methods for increasing the safety of an electrochemical cell by utilizing such separators with a safety shutdown layer.

  6. Thermodynamics and folding pathway of tetraloop receptor-mediated RNA helical packing

    Science.gov (United States)

    Vander Meulen, Kirk A.; Davis, Jared H.; Foster, Trenton R.; Record, M. Thomas; Butcher, Samuel E.

    2008-01-01

    Summary Little is known about the thermodynamic forces that drive the folding pathways of higher order RNA structure. In this study, we employ calorimetric (ITC and DSC) and spectroscopic (NMR and UV) methods to characterize the thermodynamics of the GAAA tetraloop – receptor interaction, utilizing a previously described bivalent construct. ITC studies indicate that the bivalent interaction is enthalpy-driven and highly stable, with a binding constant (Kobs) of 5.5 × 106 M−1 and enthalpy (ΔHobs°) of −33.8 kcal/mol at 45°C in 20 mM KCl and 2 mM MgCl2. Thus we derive the ΔHobs° for a single tetraloop-receptor interaction to be −16.9 kcal/mol at these conditions. UV absorbance data indicate that an increase in base stacking quality contributes to the enthalpy of complex formation. These highly favorable thermodynamics are consistent with the known critical role for the tetraloop-receptor motif in the folding of large RNAs. Additionally, a significant heat capacity change (ΔCp,obs°) of −0.24 kcal·mol−1·K−1 was determined by ITC. DSC and UV monitored thermal denaturation experiments indicate that the bivalent tetraloop-receptor construct follows a minimally 5–state unfolding pathway, and suggest the observed ΔCp,obs° for the interaction results from a temperature-dependent unbound receptor RNA structure. PMID:18845162

  7. Acoustofluidic bacteria separation

    Science.gov (United States)

    Li, Sixing; Ma, Fen; Bachman, Hunter; Cameron, Craig E.; Zeng, Xiangqun; Huang, Tony Jun

    2017-01-01

    Bacterial separation from human blood samples can help with the identification of pathogenic bacteria for sepsis diagnosis. In this work, we report an acoustofluidic device for label-free bacterial separation from human blood samples. In particular, we exploit the acoustic radiation force generated from a tilted-angle standing surface acoustic wave (taSSAW) field to separate Escherichia coli from human blood cells based on their size difference. Flow cytometry analysis of the E. coli separated from red blood cells shows a purity of more than 96%. Moreover, the label-free electrochemical detection of the separated E. coli displays reduced non-specific signals due to the removal of blood cells. Our acoustofluidic bacterial separation platform has advantages such as label-free separation, high biocompatibility, flexibility, low cost, miniaturization, automation, and ease of in-line integration. The platform can be incorporated with an on-chip sensor to realize a point-of-care sepsis diagnostic device.

  8. Rapid chemical separations

    CERN Document Server

    Trautmann, N

    1976-01-01

    A survey is given on the progress of fast chemical separation procedures during the last few years. Fast, discontinuous separation techniques are illustrated by a procedure for niobium. The use of such techniques for the chemical characterization of the heaviest known elements is described. Other rapid separation methods from aqueous solutions are summarized. The application of the high speed liquid chromatography to the separation of chemically similar elements is outlined. The use of the gas jet recoil transport method for nuclear reaction products and its combination with a continuous solvent extraction technique and with a thermochromatographic separation is presented. Different separation methods in the gas phase are briefly discussed and the attachment of a thermochromatographic technique to an on-line mass separator is shown. (45 refs).

  9. Universalities of thermodynamic signatures in topological phases

    OpenAIRE

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

    2016-01-01

    Topological insulators (superconductors) are materials that host symmetry-protected metallic edge states in an insulating (superconducting) bulk. Although they are well understood, a thermodynamic description of these materials remained elusive, firstly because the edges yield a non-extensive contribution to the thermodynamic potential, and secondly because topological field theories involve non-local order parameters, and cannot be captured by the Ginzburg-Landau formalism. Recently, this ch...

  10. Qualitative and quantitative reasoning about thermodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Skorstad, G.; Forbus, K. (Univ. of Illinois at Urbana-Champaign, IL (US))

    1989-01-01

    This paper shows how qualitative process theory can be used to express concepts of engineering thermodynamics. In particular, the authors describe how to integrate qualitative and quantitative knowledge to solve textbook problems involving thermodynamic cycles, such as gas turbine plants and steam power plants. These ideas have been implemented in a program called SCHISM. The authors describe its analysis of a sample textbook problem and discuss plans for future work.

  11. Tables of thermodynamic properties of sodium

    Energy Technology Data Exchange (ETDEWEB)

    Fink, J.K.

    1982-06-01

    The thermodynamic properties of saturated sodium, superheated sodium, and subcooled sodium are tabulated as a function of temperature. The temperature ranges are 380 to 2508 K for saturated sodium, 500 to 2500 K for subcooled sodium, and 400 to 1600 K for superheated sodium. Tabulated thermodynamic properties are enthalpy, heat capacity, pressure, entropy, density, instantaneous thermal expansion coefficient, compressibility, and thermal pressure coefficient. Tables are given in SI units and cgs units.

  12. Chemical engineering and thermodynamics using Mat lab

    Energy Technology Data Exchange (ETDEWEB)

    Kim Heon; Kim, Moon Gap; Lee, Hak Yeong; Yeo, Yeong Gu; Ham, Seong Won

    2002-02-15

    This book consists of twelve chapters and four appendixes about chemical engineering and thermodynamics using Mat lab, which deals with introduction, energy budget, entropy, thermodynamics process, generalization on any fluid, engineering equation of state for PVT properties, deviation of the function, phase equilibrium of pure fluid, basic of multicomponent, phase equilibrium of compound by state equation, activity model and reaction system. The appendixes is about summary of computer program, related mathematical formula and material property of pure component.

  13. Thermodynamical analysis of human thermal comfort

    OpenAIRE

    Prek, Matjaž

    2015-01-01

    Traditional methods of human thermal comfort analysis are based on the first law of thermodynamics. These methods use an energy balance of the human body to determine heat transfer between the body and its environment. By contrast, the second law of thermodynamics introduces the useful concept of exergy. It enables the determination of the exergy consumption within the human body dependent on human and environmental factors. Human body exergy consumption varies with the combination of environ...

  14. Molecular thermodynamics using fluctuation solution theory

    DEFF Research Database (Denmark)

    Ellegaard, Martin Dela

    to relevant experimental data is limited. This thesis addresses the issue of generating and using simple thermodynamic models within a rigorous statistical mechanical framework, the so-called fluctuation solution theory, from which relations connecting properties and phase equilibria can be obtained....... The framework relates thermodynamic variables to molecular pair correlation functions of liquid mixtures. In this thesis, application of the framework is illustrated using two approaches: 1. Solubilities of solid solutes in mixed solvent systems are determined from fluctuation solution theory application...

  15. OPTIMAL PROCESSES IN IRREVERSIBLE THERMODYNAMICS AND MICROECONOMICS

    Directory of Open Access Journals (Sweden)

    Vladimir A. Kazakov

    2004-06-01

    Full Text Available This paper describes general methodology that allows one to extend Carnot efficiency of classical thermodynamic for zero rate processes onto thermodynamic systems with finite rate. We define the class of minimal dissipation processes and show that it represents generalization of reversible processes and determines the limiting possibilities of finite rate systems. The described methodology is then applied to microeconomic exchange systems yielding novel estimates of limiting efficiencies for such systems.

  16. Hadron thermodynamics in relativistic nuclear collisions

    Science.gov (United States)

    Ammiraju, P.

    1985-01-01

    Various phenomenological models based on statistical thermodynamical considerations were used to fit the experimental data at high P sub T to a two temperature distribution. Whether this implies that the two temperatures belong to two different reaction mechanisms, or consequences of Lorentz-contraction factor, or related in a fundamental way to the intrinsic thermodynamics of Space-Time can only be revealed by further theoretical and experimental investigations of high P sub T phenomena in extremely energetic hadron-hadron collisions.

  17. Universalities of thermodynamic signatures in topological phases

    Science.gov (United States)

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

    2016-01-01

    Topological insulators (superconductors) are materials that host symmetry-protected metallic edge states in an insulating (superconducting) bulk. Although they are well understood, a thermodynamic description of these materials remained elusive, firstly because the edges yield a non-extensive contribution to the thermodynamic potential, and secondly because topological field theories involve non-local order parameters, and cannot be captured by the Ginzburg-Landau formalism. Recently, this challenge has been overcome: by using Hill thermodynamics to describe the Bernevig-Hughes-Zhang model in two dimensions, it was shown that at the topological phase transition the thermodynamic potential does not scale extensively due to boundary effects. Here, we extend this approach to different topological models in various dimensions (the Kitaev chain and Su-Schrieffer-Heeger model in one dimension, the Kane-Mele model in two dimensions and the Bernevig-Hughes-Zhang model in three dimensions) at zero temperature. Surprisingly, all models exhibit the same universal behavior in the order of the topological-phase transition, depending on the dimension. Moreover, we derive the topological phase diagram at finite temperature using this thermodynamic description, and show that it displays a good agreement with the one calculated from the Uhlmann phase. Our work reveals unexpected universalities and opens the path to a thermodynamic description of systems with a non-local order parameter. PMID:27929041

  18. Thermodynamic DFT analysis of natural gas.

    Science.gov (United States)

    Neto, Abel F G; Huda, Muhammad N; Marques, Francisco C; Borges, Rosivaldo S; Neto, Antonio M J C

    2017-08-01

    Density functional theory was performed for thermodynamic predictions on natural gas, whose B3LYP/6-311++G(d,p), B3LYP/6-31+G(d), CBS-QB3, G3, and G4 methods were applied. Additionally, we carried out thermodynamic predictions using G3/G4 averaged. The calculations were performed for each major component of seven kinds of natural gas and to their respective air + natural gas mixtures at a thermal equilibrium between room temperature and the initial temperature of a combustion chamber during the injection stage. The following thermodynamic properties were obtained: internal energy, enthalpy, Gibbs free energy and entropy, which enabled us to investigate the thermal resistance of fuels. Also, we estimated an important parameter, namely, the specific heat ratio of each natural gas; this allowed us to compare the results with the empirical functions of these parameters, where the B3LYP/6-311++G(d,p) and G3/G4 methods showed better agreements. In addition, relevant information on the thermal and mechanic resistance of natural gases were investigated, as well as the standard thermodynamic properties for the combustion of natural gas. Thus, we show that density functional theory can be useful for predicting the thermodynamic properties of natural gas, enabling the production of more efficient compositions for the investigated fuels. Graphical abstract Investigation of the thermodynamic properties of natural gas through the canonical ensemble model and the density functional theory.

  19. Thermodynamic properties of potassium oxides

    Energy Technology Data Exchange (ETDEWEB)

    Byker, H.J. (Montana State Univ., Bozeman); Eliezer, I.; Howald, R.C.; Ehlert, T.C.

    1979-09-01

    KO/sub 0/ /sub 5/ has been prepared by the reaction of excess potassium with KNO/sub 3/ in an effusion cell. Observations of the 2KO/sub 0/ /sub 5/ ..-->.. K/sub 2/O(g) equilibrium mass spectrometrically give a new value for the enthalpy of solid KO/sub 0/ /sub 5/, ..delta..H/sub f,298//sup 0/ = -170 +- 5 kJ mol/sup -1/. Observations on KO/sup +/ in the same series of experiments give good estimates for the thermodynamic properties of K/sub 2/O/sub 2/(g). This leads to an improved interpretation of data on the vaporization of KO/sub 0/ /sub 5/-K/sub 2/O/sub 2/ mixtures and solutions. Similarly literature data on the K/sub 2/O/sub 2/-KO/sub 2/ system have been collected and reexamined, leading to the values ..delta..H/sub f,298//sup 0/ = -495.4 kJ mol/sup -1/ and S/sub 298//sup 0/ = 110.1 J mol/sup -1/ K/sup -1/ for K/sub 2/O/sub 2/(s). We have calculated a preliminary phase diagram for the entire region from KO/sub 0/ /sub 5/ to KO/sub 2/, treating the liquid as solutions of O (1) in KO/sub 0/ /sub 5/ (1). Differential thermal analysis data supporting the calculated phase diagram are reported.

  20. International thermodynamic tables of the fluid state propylene (propene)

    CERN Document Server

    Angus, S; De Reuck, K M

    2013-01-01

    International Thermodynamic Tables of the Fluid State - 7 Propylene (Propene) is a compilation of internationally agreed values of the equilibrium thermodynamic properties of propylene. This book is composed of three chapters, and begins with the presentation of experimental result of thermodynamic studies compared with the equations used to generate the tables. The succeeding chapter deals with correlating equations for thermodynamic property determination of propylene. The last chapter provides the tabulations of the propylene's thermodynamic properties and constants. This book will prove

  1. Thermodynamic properties of organic compounds estimation methods, principles and practice

    CERN Document Server

    Janz, George J

    1967-01-01

    Thermodynamic Properties of Organic Compounds: Estimation Methods, Principles and Practice, Revised Edition focuses on the progression of practical methods in computing the thermodynamic characteristics of organic compounds. Divided into two parts with eight chapters, the book concentrates first on the methods of estimation. Topics presented are statistical and combined thermodynamic functions; free energy change and equilibrium conversions; and estimation of thermodynamic properties. The next discussions focus on the thermodynamic properties of simple polyatomic systems by statistical the

  2. The ADvanced SEParation (ADSEP)

    Science.gov (United States)

    1998-01-01

    The ADvanced SEParation (ADSEP) commercial payload is making use of major advances in separation technology: The Phase Partitioning Experiment (PPE); the Micorencapsulation experiment; and the Hemoglobin Separation Experiment (HSE). Using ADSEP, commercial researchers will attempt to determine the partition coefficients for model particles in a two-phase system. With this information, researchers can develop a higher resolution, more effective cell isolation procedure that can be used for many different types of research and for improved health care. The advanced separation technology is already being made available for use in ground-based laboratories.

  3. Separation of flow

    CERN Document Server

    Chang, Paul K

    2014-01-01

    Interdisciplinary and Advanced Topics in Science and Engineering, Volume 3: Separation of Flow presents the problem of the separation of fluid flow. This book provides information covering the fields of basic physical processes, analyses, and experiments concerning flow separation.Organized into 12 chapters, this volume begins with an overview of the flow separation on the body surface as discusses in various classical examples. This text then examines the analytical and experimental results of the laminar boundary layer of steady, two-dimensional flows in the subsonic speed range. Other chapt

  4. Spectroscopic Investigations of the Photophysics of Cryptophyte Light-Harvesting

    Science.gov (United States)

    Dinshaw, Rayomond

    The biological significance of photosynthesis is indisputable as it is necessary for nearly all life on earth. Photosynthesis provides chemical energy for plants, algae, and bacteria, while heterotrophic organisms rely on these species as their ultimate food source. The initial step in photosynthesis requires the absorption of sunlight to create electronic excitations. Light-harvesting proteins play the functional role of capturing solar radiation and transferring the resulting excitation to the reaction centers where it is used to carry out the chemical reactions of photosynthesis. Despite the wide variety of light-harvesting protein structures and arrangements, most light-harvesting proteins are able to utilize the captured solar energy for charge separation with near perfect quantum efficiency.1 This thesis will focus on understanding the energy transfer dynamics and photophysics of a specific subset of light-harvesting antennae known as phycobiliproteins. These proteins are extracted from cryptophyte algae and are investigated using steady-state and ultrafast spectroscopic techniques.

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

    NARCIS (Netherlands)

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

    1982-01-01

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

  6. CMEs' Speed, Travel Time, and Temperature: A Thermodynamic Approach

    Science.gov (United States)

    Durand-Manterola, Hector J.; Flandes, Alberto; Rivera, Ana Leonor; Lara, Alejandro; Niembro, Tatiana

    2017-12-01

    Due to their important role in space weather, coronal mass ejections or CMEs have been thoroughly studied in order to forecast their speed and transit time from the Sun to the Earth. We present a thermodynamic analytical model that describes the dynamics of CMEs. The thermodynamic approach has some advantages with respect to the hydrodynamic approach. First, it deals with the energy involved, which is a scalar quantity. Second, one may calculate the work done by the different forces separately and sum all contributions to determine the changes in speed, which simplifies the problem and allows us to obtain fully rigorous results. Our model considers the drag force, which dominates the dynamics of CMEs and the solar gravitational force, which has a much smaller effect, but it is, still, relevant enough to be considered. We derive an explicit analytical expression for the speed of CMEs in terms of its most relevant parameters and obtain an analytical expression for the CME temperature. The model is tested with a CME observed at three different heliocentric distances with three different spacecraft (SOHO, ACE, and Ulysses); also, with a set of 11 CMEs observed with the SOHO, Wind, and ACE spacecraft and, finally, with two events observed with the STEREO spacecraft. In all cases, we have a consistent agreement between the theoretical and the observed speeds and transit times. Additionally, for the set of 11 events, we estimate their temperatures at their departure position from their temperatures measured near the orbit of the Earth.

  7. Nonequilibrium Thermodynamics in Biological Systems

    Science.gov (United States)

    Aoki, I.

    2005-12-01

    1. Respiration Oxygen-uptake by respiration in organisms decomposes macromolecules such as carbohydrate, protein and lipid and liberates chemical energy of high quality, which is then used to chemical reactions and motions of matter in organisms to support lively order in structure and function in organisms. Finally, this chemical energy becomes heat energy of low quality and is discarded to the outside (dissipation function). Accompanying this heat energy, entropy production which inevitably occurs by irreversibility also is discarded to the outside. Dissipation function and entropy production are estimated from data of respiration. 2. Human body From the observed data of respiration (oxygen absorption), the entropy production in human body can be estimated. Entropy production from 0 to 75 years old human has been obtained, and extrapolated to fertilized egg (beginning of human life) and to 120 years old (maximum period of human life). Entropy production show characteristic behavior in human life span : early rapid increase in short growing phase and later slow decrease in long aging phase. It is proposed that this tendency is ubiquitous and constitutes a Principle of Organization in complex biotic systems. 3. Ecological communities From the data of respiration of eighteen aquatic communities, specific (i.e. per biomass) entropy productions are obtained. They show two phase character with respect to trophic diversity : early increase and later decrease with the increase of trophic diversity. The trophic diversity in these aquatic ecosystems is shown to be positively correlated with the degree of eutrophication, and the degree of eutrophication is an "arrow of time" in the hierarchy of aquatic ecosystems. Hence specific entropy production has the two phase: early increase and later decrease with time. 4. Entropy principle for living systems The Second Law of Thermodynamics has been expressed as follows. 1) In isolated systems, entropy increases with time and

  8. Optical Spectroscopic Monitoring of Parachute Yarn Aging

    Energy Technology Data Exchange (ETDEWEB)

    Tallant, D.R.; Garcia, M.J.; Simpson, R.L.; Behr, V.L.; Whinery, L.D.; Peng, L.W.

    1999-04-01

    Optical spectroscopic techniques were evaluated as nondestructive monitors of the aging of parachutes in nuclear weapons. We analyzed thermally aged samples of nylon and Kevlar webbing by photoluminescence spectroscopy and reflection spectroscopy. Infrared analysis was also performed to help understand the degradation mechanisms of the polymer materials in the webbing. The photoluminescence and reflection spectra were analyzed by chemometric data treatment techniques to see if aged-induced changes in the spectra correlated to changes in measured tensile strength. A correlation was found between the shapes of the photoluminescent bands and the measured tensile strengths. Photoluminescent spectra can be used to predict the tensile strengths of nylon and Kevlar webbing with sufficient accuracy to categorize the webbing sample as above rated tensile strength, marginal or below rated tensile strength. The instrumentation required to perform the optical spectroscopic measurement can be made rugged, compact and portable. Thus, optical spectroscopic techniques offer a means for nondestructive field monitoring of parachutes in the enduring stockpile/

  9. The second laws of quantum thermodynamics.

    Science.gov (United States)

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

    2015-03-17

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

  10. Thermodynamics Optimizes the Physiology of Life

    Directory of Open Access Journals (Sweden)

    Gladyshev Georgi

    2014-04-01

    Full Text Available Thermodynamics serves as a basis for optimal solutions of the tasks of physiology, which are solved by organisms in the characteristic process of life: evolution, development, homeostasis, and adaptation. It is stated that the quasiequilibrium thermodynamics of quasiclosed complex systems serves as an impetus of evolution, functions, and activities of all levels of biological systems’ organization.This fact predetermines the use of Gibbs’ methods and leads to a hierarchical thermodynamics in all spheres of physiology. The interaction of structurally related levels and sub-levels of biological systems is determined by the thermodynamic principle of substance stability. Thus, life is accompanied by a thermodynamic optimization of physiological functions of biological systems. Living matter, while functioning and evolving, seeks the minimum of specific Gibbs free energy of structure formation at all levels. The spontaneous search of this minimum takes place with participation of not only spontaneous, but also non-spontaneous processes, initiated by the surrounding environment. The hormone optimization of the treatment of various pathologies, presented by Dr. Sergey A. Dzugan et al. demonstrates the effectiveness of their innovative medical approach.

  11. Thermodynamics of Fluids Under Flow Second Edition

    CERN Document Server

    Jou, David; Criado-Sancho, Manuel

    2011-01-01

    This is the second edition of the book “Thermodynamics of Fluids under Flow,” which was published in 2000 and has now been corrected, expanded and updated. This is a companion book to our other title Extended irreversible thermodynamics (D. Jou, J. Casas-Vázquez and G. Lebon, Springer, 4th edition 2010), and of the textbook Understanding non-equilibrium thermodynamics (G. Lebon, D. Jou and J. Casas-Vázquez, Springer, 2008. The present book is more specialized than its counterpart, as it focuses its attention on the non-equilibrium thermodynamics of flowing fluids, incorporating non-trivial thermodynamic contributions of the flow, going beyond local equilibrium theories, i.e., including the effects of internal variables and of external forcing due to the flow. Whereas the book's first edition was much more focused on polymer solutions, with brief glimpses into ideal and real gases, the present edition covers a much wider variety of systems, such as: diluted and concentrated polymer solutions, polymer ble...

  12. Thermodynamic data-base for metal fluorides

    Energy Technology Data Exchange (ETDEWEB)

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

    2001-05-01

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

  13. Elementary statistical thermodynamics a problems approach

    CERN Document Server

    Smith, Norman O

    1982-01-01

    This book is a sequel to my Chemical Thermodynamics: A Prob­ lems Approach published in 1967, which concerned classical thermodynamics almost exclusively. Most books on statistical thermodynamics now available are written either for the superior general chemistry student or for the specialist. The author has felt the need for a text which would bring the intermediate reader to the point where he could not only appreciate the roots of the subject but also have some facility in calculating thermodynamic quantities. Although statistical thermodynamics comprises an essential part of the college training of a chemist, its treatment in general physical chem­ istry texts is, of necessity, compressed to the point where the less competent student is unable to appreciate or comprehend its logic and beauty, and is reduced to memorizing a series of formulas. It has been my aim to fill this need by writing a logical account of the foundations and applications of the sub­ ject at a level which can be grasped by an under...

  14. Nonterminal Separating Macro Grammars

    NARCIS (Netherlands)

    Hogendorp, Jan Anne

    1987-01-01

    We extend the concept of nonterminal separating (or NTS) context-free grammar to nonterminal separating $m$-macro grammar where the mode of derivation $m$ is equal to "unrestricted". "outside-in' or "inside-out". Then we show some (partial) characterization results for these NTS $m$-macro grammars.

  15. Working with Separation

    Science.gov (United States)

    Krugman, Dorothy C.

    1971-01-01

    Discusses the role of the caseworker in providing support to children experiencing separation from their families and emphasizes the need to recognize that there are differences between those separation experiences dictated by the needs of children and those dictated by arbitrary or noncasework factors. (AJ)

  16. Separation anxiety disorder

    NARCIS (Netherlands)

    Nauta, M.H.; Emmelkamp, P.M.G.; Sturmey, P.; Hersen, M.

    2012-01-01

    Separation anxiety disorder (SAD) is the only anxiety disorder that is specific to childhood; however, SAD has hardly ever been addressed as a separate disorder in clinical trials investigating treatment outcome. So far, only parent training has been developed specifically for SAD. This particular

  17. Social Separation in Monkeys.

    Science.gov (United States)

    Mineka, Susan; Suomi, Stephen J.

    1978-01-01

    Reviews phenomena associated with social separation from attachment objects in nonhuman primates. Evaluates four theoretical treatments of separation in light of existing data: Bowlby's attachment-object-loss theory, Kaufman's conservation-withdrawal theory, Seligman's learned helplessness theory, and Solomon and Corbit's opponent-process theory.…

  18. Thermodynamic properties derived from the free volume model of liquids

    Science.gov (United States)

    Miller, R. I.

    1974-01-01

    An equation of state and expressions for the isothermal compressibility, thermal expansion coefficient, heat capacity, and entropy of liquids have been derived from the free volume model partition function suggested by Turnbull. The simple definition of the free volume is used, and it is assumed that the specific volume is directly related to the cube of the intermolecular separation by a proportionality factor which is found to be a function of temperature and pressure as well as specific volume. When values of the proportionality factor are calculated from experimental data for real liquids, it is found to be approximately constant over ranges of temperature and pressure which correspond to the dense liquid phase. This result provides a single-parameter method for calculating dense liquid thermodynamic properties and is consistent with the fact that the free volume model is designed to describe liquids near the solidification point.

  19. Thermodynamic Modelling of Dolomite Behavior in Aqueous Media

    Directory of Open Access Journals (Sweden)

    Tadeusz Michałowski

    2012-01-01

    Full Text Available The compact thermodynamic approach to the systems containing calcium, magnesium, and carbonate species is referred to dissolution of dolomite, as an example of nonequilibrium ternary salt when introduced into aqueous media. The study of dolomite is based on all attainable physicochemical knowledge, involved in expressions for equilibrium constants, where the species of the system are interrelated. The species are also involved in charge and concentration balances, considered as constraints put on a closed system, separated from the environment by diathermal walls. The inferences are gained from calculations performed with use of an iterative computer program. The simulated quasistatic processes occurred under isothermal conditions, started at a preassumed pH0 value of the solution where dolomite was introduced, and are usually involved with formation of other solid phases. None simplifying assumptions in the calculations were made.

  20. [Thermodynamics of the origin of life, evolution and aging].

    Science.gov (United States)

    Gladyshev, G P

    2014-01-01

    Briefly discusses the history of the search of thermodynamic approach to explain the origin of life, evolution and aging of living beings. The origin of life is the result of requirement by the quasi-equilibrium hierarchical thermodynamics, in particular, the supramolecular thermodynamics. The evolution and aging of living beings is accompanied with changes of chemical and supramolecular compositions of living bodies, as well as with changes in the composition and structure of all hierarchies of the living world. The thermodynamic principle of substance stability predicts the existence of a single genetic code in our universe. The thermodynamic theory optimizes physiology and medicine and recommends antiaging diets and medicines. Hierarchical thermodynamics forms the design diversity of culture and art. The thermodynamic theory of origin of life, evolution and aging is the development of Clausius-Gibbs thermodynamics. Hierarchical thermodynamics is the mirror of Darwin-Wallace's-theory.

  1. Development of a THz spectroscopic imaging system

    Energy Technology Data Exchange (ETDEWEB)

    Usami, M [TOCHIGI Nikon Corporation, 770 Midori, Ohtawara, Tochigi (Japan); Iwamoto, T [TOCHIGI Nikon Corporation, 770 Midori, Ohtawara, Tochigi (Japan); Fukasawa, R [TOCHIGI Nikon Corporation, 770 Midori, Ohtawara, Tochigi (Japan); Tani, M [Kansai Advanced Research Center, Communications Research Laboratory, 588-2 Iwaoka, Nishi-ku, Kobe (Japan); Watanabe, M [Kansai Advanced Research Center, Communications Research Laboratory, 588-2 Iwaoka, Nishi-ku, Kobe (Japan); Sakai, K [Kansai Advanced Research Center, Communications Research Laboratory, 588-2 Iwaoka, Nishi-ku, Kobe (Japan)

    2002-11-07

    We have developed a real-time THz imaging system based on the two-dimensional (2D) electro-optic (EO) sampling technique. Employing the 2D EO-sampling technique, we can obtain THz images using a CCD camera at a video rate of up to 30 frames per second. A spatial resolution of 1.4 mm was achieved. This resolution was reasonably close to the theoretical limit determined by diffraction. We observed not only static objects but also moving ones. To acquire spectroscopic information, time-domain images were collected. By processing these images on a computer, we can obtain spectroscopic images. Spectroscopy for silicon wafers was demonstrated.

  2. The thermodynamics of general and local anesthesia

    CERN Document Server

    Graesboll, Kaare; Heimburg, Thomas

    2014-01-01

    General anesthetics are known to cause depression of the freezing point of transitions in biomembranes. This is a consequence of ideal mixing of the anesthetic drugs in the membrane fluid phase and exclusion from the solid phase. Such a generic law provides physical justification of the famous Meyer-Overton rule. We show here that general anesthetics, barbiturates and local anesthetics all display the same effect on melting transitions. Their effect is reversed by hydrostatic pressure. Thus, the thermodynamic behavior of local anesthetics is very similar to that of general anesthetics. We present a detailed thermodynamic analysis of heat capacity profiles of membranes in the presence of anesthetics. 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.

  3. Numerical study of the thermodynamics of clinoatacamite

    Science.gov (United States)

    Khatami, Ehsan; Helton, Joel S.; Rigol, Marcos

    2012-02-01

    We study the thermodynamic properties of the clinoatacamite compound, Cu2(OH)3Cl, by considering several approximate models. They include the Heisenberg model on (i) the uniform pyrochlore lattice, (ii) a very anisotropic pyrochlore lattice, and (iii) a kagome lattice weakly coupled to spins that sit on a triangular lattice. We utilize the exact diagonalization of small clusters with periodic boundary conditions and implement a numerical linked-cluster expansion approach for quantum lattice models with reduced symmetries, which allows us to solve model (iii) in the thermodynamic limit. We find a very good agreement between the experimental uniform susceptibility and the numerical results for models (ii) and (iii), which suggests a weak ferromagnetic coupling between the kagome and triangular layers in clinoatacamite. We also study thermodynamic properties in a geometrical transition between a planar pyrochlore lattice and the kagome lattice.

  4. Industrial Requirements for Thermodynamics and Transport Properties

    DEFF Research Database (Denmark)

    Hendriks, Eric; Kontogeorgis, Georgios; Dohrn, Ralf

    2010-01-01

    . The main results are as follows. There is (still) an acute need for accurate, reliable, and thermodynamically consistent experimental data. Quality is more important than quantity. Similarly, there is a great need for reliable predictive, rather than correlative, models covering a wide range...... of compositions, temperatures, and pressures and capable of predicting primary (phase equilibrium) and secondary (enthalpy, heat capacity, etc.) properties. It is clear that the ideal of a single model covering all requirements is not achievable, but there is a consensus that this ideal should still provide...... reactive systems (simultaneous chemical and physical equilibrium). Education in thermodynamics is perceived as key, for the future application of thermodynamics in the industry. A number of suggestions for improvement were made at all three levels (undergraduate, postgraduate, and professional development...

  5. Stochastic Thermodynamics: A Dynamical Systems Approach

    Directory of Open Access Journals (Sweden)

    Tanmay Rajpurohit

    2017-12-01

    Full Text Available In this paper, we develop an energy-based, large-scale dynamical system model driven by Markov diffusion processes to present a unified framework for statistical thermodynamics predicated on a stochastic dynamical systems formalism. Specifically, using a stochastic state space formulation, we develop a nonlinear stochastic compartmental dynamical system model characterized by energy conservation laws that is consistent with statistical thermodynamic principles. In particular, we show that the difference between the average supplied system energy and the average stored system energy for our stochastic thermodynamic model is a martingale with respect to the system filtration. In addition, we show that the average stored system energy is equal to the mean energy that can be extracted from the system and the mean energy that can be delivered to the system in order to transfer it from a zero energy level to an arbitrary nonempty subset in the state space over a finite stopping time.

  6. Relativistic Thermodynamics: A Modern 4-Vector Approach

    Directory of Open Access Journals (Sweden)

    J. Güémez

    2011-01-01

    Full Text Available Using the Minkowski relativistic 4-vector formalism, based on Einstein's equation, and the relativistic thermodynamics asynchronous formulation (Grøn (1973, the isothermal compression of an ideal gas is analyzed, considering an electromagnetic origin for forces applied to it. This treatment is similar to the description previously developed by Van Kampen (van Kampen (1969 and Hamity (Hamity (1969. In this relativistic framework Mechanics and Thermodynamics merge in the first law of relativistic thermodynamics expressed, using 4-vector notation, such as ΔUμ  =  Wμ  +  Qμ, in Lorentz covariant formulation, which, with the covariant formalism for electromagnetic forces, constitutes a complete Lorentz covariant formulation for classical physics.

  7. Maximal temperature in a simple thermodynamical system

    Science.gov (United States)

    Dai, De-Chang; Stojkovic, Dejan

    2016-06-01

    Temperature in a simple thermodynamical system is not limited from above. It is also widely believed that it does not make sense talking about temperatures higher than the Planck temperature in the absence of the full theory of quantum gravity. Here, we demonstrate that there exist a maximal achievable temperature in a system where particles obey the laws of quantum mechanics and classical gravity before we reach the realm of quantum gravity. Namely, if two particles with a given center of mass energy come at the distance shorter than the Schwarzschild diameter apart, according to classical gravity they will form a black hole. It is possible to calculate that a simple thermodynamical system will be dominated by black holes at a critical temperature which is about three times lower than the Planck temperature. That represents the maximal achievable temperature in a simple thermodynamical system.

  8. The Thermodynamics of General and Local Anesthesia

    Science.gov (United States)

    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.

  9. Thermodynamics principles characterizing physical and chemical processes

    CERN Document Server

    Honig, Jurgen M

    1999-01-01

    This book provides a concise overview of thermodynamics, and is written in a manner which makes the difficult subject matter understandable. Thermodynamics is systematic in its presentation and covers many subjects that are generally not dealt with in competing books such as: Carathéodory''s approach to the Second Law, the general theory of phase transitions, the origin of phase diagrams, the treatment of matter subjected to a variety of external fields, and the subject of irreversible thermodynamics.The book provides a first-principles, postulational, self-contained description of physical and chemical processes. Designed both as a textbook and as a monograph, the book stresses the fundamental principles, the logical development of the subject matter, and the applications in a variety of disciplines. This revised edition is based on teaching experience in the classroom, and incorporates many exercises in varying degrees of sophistication. The stress laid on a didactic, logical presentation, and on the relat...

  10. Fundamental aspects of plasma chemical physics Thermodynamics

    CERN Document Server

    Capitelli, Mario; D'Angola, Antonio

    2012-01-01

    Fundamental Aspects of Plasma Chemical Physics - Thermodynamics develops basic and advanced concepts of plasma thermodynamics from both classical and statistical points of view. After a refreshment of classical thermodynamics applied to the dissociation and ionization regimes, the book invites the reader to discover the role of electronic excitation in affecting the properties of plasmas, a topic often overlooked by the thermal plasma community. Particular attention is devoted to the problem of the divergence of the partition function of atomic species and the state-to-state approach for calculating the partition function of diatomic and polyatomic molecules. The limit of ideal gas approximation is also discussed, by introducing Debye-Huckel and virial corrections. Throughout the book, worked examples are given in order to clarify concepts and mathematical approaches. This book is a first of a series of three books to be published by the authors on fundamental aspects of plasma chemical physics.  The next bo...

  11. The calculation of thermodynamic properties of molecules

    DEFF Research Database (Denmark)

    van Speybroeck, Veronique; Gani, Rafiqul; Meier, Robert Johan

    2010-01-01

    Thermodynamic data are key in the understanding and design of chemical processes. Next to the experimental evaluation of such data, computational methods are valuable and sometimes indispensable tools in obtaining heats of formation and Gibbs free energies. The major toolboxes to obtain such quan......Thermodynamic data are key in the understanding and design of chemical processes. Next to the experimental evaluation of such data, computational methods are valuable and sometimes indispensable tools in obtaining heats of formation and Gibbs free energies. The major toolboxes to obtain...... molecules the combination of group contribution methods with group additive values that are determined with the best available computational ab initio methods seems to be a viable alternative to obtain thermodynamic properties near chemical accuracy. New developments and full use of existing tools may lead...

  12. Teaching Differentials in Thermodynamics using Spatial Visualization

    CERN Document Server

    Wang, Chih-Yueh

    2011-01-01

    The greatest difficulty that is encountered by students in Thermodynamics classes is to find relationships between variables and solve a total differential equation that relates one thermodynamic state variable to two mutually-independent state variables. Rules of differentiation, including the total differential and the cyclic rule, are fundamental to solving thermodynamics problems. However, many students do not well understand such basic mathematics principles, because the underlying geometric meaning is unclear to them. Studies have shown that proficient symbolic techniques may become an obstacle to learning in a qualitative approach. Spatial visualization allows an emergence of new reasoning for students. In this investigation, the total differential rule and the cyclic rule are interpreted geometrically.

  13. Smoothed generalized free energies for thermodynamics

    Science.gov (United States)

    van der Meer, Remco; Ng, Nelly Huei Ying; Wehner, Stephanie

    2017-12-01

    In the study of thermodynamics for nanoscale quantum systems, a family of quantities known as generalized free energies have been derived as necessary and sufficient conditions that govern state transitions. These free energies become important especially in the regime where the system of interest consists of only a few (quantum) particles. In this work, we introduce a family of smoothed generalized free energies, by constructing explicit smoothing procedures that maximize or minimize the free energy over an ɛ ball of quantum states. In contrast to previously known smoothed free energies, these quantities now allow us to make an operational statement for approximate thermodynamic state transitions. We show that these smoothed quantities converge to the standard free energy in the thermodynamic limit.

  14. Gravity and Nonequilibrium Thermodynamics of Classical Matter

    CERN Document Server

    Hu, B L

    2010-01-01

    Renewed interest in deriving gravity (more precisely, the Einstein equations) from thermodynamics considerations [1, 2] is stirred up by a recent proposal that 'gravity is an entropic force' [3] (see also [4]). Even though I find the arguments justifying such a claim in this latest proposal rather ad hoc and simplistic compared to the original one I would unreservedly support the call to explore deeper the relation between gravity and thermodynamics, this having the same spirit as my long-held view that general relativity is the hydrodynamic limit [5, 6] of some underlying theories for the microscopic structure of spacetime - all these proposals, together with that of [7, 8], attest to the emergent nature of gravity [9]. In this first paper of two we set the modest goal of studying the nonequilibrium thermodynamics of classical matter only, bringing afore some interesting prior results, without invoking any quantum considerations such as Bekenstein-Hawking entropy, holography or Unruh effect. This is for the ...

  15. A thermodynamic cycle for the solar cell

    Science.gov (United States)

    Alicki, Robert; Gelbwaser-Klimovsky, David; Jenkins, Alejandro

    2017-03-01

    A solar cell is a heat engine, but textbook treatments are not wholly satisfactory from a thermodynamic standpoint, since they present solar cells as directly converting the energy of light into electricity, and the current in the circuit as maintained by an electrostatic potential. We propose a thermodynamic cycle in which the gas of electrons in the p phase serves as the working substance. The interface between the p and n phases acts as a self-oscillating piston that modulates the absorption of heat from the photons so that it may perform a net positive work during a complete cycle of its motion, in accordance with the laws of thermodynamics. We draw a simple hydrodynamical analogy between this model and the "putt-putt" engine of toy boats, in which the interface between the water's liquid and gas phases serves as the piston. We point out some testable consequences of this model.

  16. Thermodynamic stability limits of simple monoatomic materials.

    Science.gov (United States)

    Gallington, Leighanne C; Bongiorno, Angelo

    2010-05-07

    This computational study addresses the thermodynamical stability of superheated crystals. Molecular dynamics simulations are employed to derive the caloric curves of the solid and liquid phases of a material. Caloric curves are used to derive thermodynamic state functions, the parameters of the equilibrium melting phase transition, and the regions of thermodynamical stability of the liquid and solid phases. Molecular dynamics trajectories are also analyzed to gain insight on the mechanisms leading to the instability of the homogeneous superheated solid phase. This study shows that in simple and homogeneous solids the configurational entropy is not zero and that its excitations can occur without disrupting the crystallinity of the lattice. The superheating and supercooling limits of the solid and liquid phases are found to correspond to states of equal entropy and enthalpy.

  17. Kinetics and thermodynamics of living copolymerization processes.

    Science.gov (United States)

    Gaspard, Pierre

    2016-11-13

    Theoretical advances are reported on the kinetics and thermodynamics of free and template-directed living copolymerizations. Until recently, the kinetic theory of these processes had only been established in the fully irreversible regime, in which the attachment rates are only considered. However, the entropy production is infinite in this regime and the approach to thermodynamic equilibrium cannot be investigated. For this purpose, the detachment rates should also be included. Inspite of this complication, the kinetics can be exactly solved in the regimes of steady growth and depolymerization. In this way, analytical expressions are obtained for the mean growth velocity, the statistical properties of the copolymer sequences, as well as the thermodynamic entropy production. The results apply to DNA replication, transcription and translation, allowing us to understand important aspects of molecular evolution.This article is part of the themed issue 'Multiscale modelling at the physics-chemistry-biology interface'. © 2016 The Author(s).

  18. Velocity Curve Analysis of the Spectroscopic Binary Stars PV Pup ...

    Indian Academy of Sciences (India)

    2016-01-27

    lined spectroscopic binary systems PV Pup, HD 141929, EE Cet and V921 Her, we find both the orbital and the combined spectroscopic elements of these systems. Our numerical results are in good agreement with those obtained ...

  19. Black Hole Thermodynamics and Lorentz Symmetry

    Science.gov (United States)

    Jacobson, Ted; Wall, Aron C.

    2010-08-01

    Recent developments point to a breakdown in the generalized second law of thermodynamics for theories with Lorentz symmetry violation. It appears possible to construct a perpetual motion machine of the second kind in such theories, using a black hole to catalyze the conversion of heat to work. Here we describe and extend the arguments leading to that conclusion. We suggest the inference that local Lorentz symmetry may be an emergent property of the macroscopic world with origins in a microscopic second law of causal horizon thermodynamics.

  20. Consistent thermodynamic properties of lipids systems

    DEFF Research Database (Denmark)

    Cunico, Larissa; Ceriani, Roberta; Sarup, Bent

    Physical and thermodynamic properties of pure components and their mixtures are the basic requirement for process design, simulation, and optimization. In the case of lipids, our previous works[1-3] have indicated a lack of experimental data for pure components and also for their mixtures...... different pressures, with azeotrope behavior observed. Available thermodynamic consistency tests for TPx data were applied before performing parameter regressions for Wilson, NRTL, UNIQUAC and original UNIFAC models. The relevance of enlarging experimental databank of lipids systems data in order to improve...

  1. Horizon thermodynamics from Einstein's equation of state

    Science.gov (United States)

    Hansen, Devin; Kubizňák, David; Mann, Robert B.

    2017-08-01

    By regarding the Einstein equations as equation(s) of state, we demonstrate that a full cohomogeneity horizon first law can be derived in horizon thermodynamics. In this approach both the entropy and the free energy are derived concepts, while the standard (degenerate) horizon first law is recovered by a Legendre projection from the more general one we derive. These results readily generalize to higher curvature gravities where they naturally reproduce a formula for the entropy without introducing Noether charges. Our results thus establish a way of how to formulate consistent black hole thermodynamics without conserved charges.

  2. Nonequilibrium thermodynamics and Nose-Hoover dynamics.

    Science.gov (United States)

    Esposito, Massimiliano; Monnai, Takaaki

    2011-05-12

    We show that systems driven by an external force and described by Nose-Hoover dynamics allow for a consistent nonequilibrium thermodynamics description when the thermostatted variable is initially assumed in a state of canonical equilibrium. By treating the "real" variables as the system and the thermostatted variable as the reservoir, we establish the first and second law of thermodynamics. As for Hamiltonian systems, the entropy production can be expressed as a relative entropy measuring the system-reservoir correlations established during the dynamics.

  3. An open-source thermodynamic software library

    DEFF Research Database (Denmark)

    Ritschel, Tobias Kasper Skovborg; Gaspar, Jozsef; Capolei, Andrea

    This is a technical report which accompanies the article ”An open-source thermodynamic software library” which describes an efficient Matlab and C implementation for evaluation of thermodynamic properties. In this technical report we present the model equations, that are also presented in the paper......, together with a full set of first and second order derivatives with respect to temperature and pressure, and in cases where applicable, also with respect to mole numbers. The library is based on parameters and correlations from the DIPPR database and the Peng-Robinson and the Soave-Redlich-Kwong equations...

  4. Closed power cycles thermodynamic fundamentals and applications

    CERN Document Server

    Invernizzi, Costante Mario

    2013-01-01

    With the growing attention to the exploitation of renewable energies and heat recovery from industrial processes, the traditional steam and gas cycles are showing themselves often inadequate. The inadequacy is due to the great assortment of the required sizes power and of the large kind of heat sources. Closed Power Cycles: Thermodynamic Fundamentals and Applications offers an organized discussion about the strong interaction between working fluids, the thermodynamic behavior of the cycle using them and the technological design aspects of the machines. A precise treatment of thermal engines op

  5. Qualitative and quantitative reasoning about thermodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Skorstad, G.; Forbus, K.

    1989-11-01

    One goal of qualitative physics is to capture the tacit knowledge of engineers and scientists. It is shown how Qualitative Process theory can be used to express concepts of engineering thermodynamics. In particular, it is shown how to integrate qualitative and quantitative knowledge to solve textbook problems involving thermodynamic cycles, such as gas turbine plants and steam power plants. These ideas were implemented in a program called SCHISM. Its analysis of a sample textbook problem is described and plans for future work are discussed.

  6. Numerical Simulation of Cyclic Thermodynamic Processes

    DEFF Research Database (Denmark)

    Andersen, Stig Kildegård

    2006-01-01

    This thesis is on numerical simulation of cyclic thermodynamic processes. A modelling approach and a method for finding periodic steady state solutions are described. Examples of applications are given in the form of four research papers. Stirling machines and pulse tube coolers are introduced......, compressible flow in one space dimension is presented. The implementation produces models where all the equations, which are on a form that should be understandable to someone with a background in engineering thermodynamics, can be accessed and modified individually. The implementation was designed to make...

  7. Thermodynamic significance of human basal metabolism

    Science.gov (United States)

    Wang, Cuncheng

    1993-06-01

    The human basal state, a non-equilibrium steady state, is analysed in this paper in the light of the First and Second Laws of Thermodynamics whereby the thermodynamic significance of the basal metabolic rate and its distinction to the dissipation function and exergy loss are identified. The analysis demonstrates the correct expression of the effects of the blood flow on the heat balance in a human-body bio-heat model and the relationship between the basal metabolic rate and the blood perfusion.

  8. Horizon thermodynamics from Einstein's equation of state

    Directory of Open Access Journals (Sweden)

    Devin Hansen

    2017-08-01

    Full Text Available By regarding the Einstein equations as equation(s of state, we demonstrate that a full cohomogeneity horizon first law can be derived in horizon thermodynamics. In this approach both the entropy and the free energy are derived concepts, while the standard (degenerate horizon first law is recovered by a Legendre projection from the more general one we derive. These results readily generalize to higher curvature gravities where they naturally reproduce a formula for the entropy without introducing Noether charges. Our results thus establish a way of how to formulate consistent black hole thermodynamics without conserved charges.

  9. Thermodynamics and statistical mechanics an integrated approach

    CERN Document Server

    Hardy, Robert J

    2014-01-01

    This textbook brings together the fundamentals of the macroscopic and microscopic aspects of thermal physics by presenting thermodynamics and statistical mechanics as complementary theories based on small numbers of postulates. The book is designed to give the instructor flexibility in structuring courses for advanced undergraduates and/or beginning graduate students and is written on the principle that a good text should also be a good reference. The presentation of thermodynamics follows the logic of Clausius and Kelvin while relating the concepts involved to familiar phenomena and the mod

  10. Cantera and Cantera Electrolyte Thermodynamics Objects

    Energy Technology Data Exchange (ETDEWEB)

    2015-10-19

    Cantera is a suite of object-oriented software tools for problems involving chemical kinetics, thermodynamics, and/or transport processes. It is a multi-organizational effort to create and formulate high quality 0D and 1D constitutive modeling tools for reactive transport codes.Institutions involved with the effort include Sandia, MIT, Colorado School of Mines, U. Texas, NASA, and Oak Ridge National Labs. Specific to Sandia's contributions, the Cantera Electrolyte Thermo Objects (CETO) packages is comprised of add-on routines for Cantera that handle electrolyte thermochemistry and reactions within the overall Cantera package. Cantera is a C++ Cal Tech code that handles gas phase species transport, reaction, and thermodynamics. With this addition, Cantera can be extended to handle problems involving liquid phase reactions and transport in electrolyte systems, and phase equilibrium problemsinvolving concentrated electrolytes and gas/solid phases. A full treatment of molten salt thermodynamics and transport has also been implemented in CETO. The routines themselves consist of .cpp and .h files containing C++ objects that are derived from parent Cantera objects representing thermodynamic functions. They are linked unto the main Cantera libraries when requested by the user. As an addendum to the main thermodynamics objects, several utility applications are provided. The first is multiphase Gibbs free energy minimizer based on the vcs algorithm, called vcs_cantera. This code allows for the calculation of thermodynamic equilibrium in multiple phases at constant temperature and pressure. Note, a similar code capability exists already in Cantera. This version follows the same algorithm, but gas a different code-base starting point, and is used as a research tool for algorithm development. The second program, cttables, prints out tables of thermodynamic and kinetic information for thermodynamic and kinetic objects within Cantera. This program serves as a "Get the

  11. Chromatographic hydrogen isotope separation

    Science.gov (United States)

    Aldridge, Frederick T.

    1981-01-01

    Intermetallic compounds with the CaCu.sub.5 type of crystal structure, particularly LaNiCo.sub.4 and CaNi.sub.5, exhibit high separation factors and fast equilibrium times and therefore are useful for packing a chromatographic hydrogen isotope separation colum. The addition of an inert metal to dilute the hydride improves performance of the column. A large scale mutli-stage chromatographic separation process run as a secondary process off a hydrogen feedstream from an industrial plant which uses large volumes of hydrogen can produce large quantities of heavy water at an effective cost for use in heavy water reactors.

  12. Rotary drum separator system

    Science.gov (United States)

    Barone, Michael R. (Inventor); Murdoch, Karen (Inventor); Scull, Timothy D. (Inventor); Fort, James H. (Inventor)

    2009-01-01

    A rotary phase separator system generally includes a step-shaped rotary drum separator (RDS) and a motor assembly. The aspect ratio of the stepped drum minimizes power for both the accumulating and pumping functions. The accumulator section of the RDS has a relatively small diameter to minimize power losses within an axial length to define significant volume for accumulation. The pumping section of the RDS has a larger diameter to increase pumping head but has a shorter axial length to minimize power losses. The motor assembly drives the RDS at a low speed for separating and accumulating and a higher speed for pumping.

  13. Thermodynamics of Rotating Black Holes and Black Rings: Phase Transitions and Thermodynamic Volume

    Directory of Open Access Journals (Sweden)

    Natacha Altamirano

    2014-03-01

    Full Text Available In this review we summarize, expand, and set in context recent developments on the thermodynamics of black holes in extended phase space, where the cosmological constant is interpreted as thermodynamic pressure and treated as a thermodynamic variable in its own right. We specifically consider the thermodynamics of higher-dimensional rotating asymptotically flat and AdS black holes and black rings in a canonical (fixed angular momentum ensemble. We plot the associated thermodynamic potential—the Gibbs free energy—and study its behavior to uncover possible thermodynamic phase transitions in these black hole spacetimes. We show that the multiply-rotating Kerr-AdS black holes exhibit a rich set of interesting thermodynamic phenomena analogous to the “every day thermodynamics” of simple substances, such as reentrant phase transitions of multicomponent liquids, multiple first-order solid/liquid/gas phase transitions, and liquid/gas phase transitions of the van derWaals type. Furthermore, the reentrant phase transitions also occur for multiply-spinning asymptotically flat Myers–Perry black holes. These phenomena do not require a variable cosmological constant, though they are more naturally understood in the context of the extended phase space. The thermodynamic volume, a quantity conjugate to the thermodynamic pressure, is studied for AdS black rings and demonstrated to satisfy the reverse isoperimetric inequality; this provides a first example of calculation confirming the validity of isoperimetric inequality conjecture for a black hole with non-spherical horizon topology. The equation of state P = P(V,T is studied for various black holes both numerically and analytically—in the ultraspinning and slow rotation regimes.

  14. Optical Metrology for Directed Self-assembly Patterning Using Mueller Matrix Spectroscopic Ellipsometry Based Scatterometry

    Science.gov (United States)

    Dixit, Dhairya J.

    The semiconductor industry continues to drive patterning solutions that enable devices with higher memory storage capacity, faster computing performance, lower cost per transistors, and higher transistor density. These developments in the field of semiconductor manufacturing along with the overall minimization of the size of transistors require cutting-edge metrology tools for characterization. Directed self-assembly (DSA) patterning process can be used to fabricate nanoscale line-space patterns and contact holes via thermodynamically driven micro-phase separation of block copolymer (BCP) films with boundary constraints from guiding templates. Its main advantages are high pattern resolution (~10 nm), high throughput, no requirement of a high-resolution mask, and compatibility with standard fab-equipment and processes. Although research into DSA patterning has demonstrated a high potential as a nanoscale patterning process, there are critical challenges that must be overcome before transferring DSA into high volume manufacturing, including achievement of low defect density and high process stability. For this, advances in critical dimension (CD) and overlay measurement as well as rapid defect characterization are required. Both scatterometry and critical dimension-scanning electron microscopy (CD-SEM) are routinely used for inline dimensional metrology. CD-SEM inspection is limited, as it does not easily provide detailed line-shape information, whereas scatterometry has the capability of measuring important feature dimensions including: line-width, line-shape, sidewall-angle, and thickness of the patterned samples quickly and non-destructively. The present work describes the application of Mueller matrix spectroscopic ellipsometry (MMSE) based scatterometry to optically characterize DSA patterned line- space grating and contact hole structures fabricated with phase-separated polystyrene-b-polymethylmethacrylate (PS-b-PMMA) at various integration steps of BCP DSA

  15. Thermodynamic modeling of naringenin protonation equilibria in ...

    Indian Academy of Sciences (India)

    The protonation equilibria for the flavonoid naringenin were studied at 25°C using combined multiwavelength spectroscopic and pH-potentiometric methods as a function of the ionic strength. Over a wide range of ionic strengths, 0.10–3.00 mol dm−3, the investigation was performed in different aqueous solutions of NaClO4 ...

  16. Condensation: Passenger Not Driver in Atmospheric Thermodynamics

    Directory of Open Access Journals (Sweden)

    Jack Denur

    2016-11-01

    Full Text Available The second law of thermodynamics states that processes yielding work or at least capable of yielding work are thermodynamically spontaneous, and that those costing work are thermodynamically nonspontaneous. Whether a process yields or costs heat is irrelevant. Condensation of water vapor yields work and hence is thermodynamically spontaneous only in a supersaturated atmosphere; in an unsaturated atmosphere it costs work and hence is thermodynamically nonspontaneous. Far more of Earth’s atmosphere is unsaturated than supersaturated; based on this alone evaporation is far more often work-yielding and hence thermodynamically spontaneous than condensation in Earth’s atmosphere—despite condensation always yielding heat and evaporation always costing heat. Furthermore, establishment of the unstable or at best metastable condition of supersaturation, and its maintenance in the face of condensation that would wipe it out, is always work-costing and hence thermodynamically nonspontaneous in Earth’s atmosphere or anywhere else. The work required to enable supersaturation is most usually provided at the expense of temperature differences that enable cooling to below the dew point. In the case of most interest to us, convective weather systems and storms, it is provided at the expense of vertical temperature gradients exceeding the moist adiabatic. Thus, ultimately, condensation is a work-costing and hence thermodynamically nonspontaneous process even in supersaturated regions of Earth’s or any other atmosphere. While heat engines in general can in principle extract all of the work represented by any temperature difference until it is totally neutralized to isothermality, convective weather systems and storms in particular cannot. They can extract only the work represented by partial neutralization of super-moist-adiabatic lapse rates to moist-adiabaticity. Super-moist-adiabatic lapse rates are required to enable convection of saturated air

  17. Nonequilibrium Thermodynamics Based on the Distributions Containing Lifetime as a Thermodynamic Parameter

    Directory of Open Access Journals (Sweden)

    Vasiliy Vasiliy Ryazanov

    2011-01-01

    Full Text Available To describe the nonequilibrium states of a system, we introduce a new thermodynamic parameter—the lifetime of a system. The statistical distributions which can be obtained out of the mesoscopic description characterizing the behaviour of a system by specifying the stochastic processes are written down. The change in the lifetime values by interaction with environment is expressed in terms of fluxes and sources. The expressions for the nonequilibrium entropy, temperature, and entropy production are obtained, which at small values of fluxes coincide with those derived within the frame of extended irreversible thermodynamics. The explicit expressions for the lifetime of a system and its thermodynamic conjugate are obtained.

  18. Radiochemical separation of Cobalt

    NARCIS (Netherlands)

    Erkelens, P.C. van

    1961-01-01

    A method is described for the radiochemical separation of cobalt based on the extraordinary stability of cobalt diethyldithiocarbamate. Interferences are few; only very small amounts of zinc and iron accompany cobalt, which is important in neutron-activation analysis.

  19. Separation Anxiety (For Parents)

    Science.gov (United States)

    ... older child, there might be another problem, like bullying or abuse. Separation anxiety is different from the normal feelings older kids have when they don't want a parent to leave (which can usually be overcome if ...

  20. Separation by solvent extraction

    Science.gov (United States)

    Holt, Jr., Charles H.

    1976-04-06

    17. A process for separating fission product values from uranium and plutonium values contained in an aqueous solution, comprising adding an oxidizing agent to said solution to secure uranium and plutonium in their hexavalent state; contacting said aqueous solution with a substantially water-immiscible organic solvent while agitating and maintaining the temperature at from -1.degree. to -2.degree. C. until the major part of the water present is frozen; continuously separating a solid ice phase as it is formed; separating a remaining aqueous liquid phase containing fission product values and a solvent phase containing plutonium and uranium values from each other; melting at least the last obtained part of said ice phase and adding it to said separated liquid phase; and treating the resulting liquid with a new supply of solvent whereby it is practically depleted of uranium and plutonium.

  1. Separable Arrowhead Microneedles

    Science.gov (United States)

    Chu, Leonard Y.; Prausnitz, Mark R.

    2010-01-01

    Hypodermic needles cause pain and bleeding, produce biohazardous sharp waste and require trained personnel. To address these issues, we introduce separable arrowhead microneedles that rapidly and painlessly deliver drugs and vaccines to the skin. These needles are featured by micron-size sharp tips mounted on blunt shafts. Upon insertion in the skin, the sharp-tipped polymer arrowheads encapsulating drug separate from their metal shafts and remain embedded in the skin for subsequent dissolution and drug release. The blunt metal shafts can then be discarded. Due to rapid separation of the arrowhead tips from the shafts within seconds, administration using arrowhead microneedles can be carried out rapidly, while drug release kinetics can be independently controlled based on separable arrowhead formulation. Thus, drug and vaccine delivery using arrowhead microneedles are designed to offer a quick, convenient, safe and potentially self-administered method of drug delivery as an alternative to hypodermic needles. PMID:21047538

  2. Spectroscopic, thermal and biological studies of coordination ...

    Indian Academy of Sciences (India)

    Administrator

    (Cl)(H2O)3]⋅xH2O (M = Cr(III) and Y(III), x = 5 and 6, respectively) were obtained and characterized by physicochemical and spectroscopic methods. The IR spectra of the complexes suggest that the sulfasalazine behaves as a monoanionic bidentate ligand. The thermal decomposition of the complexes as well as ...

  3. Structural, thermal and spectroscopic properties of supramolecular ...

    Indian Academy of Sciences (India)

    (H2O)4 have been reported.18 No general synthetic methodology for metal isonicotinate tetrahydrates has been reported so far. Detailed magnetic and spectroscopic properties of the compounds have not also been studied. Herein we report their high yield syntheses ... purpose of quantitative metal analysis by the gra-.

  4. An interesting spectroscopic method for chromofluorogenic ...

    Indian Academy of Sciences (India)

    537–543. c Indian Academy of Sciences. DOI 10.1007/s12039-016-1051-y. An interesting spectroscopic method for chromofluorogenic detection of cyanide ion in aqueous solution: Disruption of intramolecular charge transfer (ICT). ABDOLHAMID ALIZADEHa,b∗. , SOHRAB GHOUZIVANDa, MOHAMMAD M KHODAEIa,∗.

  5. Ultraviolet spectroscopic evaluation of bioactive saponin fraction ...

    African Journals Online (AJOL)

    Ultraviolet spectroscopic evaluation of bioactive saponin fraction from the aqueous extract of Vernonia amygdalina [Esteraeceae] leaf. Paul Chukwuemeka ADIUKWU 1*, Martina BONSU 1, Inemesit OKON-BEN 1,. Paul PEPRAH 1, Paapa MENSAH-KANE 1, Jonathan JATO 1 and Grace NAMBATYA 2. 1School of Pharmacy ...

  6. Synthesis, magnetic measurement and spectroscopic studies on ...

    African Journals Online (AJOL)

    Synthesis, magnetic measurement and spectroscopic studies on cobalt (II) complexes in thiosemicarbazones derived from P-anisaldehyde, P-tolualdehyde, P-vanillin and 9-fluorenone. ... The coordination takes place through thiolato sulphur and azonmethine /imine nitrogen atoms. The tetrahedral flattened structures have ...

  7. Synthesis, spectroscopic characterization and catalytic oxidation ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 123; Issue 3. Synthesis, spectroscopic characterization and catalytic oxidation properties of ONO/ONS donor Schiff base ruthenium(III) complexes containing PPh3/AsPh3. Priyarega M Muthu Tamizh R Karvembu R Prabhakaran K Natarajan. Volume 123 Issue 3 May ...

  8. Pulsating variable stars and large spectroscopic surveys

    Science.gov (United States)

    De Cat, Peter

    2017-09-01

    In the past decade, the research of pulsating variable stars has taken a giant leap forward thanks to the photometric measurements provided by space missions like Most, CoRoT, Kepler/K2, and Brite. These missions have provided quasi uninterrupted photometric time-series with an ultra-high quality and a total length that is not achievable from Earth. However, many of the success stories could not have been told without ground-based spectroscopic follow-up observations. Indeed, spectroscopy has some important assets as it can provide (more) accurate information about stellar parameters (like the effective temperature, surface gravity, metallicity, and abundances that are mandatory parameters for an in-depth asteroseismic study), the radial velocity (that is important for the detection of binaries and for the confirmation of cluster membership, if applicable), and the projected rotational velocity (that allows the study of the effects of rotation on pulsations). Fortunately, several large spectroscopic surveys are (becoming) available that can be used for these purposes. For some of these surveys, sub-projects have been initiated with the specific goal to complement space-based photometry. In this review, several spectroscopic surveys are introduced and compared with each other. We show that a large amount of spectroscopic data is (becoming) available for a large variety of objects.

  9. Nanoantenna-Enhanced Infrared Spectroscopic Chemical Imaging.

    Science.gov (United States)

    Kühner, Lucca; Hentschel, Mario; Zschieschang, Ute; Klauk, Hagen; Vogt, Jochen; Huck, Christian; Giessen, Harald; Neubrech, Frank

    2017-05-26

    Spectroscopic infrared chemical imaging is ideally suited for label-free and spatially resolved characterization of molecular species, but often suffers from low infrared absorption cross sections. Here, we overcome this limitation by utilizing confined electromagnetic near-fields of resonantly excited plasmonic nanoantennas, which enhance the molecular absorption by orders of magnitude. In the experiments, we evaporate microstructured chemical patterns of C60 and pentacene with nanometer thickness on top of homogeneous arrays of tailored nanoantennas. Broadband mid-infrared spectra containing plasmonic and vibrational information were acquired with diffraction-limited resolution using a two-dimensional focal plane array detector. Evaluating the enhanced infrared absorption at the respective frequencies, spatially resolved chemical images were obtained. In these chemical images, the microstructured chemical patterns are only visible if nanoantennas are used. This confirms the superior performance of our approach over conventional spectroscopic infrared imaging. In addition to the improved sensitivity, our technique provides chemical selectivity, which would not be available with plasmonic imaging that is based on refractive index sensing. To extend the accessible spectral bandwidth of nanoantenna-enhanced spectroscopic imaging, we employed nanostructures with dual-band resonances, providing broadband plasmonic enhancement and sensitivity. Our results demonstrate the potential of nanoantenna-enhanced spectroscopic infrared chemical imaging for spatially resolved characterization of organic layers with thicknesses of several nanometers. This is of potential interest for medical applications which are currently hampered by state-of-art infrared techniques, e.g., for distinguishing cancerous from healthy tissues.

  10. Molecular structure, vibrational spectroscopic studies and natural ...

    Indian Academy of Sciences (India)

    pp. 845–860. Molecular structure, vibrational spectroscopic studies and natural bond orbital analysis of 7-amino-4-trifluoromethyl coumarin ..... [15] A Frisch, A B Nielsen and A J Holder, GAUSSIANVIEW Users Manual, Gaussian. Inc., Pittsburgh, PA (2000). [16] S Selladurai and K Subramanian, Acta Crystallogr. C48, 281 ...

  11. Synthesis, molecular structure, spectroscopic investigations and ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 128; Issue 8. Synthesis, molecular structure ... The molecular geometry and spectroscopic data of the title compound have been calculated by using the density functional method (B3LYP) invoking 6-311G(d,p) basis set. UV-Vis spectra of the two forms were recorded.

  12. Hydrogen separation process

    Science.gov (United States)

    Mundschau, Michael [Longmont, CO; Xie, Xiaobing [Foster City, CA; Evenson, IV, Carl; Grimmer, Paul [Longmont, CO; Wright, Harold [Longmont, CO

    2011-05-24

    A method for separating a hydrogen-rich product stream from a feed stream comprising hydrogen and at least one carbon-containing gas, comprising feeding the feed stream, at an inlet pressure greater than atmospheric pressure and a temperature greater than 200.degree. C., to a hydrogen separation membrane system comprising a membrane that is selectively permeable to hydrogen, and producing a hydrogen-rich permeate product stream on the permeate side of the membrane and a carbon dioxide-rich product raffinate stream on the raffinate side of the membrane. A method for separating a hydrogen-rich product stream from a feed stream comprising hydrogen and at least one carbon-containing gas, comprising feeding the feed stream, at an inlet pressure greater than atmospheric pressure and a temperature greater than 200.degree. C., to an integrated water gas shift/hydrogen separation membrane system wherein the hydrogen separation membrane system comprises a membrane that is selectively permeable to hydrogen, and producing a hydrogen-rich permeate product stream on the permeate side of the membrane and a carbon dioxide-rich product raffinate stream on the raffinate side of the membrane. A method for pretreating a membrane, comprising: heating the membrane to a desired operating temperature and desired feed pressure in a flow of inert gas for a sufficient time to cause the membrane to mechanically deform; decreasing the feed pressure to approximately ambient pressure; and optionally, flowing an oxidizing agent across the membrane before, during, or after deformation of the membrane. A method of supporting a hydrogen separation membrane system comprising selecting a hydrogen separation membrane system comprising one or more catalyst outer layers deposited on a hydrogen transport membrane layer and sealing the hydrogen separation membrane system to a porous support.

  13. Wireless spectroscopic compact photonic explorer for diagnostic optical imaging.

    Science.gov (United States)

    Wang, Leming; Zhang, G; Luo, J C; Zeng, F; Wang, Q Z; Alfano, S A; Katz, A; Zevallos, M; Alfano, R R

    2005-06-01

    A remote, small-size spectroscopic-based device called Compact Photonics Explorer (CPE) was designed, assembled, and tested for medical and non-medical spectroscopic and imaging applications. Spatial images acquired using the spectroscopic CPE are presented. Operational principles are demonstrated for various biomedical and non-medical applications.

  14. Molecular Modeling of Water Interfaces: From Molecular Spectroscopy to Thermodynamics.

    Science.gov (United States)

    Nagata, Yuki; Ohto, Tatsuhiko; Backus, Ellen H G; Bonn, Mischa

    2016-04-28

    Understanding aqueous interfaces at the molecular level is not only fundamentally important, but also highly relevant for a variety of disciplines. For instance, electrode-water interfaces are relevant for electrochemistry, as are mineral-water interfaces for geochemistry and air-water interfaces for environmental chemistry; water-lipid interfaces constitute the boundaries of the cell membrane, and are thus relevant for biochemistry. One of the major challenges in these fields is to link macroscopic properties such as interfacial reactivity, solubility, and permeability as well as macroscopic thermodynamic and spectroscopic observables to the structure, structural changes, and dynamics of molecules at these interfaces. Simulations, by themselves, or in conjunction with appropriate experiments, can provide such molecular-level insights into aqueous interfaces. In this contribution, we review the current state-of-the-art of three levels of molecular dynamics (MD) simulation: ab initio, force field, and coarse-grained. We discuss the advantages, the potential, and the limitations of each approach for studying aqueous interfaces, by assessing computations of the sum-frequency generation spectra and surface tension. The comparison of experimental and simulation data provides information on the challenges of future MD simulations, such as improving the force field models and the van der Waals corrections in ab initio MD simulations. Once good agreement between experimental observables and simulation can be established, the simulation can be used to provide insights into the processes at a level of detail that is generally inaccessible to experiments. As an example we discuss the mechanism of the evaporation of water. We finish by presenting an outlook outlining four future challenges for molecular dynamics simulations of aqueous interfacial systems.

  15. Thermodynamic Properties of Hydrogen + Tetra-n-Butyl Ammonium Bromide Semi-Clathrate Hydrate

    Directory of Open Access Journals (Sweden)

    Shunsuke Hashimoto

    2010-01-01

    Full Text Available Thermodynamic stability and hydrogen occupancy on the hydrogen + tetra-n-butyl ammonium bromide semi-clathrate hydrate were investigated by means of Raman spectroscopic and phase equilibrium measurements under the three-phase equilibrium condition. The structure of mixed gas hydrates changes from tetragonal to another structure around 95 MPa and 292 K depending on surrounding hydrogen fugacity. The occupied amount of hydrogen in the semi-clathrate hydrate increases significantly associated with the structural transition. Tetra-n-butyl ammonium bromide semi-clathrate hydrates can absorb hydrogen molecules by a pressure-swing without destroying the hydrogen bonds of hydrate cages at 15 MPa or over.

  16. Biophysical influence of isocarbophos on bovine serum albumin: Spectroscopic probing

    Science.gov (United States)

    Zhang, Hua-xin; Zhou, Ying; Liu, E.

    Isocarbophos (ICP) is a phosphorous pesticide with high toxicity. It has been detected in several kinds of food and therefore can enter human body. In this paper, spectroscopic approaches including three-dimensional fluorescence (3D-FL) spectroscopy, UV-visible absorption spectroscopy and circular dichroism (CD) spectroscopy were employed to explore the binding of ICP to bovine serum albumin (BSA) at simulated physiological conditions. It was found that the fluorescence quenching of BSA was caused by the formation of ICP-BSA complex at ground state and belonged to static quenching mechanism. The binding constants, the number of binding sites, enthalpy change (ΔHθ), Gibbs free energy change (ΔGθ) and entropy change (ΔSθ) were calculated at four different temperatures according to Scatchard model and thermodynamic equations. To identify the binding location, fluorescence probe techniques were used. The results showed that warfarin, an acknowledged site marker for BSA, could be partially replaced by ICP when ICP was added to warfarin-BSA systems, which demonstrated that ICP primarily bound on Sudlow's site I in domain IIA of BSA molecule. The distance r (3.06 nm) between donor (Trp-212) and acceptor (ICP) was obtained based on Förster's non-radiation fluorescence resonance energy transfer (FRET) theory. Furthermore, the CD spectral results indicated that the secondary structure of BSA was changed in presence of ICP. The study is helpful to evaluating the toxicology of ICP and understanding its effects on the function of protein during the blood transportation process.

  17. Binding properties of palmatine to DNA: spectroscopic and molecular modeling investigations.

    Science.gov (United States)

    Mi, Ran; Tu, Bao; Bai, Xiao-Ting; Chen, Jun; Ouyang, Yu; Hu, Yan-Jun

    2015-12-01

    Palmatine, an isoquinoline alkaloid, is an important medicinal herbal extract with diverse pharmacological and biological properties. In this work, spectroscopic and molecular modeling approaches were employed to reveal the interaction between palmatine and DNA isolated from herring sperm. The absorption spectra and iodide quenching results indicated that groove binding was the main binding mode of palmatine to DNA. Fluorescence studies indicated that the binding constant (K) of palmatine and DNA was ~ 10(4)L·mol(-1). The associated thermodynamic parameters, ΔG, ΔH, and ΔS, indicated that hydrogen bonds and van der Waals forces played major roles in the interaction. The effects of chemical denaturant, thermal denaturation and pH on the interaction were investigated and provided further support for the groove binding mode. In addition to experimental approaches, molecular modeling was conducted to verify binding pattern of palmatine-DNA. Copyright © 2015 John Wiley & Sons, Ltd.

  18. Optical spectroscopic exploration of binding of Cochineal Red A with two homologous serum albumins.

    Science.gov (United States)

    Bolel, Priyanka; Mahapatra, Niharendu; Halder, Mintu

    2012-04-11

    Cochineal Red A is a negatively charged synthetic azo food colorant and a potential carcinogen. We present here the study of binding of Cochineal Red A with two homologous serum albumins, human (HSA) and bovine (BSA), in aqueous pH 7.4 buffer by optical spectroscopic techniques. Protein intrinsic fluorescence quenching by Cochineal Red A occurs through ground-state static interaction and its binding with BSA is stronger than with HSA. The magnitudes of thermodynamic parameters suggest that dye binding occurs principally via electrostatic complexation. Site-marker competitive binding shows that Cochineal Red A binds primarily to site I of serum albumins. Circular dichroic spectra indicate that dye binding results in some conformational modification of serum albumins. Increased ionic strength of the medium results in lowering of binding. This study provides an important insight into possible means of removal of dye toxicity.

  19. Life's a Gas: A Thermodynamic Theory of Biological Evolution

    National Research Council Canada - National Science Library

    Keith R Skene

    2015-01-01

      This paper outlines a thermodynamic theory of biological evolution. Beginning with a brief summary of the parallel histories of the modern evolutionary synthesis and thermodynamics, we use four physical laws and processes...

  20. Crystallization: Key thermodynamic, kinetic and hydrodynamic aspects

    Indian Academy of Sciences (India)

    In spite of the wide-spread use of crystallization, a clear understanding of the thermodynamic, kinetic and hydrodynamic aspects of the design methodologies are not yet well established. More often than not crystallization is still considered an art especially in fine-chemicals, pharmaceuticals and life-sciences sector.

  1. Investigations on nucleation thermodynamical parameters of ...

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science; Volume 23; Issue 2. Investigations on nucleation thermodynamical parameters of NdBa2Cu3O7– (Nd123) crystallization by high temperature solution growth. D P Paul R Jayavel C Subramanian P Ramasamy. Materials Synthesis Volume 23 Issue 2 April 2000 pp 79-82 ...

  2. Calorimetry and thermodynamics of living systems

    Energy Technology Data Exchange (ETDEWEB)

    Lamprecht, Ingolf

    2003-10-14

    Calorimetry of living systems and classical thermodynamics developed in parallel, from Lavoisier's early ice calorimeter experiments on guinea pigs, followed by Dubrunfaut's macrocalorimetric research of fermentation processes and Atwater-Rosa's whole-body calorimetry on humans and domestic animals, to the introduction of the famous Tian-Calvet instrument that found entrance into so many different fields of biology. In this work, six examples of living-system calorimetry and thermodynamics are presented. These are: (i) glycolytic oscillations far off the thermodynamic equilibrium; (ii) growth and energy balances in fermenting and respiring yeast cultures; (iii) direct and indirect calorimetric monitoring of electrically stimulated reptile metabolism; (iv) biologic and climatic factors influencing the temperature constancy and distribution in the mound of a wood ant colony as an example of a complex ecological system; (v) energetic considerations on the clustering of European honeybees in winter as a means to save energy and stored food as well as for their Japanese counterparts in defending against hornet predators; and (vi) energetic and evolutionary aspects of the mass specific entropy production rate, the so-called bound dissipation or psiu-function. The examples presented here are just a very personal selection of living systems from a broad spectrum at all levels of complexity. Common for all of them is that they were investigated calorimetrically on the background of classical and irreversible thermodynamics.

  3. Thermodynamic modeling to analyse composition of carbonaceous ...

    Indian Academy of Sciences (India)

    Thermodynamic modeling to analyse composition of carbonaceous coatings of MnO and other oxides of manganese grown by MOCVD. SUKANYA DHAR†, A VARADE and S A SHIVASHANKAR. ∗. Materials Research Centre, Indian Institute of Science, Bangalore 560 012, India. †Mechanical Engineering Department ...

  4. Circular Thermodynamics of Organisms and Sustainable Systems

    Directory of Open Access Journals (Sweden)

    Mae-Wan Ho

    2013-07-01

    Full Text Available A circular thermodynamics of organisms and sustainable systems is presented based on dynamic closures in nested space-time domains that enable the system to approach the ideal of zero entropy production simultaneously at equilibrium and far from equilibrium conditions.

  5. Investigations on nucleation thermodynamical parameters of ...

    Indian Academy of Sciences (India)

    Unknown

    Crystal Growth Centre, Anna University, Chennai 600 025, India. ‡Department of Physics, University of Chittagong, Chittagong 1331, Bangladesh. Abstract. Investigations on nucleation thermodynamical parameters are very essential for the successful growth of good quality single crystals from high temperature solution.

  6. Thermodynamic disequilibrium as a biomarker in Mars

    Science.gov (United States)

    Delgado-Bonal, A.; Simoncini, E.; Martín-Torres, F. J.

    2012-04-01

    Disequilibrium should be a necessary condition in planetary body atmospheres hosting life, as a consequence of the chemical interchange between the atmosphere and the living organisms. In this study, we analyze the thermodynamics of Mars atmosphere considering more than 50 reactions (including those involving traditionally considered biomarkers such as H2O or CH4), and estimating their entropy production and Gibbs free energy. Those complementary measurements provide information on the disequilibrium of the atmosphere in a measurable way. Besides the atmosphere's thermodynamic state, the interaction between surface-atmosphere has been analyzed considering the abiotic analogs of those sources of energy for life on Earth (for example iron oxidation). Using thermodynamic criteria we have studied the habitability under two different situations in Mars: the surface of the Gale crater (4.6S 137.2E),where the Mars Science Laboratory will land in August 2012, and a hypothetical cave near the equatorial zone. The study of the time-dependence of these thermodynamic quantities provides us with a complete tool to study the past and present habitability in Mars.

  7. First Law of p-brane Thermodynamics

    OpenAIRE

    Rogatko, Marek

    2009-01-01

    We study the physical process version and the equilibrium state version of the first law of thermodynamics for a charged p-brane. the general setting for our investigations is (n+p+1)-dimensional Einstein dilaton gravity with (p+2) strength form fields.

  8. Thermodynamic volume and the extended Smarr relation

    Science.gov (United States)

    Hyun, Seungjoon; Jeong, Jaehoon; Park, Sang-A.; Yi, Sang-Heon

    2017-04-01

    We continue to explore the scaling transformation in the reduced action formalism of gravity models. As an extension of our construction, we consider the extended forms of the Smarr relation for various black holes, adopting the cosmological constant as the bulk pressure as in some literatures on black holes. Firstly, by using the quasi-local formalism for charges, we show that, in a general theory of gravity, the volume in the black hole thermodynamics could be defined as the thermodynamic conjugate variable to the bulk pressure in such a way that the first law can be extended consistently. This, so called, thermodynamic volume can be expressed explicitly in terms of the metric and field variables. Then, by using the scaling transformation allowed in the reduced action formulation, we obtain the extended Smarr relation involving the bulk pressure and the thermodynamic volume. In our approach, we do not resort to Euler's homogeneous scaling of charges while incorporating the would-be hairy contribution without any difficulty.

  9. Thermodynamic Efficiency. An Issue Oriented Module.

    Science.gov (United States)

    Young, Robert D.

    This module applies basic laws of thermodynamics to the study of the efficiency at which heat can be converted to other useful forms of energy, including heat at low temperatures. The module is divided into four major sections. Section I treats energy conversion efficiency and defines the concept of first-law efficiency, the most widely used…

  10. A Thermodynamics Course Package in Onenote

    Science.gov (United States)

    Falconer, John L.; Nicodemus, Garret D.; Medlin, J. Will; deGrazia, Janet; McDanel, Katherine P.

    2014-01-01

    A ready-to-use package of active-learning materials for a semester-long chemical engineering thermodynamics course was prepared for instructors, and similar materials are being prepared for a material and energy balance course. The course package includes ConcepTests, explanations of the ConcepTests for instructors, links to screencasts, chapter…

  11. A New Thermodynamics from Nuclei to Stars

    Directory of Open Access Journals (Sweden)

    Dieter H.E. Gross

    2004-03-01

    Full Text Available Abstract: Equilibrium statistics of Hamiltonian systems is correctly described by the microcanonical ensemble. Classically this is the manifold of all points in the N-body phase space with the given total energy. Due to Boltzmann's principle, eS=tr(δ(E-H, its geometrical size is related to the entropy S(E,N,.... This definition does not invoke any information theory, no thermodynamic limit, no extensivity, and no homogeneity assumption, as are needed in conventional (canonical thermo-statistics. Therefore, it describes the equilibrium statistics of extensive as well of non-extensive systems. Due to this fact it is the fundamental definition of any classical equilibrium statistics. It can address nuclei and astrophysical objects as well. All kind of phase transitions can be distinguished sharply and uniquely for even small systems. It is further shown that the second law is a natural consequence of the statistical nature of thermodynamics which describes all systems with the same -- redundant -- set of few control parameters simultaneously. It has nothing to do with the thermodynamic limit. It even works in systems which are by far than any thermodynamic "limit".

  12. Construction of microcanonical entropy on thermodynamic pillars

    Science.gov (United States)

    Campisi, Michele

    2015-05-01

    A question that is currently highly debated is whether the microcanonical entropy should be expressed as the logarithm of the phase volume (volume entropy, also known as the Gibbs entropy) or as the logarithm of the density of states (surface entropy, also known as the Boltzmann entropy). Rather than postulating them and investigating the consequence of each definition, as is customary, here we adopt a bottom-up approach and construct the entropy expression within the microcanonical formalism upon two fundamental thermodynamic pillars: (i) The second law of thermodynamics as formulated for quasistatic processes: δ Q /T is an exact differential, and (ii) the law of ideal gases: P V =kBN T . The first pillar implies that entropy must be some function of the phase volume Ω . The second pillar singles out the logarithmic function among all possible functions. Hence the construction leads uniquely to the expression S =kBlnΩ , that is, the volume entropy. As a consequence any entropy expression other than that of Gibbs, e.g., the Boltzmann entropy, can lead to inconsistencies with the two thermodynamic pillars. We illustrate this with the prototypical example of a macroscopic collection of noninteracting spins in a magnetic field, and show that the Boltzmann entropy severely fails to predict the magnetization, even in the thermodynamic limit. The uniqueness of the Gibbs entropy, as well as the demonstrated potential harm of the Boltzmann entropy, provide compelling reasons for discarding the latter at once.

  13. Application of dhurrin for kinetics and thermodynamic ...

    African Journals Online (AJOL)

    Data obtained from the residual HCN with time were fitted into zero, first and second order kinetics models to derive reaction rate constant (Kmin-1) values which were analyzed using the Arrhenius and absolute reaction rate models Thermodynamic parameters were obtained including; activation energies (Ea), frequency ...

  14. short communication thermodynamic parameters of elasticity

    African Journals Online (AJOL)

    a

    used for autobody panels, microwave cook ware and satellite receptor antenna dishes [3]. The mechanical and rheological properties of filled natural rubber have been .... thermodynamic equation of state for elastic materials was used. The entropy decreases when. NR was filled connoting that the material tends to a more ...

  15. Thermodynamic effects of commercially available ice boots

    African Journals Online (AJOL)

    Ibrahim Eldaghayes

    Submitted: 02/08/2017. Accepted: 06/01/2018. Published: 18/01/2018. Thermodynamic effects of commercially available ice boots. Madison N. Quintanar*, Tess Pu'uwaionalani Millar and Matthew A. Burd. Department of Animal Science, California Polytechnic State University, San Luis Obispo, CA 93401, USA ...

  16. Thermodynamics of Benford's First Digit Law

    CERN Document Server

    Lemons, Don S

    2016-01-01

    Iafrate, Miller, and Strauch [Equipartition and a Distribution for Numbers: A Statistical Model for Benford's Law," arXiv:1503.08259] construct and test a statistical model for partitioning a conserved quantity. One consequence of their model is Benford's law. This Comment amplifies their work by exploring its thermodynamic consequences.

  17. THERMODYNAMIC AND ANALYTICAL STUDIES ON THE ...

    African Journals Online (AJOL)

    The equilibrium constant for the interaction at different temperatures was determined according to Benesi-Hildebrand model. The equilibrium constant and molar absorptivities varied only slightly with temperature. The thermodynamic parameters like free energy change (ΔG), enthalpy change (ΔH ) and entropy change (ΔS ) ...

  18. Thermodynamic and kinetic modelling: creep resistant materials

    DEFF Research Database (Denmark)

    Hald, John; Korcakova, L.; Danielsen, Hilmar Kjartansson

    2008-01-01

    The use of thermodynamic and kinetic modelling of microstructure evolution in materials exposed to high temperatures in power plants is demonstrated with two examples. Precipitate stability in martensitic 9–12%Cr steels is modelled including equilibrium phase stability, growth of Laves phase...

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

    African Journals Online (AJOL)

    Spectrophotometric technique was employed to investigate thermodynamic parameters associated with the interaction between amitriptyline and chloranilic acid in non-aqueous medium. The molecular complex produced a purple colour with absorption maximum at 520 nm and was stable over 9 h. The equilibrium constant ...

  20. Thermodynamics properties of diatomic molecules with general ...

    Indian Academy of Sciences (India)

    AKPAN N IKOT

    2018-01-10

    Jan 10, 2018 ... S and vibrational specific heat capacity C. These thermodynamic functions are studied for the electronic state X1 + g of K2 diatomic molecules. Keywords. Asymptotic iteration method; diatomic molecules; general molecular potential; partition function. PACS Nos 03.65.Ge; 03.65.Ca. 1. Introduction.