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Sample records for equilibrium dissociation constant

  1. A Unified Kinetics and Equilibrium Experiment: Rate Law, Activation Energy, and Equilibrium Constant for the Dissociation of Ferroin

    Science.gov (United States)

    Sattar, Simeen

    2011-01-01

    Tris(1,10-phenanthroline)iron(II) is the basis of a suite of four experiments spanning 5 weeks. Students determine the rate law, activation energy, and equilibrium constant for the dissociation of the complex ion in acid solution and base dissociation constant for phenanthroline. The focus on one chemical system simplifies a daunting set of…

  2. Ion exchange equilibrium constants

    CERN Document Server

    Marcus, Y

    2013-01-01

    Ion Exchange Equilibrium Constants focuses on the test-compilation of equilibrium constants for ion exchange reactions. The book first underscores the scope of the compilation, equilibrium constants, symbols used, and arrangement of the table. The manuscript then presents the table of equilibrium constants, including polystyrene sulfonate cation exchanger, polyacrylate cation exchanger, polymethacrylate cation exchanger, polysterene phosphate cation exchanger, and zirconium phosphate cation exchanger. The text highlights zirconium oxide anion exchanger, zeolite type 13Y cation exchanger, and

  3. Determine equilibrium dissociation constant of drug-membrane receptor affinity using the cell membrane chromatography relative standard method.

    Science.gov (United States)

    Ma, Weina; Yang, Liu; Lv, Yanni; Fu, Jia; Zhang, Yanmin; He, Langchong

    2017-06-23

    The equilibrium dissociation constant (K D ) of drug-membrane receptor affinity is the basic parameter that reflects the strength of interaction. The cell membrane chromatography (CMC) method is an effective technique to study the characteristics of drug-membrane receptor affinity. In this study, the K D value of CMC relative standard method for the determination of drug-membrane receptor affinity was established to analyze the relative K D values of drugs binding to the membrane receptors (Epidermal growth factor receptor and angiotensin II receptor). The K D values obtained by the CMC relative standard method had a strong correlation with those obtained by the frontal analysis method. Additionally, the K D values obtained by CMC relative standard method correlated with pharmacological activity of the drug being evaluated. The CMC relative standard method is a convenient and effective method to evaluate drug-membrane receptor affinity. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Using electrophoretic mobility shift assays to measure equilibrium dissociation constants: GAL4-p53 binding DNA as a model system.

    Science.gov (United States)

    Heffler, Michael A; Walters, Ryan D; Kugel, Jennifer F

    2012-01-01

    An undergraduate biochemistry laboratory experiment is described that will teach students the practical and theoretical considerations for measuring the equilibrium dissociation constant (K(D) ) for a protein/DNA interaction using electrophoretic mobility shift assays (EMSAs). An EMSA monitors the migration of DNA through a native gel; the DNA migrates more slowly when bound to a protein. To determine a K(D) the amount of unbound and protein-bound DNA in the gel is measured as the protein concentration increases. By performing this experiment, students will be introduced to making affinity measurements and gain experience in performing quantitative EMSAs. The experiment describes measuring the K(D) for the interaction between the chimeric protein GAL4-p53 and its DNA recognition site; however, the techniques are adaptable to other DNA binding proteins. In addition, the basic experiment described can be easily expanded to include additional inquiry-driven experimentation. © 2012 by The International Union of Biochemistry and Molecular Biology. Copyright © 2012 Wiley Periodicals, Inc.

  5. Measurement of the Dissociation-Equilibrium Constants for Low Affinity Antibiotic Binding Interaction with Bacterial Ribosomes by the T2 (CPMG) and Line-Broadening Methods

    Science.gov (United States)

    Verdier, L.; Gharbi-Benarous, J.; Bertho, G.; Mauvais, P.; Girault, J.-P.

    1999-10-01

    In this study the dissociation constants of the low antibiotic-ribosomes interaction were determined by the T2 (CPMG), the Carr-Purcell-Meiboom-Gill spin-echo decay rate and the line-broadening methods. Three MLSB antibiotics were studied, a macrolide roxithromycin, a ketolide HMR 3647 and a lincosamide clindamycin for their weak interaction with three bacterial ribosomes, E. coli, Staphylococcus aureus sensitive and resistant to erythromycin. Nous avons mesuré la constante de dissociation, Kd correspondant à l'interaction faible antibiotique-ribosome bactérien pour des antibiotiques de différentes classes, un macrolide (roxithromycine), un kétolide (HMR 3647) et une lincosamide (clindamycine) avec des ribosomes de différentes souches bactériennes (E. coli, Staphylococcus aureus sensible ou résistant à l'erythromycin) par deux méthodes : l'une basée sur la variation des largeurs de raies et l'autre sur les temps de relaxation transversaux T2 en utilisant une séquence CPMG.

  6. Dissociative electron attachment to ozone: rate constant

    International Nuclear Information System (INIS)

    Skalny, J.D.; Cicman, P.; Maerk, T.D.

    2002-01-01

    The rate constant for dissociative electron attachment to ozone has been derived over the energy range of 0-10 eV by using previously measured cross section data revisited here in regards to discrimination effect occurring during the extraction of ions. The obtained data for both possible channels exhibit the maximum at mean electron energies close to 1 eV. (author)

  7. Equilibrium-constant expressions for aqueous plutonium

    International Nuclear Information System (INIS)

    Silver, G.L.

    2010-01-01

    Equilibrium-constant expressions for Pu disproportionation reactions traditionally contain three or four terms representing the concentrations or fractions of the oxidation states. The expressions can be rewritten so that one of the oxidation states is replaced by a term containing the oxidation number of the plutonium. Experimental estimations of the numerical values of the constants can then be checked in several ways. (author)

  8. Determination of the Tetramer-Dimer Equilibrium Constant of Rabbit ...

    African Journals Online (AJOL)

    Hemoglobin is a tetrameric protein which is able to dissociate into dimers. The dimers can in turn dissociate into tetramers. It has been found that dimers are more reactive than tetramers. The difference in the reactivity of these two species has been used to determine the tetramerdimer dissociation constant of various ...

  9. Equilibrium dissociation pressures of lithium hydride and lithium deuteride

    International Nuclear Information System (INIS)

    Smith, H.M.; Webb, R.E.

    1977-12-01

    The equilibrium dissociation pressures of plateau composition lithium hydride and lithium deuteride have been measured from 450 to 750 0 C. These data were used to derive the relationship of dissociation pressure with temperature over this range and to calculate several thermodynamic properties of these materials. Thermodynamic properties determined included the enthalpy, entropy, and free energy of formation; the enthalpy and entropy of fusion; and the melting points

  10. Equilibrium Constant as Solution to the Open Chemical Systems

    OpenAIRE

    Zilbergleyt, B.

    2008-01-01

    According to contemporary views, equilibrium constant is relevant only to true thermodynamic equilibria in isolated systems with one chemical reaction. The paper presents a novel formula that ties-up equilibrium constant and chemical system composition at any state, isolated or open as well. Extending the logarithmic logistic map of the Discrete Thermodynamics of Chemical Equilibria, this formula maps the system population at isolated equilibrium into the population at any open equilibrium at...

  11. Analysis of the chemical equilibrium of combustion at constant volume

    Directory of Open Access Journals (Sweden)

    Marius BREBENEL

    2014-04-01

    Full Text Available Determining the composition of a mixture of combustion gases at a given temperature is based on chemical equilibrium, when the equilibrium constants are calculated on the assumption of constant pressure and temperature. In this paper, an analysis of changes occurring when combustion takes place at constant volume is presented, deriving a specific formula of the equilibrium constant. The simple reaction of carbon combustion in pure oxygen in both cases (constant pressure and constant volume is next considered as example of application, observing the changes occurring in the composition of the combustion gases depending on temperature.

  12. Photometric determination of the composition and dissociation constants of niobium (5) citrate complexes

    International Nuclear Information System (INIS)

    Grigor'eva, V.V.; Golubeva, I.V.

    1979-01-01

    Niobium (5) citrate complexes in aqueous solution (pH 1-6) are investigated. To determine the complexes composition the metal-indicator method has been applied. Experimental data have been treated by the method of equilibrium shift using somewhat changed variant of the metal-indicator method. The complex ion charge in the solution has been determined by the ion-exchange method. Dissociation constants of citrate complexes have been determined photometrically

  13. One-group constant libraries for nuclear equilibrium state

    Energy Technology Data Exchange (ETDEWEB)

    Mizutani, Akihiko; Sekimoto, Hiroshi [Tokyo Inst. of Tech. (Japan). Research Lab. for Nuclear Reactors

    1997-03-01

    One-group constant libraries for the nuclear equilibrium state were generated for both liquid sodium cooled MOX fuel type fast reactor and PWR type thermal reactor with Equilibrium Cell Iterative Calculation System (ECICS) using JENDL-3.2, -3, -2 and ENDF/B-VI nuclear data libraries. ECICS produced one-group constant sets for 129 heavy metal nuclides and 1238 fission products. (author)

  14. Titration ELISA as a Method to Determine the Dissociation Constant of Receptor Ligand Interaction.

    Science.gov (United States)

    Eble, Johannes A

    2018-02-15

    The dissociation constant describes the interaction between two partners in the binding equilibrium and is a measure of their affinity. It is a crucial parameter to compare different ligands, e.g., competitive inhibitors, protein isoforms and mutants, for their binding strength to a binding partner. Dissociation constants are determined by plotting concentrations of bound versus free ligand as binding curves. In contrast, titration curves, in which a signal that is proportional to the concentration of bound ligand is plotted against the total concentration of added ligand, are much easier to record. The signal can be detected spectroscopically and by enzyme-linked immunosorbent assay (ELISA). This is exemplified in a protocol for a titration ELISA that measures the binding of the snake venom-derived rhodocetin to its immobilized target domain of α2β1 integrin. Titration ELISAs are versatile and widely used. Any pair of interacting proteins can be used as immobilized receptor and soluble ligand, provided that both proteins are pure, and their concentrations are known. The difficulty so far has been to determine the dissociation constant from a titration curve. In this study, a mathematical function underlying titration curves is introduced. Without any error-prone graphical estimation of a saturation yield, this algorithm allows processing of the raw data (signal intensities at different concentrations of added ligand) directly by mathematical evaluation via non-linear regression. Thus, several titration curves can be recorded simultaneously and transformed into a set of characteristic parameters, among them the dissociation constant and the concentration of binding-active receptor, and they can be evaluated statistically. When combined with this algorithm, titration ELISAs gain the advantage of directly presenting the dissociation constant. Therefore, they may be used more efficiently in the future.

  15. Semiclassical Calculation of Reaction Rate Constants for Homolytical Dissociations

    Science.gov (United States)

    Cardelino, Beatriz H.

    2002-01-01

    There is growing interest in extending organometallic chemical vapor deposition (OMCVD) to III-V materials that exhibit large thermal decomposition at their optimum growth temperature, such as indium nitride. The group III nitrides are candidate materials for light-emitting diodes and semiconductor lasers operating into the blue and ultraviolet regions. To overcome decomposition of the deposited compound, the reaction must be conducted at high pressures, which causes problems of uniformity. Microgravity may provide the venue for maintaining conditions of laminar flow under high pressure. Since the selection of optimized parameters becomes crucial when performing experiments in microgravity, efforts are presently geared to the development of computational OMCVD models that will couple the reactor fluid dynamics with its chemical kinetics. In the present study, we developed a method to calculate reaction rate constants for the homolytic dissociation of III-V compounds for modeling OMCVD. The method is validated by comparing calculations with experimental reaction rate constants.

  16. Molecular equilibrium structures from experimental rotational constants and calculated vibration-rotation interaction constants

    DEFF Research Database (Denmark)

    Pawlowski, F; Jorgensen, P; Olsen, Jeppe

    2002-01-01

    A detailed study is carried out of the accuracy of molecular equilibrium geometries obtained from least-squares fits involving experimental rotational constants B(0) and sums of ab initio vibration-rotation interaction constants alpha(r)(B). The vibration-rotation interaction constants have been...... calculated for 18 single-configuration dominated molecules containing hydrogen and first-row atoms at various standard levels of ab initio theory. Comparisons with the experimental data and tests for the internal consistency of the calculations show that the equilibrium structures generated using Hartree......-Fock vibration-rotation interaction constants have an accuracy similar to that obtained by a direct minimization of the CCSD(T) energy. The most accurate vibration-rotation interaction constants are those calculated at the CCSD(T)/cc-pVQZ level. The equilibrium bond distances determined from these interaction...

  17. Determination of Henry's constant, the dissociation constant, and the buffer capacity of the bicarbonate system in ruminal fluid.

    Science.gov (United States)

    Hille, Katharina T; Hetz, Stefan K; Rosendahl, Julia; Braun, Hannah-Sophie; Pieper, Robert; Stumpff, Friederike

    2016-01-01

    Despite the clinical importance of ruminal acidosis, ruminal buffering continues to be poorly understood. In particular, the constants for the dissociation of H2CO3 and the solubility of CO2 (Henry's constant) have never been stringently determined for ruminal fluid. The pH was measured in parallel directly in the rumen and the reticulum in vivo, and in samples obtained via aspiration from 10 fistulated cows on hay- or concentrate-based diets. The equilibrium constants of the bicarbonate system were measured at 38°C both using the Astrup technique and a newly developed method with titration at 2 levels of partial pressure of CO2 (pCO2; 4.75 and 94.98 kPa), yielding mean values of 0.234 ± 0.005 mmol ∙ L(-1) ∙ kPa(-1) and 6.11 ± 0.02 for Henry's constant and the dissociation constant, respectively (n/n = 31/10). Both reticular pH and the pH of samples measured after removal were more alkalic than those measured in vivo in the rumen (by ΔpH = 0.87 ± 0.04 and 0.26 ± 0.04). The amount of acid or base required to shift the pH of ruminal samples to 6.4 or 5.8 (base excess) differed between the 2 feeding groups. Experimental results are compared with the mathematical predictions of an open 2-buffer Henderson-Hasselbalch equilibrium model. Because pCO2 has pronounced effects on ruminal pH and can decrease rapidly in samples removed from the rumen, introduction of a generally accepted protocol for determining the acid-base status of ruminal fluid with standard levels of pCO2 and measurement of base excess in addition to pH should be considered. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

  18. Algorithm for Calculating the Dissociation Constants of Ampholytes in Nonbuffer Systems

    Science.gov (United States)

    Lysova, S. S.; Skripnikova, T. A.; Zevatskii, Yu. E.

    2018-05-01

    An algorithm for calculating the dissociation constants of ampholytes in aqueous solutions is developed on the basis of spectrophotometric data in the UV and visible ranges without pH measurements of a medium and without buffer solutions. The proposed algorithm has been experimentally tested for five ampholytes of different strengths. The relative error of measuring dissociation constants is less than 5%.

  19. Dissociation constants of phosphoric acid in dimethylformamide-water mixtures at 298.15 K

    Science.gov (United States)

    Safonova, L. P.; Fadeeva, Yu. A.; Pryakhin, A. A.

    2009-10-01

    The dissociation constants of phosphoric acid (p K 1 and p K 2) in water-dimethylformamide (DMFA) mixtures (0-0.65 mole fractions of DMFA) were determined at 298.15 K by potentiometric titration. The extrapolation of these data to pure DMFA and the comparative calculation method were used to estimate the dissociation constants of the acid in DMFA.

  20. Determination of the dissociation constants of some organic complexing agents and stability constants of their uranyl complexes by spectrophotometry

    International Nuclear Information System (INIS)

    1989-01-01

    The dissociation constants of the weak acids derived from quinizarin (1,4-dihydroxy anthraquinone); QMF (2-(2-fury l methyl)), QMPH (2-(2-phenyl methyl)) and QMN (2-(2-naphthyl methyl)) quinizarin were determined. The stability constants of uranyl complexes with the above mentioned ligands were investigated by: 1. The molar-ratio method. 2. Computer program

  1. Using nonequilibrium capillary electrophoresis of equilibrium mixtures (NECEEM) for simultaneous determination of concentration and equilibrium constant.

    Science.gov (United States)

    Kanoatov, Mirzo; Galievsky, Victor A; Krylova, Svetlana M; Cherney, Leonid T; Jankowski, Hanna K; Krylov, Sergey N

    2015-03-03

    Nonequilibrium capillary electrophoresis of equilibrium mixtures (NECEEM) is a versatile tool for studying affinity binding. Here we describe a NECEEM-based approach for simultaneous determination of both the equilibrium constant, K(d), and the unknown concentration of a binder that we call a target, T. In essence, NECEEM is used to measure the unbound equilibrium fraction, R, for the binder with a known concentration that we call a ligand, L. The first set of experiments is performed at varying concentrations of T, prepared by serial dilution of the stock solution, but at a constant concentration of L, which is as low as its reliable quantitation allows. The value of R is plotted as a function of the dilution coefficient, and dilution corresponding to R = 0.5 is determined. This dilution of T is used in the second set of experiments in which the concentration of T is fixed but the concentration of L is varied. The experimental dependence of R on the concentration of L is fitted with a function describing their theoretical dependence. Both K(d) and the concentration of T are used as fitting parameters, and their sought values are determined as the ones that generate the best fit. We have fully validated this approach in silico by using computer-simulated NECEEM electropherograms and then applied it to experimental determination of the unknown concentration of MutS protein and K(d) of its interactions with a DNA aptamer. The general approach described here is applicable not only to NECEEM but also to any other method that can determine a fraction of unbound molecules at equilibrium.

  2. Determination of dissociation constants for coordination compounds of Cr(III) and Co(III) using potentiometric and spectrophotometric methods

    Energy Technology Data Exchange (ETDEWEB)

    Chylewska, A.; Jacewicz, D.; Zarzeczanska, D. [Department of Chemistry, University of Gdansk, Sobieskiego 18/19, 80-952 Gdansk (Poland); Chmurzynski, L. [Department of Chemistry, University of Gdansk, Sobieskiego 18/19, 80-952 Gdansk (Poland)], E-mail: lech@chem.univ.gda.pl

    2008-08-15

    The acid-base properties of analogous complex ions of chromium(III) and cobalt(III) in aqueous solution have been studied. The equilibrium constants for all metal complexes were determined by using potentiometric and spectrophotometric titration methods. First, dissociation constants for the studied complexes of Cr(III) and Co(III) were determined by means of the potentiometric titration method and using the STOICHIO computer programme. Then, pH-spectrophotometric titrations were performed and the OriginPro 7.5 computer programme was used to calculate the same constants. The measurements using both methods were carried out under the same conditions of temperature, T = 298.15 K, and over the same pH range 2.00-10.00, respectively. It turned out that the two methods used enabled us to obtain acidity constants in very good agreement.

  3. Determination of dissociation constants for coordination compounds of Cr(III) and Co(III) using potentiometric and spectrophotometric methods

    International Nuclear Information System (INIS)

    Chylewska, A.; Jacewicz, D.; Zarzeczanska, D.; Chmurzynski, L.

    2008-01-01

    The acid-base properties of analogous complex ions of chromium(III) and cobalt(III) in aqueous solution have been studied. The equilibrium constants for all metal complexes were determined by using potentiometric and spectrophotometric titration methods. First, dissociation constants for the studied complexes of Cr(III) and Co(III) were determined by means of the potentiometric titration method and using the STOICHIO computer programme. Then, pH-spectrophotometric titrations were performed and the OriginPro 7.5 computer programme was used to calculate the same constants. The measurements using both methods were carried out under the same conditions of temperature, T = 298.15 K, and over the same pH range 2.00-10.00, respectively. It turned out that the two methods used enabled us to obtain acidity constants in very good agreement

  4. Water dimers in the atmosphere III: equilibrium constant from a flexible potential.

    Science.gov (United States)

    Scribano, Yohann; Goldman, Nir; Saykally, R J; Leforestier, Claude

    2006-04-27

    We present new results for the water dimer equilibrium constant K(p)(T) in the range 190-390 K, using a flexible potential energy surface fitted to spectroscopical data. The increased numerical complexity due to explicit consideration of the monomer vibrations is handled via an adiabatic (6 + 6)d decoupling between intra- and intermolecular modes. The convergence of the canonical partition function of the dimer is ensured by computing all energy levels up to dissociation for total angular momentum values J = 0-5 and using an extrapolation scheme to higher values. The newly calculated values for K(p)(T) are in very good agreement with available experimental data at room temperature. At higher temperatures, an analysis of the convergence of the partition function reveals that quasi-bound states are likely to contribute to the equilibrium constant. Additional thermodynamical quantities (deltaG, deltaH, deltaS, and C(p)) have also been determined and fit to quadratic expressions a + bT + cT2.

  5. Molecular dynamics study of CO2 hydrate dissociation: Fluctuation-dissipation and non-equilibrium analysis.

    Science.gov (United States)

    English, Niall J; Clarke, Elaine T

    2013-09-07

    Equilibrium and non-equilibrium molecular dynamics (MD) simulations have been performed to investigate thermal-driven break-up of planar CO2 hydrate interfaces in liquid water at 300-320 K. Different guest compositions, at 85%, 95%, and 100% of maximum theoretical occupation, led to statistically-significant differences in the observed initial dissociation rates. The melting temperatures of each interface were estimated, and dissociation rates were observed to be strongly dependent on temperature, with higher dissociation rates at larger over-temperatures vis-à-vis melting. A simple coupled mass and heat transfer model developed previously was applied to fit the observed dissociation profiles, and this helps to identify clearly two distinct régimes of break-up; a second well-defined region is essentially independent of composition and temperature, in which the remaining nanoscale, de facto two-dimensional system's lattice framework is intrinsically unstable. From equilibrium MD of the two-phase systems at their melting point, the relaxation times of the auto-correlation functions of fluctuations in number of enclathrated guest molecules were used as a basis for comparison of the variation in the underlying, non-equilibrium, thermal-driven dissociation rates via Onsager's hypothesis, and statistically significant differences were found, confirming the value of a fluctuation-dissipation approach in this case.

  6. Tautomers and Acid Dissociation Constants of 6-Selenoguanine from Density Functional Theoretical Calculations

    International Nuclear Information System (INIS)

    Kim, Yong Seong; Jang, Yun Hee; Cho, Hyun; Hwang, Sun Gu

    2010-01-01

    The relative stabilities of the tautomers of SeG were calculated. In the aqueous phase, amino-seleno form was the major tautomer of neutral SeG with a minor contribution from the other amino-seleno form. The presence of the selenolic form was negligible from the calculations. The microscopic and macroscopic pKa values in the aqueous phase were calculated from this scheme. The calculated pKa value was in good agreement with the experimental data. These results demonstrated that this method could predict and explain the acid-base properties of SeG and could be used to understand the behavior of the species. A number of analogues of nucleic acid bases have been the target of extensive studies because of their importance in many biological studies. The oxygen of both purine and pyrimidine bases is substituted with sulfur or selenium to produce an important class of analogues. 6-Selenoguanine (SeG) has a significant activity against L5178Y lymphoma cells. However, the detailed mechanism of the antiplastic action is not known yet. Information on the acid dissociation constants and the tautomerism of the molecules is required to provide a molecular level understanding of biological processes. Proton-transfer in the nucleic acid pairs and the presence of the tautomeric equilibrium play an important role in the mispair formation during the DNA replication

  7. Prediction of acid dissociation constants of organic compounds using group contribution methods

    DEFF Research Database (Denmark)

    Zhou, Teng; Jhamb, Spardha; Liang, Xiaodong

    2018-01-01

    data-points with average absolute error of 0.23; (b) a non-linear GC model for organic compounds using 1622 data-points with average absolute error of 1.18; (c) an artificial neural network (ANN) based GC model for the organic compounds with average absolute error of 0.17. For each of the developed......In this paper, group contribution (GC) property models for the estimation of acid dissociation constants (Ka) of organic compounds are presented. Three GC models are developed to predict the negative logarithm of the acid dissociation constant pKa: (a) a linear GC model for amino acids using 180...

  8. Analysis of agonist dissociation constants as assessed by functional antagonism in guinea pig left atria

    International Nuclear Information System (INIS)

    Molenaar, P.; Malta, E.

    1986-01-01

    In electrically driven guinea pig left atria, positive inotropic responses to (-)-isoprenaline and the selective beta 1-adrenoceptor agonist RO363 were obtained in the absence and in the presence of the functional antagonists adenosine, carbachol, gallopamil, nifedipine, and Ro 03-7894. Each of the functional antagonists reduced the maximum response to both agonists and produced nonparallel rightward shifts in the cumulative concentration effect curves. For both agonists, dissociation constants (KA) were calculated using the equation described by Furchgott (1966) for irreversible antagonism. For RO363, which is a partial agonist with high agonist activity, the equations outlined for functional interaction by Mackay (1981) were also employed to calculate KA values. The KA values obtained by each method were compared with the dissociation constants (KD) for the two agonists determined from their ability to displace the radioligand (-)-[ 125 I]iodocyanopindolol from beta 1-adrenoceptors in guinea pig left atrial membrane preparations. The estimates of KA varied substantially from KD values. The KD values were taken as more accurate estimates of the true values for the dissociation constants because a high degree of correlation exists between pKD and pD2 values for a number of other beta-adrenoceptor agonists that behave as partial agonists and between pKD and pKB values for a number of beta-adrenoceptor antagonists. Thus, it appears that there are serious limitations in the current theory for using functional antagonism as a means of obtaining agonist dissociation constants

  9. Factors affecting the equilibrium constant of homolysis of complexes with metal-carbon σ bonds in aqueous solutions. Pulse radiolysis studies

    International Nuclear Information System (INIS)

    Meyerstein, D.; Ben-Gurion Univ. of the Negev, Beersheba

    1989-01-01

    Pulse-Radiolysis is a powerful technique for the determination of the equilibrium constants of the homolytic cleavage of metal-carbon σ bonds in aqueous solutions. In most systems studied the observed reaction is: L m-1 M (n+1) -R + L ↔ ML m. n + ·R. Therefore the results do not enable a direct determination of the metal-carbon bond dissociation energies. The results obtained indicate that these equilibrium constants are not directly related to the redox potential of either L .m M (n) or of ·R, or to the activation energies for the homolytic cleavage of a family of similarly substituted ethanes. (author)

  10. Extension of CE/SE method to non-equilibrium dissociating flows

    KAUST Repository

    Wen, C.Y.

    2017-12-08

    In this study, the hypersonic non-equilibrium flows over rounded nose geometries are numerically investigated by a robust conservation element and solution element (CE/SE) code, which is based on hybrid meshes consisting of triangular and quadrilateral elements. The dissociating and recombination chemical reactions as well as the vibrational energy relaxation are taken into account. The stiff source terms are solved by an implicit trapezoidal method of integration. Comparison with laboratory and numerical cases are provided to demonstrate the accuracy and reliability of the present CE/SE code in simulating hypersonic non-equilibrium flows.

  11. Weak Acid Ionization Constants and the Determination of Weak Acid-Weak Base Reaction Equilibrium Constants in the General Chemistry Laboratory

    Science.gov (United States)

    Nyasulu, Frazier; McMills, Lauren; Barlag, Rebecca

    2013-01-01

    A laboratory to determine the equilibrium constants of weak acid negative weak base reactions is described. The equilibrium constants of component reactions when multiplied together equal the numerical value of the equilibrium constant of the summative reaction. The component reactions are weak acid ionization reactions, weak base hydrolysis…

  12. Galvanic Cells and the Determination of Equilibrium Constants

    Science.gov (United States)

    Brosmer, Jonathan L.; Peters, Dennis G.

    2012-01-01

    Readily assembled mini-galvanic cells can be employed to compare their observed voltages with those predicted from the Nernst equation and to determine solubility products for silver halides and overall formation constants for metal-ammonia complexes. Results obtained by students in both an honors-level first-year course in general chemistry and…

  13. Profiles of equilibrium constants for self-association of aromatic molecules.

    Science.gov (United States)

    Beshnova, Daria A; Lantushenko, Anastasia O; Davies, David B; Evstigneev, Maxim P

    2009-04-28

    Analysis of the noncovalent, noncooperative self-association of identical aromatic molecules assumes that the equilibrium self-association constants are either independent of the number of molecules (the EK-model) or change progressively with increasing aggregation (the AK-model). The dependence of the self-association constant on the number of molecules in the aggregate (i.e., the profile of the equilibrium constant) was empirically derived in the AK-model but, in order to provide some physical understanding of the profile, it is proposed that the sources for attenuation of the equilibrium constant are the loss of translational and rotational degrees of freedom, the ordering of molecules in the aggregates and the electrostatic contribution (for charged units). Expressions are derived for the profiles of the equilibrium constants for both neutral and charged molecules. Although the EK-model has been widely used in the analysis of experimental data, it is shown in this work that the derived equilibrium constant, K(EK), depends on the concentration range used and hence, on the experimental method employed. The relationship has also been demonstrated between the equilibrium constant K(EK) and the real dimerization constant, K(D), which shows that the value of K(EK) is always lower than K(D).

  14. Dissociation constants and thermodynamic properties of amino acids used in CO2 absorption from (293 to 353) K

    NARCIS (Netherlands)

    Hamborg, E. S.; Niederer, J. P. M.; Versteeg, G. F.

    2007-01-01

    The second dissociation constants of the amino acids βalanine, taurine, sarcosine, 6-aminohexanoic acid, DL-methionine, glycine, L-phenylalanine, and L-proline and the third dissociation constants of L-glutamic acid and L-aspartic acid have been determined from electromotive force measurements at

  15. Dissociation Constants and Thermodynamic Properties of Amino Acids Used in CO2 Absorption from (293 to 353) K

    NARCIS (Netherlands)

    Hamborg, Espen; Niederer, John; Versteeg, Geert

    2007-01-01

    The second dissociation constants of the amino acids β-alanine, taurine, sarcosine, 6-aminohexanoic acid, dl-methionine, glycine, l-phenylalanine, and l-proline and the third dissociation constants of l-glutamic acid and l-aspartic acid have been determined from electromotive force measurements at

  16. Quasi-equilibrium channel model of an constant current arc

    Directory of Open Access Journals (Sweden)

    Gerasimov Alexander V.

    2003-01-01

    Full Text Available The rather simple method of calculation of electronic and gas temperature in the channel of arc of plasma generator is offered. This method is based on self-consistent two-temperature channel model of an electric arc. The method proposed enables to obtain radial allocation of gas and electronic temperatures in a non-conducting zone of an constant current arc, for prescribed parameters of discharge (current intensity and power of the discharge, with enough good precision. The results obtained can be used in model and engineering calculations to estimate gas and electronic temperatures in the channel of an arc plasma generator.

  17. Thermodynamic properties and equilibrium constant of chemical reaction in nanosystem: An theoretical and experimental study

    International Nuclear Information System (INIS)

    Du, Jianping; Zhao, Ruihua; Xue, Yongqiang

    2012-01-01

    Highlights: ► There is an obvious influence of the size on thermodynamic properties for the reaction referring nano-reactants. ► Gibbs function, enthalpy, entropy and equilibrium constant are dependent on the reactant size. ► There is an approximate linear relation between them. - Abstract: The theoretical relations of thermodynamic properties, the equilibrium constant and reactant size in nanosystem are described. The effects of size on thermodynamic properties and the equilibrium constant were studied using nanosize zinc oxide and sodium bisulfate solution as a reaction system. The experimental results indicated that the molar Gibbs free energy, the molar enthalpy and the molar entropy of the reaction decrease, but the equilibrium constant increases with decreasing reactant size. Linear trends were observed between the reciprocal of size for nano-reactant and thermodynamic variable, which are consistent with the theoretical relations.

  18. The Equilibrium Constant for Bromothymol Blue: A General Chemistry Laboratory Experiment Using Spectroscopy

    Science.gov (United States)

    Klotz, Elsbeth; Doyle, Robert; Gross, Erin; Mattson, Bruce

    2011-01-01

    A simple, inexpensive, and environmentally friendly undergraduate laboratory experiment is described in which students use visible spectroscopy to determine a numerical value for an equilibrium constant, K[subscript c]. The experiment correlates well with the lecture topic of equilibrium even though the subject of the study is an acid-base…

  19. Determination of dissociation constants of compounds with potential cognition enhancing activity by capillary zone electrophoresis

    Czech Academy of Sciences Publication Activity Database

    Lišková, A.; Křivánková, Ludmila

    2005-01-01

    Roč. 26, č. 23 (2005), s. 4429-4439 ISSN 0173-0835 R&D Projects: GA ČR GA203/05/2106; GA AV ČR IAA4031401 Institutional research plan: CEZ:AV0Z40310501 Keywords : Capillary zone electrophoresis * dissociation constants * potential nootropics Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 3.850, year: 2005

  20. Determination of acid dissociation constants of triazole fungicides by pressure assisted capillary electrophoresis

    Czech Academy of Sciences Publication Activity Database

    Konášová, Renáta; Jaklová Dytrtová, Jana; Kašička, Václav

    2015-01-01

    Roč. 1408, Aug 21 (2015), s. 243-249 ISSN 0021-9673 R&D Projects: GA ČR(CZ) GA13-17224S; GA ČR GP13-21409P Institutional support: RVO:61388963 Keywords : triazole fungicides * acid dissociation constant * pK(a) * capillary electrophoresis * ionic mobility Subject RIV: CB - Analytical Chemistry , Separation Impact factor: 3.926, year: 2015

  1. Solubility behavior of narcotic analgesics in aqueous media: solubilities and dissociation constants of morphine, fentanyl, and sufentanil.

    Science.gov (United States)

    Roy, S D; Flynn, G L

    1989-02-01

    The pH dependence of the aqueous solubility of morphine, fentanyl, and sufentanil was investigated at 35 degrees C. Dissociation constants and corresponding pKa' values of the drugs were obtained from measured free-base solubilities (determined at high pH's) and the concentrations of saturated solutions at intermediate pH's. Morphine, fentanyl, and sufentanil exhibited pKa' values of 8.08, 8.99, and 8.51, respectively. Over the pH range of 5 to 12.5 the apparent solubilities are determined by the intrinsic solubility of the free base plus the concentration of ionized drug necessary to satisfy the dissociation equilibrium at a given pH. Consequently, the drug concentrations of saturated aqueous solutions fall off precipitously as the pH is raised and ionization is suppressed. Further, at low pH's the aqueous solubility of morphine increased in a linear fashion with increases in the molar strength of citric acid which was added to acidify the medium, suggesting the formation of a soluble morphine-citrate complex.

  2. Validation of vibration-dissociation coupling models in hypersonic non-equilibrium separated flows

    Science.gov (United States)

    Shoev, G.; Oblapenko, G.; Kunova, O.; Mekhonoshina, M.; Kustova, E.

    2018-03-01

    The validation of recently developed models of vibration-dissociation coupling is discussed in application to numerical solutions of the Navier-Stokes equations in a two-temperature approximation for a binary N2/N flow. Vibrational-translational relaxation rates are computed using the Landau-Teller formula generalized for strongly non-equilibrium flows obtained in the framework of the Chapman-Enskog method. Dissociation rates are calculated using the modified Treanor-Marrone model taking into account the dependence of the model parameter on the vibrational state. The solutions are compared to those obtained using traditional Landau-Teller and Treanor-Marrone models, and it is shown that for high-enthalpy flows, the traditional and recently developed models can give significantly different results. The computed heat flux and pressure on the surface of a double cone are in a good agreement with experimental data available in the literature on low-enthalpy flow with strong thermal non-equilibrium. The computed heat flux on a double wedge qualitatively agrees with available data for high-enthalpy non-equilibrium flows. Different contributions to the heat flux calculated using rigorous kinetic theory methods are evaluated. Quantitative discrepancy of numerical and experimental data is discussed.

  3. A Simple Method to Calculate the Temperature Dependence of the Gibbs Energy and Chemical Equilibrium Constants

    Science.gov (United States)

    Vargas, Francisco M.

    2014-01-01

    The temperature dependence of the Gibbs energy and important quantities such as Henry's law constants, activity coefficients, and chemical equilibrium constants is usually calculated by using the Gibbs-Helmholtz equation. Although, this is a well-known approach and traditionally covered as part of any physical chemistry course, the required…

  4. Equilibrium method for estimating the first hydrolysis constant of tetravalent plutonium

    International Nuclear Information System (INIS)

    Silver, G.L.

    2010-01-01

    A new method for estimating the numerical value of the first hydrolysis constant of tetravalent plutonium is illustrated by examples. It uses the pH and the equilibrium fractions of two of the Pu oxidation states. They are substituted into one or more of a choice of formulas that render explicit estimates of the hydrolysis constant. (author)

  5. Increased precision for analysis of protein-ligand dissociation constants determined from chemical shift titrations

    Energy Technology Data Exchange (ETDEWEB)

    Markin, Craig J.; Spyracopoulos, Leo, E-mail: leo.spyracopoulos@ualberta.ca [University of Alberta, Department of Biochemistry (Canada)

    2012-06-15

    NMR is ideally suited for the analysis of protein-protein and protein ligand interactions with dissociation constants ranging from {approx}2 {mu}M to {approx}1 mM, and with kinetics in the fast exchange regime on the NMR timescale. For the determination of dissociation constants (K{sub D}) of 1:1 protein-protein or protein-ligand interactions using NMR, the protein and ligand concentrations must necessarily be similar in magnitude to the K{sub D}, and nonlinear least squares analysis of chemical shift changes as a function of ligand concentration is employed to determine estimates for the parameters K{sub D} and the maximum chemical shift change ({Delta}{delta}{sub max}). During a typical NMR titration, the initial protein concentration, [P{sub 0}], is held nearly constant. For this condition, to determine the most accurate parameters for K{sub D} and {Delta}{delta}{sub max} from nonlinear least squares analyses requires initial protein concentrations that are {approx}0.5 Multiplication-Sign K{sub D}, and a maximum concentration for the ligand, or titrant, of {approx}10 Multiplication-Sign [P{sub 0}]. From a practical standpoint, these requirements are often difficult to achieve. Using Monte Carlo simulations, we demonstrate that co-variation of the ligand and protein concentrations during a titration leads to an increase in the precision of the fitted K{sub D} and {Delta}{delta}{sub max} values when [P{sub 0}] > K{sub D}. Importantly, judicious choice of protein and ligand concentrations for a given NMR titration, combined with nonlinear least squares analyses using two independent variables (ligand and protein concentrations) and two parameters (K{sub D} and {Delta}{delta}{sub max}) is a straightforward approach to increasing the accuracy of measured dissociation constants for 1:1 protein-ligand interactions.

  6. Surface-dependent chemical equilibrium constants and capacitances for bare and 3-cyanopropyldimethylchlorosilane coated silica nanochannels

    DEFF Research Database (Denmark)

    Andersen, Mathias Bækbo; Frey, Jared; Pennathur, Sumita

    2011-01-01

    , and pK+ are constant and independent of surface composition. Our theoretical model consists of three parts: (i) a chemical equilibrium model of the bare or coated wall, (ii) a chemical equilibrium model of the buffered bulk electrolyte, and (iii) a self-consistent Gouy–Chapman–Stern triple-layer model...... of the electrochemical double layer coupling these two equilibrium models. To validate our model, we used both pH-sensitive dye-based capillary filling experiments as well as electro-osmotic current-monitoring measurements. Using our model we predict the dependence of ζ potential, surface charge density, and capillary...

  7. Relaxation to equilibrium following photoacid dissociation in mineral acids and buffer solutions

    International Nuclear Information System (INIS)

    Pines, D; Nibbering, E T J; Pines, E

    2007-01-01

    The relaxation to the dissociation equilibrium of a weak acid undergoing a transient pK a change in the presence of a strong mineral acid has been the subject of considerable interest both experimentally and theoretically. Here we compare this process with the analogue event taking place in a buffer solution of a weak carboxylic acid. The comparison has been performed in identical pH and ionic strength conditions and at a sufficiently short timescale where the buffer can only affect the weak acid relaxation by proton scavenging. Although the two relaxation processes have been found to differ in their temporal behaviour, they have both resulted in identical equilibrium amplitudes of the photoacid. This observation reassures the well-known chemical wisdom that pK a values measured in buffer solutions do not depend on the specific chemical reactivity of the buffer. We analyse the essentially many-body relaxation problem in terms of a re-normalized geminate recombination reaction which persists over longer times than the exponential relaxation to equilibrium of homogenously distributed populations of the reactants

  8. Using the Wolfsberg--Schactschneider program to calculate equilibrium constants for isotopic acetylenes

    International Nuclear Information System (INIS)

    Liu, D.K.K.; Pyper, J.W.

    1977-01-01

    Equilibrium constants were calculated for the gas-phase isotopic exchange reactions C 2 H 2 + C 2 D 2 = 2C 2 HD and C 2 H 2 + D 2 O = C 2 D 2 + H 2 O at temperatures ranging from 40 to 2000 0 K. No corrections to the harmonic approximation were made. The results agree quite well with experimental measurements

  9. Does the Addition of Inert Gases at Constant Volume and Temperature Affect Chemical Equilibrium?

    Science.gov (United States)

    Paiva, Joao C. M.; Goncalves, Jorge; Fonseca, Susana

    2008-01-01

    In this article we examine three approaches, leading to different conclusions, for answering the question "Does the addition of inert gases at constant volume and temperature modify the state of equilibrium?" In the first approach, the answer is yes as a result of a common students' alternative conception; the second approach, valid only for ideal…

  10. Coenzyme B12 model studies: Equilibrium constants for the pH ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 114; Issue 1. Coenzyme B12 model studies: Equilibrium constants for the H-dependent axial ligation of benzyl(aquo)cobaloxime by various N- and S-donor ligands. D Sudarshan Reddy N Ravi Kumar Reddy V Sridhar S Satyanarayana. Inorganic and Analytical ...

  11. Determination of acid dissociation constants of warfarin and hydroxywarfarins by capillary electrophoresis.

    Science.gov (United States)

    Nowak, Paweł; Olechowska, Paulina; Mitoraj, Mariusz; Woźniakiewicz, Michał; Kościelniak, Paweł

    2015-08-10

    In this work the acid dissociation constants--pKa of warfarin and its all important oxidative metabolites have been determined by capillary electrophoresis-based methods. It has resulted in a complete description of two acid-base dissociation equilibria, yet not investigated experimentally for phase I metabolites of warfarin. The capillary electrophoresis (CE) method based on the relation between effective electrophoretic mobilities and pH has proven to be a suitable tool for pKa determination, while the spectrophotometric (CE-DAD) and the internal standard methods (IS-CE), have appeared to be promising alternative approaches. The CE-DAD approach based on the change in absorbance spectra between the acidic and basic forms is a combination between capillary electrophoresis and spectrophotometric titration, and yields very consistent values of pKa1 with CE. The IS-CE, in turn, enables an estimation of pKa1 and pKa2 from only two analytical runs, however, less accurate than CE and CE-DAD. The Debye-Hückel model has been confirmed experimentally as a good predictor of pKa values at various ionic strengths. Therefore, it has been used in determination of thermodynamic pKa1 and pKa2, referring to the zero ionic strength. The results are important from the analytical, pharmacological, and theoretical points of view. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Theoretical study (ab initio and DFT methods on acidic dissociation constant of xylenol orange in aqueous solution

    Directory of Open Access Journals (Sweden)

    F. Kiani

    2017-07-01

    Full Text Available Analytical measurement of materials requires exact knowledge of their acid dissociation constant (pKa values. In recent years, quantum mechanical calculations have been extensively used to study of acidities in the aqueous solutions and the results were compared with the experimental values. In this study, a theoretical study was carried out on xylenol orange (in water solution by ab initio method. We calculated the pKa values of xylenol orange in water, using high-level ab initio (PM3, DFT (HF, B3LYP/6-31+G(d and SCRF methods. The experimental determination of these values (pKa,s is a challenge because xylenol orange has a low solubility in water. We considered several ionization reactions and equilibriums in water that constitute the indispensable theoretical basis to calculate the pKa values of xylenol orange. The results show that the calculated pKa values have a comparable agreement with the experimentally determined pKa values. Therefore, this method can be used to predict such properties for indicators, drugs and other important molecules.

  13. Simultaneous determination of equivalence volumes and acid dissociation constants from potentiometric titration data.

    Science.gov (United States)

    Papanastasiou, G; Ziogas, I

    1995-06-01

    New iterative methods for analysis of potentiometric titration data of (a) mixtures of weak monoprotic acids with their conjugate bases, (b) solutions of polyprotic (di- and triprotic) acids, and (c) mixtures of two diprotic acids are presented. These methods, using data exclusively resulting from the acidic region of the titration curve permits the accurate determination of the analytical concentration of one or more acids even if the titration is stopped well before the end point of the titration. For the titration of a solution containing a conjugate acid/base pair, the proposed procedure enables the extraction of the initial composition of the mixture, as well as the dissociation constant of the concerned acid. Thus, it is possible by this type of analysis to distinguish whether a weak acid has been contaminated by a strong base and define the extent of the contamination. On the other hand, for the titration of polyprotic acids, the proposed approach enables the extraction of the accurate values of the equivalence volume and the dissociation constants K(i) even when the ionization stages overlap. Finally, for the titration of a mixture of two diprotic acids the proposed procedure enables the determination of the composition of the mixture even if the sum of the concentrations of the acids is not known. This method can be used in the analysis of solutions containing two diastereoisomeric forms of a weak diprotic acid. The test of the proposed procedures by means of ideal and Monte Carlo simulated data revealed that these methods are fairly applicable even when the titration data are considerably obscured by 'noise' or contain an important systematic error. The proposed procedures were also successfully applied to experimental titration data.

  14. The role of equilibrium and kinetic properties in the dissociation of Gd[DTPA-bis(methylamide)] (Omniscan) at near to physiological conditions.

    Science.gov (United States)

    Baranyai, Zsolt; Brücher, Ernő; Uggeri, Fulvio; Maiocchi, Alessandro; Tóth, Imre; Andrási, Melinda; Gáspár, Attila; Zékány, László; Aime, Silvio

    2015-03-16

    [Gd(DTPA-BMA)] is the principal constituent of Omniscan, a magnetic resonance imaging (MRI) contrast agent. In body fluids, endogenous ions (Zn(2+), Cu(2+), and Ca(2+)) may displace the Gd(3+). To assess the extent of displacement at equilibrium, the stability constants of DTPA-BMA(3-) complexes of Gd(3+), Ca(2+), Zn(2+), and Cu(2+) have been determined at 37 °C in 0.15 M NaCl. The order of these stability constants is as follows: GdL≈CuL>ZnL≫CaL. Applying a simplified blood plasma model, the extent of dissociation of Omniscan (0.35 mM [Gd(DTPA-BMA)]) was found to be 17% by the formation of Gd(PO4), [Zn(DTPA-BMA)](-) (2.4%), [Cu(DTPA-BMA)](-) (0.2%), and [Ca(DTPA-BMA)](-) (17.7%). By capillary electrophoresis, the formation of [Ca(DTPA-BMA)](-) has been detected in human serum spiked with [Gd(DTPA-BMA)] (2.0 mM) at pH 7.4. Transmetallation reactions between [Gd(DTPA-BMA)] and Cu(2+) at 37 °C in the presence of citrate, phosphate, and bicarbonate ions occur by dissociation of the complex assisted by the endogenous ligands. At physiological concentrations of citrate, phosphate, and bicarbonate ions, the half-life of dissociation of [Gd(DTPA-BMA)] was calculated to be 9.3 h at pH 7.4. Considering the rates of distribution and dissociation of [Gd(DTPA-BMA)] in the extracellular space of the body, an open two-compartment model has been developed, which allows prediction of the extent of dissociation of the Gd(III) complex in body fluids depending on the rate of elimination of the contrast agent. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. A new sensitive method of dissociation constants determination based on the isohydric solutions principle.

    Science.gov (United States)

    Michałowski, Tadeusz; Pilarski, Bogusław; Asuero, Agustin G; Dobkowska, Agnieszka

    2010-10-15

    The paper provides a new formulation and analytical proposals based on the isohydric solutions concept. It is particularly stated that a mixture formed, according to titrimetric mode, from a weak acid (HX, C(0)mol/L) and a strong acid (HB, Cmol/L) solutions, assumes constant pH, independently on the volumes of the solutions mixed, provided that the relation C(0)=C+C(2)·10(pK(1)) is valid, where pK(1)=-log K(1), K(1) the dissociation constant for HX. The generalized formulation, referred to the isohydric solutions thus obtained, was extended also to more complex acid-base systems. Particularly in the (HX, HB) system, the titration occurs at constant ionic strength (I) value, not resulting from presence of a basal electrolyte. This very advantageous conjunction of the properties provides, among others, a new, very sensitive method for verification of pK(1) value. The new method is particularly useful for weak acids HX characterized by low pK(1) values. The method was tested experimentally on four acid-base systems (HX, HB), in aqueous and mixed-solvent media and compared with the literature data. Some useful (linear and hyperbolic) correlations were stated and applied for validation of pK(1) values. Finally, some practical applications of analytical interest of the isohydricity (pH constancy) principle as one formulated in this paper were enumerated, proving the usefulness of such a property which has its remote roots in the Arrhenius concept. Copyright © 2010 Elsevier B.V. All rights reserved.

  16. Potentiometric determination of acid dissociation constants (pKa) for human and veterinary antibiotics.

    Science.gov (United States)

    Qiang, Zhimin; Adams, Craig

    2004-07-01

    This work determined the acid dissociation constants (pKa) of 26 common human and veterinary antibiotics by potentiometric titration. Selected antibiotics consisted of sulfonamides, macrolides, tetracyclines, fluoroquinolones, and other miscellaneous antibiotics. After validation of analysis methods using phosphoric acid as a model compound, a second-derivative (delta2pH/deltaV2) method was primarily applied to determining pKa's from titration curves for most antibiotics due to its convenience and accuracy. For tetracyclines, however, a least-square non-linear regression method was developed to determine their pKa's because the second-derivative method cannot well distinguish the pKa,2 and pKa,3 of tetracyclines. Results indicate that the pKa values are approximately 2 and 5-7.5 for sulfonamides; 7.5-9 for macrolides; 3-4, 7-8 and 9-10 for tetracyclines; 3-4, 6, 7.5-9 and 10-11 for fluoroquinolones; while compound-specific for other miscellaneous antibiotics. The moieties corresponding to specific pKa's were identified based on chemical structures of antibiotics. In addition, the pKa's available in literature determined by various techniques are compiled in comparison with the values of this work. These results are expected to essentially facilitate the research on occurrence, fate and effects, analysis methods development, and control of antibiotics in various treatment operations.

  17. Measurement of acid dissociation constants of weak acids by cation exchange and conductometry

    Energy Technology Data Exchange (ETDEWEB)

    Dasgupta, P.K.; Nara, Osamu (Texas Tech Univ., Lubbock (USA))

    1990-06-01

    A simple strategy is presented for the determination of acid dissociation constants based on the measurement of conductance of a known concentration of the acid and/or the conductance of a solution of its fully or partially neutralized alkali-metal salts. For an n-protic acid, 2n conductance measurements are minimally necessary. In the simplest case of a typical monoprotic acid, the conductance of its alkali salt solution is measured before and after passage through an H{sup +}-form exchanger. From these data both the pK{sub a} of the acid and the equivalent conductance of the anion can be computed. The underlying equations are rigorously solved for monoprotic acids and some diprotic acid systems. For other diprotic and multiprotic acid systems, initial estimates are obtained by making approximations; the complete data set is then subjected to multiparametric fitting. The method does not require pH measurements; conductance can generally be measured accurately at low enough ionic strengths to obviate the need for major activity correction. Several experimental measurements are presented and excellent agreement with literature pK{sub a} values is observed. The reliability of the equivalent conductance values computed in this fashion is limited, however.

  18. Determination of equilibrium constants of formation and decomposition of 11-tungstophosphate heteropolyanion by the method of Raman spectroscopy

    International Nuclear Information System (INIS)

    Detusheva, L.G.; Khankhasaeva, S.Ts.; Yurchenko, Eh.N.; Lazarenko, T.P.; Kozhevnikov, I.V.

    1990-01-01

    Method of quantitative IR spectroscopy was used to determine equilibrium constants of formation of H x PW 11 O 39 (7-x)- (1) from H y P 2 W 21 O 71 (6-Y)- and W 10 O 32 4- at pH 2.8-4.0 and its decomposition at pH 7-8. Equilibrium constant of (1) formation in logarithmic coordinates changes linearly with growth of initial concentration of H 3 PW 12 O 40 (2) from 0.005 to 0.1 mol/l. Equilibrium constant of (1) decomposition is characterized by complex dependence on initial concentration of (2) due to proceeding of parallel reactions. Equilibrium concentrations of compounds in solutions of tungstophosphoric heteropolyacid at pH 3.25 and 7.68, calculated according to determined equilibrium constants and determined by the method of NMR on 31 P nuclei, were correlated

  19. Decomposition of atmospheric water content into cluster contributions based on theoretical association equilibrium constants

    International Nuclear Information System (INIS)

    Slanina, Z.

    1987-01-01

    Water vapor is treated as an equilibrium mixture of water clusters (H 2 O)/sub i/ using quantum-chemical evaluation of the equilibrium constants of water associations. The model is adapted to the conditions of atmospheric humidity, and a decomposition algorithm is suggested using the temperature and mass concentration of water as input information and used for a demonstration of evaluation of the water oligomer populations in the Earth's atmosphere. An upper limit of the populations is set up based on the water content in saturated aqueous vapor. It is proved that the cluster population in the saturated water vapor, as well as in the Earth's atmosphere for a typical temperature/humidity profile, increases with increasing temperatures

  20. Thermodynamic Modeling and Optimization of the Copper Flash Converting Process Using the Equilibrium Constant Method

    Science.gov (United States)

    Li, Ming-zhou; Zhou, Jie-min; Tong, Chang-ren; Zhang, Wen-hai; Chen, Zhuo; Wang, Jin-liang

    2018-05-01

    Based on the principle of multiphase equilibrium, a mathematical model of the copper flash converting process was established by the equilibrium constant method, and a computational system was developed with the use of MetCal software platform. The mathematical model was validated by comparing simulated outputs, industrial data, and published data. To obtain high-quality blister copper, a low copper content in slag, and increased impurity removal rate, the model was then applied to investigate the effects of the operational parameters [oxygen/feed ratio (R OF), flux rate (R F), and converting temperature (T)] on the product weights, compositions, and the distribution behaviors of impurity elements. The optimized results showed that R OF, R F, and T should be controlled at approximately 156 Nm3/t, within 3.0 pct, and at approximately 1523 K (1250 °C), respectively.

  1. Equilibrium and Dynamic Osmotic Behaviour of Aqueous Solutions with Varied Concentration at Constant and Variable Volume

    Science.gov (United States)

    Minkov, Ivan L.; Manev, Emil D.; Sazdanova, Svetla V.; Kolikov, Kiril H.

    2013-01-01

    Osmosis is essential for the living organisms. In biological systems the process usually occurs in confined volumes and may express specific features. The osmotic pressure in aqueous solutions was studied here experimentally as a function of solute concentration (0.05–0.5 M) in two different regimes: of constant and variable solution volume. Sucrose, a biologically active substance, was chosen as a reference solute for the complex tests. A custom made osmotic cell was used. A novel operative experimental approach, employing limited variation of the solution volume, was developed and applied for the purpose. The established equilibrium values of the osmotic pressure are in agreement with the theoretical expectations and do not exhibit any evident differences for both regimes. In contrast, the obtained kinetic dependences reveal striking divergence in the rates of the process at constant and varied solution volume for the respective solute concentrations. The rise of pressure is much faster at constant solution volume, while the solvent influx is many times greater in the regime of variable volume. The results obtained suggest a feasible mechanism for the way in which the living cells rapidly achieve osmotic equilibrium upon changes in the environment. PMID:24459448

  2. Determination of the Equilibrium Constants of a Weak Acid: An Experiment for Analytical or Physical Chemistry

    Science.gov (United States)

    Bonham, Russell A.

    1998-05-01

    A simple experiment, utilizing readily available equipment and chemicals, is described. It allows students to explore the concepts of chemical equilibria, nonideal behavior of aqueous solutions, least squares with adjustment of nonlinear model parameters, and errors. The relationship between the pH of a solution of known initial concentration and volume of a weak acid as it is titrated by known volumes of a monohydroxy strong base is developed rigorously assuming ideal behavior. A distinctive feature of this work is a method that avoids dealing with the problems presented by equations with multiple roots. The volume of base added is calculated in terms of a known value of the pH and the equilibrium constants. The algebraic effort involved is nearly the same as the alternative of deriving a master equation for solving for the hydrogen ion concentration or activity and results in a more efficient computational algorithm. This approach offers two advantages over the use of computer software to solve directly for the hydrogen ion concentration. First, it avoids a potentially lengthy iterative procedure encountered when the polynomial exceeds third order in the hydrogen ion concentration; and second, it provides a means of obtaining results with a hand calculator that can prove useful in checking computer code. The approach is limited to weak solutions to avoid dealing with molalities and to insure that the Debye-Hückel limiting law is applicable. The nonlinear least squares algorithm Nonlinear Fit, found in the computational mathematics library Mathematica, is utilized to fit the measured volume of added base to the calculated value as a function of the measured pH subject to variation of all the equilibrium constants as parameters (including Kw). The experiment emphasizes both data collection and data analysis aspects of the problem. Data for the titration of phosphorous acid, H3PO3, by NaOH are used to illustrate the approach. Fits of the data without corrections

  3. CONCENTRATION DEPENDENCE OF STERN LAYER CAPACITANCES AND SURFACE EQUILIBRIUM CONSTANTS IN SILICA-BASED NANOFLUIDIC CHANNELS

    DEFF Research Database (Denmark)

    Andersen, Mathias Bækbo; Frey, J.; Bruus, Henrik

    2010-01-01

    Fundamental understanding of the unique physics at the solid-liquid interface in nanofluidic channels is essential for the advancement of basic scientific knowledge and the development of novel applications for pharmaceuticals, environmental health and safety, energy harvesting and biometrics [1......]. The current models used to describe surface phenomena in nanofluidics can differ by orders of magnitude from experimentally measured values [2]. To mitigate the discrepancies, we hypothesize that the Stern-layer capacitance Cs and the surface equilibrium constants pKa, vary with the composition of the solid...

  4. Molecular-dynamics study of propane-hydrate dissociation: Fluctuation-dissipation and non-equilibrium analysis.

    Science.gov (United States)

    Ghaani, Mohammad Reza; English, Niall J

    2018-03-21

    Equilibrium and non-equilibrium molecular-dynamics (MD) simulations have been performed to investigate thermal-driven break-up of planar propane-hydrate interfaces in contact with liquid water over the 260-320 K range. Two types of hydrate-surface water-lattice molecular termination were adopted, at the hydrate edge with water, for comparison: a 001-direct surface cleavage and one with completed cages. Statistically significant differences in melting temperatures and initial break-up rates were observed between both interface types. Dissociation rates were observed to be strongly dependent on temperature, with higher rates at larger over-temperatures vis-à-vis melting. A simple coupled mass and heat transfer model, developed previously, was applied to fit the observed dissociation profiles, and this helps us to identify clearly two distinct hydrate-decomposition régimes; following a highly temperature-dependent break-up phase, a second well-defined stage is essentially independent of temperature, in which the remaining nanoscale, de facto two-dimensional system's lattice framework is intrinsically unstable. Further equilibrium MD-analysis of the two-phase systems at their melting point, with consideration of the relaxation times gleaned from the auto-correlation functions of fluctuations in a number of enclathrated guest molecules, led to statistically significant differences between the two surface-termination cases; a consistent correlation emerged in both cases between the underlying, non-equilibrium, thermal-driven dissociation rates sampled directly from melting with that from an equilibrium-MD fluctuation-dissipation approach.

  5. Surface-dependent chemical equilibrium constants and capacitances for bare and 3-cyanopropyldimethylchlorosilane coated silica nanochannels.

    Science.gov (United States)

    Andersen, Mathias Bækbo; Frey, Jared; Pennathur, Sumita; Bruus, Henrik

    2011-01-01

    We present a combined theoretical and experimental analysis of the solid-liquid interface of fused-silica nanofabricated channels with and without a hydrophilic 3-cyanopropyldimethylchlorosilane (cyanosilane) coating. We develop a model that relaxes the assumption that the surface parameters C(1), C(2), and pK(+) are constant and independent of surface composition. Our theoretical model consists of three parts: (i) a chemical equilibrium model of the bare or coated wall, (ii) a chemical equilibrium model of the buffered bulk electrolyte, and (iii) a self-consistent Gouy-Chapman-Stern triple-layer model of the electrochemical double layer coupling these two equilibrium models. To validate our model, we used both pH-sensitive dye-based capillary filling experiments as well as electro-osmotic current-monitoring measurements. Using our model we predict the dependence of ζ potential, surface charge density, and capillary filling length ratio on ionic strength for different surface compositions, which can be difficult to achieve otherwise. Copyright © 2010 Elsevier Inc. All rights reserved.

  6. Species-Specific Thiol-Disulfide Equilibrium Constant: A Tool To Characterize Redox Transitions of Biological Importance.

    Science.gov (United States)

    Mirzahosseini, Arash; Somlyay, Máté; Noszál, Béla

    2015-08-13

    Microscopic redox equilibrium constants, a new species-specific type of physicochemical parameters, were introduced and determined to quantify thiol-disulfide equilibria of biological significance. The thiol-disulfide redox equilibria of glutathione with cysteamine, cysteine, and homocysteine were approached from both sides, and the equilibrium mixtures were analyzed by quantitative NMR methods to characterize the highly composite, co-dependent acid-base and redox equilibria. The directly obtained, pH-dependent, conditional constants were then decomposed by a new evaluation method, resulting in pH-independent, microscopic redox equilibrium constants for the first time. The 80 different, microscopic redox equilibrium constant values show close correlation with the respective thiolate basicities and provide sound means for the development of potent agents against oxidative stress.

  7. The thermodynamic dissociation constants of losartan, paracetamol, phenylephrine and quinine by the regression analysis of spectrophotometric data

    International Nuclear Information System (INIS)

    Meloun, Milan; Syrovy, Tomas; Vrana, Ales

    2005-01-01

    The mixed dissociation constants of four drug acids - losartan, paracetamol, phenylephrine and quinine - at various ionic strengths I of range 0.01 and 1.0 and at temperatures of 25 and 37 deg. C were determined using SPECFIT32 and SQUAD(84) regression analysis of the pH-spectrophotometric titration data. A proposed strategy of efficient experimentation in a dissociation constants determination, followed by a computational strategy for the chemical model with a dissociation constants determination, is presented on the protonation equilibria of losartan. Indices of precise methods predict the correct number of components, and even the presence of minor ones when the data quality is high and the instrumental error is known. Improved identification of the number of species uses the second or third derivative function for some indices, namely when the number of species in the mixture is higher than 3 and when, due to large variations in the indicator values even at logarithmic scale, the indicator curve does not reach an obvious point where the slope changes. The thermodynamic dissociation constant pKaT was estimated by nonlinear regression of {pK a , I} data at 25 and 37 deg. C: for losartan pKa,1T=3.63(1) and 3.57(3), pKa,2T=4.84(1) and 4.80(3), for paracetamol pKa,1T=9.78(1) and 9.65(1), for phenylephrine pKa,1T=9.17(1) and 8.95(1), pKa,2T=10.45(1) and 10.22(1), for quinine pKa,1T=4.25(1) and 4.12(1), pKa,2T=8.72(1) and 8.46(2). Goodness-of-fit tests for various regression diagnostics enabled the reliability of the parameter estimates to be found

  8. The thermodynamic dissociation constants of losartan, paracetamol, phenylephrine and quinine by the regression analysis of spectrophotometric data

    Energy Technology Data Exchange (ETDEWEB)

    Meloun, Milan [Department of Analytical Chemistry, University of Pardubice, 53210 Pardubice (Czech Republic)]. E-mail: milan.meloun@upce.cz; Syrovy, Tomas [Department of Analytical Chemistry, University of Pardubice, 53210 Pardubice (Czech Republic)]. E-mail: tomas.syrovy@upce.cz; Vrana, Ales [IVAX Pharmaceuticals, s.r.o. 74770 Opava (Czech Republic)]. E-mail: ales_vrana@ivax-cr.com

    2005-03-21

    The mixed dissociation constants of four drug acids - losartan, paracetamol, phenylephrine and quinine - at various ionic strengths I of range 0.01 and 1.0 and at temperatures of 25 and 37 deg. C were determined using SPECFIT32 and SQUAD(84) regression analysis of the pH-spectrophotometric titration data. A proposed strategy of efficient experimentation in a dissociation constants determination, followed by a computational strategy for the chemical model with a dissociation constants determination, is presented on the protonation equilibria of losartan. Indices of precise methods predict the correct number of components, and even the presence of minor ones when the data quality is high and the instrumental error is known. Improved identification of the number of species uses the second or third derivative function for some indices, namely when the number of species in the mixture is higher than 3 and when, due to large variations in the indicator values even at logarithmic scale, the indicator curve does not reach an obvious point where the slope changes. The thermodynamic dissociation constant pKaT was estimated by nonlinear regression of {l_brace}pK{sub a}, I{r_brace} data at 25 and 37 deg. C: for losartan pKa,1T=3.63(1) and 3.57(3), pKa,2T=4.84(1) and 4.80(3), for paracetamol pKa,1T=9.78(1) and 9.65(1), for phenylephrine pKa,1T=9.17(1) and 8.95(1), pKa,2T=10.45(1) and 10.22(1), for quinine pKa,1T=4.25(1) and 4.12(1), pKa,2T=8.72(1) and 8.46(2). Goodness-of-fit tests for various regression diagnostics enabled the reliability of the parameter estimates to be found.

  9. DC electrophoresis and viscosity of realistic salt-free concentrated suspensions: non-equilibrium dissociation-association processes.

    Science.gov (United States)

    Ruiz-Reina, Emilio; Carrique, Félix; Lechuga, Luis

    2014-03-01

    Most of the suspensions usually found in industrial applications are concentrated, aqueous and in contact with the atmospheric CO2. The case of suspensions with a high concentration of added salt is relatively well understood and has been considered in many studies. In this work we are concerned with the case of concentrated suspensions that have no ions different than: (1) those stemming from the charged colloidal particles (the added counterions, that counterbalance their surface charge); (2) the H(+) and OH(-) ions from water dissociation, and (3) the ions generated by the atmospheric CO2 contamination. We call this kind of systems "realistic salt-free suspensions". We show some theoretical results about the electrophoretic mobility of a colloidal particle and the electroviscous effect of realistic salt-free concentrated suspensions. The theoretical framework is based on a cell model that accounts for particle-particle interactions in concentrated suspensions, which has been successfully applied to many different phenomena in concentrated suspensions. On the other hand, the water dissociation and CO2 contamination can be described following two different levels of approximation: (a) by local equilibrium mass-action equations, because it is supposed that the reactions are so fast that chemical equilibrium is attained everywhere in the suspension, or (b) by non-equilibrium dissociation-association kinetic equations, because it is considered that some reactions are not rapid enough to ensure local chemical equilibrium. Both approaches give rise to different results in the range from dilute to semidilute suspensions, causing possible discrepancies when comparing standard theories and experiments concerning transport properties of realistic salt-free suspensions. Copyright © 2013 Elsevier Inc. All rights reserved.

  10. The universal statistical distributions of the affinity, equilibrium constants, kinetics and specificity in biomolecular recognition.

    Directory of Open Access Journals (Sweden)

    Xiliang Zheng

    2015-04-01

    Full Text Available We uncovered the universal statistical laws for the biomolecular recognition/binding process. We quantified the statistical energy landscapes for binding, from which we can characterize the distributions of the binding free energy (affinity, the equilibrium constants, the kinetics and the specificity by exploring the different ligands binding with a particular receptor. The results of the analytical studies are confirmed by the microscopic flexible docking simulations. The distribution of binding affinity is Gaussian around the mean and becomes exponential near the tail. The equilibrium constants of the binding follow a log-normal distribution around the mean and a power law distribution in the tail. The intrinsic specificity for biomolecular recognition measures the degree of discrimination of native versus non-native binding and the optimization of which becomes the maximization of the ratio of the free energy gap between the native state and the average of non-native states versus the roughness measured by the variance of the free energy landscape around its mean. The intrinsic specificity obeys a Gaussian distribution near the mean and an exponential distribution near the tail. Furthermore, the kinetics of binding follows a log-normal distribution near the mean and a power law distribution at the tail. Our study provides new insights into the statistical nature of thermodynamics, kinetics and function from different ligands binding with a specific receptor or equivalently specific ligand binding with different receptors. The elucidation of distributions of the kinetics and free energy has guiding roles in studying biomolecular recognition and function through small-molecule evolution and chemical genetics.

  11. Extension of CE/SE method to non-equilibrium dissociating flows

    KAUST Repository

    Wen, C.Y.; Saldivar Massimi, H.; Shen, Hua

    2017-01-01

    and quadrilateral elements. The dissociating and recombination chemical reactions as well as the vibrational energy relaxation are taken into account. The stiff source terms are solved by an implicit trapezoidal method of integration. Comparison with laboratory

  12. Discovering a Change in Equilibrium Constant with Change in Ionic Strength: An Empirical Laboratory Experiment for General Chemistry

    Science.gov (United States)

    Stolzberg, Richard J.

    1999-05-01

    Students are challenged to investigate the hypothesis that an equilibrium constant, Kc, measured as a product and quotient of molar concentrations, is constant at constant temperature. Spectrophotometric measurements of absorbance of a solution of Fe3+(aq) and SCN-(aq) treated with different amounts of KNO3 are made to determine Kc for the formation of FeSCN2+(aq). Students observe a regular decrease in the value of Kc as the concentration of added KNO3 is increased.

  13. Determination of Acid Dissociation Constants (pKa) of Bicyclic Thiohydantoin-Pyrrolidine Compounds in 20% Ethanol-Water Hydroorganic Solvent

    Science.gov (United States)

    Nural, Yahya; Döndaş, H. Ali; Sarı, Hayati; Atabey, Hasan; Belveren, Samet; Gemili, Müge

    2014-01-01

    The acid dissociation constants of potential bioactive fused ring thiohydantoin-pyrrolidine compounds were determined by potentiometric titration in 20% (v/v) ethanol-water mixed at 25 ± 0.1°C, at an ionic background of 0.1 mol/L of NaCl using the HYPERQUAD computer program. Proton affinities of potential donor atoms of the ligands were calculated by AM1 and PM3 semiempiric methods. We found, potentiometrically, three different acid dissociation constants for 1a–f. We suggest that these acid dissociation constants are related to the carboxyl, enol, and amino groups. PMID:24799905

  14. Rates and equilibrium constants of the ligand-induced conformational transition of an HCN ion channel protein domain determined by DEER spectroscopy.

    Science.gov (United States)

    Collauto, Alberto; DeBerg, Hannah A; Kaufmann, Royi; Zagotta, William N; Stoll, Stefan; Goldfarb, Daniella

    2017-06-14

    Ligand binding can induce significant conformational changes in proteins. The mechanism of this process couples equilibria associated with the ligand binding event and the conformational change. Here we show that by combining the application of W-band double electron-electron resonance (DEER) spectroscopy with microfluidic rapid freeze quench (μRFQ) it is possible to resolve these processes and obtain both equilibrium constants and reaction rates. We studied the conformational transition of the nitroxide labeled, isolated carboxy-terminal cyclic-nucleotide binding domain (CNBD) of the HCN2 ion channel upon binding of the ligand 3',5'-cyclic adenosine monophosphate (cAMP). Using model-based global analysis, the time-resolved data of the μRFQ DEER experiments directly provide fractional populations of the open and closed conformations as a function of time. We modeled the ligand-induced conformational change in the protein using a four-state model: apo/open (AO), apo/closed (AC), bound/open (BO), bound/closed (BC). These species interconvert according to AC + L ⇌ AO + L ⇌ BO ⇌ BC. By analyzing the concentration dependence of the relative contributions of the closed and open conformations at equilibrium, we estimated the equilibrium constants for the two conformational equilibria and the open-state ligand dissociation constant. Analysis of the time-resolved μRFQ DEER data gave estimates for the intrinsic rates of ligand binding and unbinding as well as the rates of the conformational change. This demonstrates that DEER can quantitatively resolve both the thermodynamics and the kinetics of ligand binding and the associated conformational change.

  15. A Precise Method for Processing Data to Determine the Dissociation Constants of Polyhydroxy Carboxylic Acids via Potentiometric Titration.

    Science.gov (United States)

    Huang, Kaixuan; Xu, Yong; Lu, Wen; Yu, Shiyuan

    2017-12-01

    The thermodynamic dissociation constants of xylonic acid and gluconic acid were studied via potentiometric methods, and the results were verified using lactic acid, which has a known pKa value, as a model compound. Solutions of xylonic acid and gluconic acid were titrated with a standard solution of sodium hydroxide. The determined pKa data were processed via the method of derivative plots using computer software, and the accuracy was validated using the Gran method. The dissociation constants associated with the carboxylic acid group of xylonic and gluconic acids were determined to be pKa 1  = 3.56 ± 0.07 and pKa 1  = 3.74 ± 0.06, respectively. Further, the experimental data showed that the second deprotonation constants associated with a hydroxyl group of each of the two acids were pKa 2  = 8.58 ± 0.12 and pKa 2  = 7.06 ± 0.08, respectively. The deprotonation behavior of polyhydroxy carboxylic acids was altered using various ratios with Cu(II) to form complexes in solution, and this led to proposing a hypothesis for further study.

  16. Determination of acid-base dissociation constants of amino- and guanidinopurine nucleotide analogues and related compounds by capillary zone electroforesis

    Czech Academy of Sciences Publication Activity Database

    Šolínová, Veronika; Kašička, Václav; Koval, Dušan; Česnek, Michal; Holý, Antonín

    2006-01-01

    Roč. 27, č. 5/6 (2006), s. 1006-1019 ISSN 0173-0835 R&D Projects: GA ČR(CZ) GA203/03/0716; GA ČR(CZ) GA203/04/0098; GA AV ČR(CZ) 1QS400550501; GA MŠk(CZ) 1M0508; GA ČR(CZ) GA203/05/2539 Institutional research plan: CEZ:AV0Z40550506 Keywords : acyclic nucleoside phosphonates * capillary electrophoresis * dissociation constant Subject RIV: CC - Organic Chemistry Impact factor: 4.101, year: 2006

  17. Coupled radiative gasdynamic interaction and non-equilibrium dissociation for large-scale returned space vehicles

    International Nuclear Information System (INIS)

    Surzhikov, S.

    2012-01-01

    Graphical abstract: It has been shown that different coupled vibrational dissociation models, being applied for solving coupled radiative gasdynamic problems for large size space vehicles, exert noticeable effect on radiative heating of its surface at orbital entry on high altitudes (h ⩾ 70 km). This influence decreases with decreasing the space vehicles sizes. Figure shows translational (solid lines) and vibrational (dashed lines) temperatures in shock layer with (circle markers) and without (triangles markers) radiative-gasdynamic interaction for one trajectory point of entering space vehicle. Highlights: ► Nonequilibrium dissociation processes exert effect on radiation heating of space vehicles (SV). ► The radiation gas dynamic interaction enhances this influence. ► This influence increases with increasing the SV sizes. - Abstract: Radiative aerothermodynamics of large-scale space vehicles is considered for Earth orbital entry at zero angle of attack. Brief description of used radiative gasdynamic model of physically and chemically nonequilibrium, viscous, heat conductive and radiative gas of complex chemical composition is presented. Radiation gasdynamic (RadGD) interaction in high temperature shock layer is studied by means of numerical experiment. It is shown that radiation–gasdynamic coupling for orbital space vehicles of large size is important for high altitude part of entering trajectory. It is demonstrated that the use of different models of coupled vibrational dissociation (CVD) in conditions of RadGD interaction gives rise temperature variation in shock layer and, as a result, leads to significant variation of radiative heating of space vehicle.

  18. Chemical equilibrium calculations for the high pressure and temperature dissociation of liquid nitrogen

    Energy Technology Data Exchange (ETDEWEB)

    Hamilton, D.C.; Ree, F.H.

    1987-07-01

    Calculations are reported for the equation-of-state properties of shock-compressed liquid nitrogen. The statistical mechanical, chemical equilibrium calculations, which allow for the simultaneous presence of both the diatomic and monatomic forms of nitrogen, show good agreement with recent dynamic experiments.

  19. Chemical equilibrium calculations for the high pressure and temperature dissociation of liquid nitrogen

    International Nuclear Information System (INIS)

    Hamilton, D.C.; Ree, F.H.

    1987-07-01

    Calculations are reported for the equation-of-state properties of shock-compressed liquid nitrogen. The statistical mechanical, chemical equilibrium calculations, which allow for the simultaneous presence of both the diatomic and monatomic forms of nitrogen, show good agreement with recent dynamic experiments

  20. Spectroscopic constants and the potential energy curve of the iodine weakly bound 0+g state correlating with the I(2P1/2) + I(2P1/2) dissociation limit

    International Nuclear Information System (INIS)

    Akopyan, M E; Baturo, V V; Lukashov, S S; Poretsky, S A; Pravilov, A M

    2013-01-01

    The stepwise three-step three-colour aser excitation scheme and rotational as well as rovibrational energy transfer processes in the 0 + g state induced by collisions with He and Ar atoms are used for determination of rovibronic level energies of the weakly bound 0 + g state correlating with the I( 2 P 1/2 ) + I( 2 P 1/2 ) dissociation limit. Dunham coefficients of the state, Y i0 (i = 0–3), Y i1 (i = 0–3) and Y 02 for the v 0 g + = 0–16 and J 0 g + ≈ 14–135 ranges as well as the dissociation energy of the state, D e , and equilibrium I–I distance of the state, R e , are determined. The potential energy curve of the state constructed using these constants is also reported. (paper)

  1. Isotopic equilibrium constants of the deuterium exchange between HDO and H2S, H2Se and H2Te

    International Nuclear Information System (INIS)

    Marx, D.

    1959-11-01

    We have determined experimentally the equilibrium constant K of each of the following isotope exchanges: SH 2 + OHD ↔ SHD + OH 2 ; SeH 2 + OHD ↔ SeHD + OH 2 ; TeH 2 + OHD ↔ TeHD + OH 2 . In gaseous phase, statistical thermodynamics leads to the expression: K (Z OHD x Z RH 2 )/(Z OH 2 x Z RHD ) x e W/T (R being the elements S, Se or Te). Z, the partition functions, have been calculated and, through our experimental results, the constant W has been determined. Having obtained W, the equilibrium constant K has been calculated for a series of temperatures. (author) [fr

  2. Reduced neurophysin immunoreactivity in rat suprachiasmatic nucleus parallels dissociation of circadian feeding rhythm in constant light

    NARCIS (Netherlands)

    Steinhorst, B; Mai, JK; Rietveld, WJ

    Several distinct neuronal populations can be outlined in the suprachiasmatic nucleus (SCN) by employing immunohistochemistry. Understanding their interaction may serve as the key to the proc esses involved in the generation of circadian rhythms by the SCN. 15 adult rats were exposed to constant dim

  3. Equilibrium constants in aqueous lanthanide and actinide chemistry from time-resolved fluorescence spectroscopy: The role of ground and excited state reactions

    International Nuclear Information System (INIS)

    Billard, I.; Luetzenkirchen, K.

    2003-01-01

    Equilibrium constants for aqueous reactions between lanthanide or actinide ions and (in-) organic ligands contain important information for various radiochemical problems, such as nuclear reprocessing or the migration of radioelements in the geosphere. We study the conditions required to determine equilibrium constants by time-resolved fluorescence spectroscopy measurements. Based on a simulation study it is shown that the possibility to determine equilibrium constants depends upon the reaction rates in the photoexcited states of the lanthanide or actinide ions. (orig.)

  4. Determination of dissociation constants or propionic acid and lactic acid (2-hydroxypropionic acid) by potentiometry and conductometry

    International Nuclear Information System (INIS)

    Saeeduddin; Khanzada, A.W.K.

    2004-01-01

    Dissociation constants of propionic acid and 2-hydroxypropionic acid (lactic acid) have been studied at different temperatures between 25 to 50 deg. C interval. Propionic acid is analyzed by conductometry while 2-hydroxypropionic acid is analyzed by potentiometry. Both investigated compounds are symmetrical carboxylic acids having same length of carbon chain but are markedly different in ionic behavior. We were interested to see how the hydroxyl group (-OH) induction in propionic acid affects on pKa values of 2-hydroxypropionic acid. We observed that as temperature increases pKa values increase. The increase is observed for both the investigated compounds. PKa values of 2-hydroxypropionic acid are lower as compared to propionic acid because of electron withdrawing (-OH). (author)

  5. Determination of acid-base dissociation constants of azahelicenes by capillary zone electrophoresis

    Czech Academy of Sciences Publication Activity Database

    Ehala, Sille; Míšek, Jiří; Stará, Irena G.; Starý, Ivo; Kašička, Václav

    2008-01-01

    Roč. 31, č. 14 (2008), s. 2686-2693 ISSN 1615-9306 R&D Projects: GA ČR(CZ) GA203/06/1044; GA ČR GA203/08/1428; GA ČR GA203/07/1664; GA MŠk LC512 Institutional research plan: CEZ:AV0Z40550506 Keywords : acidity constant * azahelicenes * non-aqueous capillary electrophoresis Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.746, year: 2008

  6. The reactions of neutral iron clusters with D2O: Deconvolution of equilibrium constants from multiphoton processes

    International Nuclear Information System (INIS)

    Weiller, B.H.; Bechthold, P.S.; Parks, E.K.; Pobo, L.G.; Riley, S.J.

    1989-01-01

    The chemical reactions of neutral iron clusters with D 2 O are studied in a continuous flow tube reactor by molecular beam sampling and time-of-flight mass spectrometry with laser photoionization. Product distributions are invariant to a four-fold change in reaction time demonstrating that equilibrium is attained between free and adsorbed D 2 O. The observed negative temperature dependence is consistent with an exothermic, molecular addition reaction at equilibrium. Under our experimental conditions, there is significant photodesorption of D 2 O (Fe/sub n/(D 2 O)/sub m/ + hν → Fe/sub n/ + m D 2 O) along with ionization due to absorption of multiple photons from the ionizing laser. Using a simple model based on a rate equation analysis, we are able to quantitatively deconvolute this desorption process from the equilibrium constants. 8 refs., 1 fig

  7. Modelling of the migration of lanthanoids and actinoids in ground water; the medium dependence of equilibrium constants

    International Nuclear Information System (INIS)

    Biedermann, G.; Bruno, J.; Ferri, D.; Grenthe, I.; Salvatore, F.; Spahiu, K.

    1982-01-01

    The examples given in this communication indicate that it is possible to obtain a good estimate of the medium dependence of equilibrium constants by using the specific interaction theory. The theory is applicable both when extrapolating equilibrium constants to zero ionic strength and for the estimation of activity coefficients in mixtures of electrolytes. Many interaction coefficients are available in the literature, or can be calculated from published mean activity coefficient or isopiestic data. The magnitude of interaction coefficients can often be correlated with the charge and size of ions. This offers a possibility to estimate the coefficients for complexes, for which direct experimental information is difficult to get. The specific interaction theory is superior to the empirical equations of the Davies type. There is superior to the empirical equations of the Davies type. There is sufficient experimental information on interaction coefficients to warrant the implementation of the specific interaction approach in existing specifiation codes

  8. Determination, at equilibrium, of association constants of labelled or unlabelled ligands by a non-graphical method

    International Nuclear Information System (INIS)

    Goertz, G.; Longchampt, J.; Crepy, O.; Judas, O.; Jayle, M.-F.

    1976-01-01

    Determination, at equilibrium of association constants of labelled or unlabelled ligands by a non-graphical method are described. This work deals with the determination of association constants at equilibrium by a non-graphical method in binding systems containing one specific receptor. Equations have been derived from that originally described by Lea (Biochim. Biophys. Acta, 322, 68-74), the terms of which are obtained from the data of simple displacement curves of a bound radioactive ligand by unlabelled competitors identical or different in nature. By knowing the function relating the variations of the bound ligand (B) to the affinity constant (Ksub(i)) and the quantity (Msub(i)) of competitor for a given system, it is possible to calculate any of these parameters when the two others are measured. Thus, it becomes easy to compare the relative affinities of different receptors for the same ligand or that of one receptor for various labelled or unlabelled ligands. Furthermore, theoretical displacement curves can be drawn and compared to experimental data, only when knowing the affinity constant of a specific binding system in given conditions. These modes of calculation have been tested in a study of interactions between various steroids and a fraction of human serum proteins precipitated by ammonium sulfate (30-45%) and containing the sex hormone-binding globulin. Association constants thus obtained agree well with those reported in the literature and determined by graphical procedures

  9. METHOD FOR THE MEASUREMENT OF SITE-SPECIFIC TAUTOMERIC AND ZWITTERIONIC MICROSPECIES EQUILIBRIUM CONSTANTS

    Science.gov (United States)

    We describe a method for the individual measurement of simultaneously occurring, unimolecular, site-specific “microequilibrium” constants as in, for example, prototropic tautomerism and zwitterionic equilibria. Our method represents an elaboration of that of Nygren et al. (Anal. ...

  10. A procedure to find thermodynamic equilibrium constants for CO2 and CH4 adsorption on activated carbon.

    Science.gov (United States)

    Trinh, T T; van Erp, T S; Bedeaux, D; Kjelstrup, S; Grande, C A

    2015-03-28

    Thermodynamic equilibrium for adsorption means that the chemical potential of gas and adsorbed phase are equal. A precise knowledge of the chemical potential is, however, often lacking, because the activity coefficient of the adsorbate is not known. Adsorption isotherms are therefore commonly fitted to ideal models such as the Langmuir, Sips or Henry models. We propose here a new procedure to find the activity coefficient and the equilibrium constant for adsorption which uses the thermodynamic factor. Instead of fitting the data to a model, we calculate the thermodynamic factor and use this to find first the activity coefficient. We show, using published molecular simulation data, how this procedure gives the thermodynamic equilibrium constant and enthalpies of adsorption for CO2(g) on graphite. We also use published experimental data to find similar thermodynamic properties of CO2(g) and of CH4(g) adsorbed on activated carbon. The procedure gives a higher accuracy in the determination of enthalpies of adsorption than ideal models do.

  11. A Simple Model to Access Equilibrium Constants of Reactions Type A ⇋ B Using Monte Carlo Simulation.

    Directory of Open Access Journals (Sweden)

    R. R. Farias, L. A. M. Cardoso, N. M. Oliveira Neto

    2011-01-01

    Full Text Available A simple theoretical model to describe equilibrium properties of homogeneous re-versible chemical reactions is proposed and applied to an A ⇋ B type reaction. Forthis purpose the equilibrium properties are analyzed by usual Monte Carlo simula-tion. It is shown that the equilibrium constant (Ke for this kind of reaction exhibitsdistinct characteristics for Eba 1, where Eba is the ratio be-tween the reverse and forward activation energies. For Eba 1 and increase(decrease the temperature our results recover the principle of Le Chˆtelier applied ato temperature effects. The special and interesting case is obtained for Eba = 1 sinceKe = 1 for all range of temperature. Another important parameter in our analysisis θA , defined as temperature measured with relation the activation energy of theforward reaction. For fixed values of Eba and for θA ≫ 1 the equilibrium constantapproaches 1, showing that all transitions are equally likely, no matter the differencein the energy barriers. The data obtained in our simulations show the well knownrelationship between Ke , Eb , Ea and kB T . Finally we argue that this theoreticalmodel can be applied to a family of homogeneous chemical reactions characterizedby the same Eba and θA showing the broad application of this stochastic model tostudy chemical reactions. Some of these results will be discussed in terms of collisiontheory.

  12. Synthesis and Determination of Acid Dissociation Constants in Dimethyl Sulfoxide–Water Hydroorganic Solvent of 5,5-Diphenylpyrrolidine N-Aroylthiourea Derivatives

    Directory of Open Access Journals (Sweden)

    Yahya Nural

    2017-08-01

    Full Text Available Novel 5,5-diphenylpyrrolidineN-aroylthioureas, containing 4-methylbenzoyl, 2-chlorobenzoyl,2,4-dichlorobenzoyl, and2-naphthoyl, were synthesized and their structural analysis was performed using 1H nuclear magnetic resonance (NMR, 13C NMR, Fourier transform infrared spectroscopy, mass spectrometry (MS, and high-resolution MS (HRMS techniques. The acid dissociation constants of the 5,5-diphenylpyrrolidineN-aroylthiourea derivative compounds were determined using Hyperquad computer program for data obtained using potentiometric titration method in 25% (v/v dimethyl sulfoxide–water hydroorganic solvent in the presence of 0.1 mol×L-1 ionic strength of NaCl and in the acidic medium at 25±0.1°C, using sodium hydroxide base as a titrant. Two acid dissociation constants were obtained for 3a, 3b, and 3d, and it was suggested that they were related to N-H and enol groups. Furthermore, three acid dissociation constants obtained for 3a indicated that they were related to N-H, enthiol, and enol groups, and four acid dissociation constants obtained for 3c suggested that they were related to N-H, enthiol, enol, and carboxyl groups.

  13. Determination of the Acid Dissociation Constant of a Phenolic Acid by High Performance Liquid Chromatography: An Experiment for the Upper Level Analytical Chemistry Laboratory

    Science.gov (United States)

    Raboh, Ghada

    2018-01-01

    A high performance liquid chromatography (HPLC) experiment for the upper level analytical chemistry laboratory is described. The students consider the effect of mobile-phase composition and pH on the retention times of ionizable compounds in order to determine the acid dissociation constant, K[subscript a], of a phenolic acid. Results are analyzed…

  14. Determination of intrinsic equilibrium constants at an alumina/electrolyte interface

    Directory of Open Access Journals (Sweden)

    SLOBODAN K. MILONJIC

    2004-12-01

    Full Text Available Intrinsic ionization and complexation constants at an alumina/electrolyte interface were studied by the site binding model, while the sorption of alkali cations from aqueous solutions was interpreted by the triple-layer model. The surface properties of alumina were investigated by the potentiometric acid-base titration method. The point of zero charge (pHpzc of alumina obtained by this method was found to be 7.2. The obtained mean values of the intrinsic protonation and ionization constants of the surface hydroxyl groups and the intrinsic surface complexation constant, in different electrolytes, are pKinta1 = 4.4, pKinta2 = 9.6 and pKintM+ = 9.5, respectively.

  15. Effect of oxygen atoms dissociated by non-equilibrium plasma on flame of methane oxygen and argon pre-mixture gas

    Science.gov (United States)

    Akashi, Haruaki; Yoshinaga, Tomokazu; Sasaki, Koichi

    2014-10-01

    For more efficient way of combustion, plasma-assisted combustion has been investigated by many researchers. But it is very difficult to clarify the effect of plasma even on the flame of methane. Because there are many complex chemical reactions in combustion system. Sasaki et al. has reported that the flame length of methane and air premixed burner shortened by irradiating microwave power. They also measured emission from Second Positive Band System of nitrogen during the irradiation. The emission indicates existence of high energy electrons which are accelerated by the microwave. The high energy electrons also dissociate oxygen molecules easily and oxygen atom would have some effects on the flame. But the dissociation ratio of oxygen molecules by the non-equilibrium plasma is significantly low, compared to that in the combustion reaction. To clarify the effect of dissociated oxygen atoms on the flame, dependence of dissociation ratio of oxygen on the flame has been examined using CHEMKIN. It is found that in the case of low dissociation ratio of 10-6, the ignition of the flame becomes slightly earlier. It is also found that in the case of high dissociation ratio of 10-3, the ignition time becomes significantly earlier by almost half. This work was supported by KAKENHI (22340170).

  16. A Virtual Mixture Approach to the Study of Multistate Equilibrium: Application to Constant pH Simulation in Explicit Water

    Science.gov (United States)

    Wu, Xiongwu; Brooks, Bernard R.

    2015-01-01

    Chemical and thermodynamic equilibrium of multiple states is a fundamental phenomenon in biology systems and has been the focus of many experimental and computational studies. This work presents a simulation method to directly study the equilibrium of multiple states. This method constructs a virtual mixture of multiple states (VMMS) to sample the conformational space of all chemical states simultaneously. The VMMS system consists of multiple subsystems, one for each state. The subsystem contains a solute and a solvent environment. The solute molecules in all subsystems share the same conformation but have their own solvent environments. Transition between states is implicated by the change of their molar fractions. Simulation of a VMMS system allows efficient calculation of relative free energies of all states, which in turn determine their equilibrium molar fractions. For systems with a large number of state transition sites, an implicit site approximation is introduced to minimize the cost of simulation. A direct application of the VMMS method is for constant pH simulation to study protonation equilibrium. Applying the VMMS method to a heptapeptide of 3 ionizable residues, we calculated the pKas of those residues both with all explicit states and with implicit sites and obtained consistent results. For mouse epidermal growth factor of 9 ionizable groups, our VMMS simulations with implicit sites produced pKas of all 9 ionizable groups and the results agree qualitatively with NMR measurement. This example demonstrates the VMMS method can be applied to systems of a large number of ionizable groups and the computational cost scales linearly with the number of ionizable groups. For one of the most challenging systems in constant pH calculation, SNase Δ+PHS/V66K, our VMMS simulation shows that it is the state-dependent water penetration that causes the large deviation in lysine66’s pKa. PMID:26506245

  17. A Virtual Mixture Approach to the Study of Multistate Equilibrium: Application to Constant pH Simulation in Explicit Water.

    Directory of Open Access Journals (Sweden)

    Xiongwu Wu

    2015-10-01

    Full Text Available Chemical and thermodynamic equilibrium of multiple states is a fundamental phenomenon in biology systems and has been the focus of many experimental and computational studies. This work presents a simulation method to directly study the equilibrium of multiple states. This method constructs a virtual mixture of multiple states (VMMS to sample the conformational space of all chemical states simultaneously. The VMMS system consists of multiple subsystems, one for each state. The subsystem contains a solute and a solvent environment. The solute molecules in all subsystems share the same conformation but have their own solvent environments. Transition between states is implicated by the change of their molar fractions. Simulation of a VMMS system allows efficient calculation of relative free energies of all states, which in turn determine their equilibrium molar fractions. For systems with a large number of state transition sites, an implicit site approximation is introduced to minimize the cost of simulation. A direct application of the VMMS method is for constant pH simulation to study protonation equilibrium. Applying the VMMS method to a heptapeptide of 3 ionizable residues, we calculated the pKas of those residues both with all explicit states and with implicit sites and obtained consistent results. For mouse epidermal growth factor of 9 ionizable groups, our VMMS simulations with implicit sites produced pKas of all 9 ionizable groups and the results agree qualitatively with NMR measurement. This example demonstrates the VMMS method can be applied to systems of a large number of ionizable groups and the computational cost scales linearly with the number of ionizable groups. For one of the most challenging systems in constant pH calculation, SNase Δ+PHS/V66K, our VMMS simulation shows that it is the state-dependent water penetration that causes the large deviation in lysine66's pKa.

  18. A Virtual Mixture Approach to the Study of Multistate Equilibrium: Application to Constant pH Simulation in Explicit Water.

    Science.gov (United States)

    Wu, Xiongwu; Brooks, Bernard R

    2015-10-01

    Chemical and thermodynamic equilibrium of multiple states is a fundamental phenomenon in biology systems and has been the focus of many experimental and computational studies. This work presents a simulation method to directly study the equilibrium of multiple states. This method constructs a virtual mixture of multiple states (VMMS) to sample the conformational space of all chemical states simultaneously. The VMMS system consists of multiple subsystems, one for each state. The subsystem contains a solute and a solvent environment. The solute molecules in all subsystems share the same conformation but have their own solvent environments. Transition between states is implicated by the change of their molar fractions. Simulation of a VMMS system allows efficient calculation of relative free energies of all states, which in turn determine their equilibrium molar fractions. For systems with a large number of state transition sites, an implicit site approximation is introduced to minimize the cost of simulation. A direct application of the VMMS method is for constant pH simulation to study protonation equilibrium. Applying the VMMS method to a heptapeptide of 3 ionizable residues, we calculated the pKas of those residues both with all explicit states and with implicit sites and obtained consistent results. For mouse epidermal growth factor of 9 ionizable groups, our VMMS simulations with implicit sites produced pKas of all 9 ionizable groups and the results agree qualitatively with NMR measurement. This example demonstrates the VMMS method can be applied to systems of a large number of ionizable groups and the computational cost scales linearly with the number of ionizable groups. For one of the most challenging systems in constant pH calculation, SNase Δ+PHS/V66K, our VMMS simulation shows that it is the state-dependent water penetration that causes the large deviation in lysine66's pKa.

  19. Detection analysis of surface hydroxyl active sites and simulation calculation of the surface dissociation constants of aqueous diatomite suspensions

    Science.gov (United States)

    Ma, Shu-Cui; Wang, Zhi-Gang; Zhang, Ji-Lin; Sun, De-Hui; Liu, Gui-Xia

    2015-02-01

    The surface properties of the diatomite were investigated using nitrogen adsorption/deadsorption isotherms, TG-DSC, FTIR, and XPS, and surface protonation-deprotonation behavior was determined by continuous acid-base potentiometric titration technique. The diatomite sample with porous honeycomb structure has a BET specific surface area of 10.21 m2/g and large numbers of surface hydroxyl functional groups (i.e. tbnd Si-OH, tbnd Fe-OH, and tbnd Al-OH). These surface hydroxyls can be protonated or deprotonated depending on the pH of the suspension. The experimental potentiometric data in two different ionic strength solutions (0.1 and 0.05 mol/L NaCl) were fitted using ProtoFit GUI V2.1 program by applying diffuse double layer model (DLM) with three amphoteric sites and minimizing the sum of squares between a dataset derivative function and a model derivative function. The optimized surface parameters (i.e. surface dissociation constants (log K1, log K2) and surface site concentrations (log C)) of the sample were obtained. Based on the optimized surface parameters, the surface species distribution was calculated using Program-free PHREEQC 3.1.2. Thus, this work reveals considerable new information about surface protonation-deprotonation processes and surface adsorptive behaviors of the diatomite, which helps us to effectively use the cheap and cheerful diatomite clay adsorbent.

  20. Effect of temperature on a free energy and equilibrium constants during dry flue gas desulphurisation chemical reactions

    Directory of Open Access Journals (Sweden)

    Kuburović Miloš

    2002-01-01

    Full Text Available During dry flue gas desulphurisation (FGD dry particles of reagents are inserted (injected in the stream of flue gas, where they bond SO2. As reagents, the most often are used compounds of calcium (CaCO3, CaO or Ca(OH2. Knowledge of free energy and equilibrium constants of chemical reactions during dry FGD is necessary for understanding of influence of flue gas temperature to course of these chemical reactions as well as to SO2 bonding from flue gases.

  1. Use of equilibrium constant expression for initial screening of potential antithyroid agents

    International Nuclear Information System (INIS)

    Fatima, I.; Nanawar, M.A.; Tasneem, A.

    2011-01-01

    Synthetic antithyroid agents act through inhibition of enzyme or by making stable charge transfer (CT) complex with iodine. Iodine acts as s-acceptor and the synthetic compound as n-donor. Study of CT complexation of various drugs with iodine using UV/visible spectroscopy has revealed a positive correlation between the formation constant (Kc) and in vivo an activity. Some alkyl derivatives of 9H-purine-6-thiol were synthesized and evaluated in vitro as well as in vivo for potential antithyroid effects. The compounds exhibited 1:1 charge transfer complexation with iodine and have quite high values of formation constants. The blood assays of rats treated with these compounds and histological study of the thyroid tissues indicated the hyperactivity of gland. These compounds are expected to have lesser side effects as the sulfa group, a cause of toxicity in many medicines, is blocked. Phenyl derivative proved to be the most potent antithyroid agent comparable with methimazole. (author)

  2. Acid dissociation constant and apparent nucleophilicity of lysine-501 of the alpha-polypeptide of sodium and potassium ion activated adenosinetriphosphatase

    International Nuclear Information System (INIS)

    Xu, K.Y.

    1989-01-01

    A combination of competitive labeling with [ 3 H]acetic anhydride and immunoaffinity chromatography is described that permits the assignment of the acid dissociation constant and the absolute nucleophilicity of individual lysines in a native enzyme. The acid dissociation constant of lysine-501 of the alpha-polypeptide in native (Na+ + K+)-ATPase was determined. This lysine had a normal pKa of 10.4. The rate constant for the reaction of the free base of lysine-501 with acetic anhydride at 10 degrees C is 400 M-1 s-1. This value is only 30% that for a fully accessible lysine in a protein. The lower than normal apparent nucleophilicity suggests that lysine-501 is hindered from reacting with its intrinsic nucleophilicity by the tertiary structure of the enzyme and is consistent with its location within a pocket that forms the active site upon the surface of the native protein

  3. Effects of alkyl chain length and solvents on thermodynamic dissociation constants of the ionic liquids with one carboxyl group in the alkyl chain of imidazolium cations.

    Science.gov (United States)

    Chen, Yuehua; Wang, Huiyong; Wang, Jianji

    2014-05-01

    Thermodynamic dissociation constants of the Brønsted acidic ionic liquids (ILs) are important for their catalytic and separation applications. In this work, a series of imidazolium bromides with one carboxylic acid substitute group in their alkyl chain ([{(CH2)nCOOH}mim]Br, n = 1,3,5,7) have been synthesized, and their dissociation constants (pKa) at different ionic strengths have been determined in aqueous and aqueous organic solvents at 0.1 mole fraction (x) of ethanol, glycol, iso-propanol, and dimethyl sulfoxide by potentiometric titrations at 298.2 K. The standard thermodynamic dissociation constants (pKa(T)) of the ILs in these solvents were calculated from the extended Debye-Hückel equation. It was found that the pKa values increased with the increase of ionic strength of the media and of the addition of organic solvent in water. The pKa(T) values also increased with the increase of the alkyl chain length of cations of the ILs. In addition, the effect of solvent nature on pKa(T) values is interpreted from solvation of the dissociation components and their Gibbs energy of transfer from water to aqueous organic solutions.

  4. Detection analysis of surface hydroxyl active sites and simulation calculation of the surface dissociation constants of aqueous diatomite suspensions

    International Nuclear Information System (INIS)

    Ma, Shu-Cui; Wang, Zhi-Gang; Zhang, Ji-Lin; Sun, De-Hui; Liu, Gui-Xia

    2015-01-01

    Highlights: • To examine surface hydroxyl functional groups of the calcined diatomite by TGA-DSC, FTIR, and XPS. • To calculate the optimized log K 1 , log K 2 and log C values and the surface species distribution of each surface reactive site using ProtoFit and PHREEQC, respectively. - Abstract: The surface properties of the diatomite were investigated using nitrogen adsorption/deadsorption isotherms, TG-DSC, FTIR, and XPS, and surface protonation–deprotonation behavior was determined by continuous acid–base potentiometric titration technique. The diatomite sample with porous honeycomb structure has a BET specific surface area of 10.21 m 2 /g and large numbers of surface hydroxyl functional groups (i.e. ≡Si-OH, ≡Fe-OH, and ≡Al-OH). These surface hydroxyls can be protonated or deprotonated depending on the pH of the suspension. The experimental potentiometric data in two different ionic strength solutions (0.1 and 0.05 mol/L NaCl) were fitted using ProtoFit GUI V2.1 program by applying diffuse double layer model (DLM) with three amphoteric sites and minimizing the sum of squares between a dataset derivative function and a model derivative function. The optimized surface parameters (i.e. surface dissociation constants (log K 1 , log K 2 ) and surface site concentrations (log C)) of the sample were obtained. Based on the optimized surface parameters, the surface species distribution was calculated using Program-free PHREEQC 3.1.2. Thus, this work reveals considerable new information about surface protonation–deprotonation processes and surface adsorptive behaviors of the diatomite, which helps us to effectively use the cheap and cheerful diatomite clay adsorbent

  5. Detection analysis of surface hydroxyl active sites and simulation calculation of the surface dissociation constants of aqueous diatomite suspensions

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Shu-Cui [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Key Laboratory of Applied Chemistry and Nanotechnology at Universities of Jilin Province, Changchun University of Science and Technology, Changchun 130022 (China); Wang, Zhi-Gang [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Zhang, Ji-Lin, E-mail: zjl@ciac.ac.cn [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Sun, De-Hui [Changchun Institute Technology, Changchun 130012 (China); Liu, Gui-Xia, E-mail: liuguixia22@163.com [Key Laboratory of Applied Chemistry and Nanotechnology at Universities of Jilin Province, Changchun University of Science and Technology, Changchun 130022 (China)

    2015-02-01

    Highlights: • To examine surface hydroxyl functional groups of the calcined diatomite by TGA-DSC, FTIR, and XPS. • To calculate the optimized log K{sub 1}, log K{sub 2} and log C values and the surface species distribution of each surface reactive site using ProtoFit and PHREEQC, respectively. - Abstract: The surface properties of the diatomite were investigated using nitrogen adsorption/deadsorption isotherms, TG-DSC, FTIR, and XPS, and surface protonation–deprotonation behavior was determined by continuous acid–base potentiometric titration technique. The diatomite sample with porous honeycomb structure has a BET specific surface area of 10.21 m{sup 2}/g and large numbers of surface hydroxyl functional groups (i.e. ≡Si-OH, ≡Fe-OH, and ≡Al-OH). These surface hydroxyls can be protonated or deprotonated depending on the pH of the suspension. The experimental potentiometric data in two different ionic strength solutions (0.1 and 0.05 mol/L NaCl) were fitted using ProtoFit GUI V2.1 program by applying diffuse double layer model (DLM) with three amphoteric sites and minimizing the sum of squares between a dataset derivative function and a model derivative function. The optimized surface parameters (i.e. surface dissociation constants (log K{sub 1}, log K{sub 2}) and surface site concentrations (log C)) of the sample were obtained. Based on the optimized surface parameters, the surface species distribution was calculated using Program-free PHREEQC 3.1.2. Thus, this work reveals considerable new information about surface protonation–deprotonation processes and surface adsorptive behaviors of the diatomite, which helps us to effectively use the cheap and cheerful diatomite clay adsorbent.

  6. Computational Approaches to the Chemical Equilibrium Constant in Protein-ligand Binding.

    Science.gov (United States)

    Montalvo-Acosta, Joel José; Cecchini, Marco

    2016-12-01

    The physiological role played by protein-ligand recognition has motivated the development of several computational approaches to the ligand binding affinity. Some of them, termed rigorous, have a strong theoretical foundation but involve too much computation to be generally useful. Some others alleviate the computational burden by introducing strong approximations and/or empirical calibrations, which also limit their general use. Most importantly, there is no straightforward correlation between the predictive power and the level of approximation introduced. Here, we present a general framework for the quantitative interpretation of protein-ligand binding based on statistical mechanics. Within this framework, we re-derive self-consistently the fundamental equations of some popular approaches to the binding constant and pinpoint the inherent approximations. Our analysis represents a first step towards the development of variants with optimum accuracy/efficiency ratio for each stage of the drug discovery pipeline. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Uncertain Henry's law constants compromise equilibrium partitioning calculations of atmospheric oxidation products

    Directory of Open Access Journals (Sweden)

    C. Wang

    2017-06-01

    Full Text Available Gas–particle partitioning governs the distribution, removal, and transport of organic compounds in the atmosphere and the formation of secondary organic aerosol (SOA. The large variety of atmospheric species and their wide range of properties make predicting this partitioning equilibrium challenging. Here we expand on earlier work and predict gas–organic and gas–aqueous phase partitioning coefficients for 3414 atmospherically relevant molecules using COSMOtherm, SPARC Performs Automated Reasoning in Chemistry (SPARC, and poly-parameter linear free-energy relationships. The Master Chemical Mechanism generated the structures by oxidizing primary emitted volatile organic compounds. Predictions for gas–organic phase partitioning coefficients (KWIOM/G by different methods are on average within 1 order of magnitude of each other, irrespective of the numbers of functional groups, except for predictions by COSMOtherm and SPARC for compounds with more than three functional groups, which have a slightly higher discrepancy. Discrepancies between predictions of gas–aqueous partitioning (KW/G are much larger and increase with the number of functional groups in the molecule. In particular, COSMOtherm often predicts much lower KW/G for highly functionalized compounds than the other methods. While the quantum-chemistry-based COSMOtherm accounts for the influence of intra-molecular interactions on conformation, highly functionalized molecules likely fall outside of the applicability domain of the other techniques, which at least in part rely on empirical data for calibration. Further analysis suggests that atmospheric phase distribution calculations are sensitive to the partitioning coefficient estimation method, in particular to the estimated value of KW/G. The large uncertainty in KW/G predictions for highly functionalized organic compounds needs to be resolved to improve the quantitative treatment of SOA formation.

  8. Equilibrium star formation in a constant Q disc: model optimization and initial tests

    Science.gov (United States)

    Zheng, Zheng; Meurer, Gerhardt R.; Heckman, Timothy M.; Thilker, David A.; Zwaan, Martin A.

    2013-10-01

    We develop a model for the distribution of the interstellar medium (ISM) and star formation in galaxies based on recent studies that indicate that galactic discs stabilize to a constant stability parameter, which we combine with prescriptions of how the phases of the ISM are determined and for the star formation law (SFL). The model predicts the gas surface mass density and star formation intensity of a galaxy given its rotation curve, stellar surface mass density and the gas velocity dispersion. This model is tested on radial profiles of neutral and molecular ISM surface mass density and star formation intensity of 12 galaxies selected from the H I Nearby Galaxy Survey sample. Our tests focus on intermediate radii (0.3 to 1 times the optical radius) because there are insufficient data to test the outer discs and the fits are less accurate in detail in the centre. Nevertheless, the model produces reasonable agreement with the ISM mass and star formation rate integrated over the central region in all but one case. To optimize the model, we evaluate four recipes for the stability parameter, three recipes for apportioning the ISM into molecular and neutral components, and eight versions of the SFL. We find no clear-cut best prescription for the two-fluid (gas and stars) stability parameter Q2f and therefore for simplicity, we use the Wang and Silk approximation (QWS). We found that an empirical scaling between the molecular-to-neutral ISM ratio (Rmol) and the stellar surface mass density proposed by Leroy et al. works marginally better than the other two prescriptions for this ratio in predicting the ISM profiles, and noticeably better in predicting the star formation intensity from the ISM profiles produced by our model with the SFLs we tested. Thus, in the context of our modelled ISM profiles, the linear molecular SFL and the two-component SFL work better than the other prescriptions we tested. We incorporate these relations into our `constant Q disc' model.

  9. Evaluation of equilibrium constants for deprotonation and lactonisation of α-D-isosaccharinic acid

    International Nuclear Information System (INIS)

    Rai, Dhanpat; Kitamura, Akira

    2016-01-01

    A great deal of disagreement exists in the literature regarding the intrinsic deprotonation and lactonisation constants of α-D-isosaccharinic acid (ISA). Based on a combination of nuclear magnetic resonance and interpretations using the specific ion interaction theory (SIT) of extensive experimental Ca(ISA) 2 (cr) solubility data involving α-D-isosaccharinic acid, the reliable value of log 10 K° for [HISA(aq) ⇌ ISA - + H + ] is -3.27 ± 0.01 and for [HISA(aq) ⇌ ISL(α-D-isosaccharinate-1,4-lactone)(aq) + H 2 O] is 0.49 ± 0.09. These data also provide log 10 K° of -3.76 ± 0.09 for the reaction [ISL(aq) + H 2 O ⇌ ISA - + H + ] and -3.88 ± 0.09 for the composite reaction [HISA(aq) + ISL(aq) ⇌ ISA - + H + ]. Reinterpretation of extensive Ca(ISA) 2 (cr) solubility data using the SIT activity coefficient model provides log 10 K° of -6.40 ± 0.09 for [Ca(ISA) 2 (cr) ⇌ Ca 2+ + 2(ISA) - ] and of 1.70 ± 0.09 for [Ca 2+ + ISA - ⇌ CaISA + ] which are consistent with all of the available values. (author)

  10. The dissociation constants of the cytostatic bosutinib by nonlinear least-squares regression of multiwavelength spectrophotometric and potentiometric pH-titration data.

    Science.gov (United States)

    Meloun, Milan; Nečasová, Veronika; Javůrek, Milan; Pekárek, Tomáš

    2016-02-20

    Potentiometric and spectrophotometric pH-titration of the multiprotic cytostatics bosutinib for dissociation constants determination were compared. Bosutinib treats patients with positive chronic myeloid leukemia. Bosutinib exhibits four protonatable sites in a pH range from 2 to 11, where two pK are well separated (ΔpK>3), while the other two are near dissociation constants. In the neutral medium, bosutinib occurs in the slightly water soluble form LH that can be protonated to the soluble cation LH4(3+). The molecule LH can be dissociated to still difficultly soluble anion L(-). The set of spectra upon pH from 2 to 11 in the 239.3-375.0nm was divided into two absorption bands: the first one from 239.3 to 290.5nm and the second from 312.3 to 375.0nm, which differ in sensitivity of chromophores to a pH change. Estimates of pK of the entire set of spectra were compared with those of both absorption bands. Due to limited solubility of bosutinib the protonation in a mixed aqueous-methanolic medium was studied. In low methanol content of 3-6% three dissociation constants can be reliably determined with SPECFIT/32 and SQUAD(84) and after extrapolation to zero content of methanol they lead to pKc1=3.43(12), pKc2=4.54(10), pKc3=7.56(07) and pKc4=11.04(05) at 25°C and pKc1=3.44(06), pKc2=5.03(08) pKc3=7.33(05) and pKc4=10.92(06) at 37°C. With an increasing content of methanol in solvent the dissociation of bosutinib is suppressed and the percentage of LH3(2+) decreases and LH prevails. From the potentiometric pH-titration at 25°C the concentration dissociation constants were estimated with ESAB pKc1=3.51(02), pKc2=4.37(02), pKc3=7.97(02) and pKc4=11.05(03) and with HYPERQUAD: pKc1=3.29(12), pKc2=4.24(10), pKc3=7.95(07) and pKc4=11.29(05). Copyright © 2015 Elsevier B.V. All rights reserved.

  11. Determination of Equilibrium Constant and Relative Brightness in FRET-FCS by Including the Third-Order Correlations.

    Science.gov (United States)

    Meng, Lingyi; He, Shanshan; Zhao, Xin Sheng

    2017-12-21

    Fluorescence correlation spectroscopy (FCS) encodes the information on the equilibrium constant (K), the relative fluorescence brightness of fluorophore (Q), and the forward and backward reaction rate constants (k + and k - ) on a physical or chemical relaxation. However, it has been a long-standing problem to completely resolve the FCS data to get the thermodynamic and kinetic information. Recently, we have solved the problem for fluorescence autocorrelation spectroscopy (FACS). Here, we extend the method to fluorescence cross-correlation spectroscopy (FCCS), which appears when FCS is coupled with fluorescence resonance energy transfer (FRET). Among 12 total second-order and third-order pre-exponential factors in a relaxation process probed by the FRET-FCS technique, 3 are independent. We presented and discussed 3 sets of explicit solutions to use these pre-exponential factors to calculate K and Q. Together with the relaxation time, the acquired K will allow people to obtain k + and k - , so that the goal of deciphering the FRET-FCS data will be fully reached. The theory is verified by extensive computer simulations and tested experimentally on a system of oligonucleotide hybridization.

  12. Effect of Temperature on Acidity and Hydration Equilibrium Constants of Delphinidin-3-O- and Cyanidin-3-O-sambubioside Calculated from Uni- and Multiwavelength Spectroscopic Data.

    Science.gov (United States)

    Vidot, Kévin; Achir, Nawel; Mertz, Christian; Sinela, André; Rawat, Nadirah; Prades, Alexia; Dangles, Olivier; Fulcrand, Hélène; Dornier, Manuel

    2016-05-25

    Delphinidin-3-O-sambubioside and cyanidin-3-O-sambubioside are the main anthocyanins of Hibiscus sabdariffa calyces, traditionally used to make a bright red beverage by decoction in water. At natural pH, these anthocyanins are mainly in their flavylium form (red) in equilibrium with the quinonoid base (purple) and the hemiketal (colorless). For the first time, their acidity and hydration equilibrium constants were obtained from a pH-jump method followed by UV-vis spectroscopy as a function of temperature from 4 to 37 °C. Equilibrium constant determination was also performed by multivariate curve resolution (MCR). Acidity and hydration constants of cyanidin-3-O-sambubioside at 25 °C were 4.12 × 10(-5) and 7.74 × 10(-4), respectively, and were significantly higher for delphinidin-3-O-sambubioside (4.95 × 10(-5) and 1.21 × 10(-3), respectively). MCR enabled the obtaining of concentration and spectrum of each form but led to overestimated values for the equilibrium constants. However, both methods showed that formations of the quinonoid base and hemiketal were endothermic reactions. Equilibrium constants of anthocyanins in the hibiscus extract showed comparable values as for the isolated anthocyanins.

  13. Colorimetric Determination of the Iron(III)-Thiocyanate Reaction Equilibrium Constant with Calibration and Equilibrium Solutions Prepared in a Cuvette by Sequential Additions of One Reagent to the Other

    Science.gov (United States)

    Nyasulu, Frazier; Barlag, Rebecca

    2011-01-01

    The well-known colorimetric determination of the equilibrium constant of the iron(III-thiocyanate complex is simplified by preparing solutions in a cuvette. For the calibration plot, 0.10 mL increments of 0.00100 M KSCN are added to 4.00 mL of 0.200 M Fe(NO[subscript 3])[subscript 3], and for the equilibrium solutions, 0.50 mL increments of…

  14. Determination of the equilibrium constant of FeZrCl6 formation from FeCl3 and ZrCl4

    International Nuclear Information System (INIS)

    Berdonosov, S.S.; Kharisov, B.I.; Nikitin, M.I.

    1992-01-01

    Equilibrium pressures of chlorine formed in the course of reaction FeCl 3 +ZrCl 4 ↔ FeZrCl 6 +0.5 Cl 2 were determined at the temperatures of 250-325 deg C. The values of equilibrium constant K p of the reaction mentioned at the temperatures of 250, 275, 300 and 325 deg were calculated, taking into consideration the determined values of p Cl2 and literature data on equilibrium pressures of ZrCl 4 and FeCl 3 vapours

  15. On determination of the degree of dissociation of hydrogen in non-equilibrium plasmas by means of emission spectroscopy: II. Experimental verification

    International Nuclear Information System (INIS)

    Lavrov, B P; Lang, N; Pipa, A V; Roepcke, J

    2006-01-01

    The method of spectroscopic determination of the degree of dissociation of hydrogen in non-equilibrium plasma, proposed in our previous paper, was verified under various plasma conditions. Three different gas discharges have been used, namely: (i) a DC-arc discharge (ii) an RF discharge, f = 200 kHz and (iii) an MW discharge, f = 2.45 GHz, under pressure p = 0.3-8 mbar. Relative intensities of atomic and molecular spectroscopic lines, the H α and H β line and the (2-2)Q1 line of the Fulcher-α system, and the gas temperature were measured in a wide range of discharge conditions and used for the determination of the degree of dissociation of hydrogen. It is shown that the method leads to plausible results in the whole range of discharge conditions studied in this paper. In particular, for the first time an influence of the redistribution of the population density of excited hydrogen atoms among fine structure sublevels on values of the degree of dissociation of hydrogen obtained by the method was investigated experimentally. It is also shown, that the influence is rather significant. The assumption of Boltzmann populations of the sublevels is more appropriate than neglecting the redistribution after electron impact excitation for p > 1 mbar

  16. A hetero retro Diels-Alder reaction in aqueous solution : A dramatic water-induced increase of the equilibrium constant and inhibition of cycloreversion

    NARCIS (Netherlands)

    Wijnen, J.W; Engberts, J.B.F.N.

    The adduct of the Diels-Alder reaction of nitrosobenzene with cyclopentadiene is not stable in solution. The equilibrium constant for the reaction depends strongly on the medium and water induces a spectacular shift to the adduct. Comparison with the bimolecular addition of nitrosobenzene to

  17. Understanding Chemical Equilibrium Using Entropy Analysis: The Relationship between [delta]S[subscript tot](sys[superscript o]) and the Equilibrium Constant

    Science.gov (United States)

    Bindel, Thomas H.

    2010-01-01

    Entropy analyses as a function of the extent of reaction are presented for a number of physicochemical processes, including vaporization of a liquid, dimerization of nitrogen dioxide, and the autoionization of water. Graphs of the total entropy change versus the extent of reaction give a visual representation of chemical equilibrium and the second…

  18. I. Dissociation free energies of drug-receptor systems via non-equilibrium alchemical simulations: a theoretical framework.

    Science.gov (United States)

    Procacci, Piero

    2016-06-01

    In this contribution I critically revise the alchemical reversible approach in the context of the statistical mechanics theory of non-covalent bonding in drug-receptor systems. I show that most of the pitfalls and entanglements for the binding free energy evaluation in computer simulations are rooted in the equilibrium assumption that is implicit in the reversible method. These critical issues can be resolved by using a non-equilibrium variant of the alchemical method in molecular dynamics simulations, relying on the production of many independent trajectories with a continuous dynamical evolution of an externally driven alchemical coordinate, completing the decoupling of the ligand in a matter of a few tens of picoseconds rather than nanoseconds. The absolute binding free energy can be recovered from the annihilation work distributions by applying an unbiased unidirectional free energy estimate, on the assumption that any observed work distribution is given by a mixture of normal distributions, whose components are identical in either direction of the non-equilibrium process, with weights regulated by the Crooks theorem. I finally show that the inherent reliability and accuracy of the unidirectional estimate of the decoupling free energies, based on the production of a few hundreds of non-equilibrium independent sub-nanosecond unrestrained alchemical annihilation processes, is a direct consequence of the funnel-like shape of the free energy surface in molecular recognition. An application of the technique to a real drug-receptor system is presented in the companion paper.

  19. Method for accurate determination of dissociation constants of optical ratiometric systems: chemical probes, genetically encoded sensors, and interacting molecules.

    Science.gov (United States)

    Pomorski, Adam; Kochańczyk, Tomasz; Miłoch, Anna; Krężel, Artur

    2013-12-03

    Ratiometric chemical probes and genetically encoded sensors are of high interest for both analytical chemists and molecular biologists. Their high sensitivity toward the target ligand and ability to obtain quantitative results without a known sensor concentration have made them a very useful tool in both in vitro and in vivo assays. Although ratiometric sensors are widely used in many applications, their successful and accurate usage depends on how they are characterized in terms of sensing target molecules. The most important feature of probes and sensors besides their optical parameters is an affinity constant toward analyzed molecules. The literature shows that different analytical approaches are used to determine the stability constants, with the ratio approach being most popular. However, oversimplification and lack of attention to detail results in inaccurate determination of stability constants, which in turn affects the results obtained using these sensors. Here, we present a new method where ratio signal is calibrated for borderline values of intensities of both wavelengths, instead of borderline ratio values that generate errors in many studies. At the same time, the equation takes into account the cooperativity factor or fluorescence artifacts and therefore can be used to characterize systems with various stoichiometries and experimental conditions. Accurate determination of stability constants is demonstrated utilizing four known optical ratiometric probes and sensors, together with a discussion regarding other, currently used methods.

  20. Determination of acid-base dissociation constants of very weak zwitterionic heterocyclic bases by capillary zone electrophoresis

    Czech Academy of Sciences Publication Activity Database

    Ehala, Sille; Grishina, Anastasia; Sheshenev, Andrey; Lyapkalo, Ilya; Kašička, Václav

    2010-01-01

    Roč. 1217, - (2010), s. 8048-8053 ISSN 0021-9673 R&D Projects: GA ČR(CZ) GA203/08/1428; GA ČR(CZ) GA203/09/0675 Institutional research plan: CEZ:AV0Z40550506 Keywords : acidity constant * capillary zone electrophoresis * zwitterionic heterocyclic bases Subject RIV: CC - Organic Chemistry Impact factor: 4.194, year: 2010

  1. A survey of the reaction rate constants for the thermal dissociation and recombination of nitrogen and oxygen

    Science.gov (United States)

    Marraffa, Lionel; Dulikravich, George S.; Keeney, Timothy C.; Deiwert, George S.

    1988-01-01

    The objective of the present report is to survey the various values of forward and backward reaction rate constants used by investigators in the field of high-temperature (T greater than 2000 K) gas reactions involving nitrogen and oxygen only. The objective is to find those values that correlate well so that they can be used for the studies of hypersonic flow and supersonic combustion with reasonable confidence. Relatively good agreement among these various values is observed for temperatures lower than 10,000 K.

  2. Use of the cation exchange equilibrium method for the determination of stability constants of Co(II) with soil humic and fulvic acids

    International Nuclear Information System (INIS)

    Du, J.Z.; Zhou, C.Y.; Dong, W.M.; Tao, Z.Y.

    1999-01-01

    The stability constants for tracer concentrations of Co(II) complexes with both the red earth humic and fulvic acids were determined at pH 5.9 and ionic strength 0.010 mol/l by using the ARDAKANI-STEVENSON cation exchange equilibrium method and the radiotracer 60 Co. It was found that the 1:1 complexes of Co(II) with the red earth humic and fulvic acids were formed and that the average values of logβ (stability constant) of humic and fulvic acid complexes were 5.76±0.19 and 4.42±0.03, respectively. (author)

  3. Calculation of the acid-base equilibrium constants at the alumina/electrolyte interface from the ph dependence of the adsorption of singly charged ions (Na+, Cl-)

    Science.gov (United States)

    Gololobova, E. G.; Gorichev, I. G.; Lainer, Yu. A.; Skvortsova, I. V.

    2011-05-01

    A procedure was proposed for the calculation of the acid-base equilibrium constants at an alumina/electrolyte interface from experimental data on the adsorption of singly charged ions (Na+, Cl-) at various pH values. The calculated constants (p K {1/0}= 4.1, p K {2/0}= 11.9, p K {3/0}= 8.3, and p K {4/0}= 7.7) are shown to agree with the values obtained from an experimental pH dependence of the electrokinetic potential and the results of potentiometric titration of Al2O3 suspensions.

  4. Calculating Equilibrium Constants in the SnCl2-H2O-NaOH System According to Potentiometric Titration Data

    Science.gov (United States)

    Maskaeva, L. N.; Fedorova, E. A.; Yusupov, R. A.; Markov, V. F.

    2018-05-01

    The potentiometric titration of tin chloride SnCl2 is performed in the concentration range of 0.00009-1.1 mol/L with a solution of sodium hydroxide NaOH. According to potentiometric titration data based on modeling equilibria in the SnCl2-H2O-NaOH system, basic equations are generated for the main processes, and instability constants are calculated for the resulting hydroxo complexes and equilibrium constants of low-soluble tin(II) compounds. The data will be of interest for specialists in the field of theory of solutions.

  5. Analysis of responsive characteristics of ionic-strength-sensitive hydrogel with consideration of effect of equilibrium constant by a chemo-electro-mechanical model.

    Science.gov (United States)

    Li, Hua; Lai, Fukun; Luo, Rongmo

    2009-11-17

    A multiphysics model is presented in this paper for analysis of the influence of various equilibrium constants on the smart hydrogel responsive to the ionic strength of environmental solution, and termed the multieffect-coupling ionic-strength stimulus (MECis) model. The model is characterized by a set of partial differential governing equations by consideration of the mass and momentum conservations of the system and coupled chemical, electrical, and mechanical multienergy domains. The Nernst-Planck equations are derived by the mass conservation of the ionic species in both the interstitial fluid of the hydrogel and the surrounding solution. The binding reaction between the fixed charge groups of the hydrogel and the mobile ions in the solution is described by the fixed charge equation, which is based on the Langmuir monolayer theory. As an important effect for the binding reaction, the equilibrium constant is incorporated into the fixed charge equation. The kinetics of the hydrogel swelling/deswelling is illustrated by the mechanical equation, based on the law of momentum conservation for the solid polymeric networks matrix within the hydrogel. The MECis model is examined by comparison of the numerical simulations and experiments from open literature. The analysis of the influence of different equilibrium constants on the responsive characteristics of the ionic-strength-sensitive hydrogel is carried out with detailed discussion.

  6. Standard Gibbs energies of formation and equilibrium constants from ab-initio calculations: Covalent dimerization of NO2 and synthesis of NH3

    International Nuclear Information System (INIS)

    Awasthi, Neha; Ritschel, Thomas; Lipowsky, Reinhard; Knecht, Volker

    2013-01-01

    Highlights: • ΔG and K eq for NO 2 dimerization and NH 3 synthesis calculated via ab-initio methods. • Vis-á-vis experiments, W1 and CCSD(T) are accurate and G3B3 also does quite well. • CBS-APNO most accurate for NH 3 reaction but shows limitations in modeling NO 2 . • Temperature dependence of ΔG and K eq is calculated for the NH 3 reaction. • Good agreement of calculated K eq with experiments and the van’t Hoff approximation. -- Abstract: Standard quantum chemical methods are used for accurate calculation of thermochemical properties such as enthalpies of formation, entropies and Gibbs energies of formation. Equilibrium reactions are widely investigated and experimental measurements often lead to a range of reaction Gibbs energies and equilibrium constants. It is useful to calculate these equilibrium properties from quantum chemical methods in order to address the experimental differences. Furthermore, most standard calculation methods differ in accuracy and feasibility of the system size. Hence, a systematic comparison of equilibrium properties calculated with different numerical algorithms would provide a useful reference. We select two well-known gas phase equilibrium reactions with small molecules: covalent dimer formation of NO 2 (2NO 2 ⇌ N 2 O 4 ) and the synthesis of NH 3 (N 2 + 3 H 2 ⇌ 2NH 3 ). We test four quantum chemical methods denoted by G3B3, CBS-APNO, W1 and CCSD(T) with aug-cc-pVXZ basis sets (X = 2, 3, and 4), to obtain thermochemical data for NO 2 , N 2 O 4 , and NH 3 . The calculated standard formation Gibbs energies Δ f G° are used to calculate standard reaction Gibbs energies Δ r G° and standard equilibrium constants K eq for the two reactions. Standard formation enthalpies Δ f H° are calculated in a more reliable way using high-level methods such as W1 and CCSD(T). Standard entropies S° for the molecules are calculated well within the range of experiments for all methods, however, the values of standard formation

  7. The effect of realistic forces in finite epitaxial islands: Equilibrium structure, stability limits and substrate-induced dissociation of migrating clusters

    Science.gov (United States)

    Milchev, Andrey; Markov, Ivan

    1985-06-01

    The behaviour of finite epitaxial islands in the periodic field of the substrate is theoretically investigated. The harmonic interactions, traditionally adopted in the model of Frank and Van der Merwe, are replaced by Toda and Morse potentials and sets of difference recursion equations, governing the equilibrium properties of the system, are derived and solved numerically. It is shown that allowing for anharmonicity in the interactions in the deposit reveals several qualiatively new effects, such as: (1) The existence of substrate-induced rupture of anharmonic clusters which migrate on the substrate. It is predicted that such dissociation should be enhanced, if (a) the energy barrier for surface diffusion is increased, (b) the natural incompatibility between substrate and deposit is decreased, and (c) the size of the clusters grows. (2) A split in the misfit stability limits for pseudomorphism and for spontaneous generation of misfit dislocations with respect to the sign of the misfit. The limits corresponding to negative misfit rapidly increase while the positive misfit limits decrease (in absolute terms) with growing degree of anharmonicity. (3) A marked asymmetry in the magnitude of various properties of the clusters, such as adhesion to the substrate, activation energy for surface diffusion, mean strain, dislocation lengths, etc., with respect to the sign of the mismatch between surface and deposit.

  8. Equilibrium dialysis-ligand exchange: adaptation of the method for determination of conditional stability constants of radionuclide-fulvic acid complexes

    International Nuclear Information System (INIS)

    Glaus, M.A.; Hummel, W.; Van Loon, L.R.

    1995-01-01

    The equilibrium dialysis-ligand exchange technique (EDLE) is used to determine conditional stability constants for the complexation of metal ions with humic acid, particularly in high pH solutions. Here, this technique has been adapted to measure conditional stability constants with fulvic acid. Fulvic acid permeates across all membranes during the experiment. The quantities involved therefore have to be determined analytically and taken into account when calculating the conditional stability constants. Co(II) and Laurentian Soil fulvic (LFA) acid were selected as a test system in order to investigate the time scale required to establish chemical and diffusion equilibria. After an incubation time of approximately two days, the conditional stability constants measured for the formation of Co-LFA-complexes are not time dependent, although across the whole time period investigated, LFA was still diffusing in increasing amounts across the dialysis membrane. This work demonstrates that the modified EDLE technique can be used in the determination of conditional metal stability constants of fulvic acid. (authors)

  9. DNA unwinding induced by photoaddition of psoralen derivatives and determination of dark-binding equilibrium constants by gel electrophoresis

    International Nuclear Information System (INIS)

    Wiesehahn, G.; Hearst, J.E.

    1978-01-01

    Derivatives of furo[3,2-g]coumarin (psoralen) can bind to the DNA double helix and, in the presence of long-wavelength uv light, the bound psoralen may react covalently with pyrimidine residues on one or both strands of the helix. By using agarose gel electrophoresis, we have determined the unwinding angle associated with each of four different psoralen derivatives to be 28 0 +- 4 0 . For 4,5',8-trimethylpsoralen (trioxsalen) the unwinding angle was found to be independent of the initial DNA superhelix density in the range that is accessible to agarose gel electrophoresis. Also by using agarose gel electrophoresis, we have determined the unwinding angle for ethidium intercalation. This was done by the total relaxation of supercoiled DNA in the presence of a series of ethidium concentrations. By using published values for the association constant for ethidium binding to DNA and evaluating the final superhelix density (after removal of ethidium) of the DNA on gels, we calculated an unwinding angle of 29 0 +- 3 0 . Assuming an unwinding angle of 28 0 for the noncovalent intercalation of psoralen derivatives, we used the same procedure to determine intercalation binding constants. The association constants for 4'-aminomethyltrioxsalen were 300 to 1400 M -1 in NaCl at 0.2 to 0.05 M and 300 to 2500 M -1 in Mg 2+ at 4 to 0.5 mM. The association constant for 4'-hydroxymethyltrioxsalen in 0.5 mM Mg 2+ was determined to be 70 M -1

  10. GRAPHICAL DETERMINATION OF DISSOCIATION CONSTANT ...

    African Journals Online (AJOL)

    DR. AMINU

    conform to the general equation of straight – line graph; y = mx + c, where y = pH, m = slope, x = log. [HA]/[A] and C = intercept = pKa. Thus the pKa is obtained as the intercept of the graph of pH versus – log [HA]/[A] as shown in Figures 1,2 and 3 for glycine, alanine and valine respectively. The values obtained were 9.87 ...

  11. Acid dissociation constants of uridine-5 Prime -diphosphate compounds determined by {sup 31}phosphorus nuclear magnetic resonance spectroscopy and internal pH referencing

    Energy Technology Data Exchange (ETDEWEB)

    Jancan, Igor [Louisiana State University, Department of Chemistry, Baton Rouge, LA 70803 (United States); Macnaughtan, Megan A., E-mail: macnau@lsu.edu [Louisiana State University, Department of Chemistry, Baton Rouge, LA 70803 (United States)

    2012-10-24

    Highlights: Black-Right-Pointing-Pointer The first reported phosphate and imide pK{sub a} values of UDP-GlcNAc and UDP-S-GlcNAc. Black-Right-Pointing-Pointer New role for the monosaccharide in the imide pK{sub a} of uridine-5 Prime -phosphate compounds. Black-Right-Pointing-Pointer UDP-S-GlcNAc and UDP-GlcNAc have the same phosphate pK{sub a}, unlike thioyl analogs. Black-Right-Pointing-Pointer The {sup 31}P chemical shift of inorganic phosphate is a viable internal pH reference. Black-Right-Pointing-Pointer Stability of the external {sup 31}P chemical shift reference is essential. - Abstract: The acid dissociation constant (pK{sub a}) of small, biological molecules is an important physical property used for investigating enzyme mechanisms and inhibitor design. For phosphorus-containing molecules, the {sup 31}P nuclear magnetic resonance (NMR) chemical shift is sensitive to the local chemical environment, particularly to changes in the electronic state of the molecule. Taking advantage of this property, we present a {sup 31}P NMR approach that uses inorganic phosphate buffer as an internal pH reference to determine the pK{sub a} values of the imide and second diphosphate of uridine-5 Prime -diphosphate compounds, including the first reported values for UDP-GlcNAc and UDP-S-GlcNAc. New methods for using inorganic phosphate buffer as an internal pH reference, involving mathematical correction factors and careful control of the chemical shift reference sample, are illustrated. A comparison of the newly determined imide and diphosphate pK{sub a} values of UDP, UDP-GlcNAc, and UDP-S-GlcNAc with other nucleotide phosphate and thio-analogs reveals the significance of the monosaccharide and sulfur position on the pK{sub a} values.

  12. Investigation of complexing equilibrium of polyacrylate-anion with cadmium ions by polarographic method

    Energy Technology Data Exchange (ETDEWEB)

    Avlyanov, Zh K; Kabanov, N M; Zezin, A B

    1985-01-01

    Polarographic investigation of cadmium complex with polyacrylate-anion in aqueous KCl solution is carried out. It is shown that the polarographic method allows one to define equilibrium constants of polymer metallic complex (PMC) formation even in the case when current magnitudes are defined by PMC dissociation reaction kinetic characteristics. The obtained equilibrium constants of stepped complexing provide the values of mean coordination PAAxCd complex number of approximately 1.5, that coincides with the value obtained by the potentiometric method.

  13. Investigation of complexing equilibrium of polyacrylate-anion with cadmium ions by polarographic method

    International Nuclear Information System (INIS)

    Avlyanov, Zh.K.; Kabanov, N.M.; Zezin, A.B.

    1985-01-01

    Polarographic investigation of cadmium complex with polyacrylate-anion in aqueous KCl solution is carried out. It is shown that the polarographic method allows one to define equilibrium constants of polymer metallic complex (PMC) formation even in the case, when current magnitudes are defined by PMC dissociation reaction kinetic characteristics. The obtained equilibrium constants of stepped complexing provide the values of mean coordination PAAxCd complex number of approximately 1.5, that coinsides with the value obtained by the potentiometric method

  14. Studies of Redox Equilibria at Elevated Temperatures I. The Estimation of Equilibrium Constants and Standard Potentials for Aqueous Systems up to 374 deg C

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Derek

    1969-07-01

    A method is described for the estimation of equilibrium constants for aqueous systems at temperatures up to 374 deg C from entropy and free energy data for 25 deg C and data on the variation of heat capacity with temperature. Partial molal heat capacities of aqueous ions are estimated on the basis of the principle that, with suitably chosen standard states, the partial molal entropies of ions of a particular class at any given temperature are linearly related to the corresponding entropies at some reference temperature. The method suggested is compared with other methods, based on the Van't Hoff isobar and on an extension of the conventional scale of ionic free energy at 25 deg C, and the general dependence of aqueous equilibria on ionic heat capacity is considered.

  15. Fundamental study of ionization and dissociation processes caused by electron impact in aromatic molecules; application of the quasi-equilibrium theory to phenanthrene and to methylphenanthrenes; Etudes fondamentales des processus d'ionisation et de dissociation des molecules aromatiques par impact electronique et application de la theorie du quasi-equilibre au phenanthrene et aux methyl-phenanthrenes

    Energy Technology Data Exchange (ETDEWEB)

    Nounou, P [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1969-07-01

    The quasi-equilibrium theory has been applied only to the family of long chain aliphatic hydrocarbons. We have tried to extend it to phenanthrene and methyl-phenanthrenes molecules, i.e. to aromatic molecules possessing a great number of degrees of freedom. In a first part, we have attempted to give a method of interpretation of the ionization and dissociation processes of the phenanthrenic molecules. These preliminary experimental studies of the behaviour under electron impact of the compounds provide us a great wealth of information about important structural transformations of the molecular and fragment ions, and also about auto-ionization and excitation processes of the studied molecules. The experimental study of the metastable peaks has then confirmed the validity of the preceding dissociation processes, while it gave with more accuracy some thermodynamical values in connection with decomposition reactions. The three studies of the ionization, then dissociation processes and of the metastable peaks, represent the three phases of a general method of interpretation of the fragmentation in mass spectrometry. In order to give this method a theoretical basis, we have carried out the molecular diagrams of each of the studied, compounds, showing by this way the aid of Quantum Mechanics to the study of excited and ionic states. In a second part, we have carried out the mass spectra of the phenanthrene and methyl-phenanthrenes molecules by means of the rate constants expression given by ROSENSTOCK. We have proposed new methods of calculation of the frequency factors, for the aliphatic molecules as well as the aromatic ones. If the rather good agreement observed between the experimental and calculated results cannot be surely attributed to the validity of the theory, however it out-lines the interest presented by the application of this theory to large aromatic molecules. Furthermore, the results at which we arrived provide us with interesting information about the

  16. Comparison of the binding constant (Ksub(D)) of /sup 125/I-labelled 3-(4-iodophenoxy)-1-isopropylaminopropan-2-ol obtained on. beta. -adrenoceptors in guinea-pig myocardial membranes, with its dissociation constants (Ksub(B)) obtained on guinea-pig isolated atria and trachea

    Energy Technology Data Exchange (ETDEWEB)

    O' Donnell, S R [Queensland Univ., Brisbane (Australia). Dept. Of Physiology; Woodcock, E A

    1978-02-01

    The dissociation constant of binding (Ksub(D) of /sup 125/I-labelled 3-(4-iodophenoxy)-isopropylaminopropan-2-ol (IIP) to guinea pig myocardial membrane preparations was 2.2 x 10/sup -8/M. In pharmacological experiments with non-labelled material and 60 min contact time, IIP produced a parallel shift in the orciprenaline concentration-response line on guinea-pig isolated tracheal and atrial preparations. The dissociation constant (Ksub(B) of IIP was 2.9 x 10/sup -8/M on atria (pA/sub 2/ 7.54) and 3.3 x 10/sup -8/M on trachea (PA/sub 2/ 7.48). These values indicate that IIP is not a selective B-adrenoceptor blocking drug. In addition, agreement was found between the affinity constant of this antagonist for B-adrenoceptors as determined by a direct binding study and an indirect pharmacological study.

  17. Association equilibrium constants and populations of clusters (H2O)n(g) and (D2O)n(g): differences between isotopomers and a possible relation to isotope enrichment

    International Nuclear Information System (INIS)

    Slanina, Z.

    1986-01-01

    Equilibrium constants of H 2 O(g) and D 2 O(g) associations to clusters (H 2 O) n (g) and (D 2 O) n (g) were calculated on the basis of the ab initio SCF CI MCY-B water-water pair potential. Populations of the components of equilibrium cluster mixtures were evaluated at various temperatures and pressures for both isotopomeric series. Differences between the H and D steam are pointed out and possible consequences are discussed. (author)

  18. Thermogravimetric analysis and dissociation pressure of caesium trihalides

    International Nuclear Information System (INIS)

    Harris, G.S.; McKechnie, J.S.

    1982-01-01

    We have carried out a thermogravimetric study of caesium trihalides to obtain, from the procedural decomposition temperatures, an order of apparent thermal stability which could be compared with the order of thermodynamic stability obtained from vapour pressure measurements. Thermogravimetric analysis could also prove to be a useful method for rapid analysis of metal polyhalides. The thermograms indicated a one-step decomposition for each compound; the procedural decomposition temperatures and percentage weight losses obtained are given. Dissociation pressures were measured and values of equilibrium constant and enthalpy of dissociation were calculated. The results are given. The 'stability' order obtained is discussed. (U.K.)

  19. Chemical Principles Revisited: Chemical Equilibrium.

    Science.gov (United States)

    Mickey, Charles D.

    1980-01-01

    Describes: (1) Law of Mass Action; (2) equilibrium constant and ideal behavior; (3) general form of the equilibrium constant; (4) forward and reverse reactions; (5) factors influencing equilibrium; (6) Le Chatelier's principle; (7) effects of temperature, changing concentration, and pressure on equilibrium; and (8) catalysts and equilibrium. (JN)

  20. The ion exchange properties and equilibrium constants of Li+, Na+ and K+ on zirconium phosphate highly dispersed on a cellulose acetate fibers surface

    Directory of Open Access Journals (Sweden)

    Borgo Claudemir Adriano

    2004-01-01

    Full Text Available Highly dispersed zirconium phosphate was prepared by reacting celullose acetate/ZrO2 (ZrO2 = 11 wt%, 1.0 mmol g-1 of zirconium atom per gram of the material with phosphoric acid. High power decoupling magic angle spinning (HPDEC-MAS 31P NMR and X-ray photoelectron spectroscopy data indicated that HPO4(2- is the species present on the membrane surface. The specific concentration of acidic centers, determined by ammonia gas adsorption, is 0.60 mmol g-1. The ion exchange capacities for Li+, Na+ and K+ ions were determined from ion exchange isotherms at 298 K and showed the following values (in mmol g-1: Li+= 0.05, Na+= 0.38 and K+= 0.57. Due to the strong cooperative effect, the H+/Na+ and H+/K+ ion exchange is of non ideal nature. These ion exchange equilibria were treated with the use of models of fixed tridentate centers, which consider the surface of the sorbent as polyfunctional sorption centers. Both the observed ion exchange capacities with respect to the alkaline metal ions and the equilibrium constants are discussed by taking into consideration the sequence of the ionic hydration radii for Li+, Na+ and K+. The matrix affinity for the ions decreases with increasing the cations hydration radii from K+ to Li+. The high values of the separation factors S Na+/Li+ and S K+/Li+ (up to several hundreds support the application of this material for the quantitative separation of Na+ and K+ from Li+ from a mixture containing these three ions.

  1. FORMATION CONSTANTS AND THERMODYNAMIC ...

    African Journals Online (AJOL)

    KEY WORDS: Metal complexes, Schiff base ligand, Formation constant, DFT calculation ... best values for the formation constants of the proposed equilibrium model by .... to its positive charge distribution and the ligand deformation geometry.

  2. Atom and molecule projectile and fast aggregate excitation, ionization and dissociation in thin targets in the out-of-charge equilibrium field

    International Nuclear Information System (INIS)

    Clouvas, A.

    1985-12-01

    The aim of this experimental study is to confirm the possible existence of bound states for light atomic and molecular projectiles inside solid targets, in the MeV energy range. For this purpose we have used, various experimental methods such as charge state distribution measurements, energy loss measurements, beam foil spectroscopy and electron spectroscopy. It was confirmed that bound states of light atomic and molecular projectiles can exist in a solid medium. The various cross sections (charge exchange, excitation, ionisation, dissociation) relative to these bound states have been measured [fr

  3. Rate constants of the equilibrium reactions SO⨪4 + HNO3 ⇄ HSO-4 + NO3 and SO⨪4 + NO-3 ⇄ SO2-4 + NO3

    DEFF Research Database (Denmark)

    Løgager, T.; Sehested, K.; Holcman, J.

    1993-01-01

    Rate constants of the following equilibrium reactions were determined by pulse radiolysis at high solute concentrations: SO4.- + HNO, half arrow right over half arrow left HSO4- + NO3. [k(f) = (2.7 +/- 0.5) x 10(6) M-1 s-1, k(r) = (5.6 +/- 1.0) x 10(3) M-1 s-1] and SO4.- + NO3- half arrow right...

  4. The /sup 13/C-/sup 13/C spin-spin coupling constants and the conformational equilibrium of alkyl phenyl sulfides

    Energy Technology Data Exchange (ETDEWEB)

    Krividin, L.B.; Kalabin, G.A.

    1985-08-10

    The authors measure the direct geminal and vicinal spinspin coupling constants between the C-13 nuclei of the phenyl group in the series of alkyl phenyl sulfides C/sub 6/H/sub 5/SR. It was shown that the variation in most of the discussed constants is determined by the ratio of the planar and orthogonal conformers. Linear relationships were obtained between the C-13-C-13 constants and the fractions of the planar conformer. The C-13-C-13 spin-spin coupling constants in the planar and orthogonal conformers of the compounds were calculated by means of empirical relationships.

  5. Determination of the dissociation constant of molten Li/sub 2/CO/sub 3//Na/sub 2/CO/sub 3//K/sub 2/CO/sub 3/ using a stabilized zirconia oxide-ion indicator

    Energy Technology Data Exchange (ETDEWEB)

    Ito, Yasuhiko; Tsuru, Kiyoshi; Oishi, Jun; Miyazaki, Yoshinori; Kodama, Teruo

    1985-09-01

    An Li/sub 2/CO/sub 3//Na/sub 2/CO/sub 3//K/sub 2/CO/sub 3/ eutectic melt has been selected as an example of a molten-carbonate system and the suitability of a stabilized zirconia-air electrode as an oxide-ion concentration indicator for this melt has been confirmed. With this indicator, the dissociation constant of the reaction CO/sub 3//sup 2 -/(l)=CO/sub 2/(g)+O/sup 2 -/(l) in this melt has been determined to be Ksub(d)=P sub(CO/sub 2/) (O/sup 2 -/)=4.03 x 10/sup -3/ Pa at 873 K. Reproducible measurements were obtained throughout the experiment and this method might find further application in the study of reactions related to the oxide ion in carbonate melts. (orig.).

  6. Use of an exchange method to estimate the association and dissociation rate constants of cadmium complexes formed with low-molecular-weight organic acids commonly exuded by plant roots.

    Science.gov (United States)

    Schneider, André; Nguyen, Christophe

    2011-01-01

    Organic acids released from plant roots can form complexes with cadmium (Cd) in the soil solution and influence metal bioavailability not only due to the nature and concentration of the complexes but also due to their lability. The lability of a complex influences its ability to buffer changes in the concentration of free ions (Cd); it depends on the association (, m mol s) and dissociation (, s) rate constants. A resin exchange method was used to estimate and (m mol s), which is the conditional estimate of depending on the calcium (Ca) concentration in solution. The constants were estimated for oxalate, citrate, and malate, three low-molecular-weight organic acids commonly exuded by plant roots and expected to strongly influence Cd uptake by plants. For all three organic acids, the and estimates were around 2.5 10 m mol s and 1.3 × 10 s, respectively. Based on the literature, these values indicate that the Cd- low-molecular-weight organic acids complexes formed between Cd and low-molecular-weight organic acids may be less labile than complexes formed with soil soluble organic matter but more labile than those formed with aminopolycarboxylic chelates. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

  7. Spectroscopic constants and potential energy curve of the iodine weakly bound 1u state correlating with the I(2P1/2) + I(2P1/2) dissociation limit

    International Nuclear Information System (INIS)

    Akopyan, M E; Baturo, V V; Lukashov, S S; Poretsky, S A; Pravilov, A M

    2015-01-01

    The stepwise three-step three-color laser population of the I 2 (β1 g , ν β , J β ) rovibronic states via the B0 u + , ν B , J B rovibronic states and rovibronic levels of the 1 u (bb) and 0 g + (bb) states mixed by hyperfine interaction is used for determination of rovibronic level energies of the weakly bound I 2 (1 u (bb)) state. Dunham coefficients of the state, Y i0 (i = 0–3), Y i1 (i = 0–2), Y 02 and Y 12 for the v 1 u  = 1–5, 8, 10, 15 and J 1 u  ≈ 9–87 ranges, the dissociation energy of the state, D e , and equilibrium I–I distance, R e , as well as the potential energy curve are determined. There are aperiodicities in the excitation spectrum corresponding to the β, ν β  = 23, J β  ← 1 u (bb), ν 1u  = 4, 5, J 1u progressions in the I 2  + Rg = He, Ar mixture, namely, a great number of lines which do not coincide with the R or P line progressions. Their positions conflict with the ΔJ-even selection rule. Furthermore, they do not correspond to the ΔJ-odd progression. (paper)

  8. Thermodynamic and microscopic equilibrium constants of molecular species formed from pyridoxal 5'-phosphate and 2-amino-3-phosphonopropionic acid in aqueous and D2O solution

    International Nuclear Information System (INIS)

    Szpoganicz, B.; Martell, A.E.

    1984-01-01

    Schiff base formation between pyridoxal 5'-phosphate (PLP) and 2-amino-3-phosphonopropionic acid (APP) has been investigated by measurement of the corresponding NMR and electronic absorption spectra. A value of 0.26 was found for the formation constant of the completely deprotonated Schiff base species, and is much smaller than the values reported for pyridoxal-β-chloroalanine and pyridoxal-O-phosphoserine. The protonation constants for the aldehyde and hydrate forms of PLP were determined in D 2 O by measurement of the variation of chemical shifts with pD (pH in D 2 O). The hydration constants of PLP were determined in a pD range 2-12, and species distributions were calculated. The protonation constants of the APP-PLP Schiff base determined by NMR in D 2 O were found to have the log values 12.54, 8.10, 6.70, and 5.95, and the species distributions were calculated for a range of pD values. Evidence is reported for hydrogen bonding involving the phosphate and phosphonate groups of the diprotonated Schiff base. The cis and trans forms of the Schiff bases were distinguished with the aid of the nuclear Overhauser effect. 43 references, 9 figures, 3 tables

  9. Benzodiazepine receptor equilibrium constants for flumazenil and midazolam determined in humans with the single photon emission computer tomography tracer [123I]iomazenil

    DEFF Research Database (Denmark)

    Videbaek, C; Friberg, L; Holm, S

    1993-01-01

    twice, once without receptor blockade and once with a constant degree of partial blockade of the benzodiazepine receptors by infusion of nonradioactive flumazenil (Lanexat) or midazolam (Dormicum). Single photon emission computer tomography and blood sampling were performed intermittently for 6 h after...

  10. Equilibrium constant and nitrogen activity and the parameters of interaction eN(N), rN(N,Cr), rN(N,Mn) in high nitrogen steels of Fe-Cr-Mn-N type

    International Nuclear Information System (INIS)

    Svyazhin, A.G.; Siwka, J.; Rashev, T.

    1999-01-01

    In the paper a description of a thermodynamic of liquid solutions of Fe-Cr-Mn-N type with using a concept of parameters of an interaction has been presented. A temperature relationship of the equilibrium constant K N(Fe) and values of self interaction parameters e N (N) , r N (N,Cr) , r N (N,Mn) and t N (N,Cr,Cr) has been determined for mean values of temperatures of liquid metal equal 1990 K and 2090 K. By application of a theory of regular solutions those values were recalculated for a temperature 1873 K. (orig.)

  11. Isotopic equilibrium constants of the deuterium exchange between HDO and H{sub 2}S, H{sub 2}Se and H{sub 2}Te; Etude des constantes des equilibres isotopiques du deuterium entre l'eau et les hydrures des metalloides de la deuxieme famille

    Energy Technology Data Exchange (ETDEWEB)

    Marx, D [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1959-11-15

    We have determined experimentally the equilibrium constant K of each of the following isotope exchanges: SH{sub 2} + OHD {r_reversible} SHD + OH{sub 2}; SeH{sub 2} + OHD {r_reversible} SeHD + OH{sub 2}; TeH{sub 2} + OHD {r_reversible} TeHD + OH{sub 2}. In gaseous phase, statistical thermodynamics leads to the expression: K (Z{sub OHD} x Z{sub RH{sub 2}})/(Z{sub OH{sub 2}} x Z{sub RHD}) x e{sup W/T} (R being the elements S, Se or Te). Z, the partition functions, have been calculated and, through our experimental results, the constant W has been determined. Having obtained W, the equilibrium constant K has been calculated for a series of temperatures. (author) [French] Nous avons determine experimentalement la constante K de chacun des equilibres isotopiques suivants: SH{sub 2} + OHD {r_reversible} SHD + OH{sub 2}; SeH{sub 2} + OHD {r_reversible} SeHD + OH{sub 2}; TeH{sub 2} + OHD {r_reversible} TeHD + OH{sub 2}. En phase gazeuse, la thermodynamique donne l'expression: K = (Z{sub OHD} x Z{sub RH{sub 2}})/(Z{sub OH{sub 2}} x Z{sub RHD}) x e{sup W/T} (R representant un atome de soufre, selenium ou tellure). Les fonctions de partition Z de chacune des molecules ont ete calculees et, grace a nos resultats experimentaux, nous avons determine la constante W. Connaissant W, la constante d'equilibre K a pu etre tabulee en fonction de la temperature. (auteur)

  12. Non-equilibrium thermodynamics and energy distribution function of neutron gas in constant power reactor under coupling of neutrons and medium

    International Nuclear Information System (INIS)

    Hayasaka, Hideo

    1983-01-01

    The thermodynamics and the energy distribution function of the neutron gas in a constant power reactor are considered, taking into account the burn-up of fuel. To separate the secular motion of neutrons owing to fuel burn-up and the microscopic fluctuations of neutrons around this motion, a long time of the order of several months is divided into m equal intervals, and the respective states corresponding to m small time intervals are treated as quasi-stationary states. The local energy distribution function of the neutron gas in the quasi-stationary state is given by a generalized Boltzmann distribution specified by the respective generalized activity coefficient for each subsystem. The effects of fuel burn-up on the respective distribution functions for successive small time intervals are taken into account through various quantities relating to reactor physics, depending upon the fuel burn-up, by successive approximation. (author)

  13. Calculation of the total plasma concentration of nonvolatile weak acids and the effective dissociation constant of nonvolatile buffers in plasma for use in the strong ion approach to acid-base balance in cats.

    Science.gov (United States)

    McCullough, Sheila M; Constable, Peter D

    2003-08-01

    To determine values for the total concentration of nonvolatile weak acids (Atot) and effective dissociation constant of nonvolatile weak acids (Ka) in plasma of cats. Convenience plasma samples of 5 male and 5 female healthy adult cats. Cats were sedated, and 20 mL of blood was obtained from the jugular vein. Plasma was tonometered at 37 degrees C to systematically vary PCO2 from 8 to 156 mm Hg, thereby altering plasma pH from 6.90 to 7.97. Plasma pH, PCO2, and concentrations of quantitatively important strong cations (Na+, K+, and Ca2+), strong anions (Cl-, lactate), and buffer ions (total protein, albumin, and phosphate) were determined. Strong ion difference was estimated from the measured strong ion concentrations and nonlinear regression used to calculate Atot and Ka from the measured pH and PCO2 and estimated strong ion difference. Mean (+/- SD) values were as follows: Atot = 24.3 +/- 4.6 mmol/L (equivalent to 0.35 mmol/g of protein or 0.76 mmol/g of albumin); Ka = 0.67 +/- 0.40 x 10(-7); and the negative logarithm (base 10) of Ka (pKa) = 7.17. At 37 degrees C, pH of 7.35, and a partial pressure of CO2 (PCO2) of 30 mm Hg, the calculated venous strong ion difference was 30 mEq/L. These results indicate that at a plasma pH of 7.35, a 1 mEq/L decrease in strong ion difference will decrease pH by 0.020, a 1 mm Hg decrease in PCO2 will increase plasma pH by 0.011, and a 1 g/dL decrease in albumin concentration will increase plasma pH by 0.093.

  14. IR absorption spectrum (4200-3100 cm-1) of H2O and (H2O)2 in CCl4. Estimates of the equilibrium constant and evidence that the atmospheric water absorption continuum is due to the water dimer

    International Nuclear Information System (INIS)

    Nicolaisen, Flemming M.

    2009-01-01

    IR absorption spectra, 4200-3100 cm -1 , of water in CCl 4 solutions are presented. It is shown that for saturated solutions significant amounts of water are present as dimer (ca. 2%). The IR spectra of the monomer and dimer are retrieved. The integrated absorption coefficients of the monomer absorption are significantly enhanced relative to the gas phase values. The dimer spectrum consists of 5 bands, of which 4 were expected from data from cold beams and cold matrices. The origin of the 'extra' band is discussed. In addition it is argued that the dimer absorption bands intensities must be enhanced relative to the gas phase values. Based on recent calculations of band strengths, and observed frequency shifts relative to the gas phase, the intensity enhancement factors are estimated as well as the monomer/dimer equilibrium constant in CCl 4 solution at T=296 K (K c =1.29 mol -1 L). It is noted that the observed dimer spectrum has a striking resemblance with the water vapour continuum determined by Burch in 1985 which was recently remeasured by Paynter et al. and it is concluded that the atmospheric water absorption continuum in the investigated spectral region must be due to water dimer. Based on the newly published spectral data a revised value of the gas phase equilibrium constant is suggested (K p =0.035 atm -1 at T=296 K) as well as a value for the standard enthalpy of formation, ΔH 0 =15.4 kJ mol -1 .

  15. STABILITY CONSTANT OF THE TRISGLYCINATO METAL ...

    African Journals Online (AJOL)

    DR. AMINU

    overall stability constants of the complexes were found to be similar. Keywords: Glycinato, titration ... +. −. = 1 where Ka = dissociation constant of the amino acid. [ ]+. H = concentration of the .... Synthesis and techniques in inorganic chemistry.

  16. Is the sun constant

    International Nuclear Information System (INIS)

    Blake, J.B.; Dearborn, D.S.P.

    1979-01-01

    Small fluctuations in the solar constant can occur on timescales much shorter than the Kelvin time. Changes in the ability of convection to transmit energy through the superadiabatic and transition regions of the convection zone cause structure adjustments which can occur on a time scale of days. The bulk of the convection zone reacts to maintain hydrostatic equilibrium (though not thermal equilibrium) and causes a luminosity change. While small radius variations will occur, most of the change will be seen in temperature

  17. Electrochemical quantification of the thermodynamic equilibrium constant of the tenoxicam-β-cyclodextrin inclusion complex formed on the surface of a poly-β cyclodextrin-modified carbon paste electrode

    International Nuclear Information System (INIS)

    Guzmán-Hernández, D.S.; Palomar-Pardavé, M.; Rojas-Hernández, A.; Corona-Avendaño, S.; Romero-Romo, M.; Ramírez-Silva, M.T.

    2014-01-01

    Graphical abstract: - Highlights: • A carbon paste electrode (CPE) was modified with a β-CD polymer. • Tenoxicam oxidation on the CPE/poly-β-CD was adsorption controlled. • Influence of pH, scan rate, angular velocity and concentration was evaluated. • Fittings of i-E plots were done considering an irreversible surface reaction. • Electrochemical evaluation of the surface inclusion constant is presented. - Abstract: In this work it is shown that when a carbon paste electrode, CPE, is modified with a β-cyclodextrin polymer, the tenoxicam oxidation becomes an adsorption controlled process due to formation of a surface inclusion complex with the β-CD molecules comprising the surface of the polymer. It was found that such surface inclusion complex can be formed independently of the tenoxicam predominant species, Tenox’, in the aqueous solution namely: H 2 Tenox + , HTenox or Tenox − , depending on the solution pH. The electrochemical quantification of the thermodynamic constant of the equilibrium Tenox’ + β-CD (polymer) = Tenox’-β-CD (polymer) was estimated as log K incl. = 4.26 ± 0.01. Furthermore, from the analyses of the experimental voltammograms according with Laviron's equation for an irreversible surface reaction [E. Laviron, J. Electroanal. Chem. 52 (1974) 355-393] it is shown that the surface concentration, Γ R , of tenoxicam increases as its concentration in solution does, reaching a maximum value of 1.51 × 10 −10 mol cm −2 at 64 μM

  18. The Conceptual Change Approach to Teaching Chemical Equilibrium

    Science.gov (United States)

    Canpolat, Nurtac; Pinarbasi, Tacettin; Bayrakceken, Samih; Geban, Omer

    2006-01-01

    This study investigates the effect of a conceptual change approach over traditional instruction on students' understanding of chemical equilibrium concepts (e.g. dynamic nature of equilibrium, definition of equilibrium constant, heterogeneous equilibrium, qualitative interpreting of equilibrium constant, changing the reaction conditions). This…

  19. Dissociative diffusion mechanism in vacancy-rich materials according to mass action kinetics

    Directory of Open Access Journals (Sweden)

    N. J. Biderman

    2016-05-01

    Full Text Available Two sets of diffusion-reaction numerical simulations using a finite difference method (FDM were conducted to investigate fast impurity diffusion via interstitial sites in vacancy-rich materials such as Cu(In,GaSe2 (CIGS and Cu2ZnSn(S, Se4 (CZTSSe or CZTS via the dissociative diffusion mechanism where the interstitial diffuser ultimately reacts with a vacancy to produce a substitutional. The first set of simulations extends the standard interstitial-limited dissociative diffusion theory to vacancy-rich material conditions where vacancies are annihilated in large amounts, introducing non-equilibrium vacancy concentration profiles. The second simulation set explores the vacancy-limited dissociative diffusion where impurity incorporation increases the equilibrium vacancy concentration. In addition to diffusion profiles of varying concentrations and shapes that were obtained in all simulations, some of the profiles can be fitted with the constant- and limited-source solutions of Fick’s second law despite the non-equilibrium condition induced by the interstitial-vacancy reaction. The first set of simulations reveals that the dissociative diffusion coefficient in vacancy-rich materials is inversely proportional to the initial vacancy concentration. In the second set of numerical simulations, impurity-induced changes in the vacancy concentration lead to distinctive diffusion profile shapes. The simulation results are also compared with published data of impurity diffusion in CIGS. According to the characteristic properties of diffusion profiles from the two set of simulations, experimental detection of the dissociative diffusion mechanism in vacancy-rich materials may be possible.

  20. Non-equilibrium reaction rates in chemical kinetic equations

    Science.gov (United States)

    Gorbachev, Yuriy

    2018-05-01

    Within the recently proposed asymptotic method for solving the Boltzmann equation for chemically reacting gas mixture, the chemical kinetic equations has been derived. Corresponding one-temperature non-equilibrium reaction rates are expressed in terms of specific heat capacities of the species participate in the chemical reactions, bracket integrals connected with the internal energy transfer in inelastic non-reactive collisions and energy transfer coefficients. Reactions of dissociation/recombination of homonuclear and heteronuclear diatomic molecules are considered. It is shown that all reaction rates are the complex functions of the species densities, similarly to the unimolecular reaction rates. For determining the rate coefficients it is recommended to tabulate corresponding bracket integrals, additionally to the equilibrium rate constants. Correlation of the obtained results with the irreversible thermodynamics is established.

  1. Synthesis, crystal structure, DFT studies, acid dissociation constant, and antimicrobial activity of methyl 2-(4-chlorophenyl)-7a-((4-chlorophenyl)carbamothioyl)-1-oxo-5,5-diphenyl-3-thioxo-hexahydro-1H-pyrrolo[1,2-e]imidazole-6-carboxylate

    Science.gov (United States)

    Nural, Yahya; Gemili, Muge; Seferoglu, Nurgul; Sahin, Ertan; Ulger, Mahmut; Sari, Hayati

    2018-05-01

    A novel bicyclic thiohydantoin fused to pyrrolidine compound, methyl 2-(4-chlorophenyl)-7a-((4-chlorophenyl)carbamothioyl)-1-oxo-5,5-diphenyl-3-thioxo-hexahydro-1H-pyrrolo[1,2-e]imidazole-6-carboxylate, was synthesized by the cyclization reaction of dimethyl 5,5-diphenylpyrrolidine-2,4-dicarboxylate and 4-chlorophenyl isothiocyanate in the presence of 4-(dimethylamino)pyridine to form methyl 2-(4-chlorophenyl)-1-oxo-5,5-diphenyl-3-thioxo-hexahydro-1H-pyrrolo[1,2-e]imidazole-6-carboxylate with concomitant addition reaction of the 4-chlorophenyl isothiocyanate in 79% yield. The structural characterization was performed by NMR, FT-IR, MS and HRMS techniques, and the stereochemistry of the compound was determined by single crystal X-ray diffraction study. In addition, the molecular structure and 1H and 13C NMR chemical shifts of the compound were obtained with the density functional theory and Hartree-Fock calculations. Acid dissociation constants of the compound were determined using potentiometric titration method in 25% (v/v) dimethyl sulfoxide-water hydroorganic solvent at 25 ± 0.1 °C, at an ionic background of 0.1 mol/L of NaCl using the HYPERQUAD computer program. Four acid dissociation constants were obtained for the compound, and we suggest that these acid dissociation constants are related to the NH, for two groups of enthiols and enol groups. Antimicrobial activity study was performed against S. aureus, B. subtilis, A. hydrophila, E. coli and A. baumannii as bacterial standard strains, and against M. tuberculosis H37Rv as mycobacterial strain. The compound exhibited antibacterial activity in the range of 31.25-62.5 μg/mL, and antimycobacterial activity with a MIC value of 40 μg/mL against the indicated strains.

  2. A Printed Equilibrium Dialysis Device with Integrated Membranes for Improved Binding Affinity Measurements.

    Science.gov (United States)

    Pinger, Cody W; Heller, Andrew A; Spence, Dana M

    2017-07-18

    Equilibrium dialysis is a simple and effective technique used for investigating the binding of small molecules and ions to proteins. A three-dimensional (3D) printer was used to create a device capable of measuring binding constants between a protein and a small ion based on equilibrium dialysis. Specifically, the technology described here enables the user to customize an equilibrium dialysis device to fit their own experiments by choosing membranes of various material and molecular-weight cutoff values. The device has dimensions similar to that of a standard 96-well plate, thus being amenable to automated sample handlers and multichannel pipettes. The device consists of a printed base that hosts multiple windows containing a porous regenerated-cellulose membrane with a molecular-weight cutoff of ∼3500 Da. A key step in the fabrication process is a print-pause-print approach for integrating membranes directly into the windows subsequently inserted into the base. The integrated membranes display no leaking upon placement into the base. After characterizing the system's requirements for reaching equilibrium, the device was used to successfully measure an equilibrium dissociation constant for Zn 2+ and human serum albumin (K d = (5.62 ± 0.93) × 10 -7 M) under physiological conditions that is statistically equal to the constants reported in the literature.

  3. Grinding kinetics and equilibrium states

    Science.gov (United States)

    Opoczky, L.; Farnady, F.

    1984-01-01

    The temporary and permanent equilibrium occurring during the initial stage of cement grinding does not indicate the end of comminution, but rather an increased energy consumption during grinding. The constant dynamic equilibrium occurs after a long grinding period indicating the end of comminution for a given particle size. Grinding equilibrium curves can be constructed to show the stages of comminution and agglomeration for certain particle sizes.

  4. Implementing an Equilibrium Law Teaching Sequence for Secondary School Students to Learn Chemical Equilibrium

    Science.gov (United States)

    Ghirardi, Marco; Marchetti, Fabio; Pettinari, Claudio; Regis, Alberto; Roletto, Ezio

    2015-01-01

    A didactic sequence is proposed for the teaching of chemical equilibrium law. In this approach, we have avoided the kinetic derivation and the thermodynamic justification of the equilibrium constant. The equilibrium constant expression is established empirically by a trial-and-error approach. Additionally, students learn to use the criterion of…

  5. Spectrophotometric determination of association constant

    DEFF Research Database (Denmark)

    2016-01-01

    Least-squares 'Systematic Trial-and-Error Procedure' (STEP) for spectrophotometric evaluation of association constant (equilibrium constant) K and molar absorption coefficient E for a 1:1 molecular complex, A + B = C, with error analysis according to Conrow et al. (1964). An analysis of the Charge...

  6. Nuclear constants

    International Nuclear Information System (INIS)

    Foos, J.

    1999-01-01

    This paper is written in two tables. The first one describes the different particles (bosons and fermions). The second one gives the isotopes nuclear constants of the different elements, for Z = 1 to 56. (A.L.B.)

  7. Nuclear constants

    International Nuclear Information System (INIS)

    Foos, J.

    2000-01-01

    This paper is written in two tables. The first one describes the different particles (bosons and fermions). The second one gives the isotopes nuclear constants of the different elements, for Z = 56 to 68. (A.L.B.)

  8. Nuclear constants

    International Nuclear Information System (INIS)

    Foos, J.

    1998-01-01

    This paper is made of two tables. The first table describes the different particles (bosons and fermions) while the second one gives the nuclear constants of isotopes from the different elements with Z = 1 to 25. (J.S.)

  9. Nuclear constants

    International Nuclear Information System (INIS)

    Foos, J.

    1999-01-01

    This paper is written in two tables. The first one describes the different particles (bosons and fermions). The second one gives the isotopes nuclear constants of the different elements, for Z = 56 to 68. (A.L.B.)

  10. Dissociation dynamics of methylal

    Energy Technology Data Exchange (ETDEWEB)

    Beaud, P; Frey, H -M; Gerber, T; Mischler, B; Radi, P P; Tzannis, A -P [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    The dissociation of methylal is investigated using mass spectrometry, combined with a pyrolytic radical source and femtosecond pump probe experiments. Based on preliminary results two reaction paths of methylal dissociation are proposed and discussed. (author) 4 fig., 3 refs.

  11. Thermodynamic chemical energy transfer mechanisms of non-equilibrium, quasi-equilibrium, and equilibrium chemical reactions

    International Nuclear Information System (INIS)

    Roh, Heui-Seol

    2015-01-01

    Chemical energy transfer mechanisms at finite temperature are explored by a chemical energy transfer theory which is capable of investigating various chemical mechanisms of non-equilibrium, quasi-equilibrium, and equilibrium. Gibbs energy fluxes are obtained as a function of chemical potential, time, and displacement. Diffusion, convection, internal convection, and internal equilibrium chemical energy fluxes are demonstrated. The theory reveals that there are chemical energy flux gaps and broken discrete symmetries at the activation chemical potential, time, and displacement. The statistical, thermodynamic theory is the unification of diffusion and internal convection chemical reactions which reduces to the non-equilibrium generalization beyond the quasi-equilibrium theories of migration and diffusion processes. The relationship between kinetic theories of chemical and electrochemical reactions is also explored. The theory is applied to explore non-equilibrium chemical reactions as an illustration. Three variable separation constants indicate particle number constants and play key roles in describing the distinct chemical reaction mechanisms. The kinetics of chemical energy transfer accounts for the four control mechanisms of chemical reactions such as activation, concentration, transition, and film chemical reactions. - Highlights: • Chemical energy transfer theory is proposed for non-, quasi-, and equilibrium. • Gibbs energy fluxes are expressed by chemical potential, time, and displacement. • Relationship between chemical and electrochemical reactions is discussed. • Theory is applied to explore nonequilibrium energy transfer in chemical reactions. • Kinetics of non-equilibrium chemical reactions shows the four control mechanisms

  12. DETERMINATION OF STABILITY CONSTANTS OF MANGANESE (II ...

    African Journals Online (AJOL)

    DR. AMINU

    Keywords: Amino acids, dissociation constant, potentiometry, stability constant. INTRODUCTION. Acids – base titration involves the gradual addition or removal of protons for example using the deprotic form of glycine. The plot has two distinct stages corresponding to the deprotonation of the two different groups on glycine.

  13. Are fundamental constants really constant

    International Nuclear Information System (INIS)

    Norman, E.B.

    1986-01-01

    Reasons for suspecting that fundamental constants might change with time are reviewed. Possible consequences of such variations are examined. The present status of experimental tests of these ideas is discussed

  14. Communication: The highest frequency hydrogen bond vibration and an experimental value for the dissociation energy of formic acid dimer

    DEFF Research Database (Denmark)

    Kollipost, F.; Larsen, René Wugt; Domanskaya, A.V.

    2012-01-01

    The highest frequency hydrogen bond fundamental of formic acid dimer, ν24 (Bu), is experimentally located at 264 cm−1. FTIR spectra of this in-plane bending mode of (HCOOH)2 and band centers of its symmetric D isotopologues (isotopomers) recorded in a supersonic slit jet expansion are presented...... thermodynamics treatment of the dimerization process up to room temperature. We obtain D0 = 59.5(5) kJ/mol as the best experimental estimate for the dimer dissociation energy at 0 K. Further improvements have to wait for a more consistent determination of the room temperature equilibrium constant....

  15. Local equilibrium

    Energy Technology Data Exchange (ETDEWEB)

    Anon.

    1984-12-15

    From 3-6 September the First International Workshop on Local Equilibrium in Strong Interaction Physics took place in Bad-Honnef at the Physics Centre of the German Physical Society. A number of talks covered the experimental and theoretical investigation of the 'hotspots' effect, both in high energy particle physics and in intermediate energy nuclear physics.

  16. Equilibrium Dialysis

    African Journals Online (AJOL)

    context of antimicrobial therapy in malnutrition. Dialysis has in the past presented technical problems, being complicated and time-consuming. A new dialysis system based on the equilibrium technique has now become available, and it is the principles and practical application of this apparatus (Kontron Diapack; Kontron.

  17. Strategic Equilibrium

    NARCIS (Netherlands)

    van Damme, E.E.C.

    2000-01-01

    An outcome in a noncooperative game is said to be self-enforcing, or a strategic equilibrium, if, whenever it is recommended to the players, no player has an incentive to deviate from it.This paper gives an overview of the concepts that have been proposed as formalizations of this requirement and of

  18. Maximin equilibrium

    NARCIS (Netherlands)

    Ismail, M.S.

    2014-01-01

    We introduce a new concept which extends von Neumann and Morgenstern's maximin strategy solution by incorporating `individual rationality' of the players. Maximin equilibrium, extending Nash's value approach, is based on the evaluation of the strategic uncertainty of the whole game. We show that

  19. Experimental determination of thermodynamic equilibrium in biocatalytic transamination

    DEFF Research Database (Denmark)

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

    2012-01-01

    The equilibrium constant is a critical parameter for making rational design choices in biocatalytic transamination for the synthesis of chiral amines. However, very few reports are available in the scientific literature determining the equilibrium constant (K) for the transamination of ketones....... Various methods for determining (or estimating) equilibrium have previously been suggested, both experimental as well as computational (based on group contribution methods). However, none of these were found suitable for determining the equilibrium constant for the transamination of ketones. Therefore...

  20. Photodissociation constant of NO2

    International Nuclear Information System (INIS)

    Nootebos, M.A.; Bange, P.

    1992-01-01

    The velocity of the dissociation of NO 2 into ozone and NO mainly depends on the ultraviolet sunlight quantity, and with that the cloudiness. A correct value for this reaction constant is important for the accurate modelling of O 3 - and NO 2 -concentrations in plumes of electric power plants, in particular in the case of determination of the amount of photochemical summer smog. An advanced signal processing method (deconvolution, correlation) was applied on the measurements. The measurements were carried out from aeroplanes

  1. Sweatshop equilibrium

    OpenAIRE

    Chau, Nancy H.

    2009-01-01

    This paper presents a capability-augmented model of on the job search, in which sweatshop conditions stifle the capability of the working poor to search for a job while on the job. The augmented setting unveils a sweatshop equilibrium in an otherwise archetypal Burdett-Mortensen economy, and reconciles a number of oft noted yet perplexing features of sweatshop economies. We demonstrate existence of multiple rational expectation equilibria, graduation pathways out of sweatshops in complete abs...

  2. Zero-Point Energy Constraint for Unimolecular Dissociation Reactions. Giving Trajectories Multiple Chances To Dissociate Correctly.

    Science.gov (United States)

    Paul, Amit K; Hase, William L

    2016-01-28

    A zero-point energy (ZPE) constraint model is proposed for classical trajectory simulations of unimolecular decomposition and applied to CH4* → H + CH3 decomposition. With this model trajectories are not allowed to dissociate unless they have ZPE in the CH3 product. If not, they are returned to the CH4* region of phase space and, if necessary, given additional opportunities to dissociate with ZPE. The lifetime for dissociation of an individual trajectory is the time it takes to dissociate with ZPE in CH3, including multiple possible returns to CH4*. With this ZPE constraint the dissociation of CH4* is exponential in time as expected for intrinsic RRKM dynamics and the resulting rate constant is in good agreement with the harmonic quantum value of RRKM theory. In contrast, a model that discards trajectories without ZPE in the reaction products gives a CH4* → H + CH3 rate constant that agrees with the classical and not quantum RRKM value. The rate constant for the purely classical simulation indicates that anharmonicity may be important and the rate constant from the ZPE constrained classical trajectory simulation may not represent the complete anharmonicity of the RRKM quantum dynamics. The ZPE constraint model proposed here is compared with previous models for restricting ZPE flow in intramolecular dynamics, and connecting product and reactant/product quantum energy levels in chemical dynamics simulations.

  3. Dissociation in small molecules

    International Nuclear Information System (INIS)

    Dehmer, P.M.

    1982-01-01

    The study of molecular dissociation processes is one of the most interesting areas of modern spectroscopy owing to the challenges presented bt even the simplest of diatomic molecules. This paper reviews the commonly used descriptions of molecular dissociation processes for diatomic molecules, the selection rules for predissociation, and a few of the principles to be remembered when one is forced to speculate about dissociation mechanisms in a new molecule. Some of these points will be illustrated by the example of dissociative ionization in O 2

  4. Equilibrium Trust

    OpenAIRE

    Luca Anderlini; Daniele Terlizzese

    2009-01-01

    We build a simple model of trust as an equilibrium phenomenon, departing from standard "selfish" preferences in a minimal way. Agents who are on the receiving end of an other to transact can choose whether to cheat and take away the entire surplus, taking into account a "cost of cheating." The latter has an idiosyncratic component (an agent's type), and a socially determined one. The smaller the mass of agents who cheat, the larger the cost of cheating suffered by those who cheat. Depending o...

  5. Pulsed IR Heating Studies of Single-Molecule DNA Duplex Dissociation Kinetics and Thermodynamics

    Science.gov (United States)

    Holmstrom, Erik D.; Dupuis, Nicholas F.; Nesbitt, David J.

    2014-01-01

    Single-molecule fluorescence spectroscopy is a powerful technique that makes it possible to observe the conformational dynamics associated with biomolecular processes. The addition of precise temperature control to these experiments can yield valuable thermodynamic information about equilibrium and kinetic rate constants. To accomplish this, we have developed a microscopy technique based on infrared laser overtone/combination band absorption to heat small (≈10−11 liter) volumes of water. Detailed experimental characterization of this technique reveals three major advantages over conventional stage heating methods: 1), a larger range of steady-state temperatures (20–100°C); 2), substantially superior spatial (≤20 μm) control; and 3), substantially superior temporal (≈1 ms) control. The flexibility and breadth of this spatial and temporally resolved laser-heating approach is demonstrated in single-molecule fluorescence assays designed to probe the dissociation of a 21 bp DNA duplex. These studies are used to support a kinetic model based on nucleic acid end fraying that describes dissociation for both short (10 bp) DNA duplexes. These measurements have been extended to explore temperature-dependent kinetics for the 21 bp construct, which permit determination of single-molecule activation enthalpies and entropies for DNA duplex dissociation. PMID:24411254

  6. Catalytic methanol dissociation

    International Nuclear Information System (INIS)

    Alcinikov, Y.; Fainberg, V.; Garbar, A.; Gutman, M.; Hetsroni, G.; Shindler, Y.; Tatrtakovsky, L.; Zvirin, Y.

    1998-01-01

    Results of the methanol dissociation study on copper/potassium catalyst with alumina support at various temperatures are presented. The following gaseous and liquid products at. The catalytic methanol dissociation is obtained: hydrogen, carbon monoxide, carbon dioxide, methane, and dimethyl ether. Formation rates of these products are discussed. Activation energies of corresponding reactions are calculated

  7. Dissociation in mediation

    Directory of Open Access Journals (Sweden)

    Daniela Muraru

    2008-01-01

    Full Text Available This paper approaches several texts that are part of the so-called discourse of mediation, adopting a pragma-dialectical perspective of the theory of dissociation. It is an attempt to identify the uses of dissociative patterns, with special emphasis on the indicators of dissociation. The paper investigates the various uses of the concept of dissociation as a discursive technique in the argumentation on the different aspects that are involved in international conflict, such as the discussion of the notion of peace. The purpose is to identify the role of dissociation, as a device strategically used by the mediator to help the parties minimize the disagreement space, and come to a conflict resolution.

  8. 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...

  9. Equilibrium calculations, ch. 6

    International Nuclear Information System (INIS)

    Deursen, A.P.J. van

    1976-01-01

    A calculation is presented of dimer intensities obtained in supersonic expansions. There are two possible limiting considerations; the dimers observed are already present in the source, in thermodynamic equilibrium, and are accelerated in the expansion. Destruction during acceleration is neglected, as are processes leading to newly formed dimers. On the other hand one can apply a kinetic approach, where formation and destruction processes are followed throughout the expansion. The difficulty of this approach stems from the fact that the density, temperature and rate constants have to be known at all distances from the nozzle. The simple point of view has been adopted and the measured dimer intensities are compared with the equilibrium concentration in the source. The comparison is performed under the assumption that the detection efficiency for dimers is twice the detection efficiency for monomers. The experimental evidence against the simple point of view that the dimers of the onset region are formed in the source already, under equilibrium conditions, is discussed. (Auth.)

  10. Determination of dissociation constants of cytokinins by capillary zone electrophoresis

    Czech Academy of Sciences Publication Activity Database

    Barták, P.; Bednář, P.; Stránský, Z.; Boček, Petr; Vespalec, Radim

    2000-01-01

    Roč. 878, č. 2 (2000), s. 249-259 ISSN 0021-9673 R&D Projects: GA MŠk VS96021; GA AV ČR IAA4031703; GA ČR GA203/99/0044 Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.551, year: 2000

  11. Solvation numbers and hydration constant for thorium(IV) in ethanol-water medium

    International Nuclear Information System (INIS)

    Sedaira, H.; Idriss, K.A.; Hashem, E.Y.

    1996-01-01

    The solvation number and hydration constant of Th 4+ in ethanol-water medium were determined at 25 degrees C using UV-spectral and electrochemical measurements. A solvate formation equilibrium is demonstrated and characterized. Three molecules of ethanol (S) can bond to the metal cation with strengths comparable to that for H 2 O to form ThS 3 (H 2 O) 3 4+ . Formation of thorium monochelate with lawsone (2-hydroxy-1.4-naphthoquinone) eliminates bonding with alcohol molecules. The dissociation constant of the chelating agent s K a and the formation contant of the monochelated metal ion s K f * that are essentially independent of the solution composition are evaluated. Hydration titrations involving thorium-lawsone monochlate are performed and the data obtained from the changes of pH with solvent composition are analyzed. The solution independent constant, s K f * for thorium-lawsone complex formation in mixed aqueous ethanol is given by log x K f * =vpK a + log s K h - log [LH] - vpH + 3 log v where vpK a is the dissociation constant of the chelating agent LH in the solvent system of v volume fraction of water and s K h is the solution-independent hydration constant of thorium (IV) in the solvent system. Log-values for the constants s K h , s K f * and s K z * are found to be 7.8 ±0.02, 11.38±0.04 and -0.753, respectively

  12. Description of the equilibrium conditions of chemical reactions in various solvents

    International Nuclear Information System (INIS)

    Roehl, H.

    1983-01-01

    Empirical knowledge is taken as the basis for establishing a method to predict the equilibrium conditions of reactions of macrocyclic polyethers and monovalent metal cations in various solvents. The reactions in the solvents under review can be well described by the donor number DN according to Gutmann, and by the parameters alpha and pi-asterisk for the H bonding donor and polarity/polarisability, respectively, using a three-parameter equation according to Kamlet/Taft. This applies to both protic and aprotic solvents. The calculations rely on data found in the literature and on own experimental results obtained by microcalorimetric examinations. The evaluation methods evolved for this purpose also allow, by means of additional dilution experiments, to convert the ''integral'', microcalorimetrically obtained complex stability constants, (i.e. those non-discriminating between different types of state such as ions or ion pairs) to the corresponding ''differentiating'' constants (referring to purely ionic quantities), and this applied to the various solvents used. The method does not use foreign ions and can thus also be applied to those cases for which the normal standardisation of reaction conditions published in the literature cannot be maintained (e.g. for reasons of solubility). In some cases it was possible to obtain additional information on the dissociation behaviour of the salts used, which revealed differently strong inclination to form higher aggregations in solution, as shown e.g. by the strong concentration dependence of the salt ion pair dissociation constants obtained. (orig./EF) [de

  13. Simultaneous Speciation, Structure, and Equilibrium Constant Determination in the Ni2+-EDTA-CN- Ternary System via High-Resolution Laboratory X-ray Absorption Fine Structure Spectroscopy and Theoretical Calculations.

    Science.gov (United States)

    Bajnóczi, Éva G; Németh, Zoltán; Vankó, György

    2017-11-20

    Even quite simple chemical systems can involve many components and chemical states, and sometimes it can be very difficult to differentiate them by their hardly separable physical-chemical properties. The Ni II -EDTA-CN - (EDTA = ethylenediaminetetraacetic acid) ternary system is a good example for this problem where, in spite of its fairly simple components and numerous investigations, several molecular combinations can exist, all of them not having been identified unambiguously yet. In order to achieve a detailed understanding of the reaction steps and chemical equilibria, methods are required in which the structural transitions in the different reaction steps can be followed via element-selective complex spectral feature sets. With the help of our recently developed von Hámos type high-resolution laboratory X-ray absorption spectrometer, both the structural variations and stability constants of the forming complexes were determined from the same measurement series, proving that X-ray absorption spectroscopy can be considered as a multifaced, table-top tool in coordination chemistry. Furthermore, with the help of theoretical calculations, independent structural evidence was also given for the formation of the [NiEDTA(CN)] 3- mixed complex.

  14. THE ABUNDANCE OF MOLECULAR HYDROGEN AND ITS CORRELATION WITH MIDPLANE PRESSURE IN GALAXIES: NON-EQUILIBRIUM, TURBULENT, CHEMICAL MODELS

    International Nuclear Information System (INIS)

    Mac Low, Mordecai-Mark; Glover, Simon C. O.

    2012-01-01

    Observations of spiral galaxies show a strong linear correlation between the ratio of molecular to atomic hydrogen surface density R mol and midplane pressure. To explain this, we simulate three-dimensional, magnetized turbulence, including simplified treatments of non-equilibrium chemistry and the propagation of dissociating radiation, to follow the formation of H 2 from cold atomic gas. The formation timescale for H 2 is sufficiently long that equilibrium is not reached within the 20-30 Myr lifetimes of molecular clouds. The equilibrium balance between radiative dissociation and H 2 formation on dust grains fails to predict the time-dependent molecular fractions we find. A simple, time-dependent model of H 2 formation can reproduce the gross behavior, although turbulent density perturbations increase molecular fractions by a factor of few above it. In contradiction to equilibrium models, radiative dissociation of molecules plays little role in our model for diffuse radiation fields with strengths less than 10 times that of the solar neighborhood, because of the effective self-shielding of H 2 . The observed correlation of R mol with pressure corresponds to a correlation with local gas density if the effective temperature in the cold neutral medium of galactic disks is roughly constant. We indeed find such a correlation of R mol with density. If we examine the value of R mol in our local models after a free-fall time at their average density, as expected for models of molecular cloud formation by large-scale gravitational instability, our models reproduce the observed correlation over more than an order-of-magnitude range in density.

  15. The Abundance of Molecular Hydrogen and Its Correlation with Midplane Pressure in Galaxies: Non-equilibrium, Turbulent, Chemical Models

    Science.gov (United States)

    Mac Low, Mordecai-Mark; Glover, Simon C. O.

    2012-02-01

    Observations of spiral galaxies show a strong linear correlation between the ratio of molecular to atomic hydrogen surface density R mol and midplane pressure. To explain this, we simulate three-dimensional, magnetized turbulence, including simplified treatments of non-equilibrium chemistry and the propagation of dissociating radiation, to follow the formation of H2 from cold atomic gas. The formation timescale for H2 is sufficiently long that equilibrium is not reached within the 20-30 Myr lifetimes of molecular clouds. The equilibrium balance between radiative dissociation and H2 formation on dust grains fails to predict the time-dependent molecular fractions we find. A simple, time-dependent model of H2 formation can reproduce the gross behavior, although turbulent density perturbations increase molecular fractions by a factor of few above it. In contradiction to equilibrium models, radiative dissociation of molecules plays little role in our model for diffuse radiation fields with strengths less than 10 times that of the solar neighborhood, because of the effective self-shielding of H2. The observed correlation of R mol with pressure corresponds to a correlation with local gas density if the effective temperature in the cold neutral medium of galactic disks is roughly constant. We indeed find such a correlation of R mol with density. If we examine the value of R mol in our local models after a free-fall time at their average density, as expected for models of molecular cloud formation by large-scale gravitational instability, our models reproduce the observed correlation over more than an order-of-magnitude range in density.

  16. Prediction of phase equilibrium for gas hydrate in the presence of organic inhibitors and electrolytes by using an explicit pressure-dependent Langmuir adsorption constant in the van der Waals–Platteeuw model

    International Nuclear Information System (INIS)

    Chin, Huai-Ying; Hsieh, Min-Kang; Chen, Yan-Ping; Chen, Po-Chun; Lin, Shiang-Tai; Chen, Li-Jen

    2013-01-01

    Highlights: • The hydrate phase is described by the van der Waals and Platteeuw model. • An explicit pressure-dependent Langmuir adsorption constant is used in our model. • Phase behavior of gas hydrates with organic inhibitors and electrolytes predicted. • Our model well predicts phase behavior of gas hydrates at high pressures. -- Abstract: A new approach is developed for the prediction of the melting curve of gas hydrate with single or multiple additives, including organic inhibitors and electrolytes. This is made possible by combining a predictive equation of state for the fluid phase, the Peng–Robinson–Stryjek–Vera equation of state (PRSV EoS) combined with the COSMO-SAC activity coefficient model through the first order modified Huron–Vidal (MHV1) mixing rule, and a modified van der Waals–Platteeuw model for the hydrate phase. We have examined this method for the change of the melting condition of gas hydrate upon addition of single organic inhibitor, single electrolyte, and a mixture of organic and electrolyte. The absolute average relative deviation in temperature (AARD-T) for these three types of systems are 0.79% (695 data points, T from 230.2 K to 294.0 K, P from 0.10 MPa to 33.9 MPa), 0.16% (810 data points, T from 259.5 K to 299.1 K, P from 0.13 MPa to 71.56 MPa), and 1.56% (316 data points, T from 248.2 K to 292.9 K, P from 0.90 MPa to 73.28 MPa), respectively. We believe that the proposed model is useful for the exploitation of natural or synthetic gas hydrates with multiple additives

  17. Exploring Chemical Equilibrium with Poker Chips: A General Chemistry Laboratory Exercise

    Science.gov (United States)

    Bindel, Thomas H.

    2012-01-01

    A hands-on laboratory exercise at the general chemistry level introduces students to chemical equilibrium through a simulation that uses poker chips and rate equations. More specifically, the exercise allows students to explore reaction tables, dynamic chemical equilibrium, equilibrium constant expressions, and the equilibrium constant based on…

  18. Flux Jacobian Matrices For Equilibrium Real Gases

    Science.gov (United States)

    Vinokur, Marcel

    1990-01-01

    Improved formulation includes generalized Roe average and extension to three dimensions. Flux Jacobian matrices derived for use in numerical solutions of conservation-law differential equations of inviscid flows of ideal gases extended to real gases. Real-gas formulation of these matrices retains simplifying assumptions of thermodynamic and chemical equilibrium, but adds effects of vibrational excitation, dissociation, and ionization of gas molecules via general equation of state.

  19. Yeast hexokinase: substrate-induced association--dissociation reactions in the binding of glucose to hexokinase P-II.

    Science.gov (United States)

    Hoggett, J G; Kellett, G L

    1976-06-15

    A method is described for the purification of native hexokinases P-I and P-II from yeast using preparative isoelectric focussing to separate the isozymes. The binding of glucose to hexokinase P-II, and the effect of this on the monomer--dimer association--dissociation reaction have been investigated quantitatively by a combination of titrations of intrinsic protein fluorescence and equilibrium ultracentrifugation. Association constants for the monomer-dimer reaction decreased with increasing pH, ionic strength and concentration of glucose. Saturating concentrations of glucose did not bring about complete dissociation of the enzyme showing that both sites were occupired in the dimer. At pH 8.0 and high ionic strength, where the enzyme existed as monomer, the dissociation constant of the enzyme-glucose complex was 3 X 10(-4) mol 1(-1) and was independent of the concentration of enzyme. Binding to the dimeric form at low pH and ionic strength (I=0.02 mol 1(-1), pH less than 7.5) was also independent of enzyme concentration (in the range 10-1000 mug ml-1) but was much weaker. The process could be described by a single dissociation constant, showing that the two available sites on the dimer were equivalent and non-cooperative; values of the intrinsic dissociation constant varied from 2.5 X 10(-3) mol 1(-1) at pH 7.0 to 6 X 10(-3) at pH 6.5. Under intermediate conditions (pH 7.0, ionic strength=0.15 mol 1(-1)), where monomer and dimer coexisted, the binding of glucose showed weak positive cooperatively (Hill coefficient 1.2); in addition, the binding was dependent upon the concentration of enzyme in the direction of stronger binding at lower concentrations. The results show that the phenomenon of half-sites reactivity observed in the binding of glucose to crystalline hexokinase P-II does not occur in solution; the simplest explanation of our finding the two sites to be equivalent is that the dimer results from the homologous association of two identical subunits.

  20. Duality in diffraction dissociations

    International Nuclear Information System (INIS)

    Santoro, Alberto.

    1977-01-01

    Diffractive dissociations (aN→a*πN) are naturally explained and a model that accounts for the three-variable correlation (mass-transfer-Jackson angle correlation) is presented. This model takes into account the three possible exchanges: t (pion), u(a*) and s(a) channel exchanger. The physical consequences of the model are: a strong mass-slope correlation due to the zeros of the amplitude, a factorization of diffractive dissociations (factorization of the Pomeron), the possibility of extending this model to double diffractive dissociation and diffraction by nuclei. This model was applied to the NN→NπN reaction. Using the usual parameters of the Deck model, a comparison is made with experiments for all available distributions. the strong slope of the peak at 1400 MeV is naturally explained [fr

  1. A Strategic-Equilibrium Based

    Directory of Open Access Journals (Sweden)

    Gabriel J. Turbay

    2011-03-01

    Full Text Available The strategic equilibrium of an N-person cooperative game with transferable utility is a system composed of a cover collection of subsets of N and a set of extended imputations attainable through such equilibrium cover. The system describes a state of coalitional bargaining stability where every player has a bargaining alternative against any other player to support his corresponding equilibrium claim. Any coalition in the sable system may form and divide the characteristic value function of the coalition as prescribed by the equilibrium payoffs. If syndicates are allowed to form, a formed coalition may become a syndicate using the equilibrium payoffs as disagreement values in bargaining for a part of the complementary coalition incremental value to the grand coalition when formed. The emergent well known-constant sum derived game in partition function is described in terms of parameters that result from incumbent binding agreements. The strategic-equilibrium corresponding to the derived game gives an equal value claim to all players.  This surprising result is alternatively explained in terms of strategic-equilibrium based possible outcomes by a sequence of bargaining stages that when the binding agreements are in the right sequential order, von Neumann and Morgenstern (vN-M non-discriminatory solutions emerge. In these solutions a preferred branch by a sufficient number of players is identified: the weaker players syndicate against the stronger player. This condition is referred to as the stronger player paradox.  A strategic alternative available to the stronger players to overcome the anticipated not desirable results is to voluntarily lower his bargaining equilibrium claim. In doing the original strategic equilibrium is modified and vN-M discriminatory solutions may occur, but also a different stronger player may emerge that has eventually will have to lower his equilibrium claim. A sequence of such measures converges to the equal

  2. Dissociative symptoms in kleptomania.

    Science.gov (United States)

    Grant, Jon E

    2004-02-01

    Many patients with kleptomania report an altered state of consciousness during acts of theft. The purpose of this investigation was to clarify a possible link between dissociation and kleptomania, a disabling disorder whose phenomenology remains understudied. 26 adult outpatients who met DSM-IV criteria for kleptoania were administered the Dissociative Experiences Scale and compared to 22 normal controls. The patients with kleptomania had scores that differed significantly from those reported by normal controls. There were no statistically significant differences by sex. Because kleptomania patients seeking treatment with medication may differ from others with kleptomania, further studies are needed.

  3. Dissociation and psychosis in dissociative identity disorder and schizophrenia.

    Science.gov (United States)

    Laddis, Andreas; Dell, Paul F

    2012-01-01

    Dissociative symptoms, first-rank symptoms of schizophrenia, and delusions were assessed in 40 schizophrenia patients and 40 dissociative identity disorder (DID) patients with the Multidimensional Inventory of Dissociation (MID). Schizophrenia patients were diagnosed with the Structured Clinical Interview for the DSM-IV Axis I Disorders; DID patients were diagnosed with the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised. DID patients obtained significantly (a) higher dissociation scores; (b) higher passive-influence scores (first-rank symptoms); and (c) higher scores on scales that measure child voices, angry voices, persecutory voices, voices arguing, and voices commenting. Schizophrenia patients obtained significantly higher delusion scores than did DID patients. What is odd is that the dissociation scores of schizophrenia patients were unrelated to their reports of childhood maltreatment. Multiple regression analyses indicated that 81% of the variance in DID patients' dissociation scores was predicted by the MID's Ego-Alien Experiences Scale, whereas 92% of the variance in schizophrenia patients' dissociation scores was predicted by the MID's Voices Scale. We propose that schizophrenia patients' responses to the MID do not index the same pathology as do the responses of DID patients. We argue that neither phenomenological definitions of dissociation nor the current generation of dissociation instruments (which are uniformly phenomenological in nature) can distinguish between the dissociative phenomena of DID and what we suspect are just the dissociation-like phenomena of schizophrenia.

  4. Dissociative Identity Disorder

    Science.gov (United States)

    Schmidt, Tom

    2007-01-01

    Few psychological disorders in the Diagnostic Statistical Manual have generated as much controversy as Dissociative Identity Disorder (DID). For the past 35 years diagnoses of DID, previously referred to as Multiple Personality Disorder (MPD), have increased exponentially, causing various psychological researchers and clinicians to question the…

  5. Resonances in dissociative recombination: Trends and patterns

    Energy Technology Data Exchange (ETDEWEB)

    Orel, A E; Ngassam, V; Royal, J [Department of Applied Science, University of California, Davis (United States); Roos, J B; Larson, A, E-mail: aeorel@ucdavis.ed [Department of Theoretical Chemistry, Royal Institute of Technology, Stockholm (Sweden)

    2009-11-15

    In dissociative recombination, the kinetic energy of the incident electron is transferred into excitation of the electrons of the target ion and then into kinetic energy of the fragments. In general, this proceeds via a resonance where the electron is temporarily trapped by the ion, leading to efficient energy transfer. The study of dissociative recombination is the study of these resonances, Rydberg states converging to the ground and excited states of the ion. For a number of systems, we have studied the electronic states involved in dissociative recombination, including the ground and excited states of the ion, the resonant states and the bound Rydberg states of the system, by combining electron scattering calculations with multi-reference configuration interaction quantum chemistry calculations. We will report on trends and patterns in these resonance states. We will discuss studies of dissociative recombination of the rare-gas ions, moving down the periodic table from He{sup +}{sub 2} to Ne{sup +}{sub 2} to Ar{sup +}{sub 2}, where the ground electronic state of the ion is constant, but its polarizability increases. We will also present results on isoelectronic polyatomic systems, such as HCO{sup +} and HCNH{sup +}, as well as the effects of changing the electronic structure slightly such as HCN{sup +}/HNC{sup +} and H{sub 2}CO{sup +}.

  6. Neurophysiological correlates of dissociative symptoms

    NARCIS (Netherlands)

    Kruijs, van der S.J.M.; Bodde, N.M.G; Carrette, E.C.B.; Lazeron, R.H.C; Vonck, K.E.J.; Boon, P.A.J.M.; Langereis, G.R.; Cluitmans, P.J.M.; Feijs, L.M.G.; Hofman, P.A.M.; Backes, W.H.; Jansen, J.F.A.; Aldenkamp, A.P.

    2014-01-01

    Objective: Dissociation is a mental process with psychological and somatoform manifestations, which is closely related to hypnotic suggestibility and essentially shows the ability to obtain distance from reality. An increased tendency to dissociate is a frequently reported characteristic of patients

  7. A nonaqueous potentiometric titration study of the dissociation of t-butyl methacrylate-methacrylic acid copolymers.

    Science.gov (United States)

    Nakatani, Kiyoharu; Yamashita, Jun; Sekine, Tomomi; Toriumi, Minoru; Itani, Toshiro

    2003-05-01

    The dissociation of t-butyl methacrylate-methacrylic acid copolymers in dimethyl sulfoxide was analyzed by a nonaqueous potentiometric titration technique. The negative logarithm of the dissociation constant of the monomer unit of a methacrylic acid (MAA) monotonously increased with the increasing degree of dissociation corresponding to the titrant/MAA amount ratio, and was highly influenced by the copolymerization ratio. The results are discussed in terms of the suppression of the dissociation of MAA by a neighboring charged methacrylate anion unit.

  8. Three dimensions of dissociative amnesia.

    Science.gov (United States)

    Dell, Paul F

    2013-01-01

    Principal axis factor analysis with promax rotation extracted 3 factors from the 42 memory and amnesia items of the Multidimensional Inventory of Dissociation (MID) database (N = 2,569): Discovering Dissociated Actions, Lapses of Recent Memory and Skills, and Gaps in Remote Memory. The 3 factors' shared variance ranged from 36% to 64%. Construed as scales, the 3 factor scales had Cronbach's alpha coefficients of .96, .94, and .93, respectively. The scales correlated strongly with mean Dissociative Experiences Scale scores, mean MID scores, and total scores on the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised (SCID-D-R). What is interesting is that the 3 amnesia factors exhibited a range of correlations with SCID-D-R Amnesia scores (.52, .63, and .70, respectively), suggesting that the SCID-D-R Amnesia score emphasizes gaps in remote memory over amnesias related to dissociative identity disorder. The 3 amnesia factor scales exhibited a clinically meaningful pattern of significant differences among dissociative identity disorder, dissociative disorder not otherwise specified-1, dissociative amnesia, depersonalization disorder, and nonclinical participants. The 3 amnesia factors may have greater clinical utility for frontline clinicians than (a) amnesia as discussed in the context of the Diagnostic and Statistical Manual of Mental Disorders, Fourth Edition, nosology of the dissociative disorders or (b) P. Janet's (1893/1977 ) 4-fold classification of dissociative amnesia. The author recommends systematic study of the phenomenological differences within specific dissociative symptoms and their differential relationship to specific dissociative disorders.

  9. Oppositely charged colloids out of equilibrium

    Science.gov (United States)

    Vissers, T.

    2010-11-01

    Colloids are particles with a size in the range of a few nanometers up to several micrometers. Similar to atomic and molecular systems, they can form gases, liquids, solids, gels and glasses. Colloids can be used as model systems because, unlike molecules, they are sufficiently large to be studied directly with light microscopy and move sufficiently slow to study their dynamics. In this thesis, we study binary systems of polymethylmethacrylate (PMMA) colloidal particles suspended in low-polar solvent mixtures. Since the ions can still partially dissociate, a surface charge builds up which causes electrostatic interactions between the colloids. By carefully tuning the conditions inside the suspension, we make two kinds of particles oppositely charged. To study our samples, we use Confocal Laser Scanning Microscopy (CLSM). The positively and negatively charged particles can be distinguished by a different fluorescent dye. Colloids constantly experience a random motion resulting from random kicks of surrounding solvent molecules. When the attractions between the oppositely charged particles are weak, the particles can attach and detach many times and explore a lot of possible configurations and the system can reach thermodynamic equilibrium. For example, colloidal ‘ionic’ crystals consisting of thousands to millions of particles can form under the right conditions. When the attractions are strong, the system can become kinetically trapped inside a gel-like state. We observe that when the interactions change again, crystals can even emerge again from this gel-like phase. By using local order parameters, we quantitatively study the crystallization of colloidal particles and identify growth defects inside the crystals. We also study the effect of gravity on the growth of ionic crystals by using a rotating stage. We find that sedimentation can completely inhibit crystal growth and plays an important role in crystallization from the gel-like state. The surface

  10. Ion-exchange equilibrium of N-acetyl-D-neuraminic acid on a strong anionic exchanger.

    Science.gov (United States)

    Wu, Jinglan; Ke, Xu; Zhang, Xudong; Zhuang, Wei; Zhou, Jingwei; Ying, Hanjie

    2015-09-15

    N-acetyl-D-neuraminic acid (Neu5Ac) is a high value-added product widely applied in the food industry. A suitable equilibrium model is required for purification of Neu5Ac based on ion-exchange chromatography. Hence, the equilibrium uptake of Neu5Ac on a strong anion exchanger, AD-1 was investigated experimentally and theoretically. The uptake of Neu5Ac by the hydroxyl form of the resin occurred primarily by a stoichiometric exchange of Neu5Ac(-) and OH(-). The experimental data showed that the selectivity coefficient for the exchange of Neu5Ac(-) with OH(-) was a non-constant quantity. Subsequently, the Saunders' model, which took into account the dissociation reactions of Neu5Ac and the condition of electroneutrality, was used to correlate the Neu5Ac sorption isotherms at various solution pHs and Neu5Ac concentrations. The model provided an excellent fit to the binary exchange data for Cl(-)/OH(-) and Neu5Ac(-)/OH(-), and an approximate prediction of equilibrium in the ternary system Cl(-)/Neu5Ac(-)/OH(-). This basic information combined with the general mass transfer model could lay the foundation for the prediction of dynamic behavior of fixed bed separation process afterwards. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Computation of Phase Equilibrium and Phase Envelopes

    DEFF Research Database (Denmark)

    Ritschel, Tobias Kasper Skovborg; Jørgensen, John Bagterp

    formulate the involved equations in terms of the fugacity coefficients. We present expressions for the first-order derivatives. Such derivatives are necessary in computationally efficient gradient-based methods for solving the vapor-liquid equilibrium equations and for computing phase envelopes. Finally, we......In this technical report, we describe the computation of phase equilibrium and phase envelopes based on expressions for the fugacity coefficients. We derive those expressions from the residual Gibbs energy. We consider 1) ideal gases and liquids modeled with correlations from the DIPPR database...... and 2) nonideal gases and liquids modeled with cubic equations of state. Next, we derive the equilibrium conditions for an isothermal-isobaric (constant temperature, constant pressure) vapor-liquid equilibrium process (PT flash), and we present a method for the computation of phase envelopes. We...

  12. Nonequilibrium method for estimating the first hydrolysis constant of tetravalent plutonium

    International Nuclear Information System (INIS)

    Silver, G.L.

    2010-01-01

    Six discrete formulas are used to estimate the equilibrium constant of the first hydrolysis reaction of tetravalent plutonium. They apply the pH, the oxidation number, one equilibrium constant, and fractions of two of the plutonium oxidation states. The new formulas are not restricted to the equilibrium condition. (author)

  13. Equilibrium Droplets on Deformable Substrates: Equilibrium Conditions.

    Science.gov (United States)

    Koursari, Nektaria; Ahmed, Gulraiz; Starov, Victor M

    2018-05-15

    Equilibrium conditions of droplets on deformable substrates are investigated, and it is proven using Jacobi's sufficient condition that the obtained solutions really provide equilibrium profiles of both the droplet and the deformed support. At the equilibrium, the excess free energy of the system should have a minimum value, which means that both necessary and sufficient conditions of the minimum should be fulfilled. Only in this case, the obtained profiles provide the minimum of the excess free energy. The necessary condition of the equilibrium means that the first variation of the excess free energy should vanish, and the second variation should be positive. Unfortunately, the mentioned two conditions are not the proof that the obtained profiles correspond to the minimum of the excess free energy and they could not be. It is necessary to check whether the sufficient condition of the equilibrium (Jacobi's condition) is satisfied. To the best of our knowledge Jacobi's condition has never been verified for any already published equilibrium profiles of both the droplet and the deformable substrate. A simple model of the equilibrium droplet on the deformable substrate is considered, and it is shown that the deduced profiles of the equilibrium droplet and deformable substrate satisfy the Jacobi's condition, that is, really provide the minimum to the excess free energy of the system. To simplify calculations, a simplified linear disjoining/conjoining pressure isotherm is adopted for the calculations. It is shown that both necessary and sufficient conditions for equilibrium are satisfied. For the first time, validity of the Jacobi's condition is verified. The latter proves that the developed model really provides (i) the minimum of the excess free energy of the system droplet/deformable substrate and (ii) equilibrium profiles of both the droplet and the deformable substrate.

  14. Teaching Chemical Equilibrium with the Jigsaw Technique

    Science.gov (United States)

    Doymus, Kemal

    2008-03-01

    This study investigates the effect of cooperative learning (jigsaw) versus individual learning methods on students’ understanding of chemical equilibrium in a first-year general chemistry course. This study was carried out in two different classes in the department of primary science education during the 2005-2006 academic year. One of the classes was randomly assigned as the non-jigsaw group (control) and other as the jigsaw group (cooperative). Students participating in the jigsaw group were divided into four “home groups” since the topic chemical equilibrium is divided into four subtopics (Modules A, B, C and D). Each of these home groups contained four students. The groups were as follows: (1) Home Group A (HGA), representin g the equilibrium state and quantitative aspects of equilibrium (Module A), (2) Home Group B (HGB), representing the equilibrium constant and relationships involving equilibrium constants (Module B), (3) Home Group C (HGC), representing Altering Equilibrium Conditions: Le Chatelier’s principle (Module C), and (4) Home Group D (HGD), representing calculations with equilibrium constants (Module D). The home groups then broke apart, like pieces of a jigsaw puzzle, and the students moved into jigsaw groups consisting of members from the other home groups who were assigned the same portion of the material. The jigsaw groups were then in charge of teaching their specific subtopic to the rest of the students in their learning group. The main data collection tool was a Chemical Equilibrium Achievement Test (CEAT), which was applied to both the jigsaw and non-jigsaw groups The results indicated that the jigsaw group was more successful than the non-jigsaw group (individual learning method).

  15. Phase equilibrium condition of marine carbon dioxide hydrate

    International Nuclear Information System (INIS)

    Sun, Shi-Cai; Liu, Chang-Ling; Ye, Yu-Guang

    2013-01-01

    Highlights: ► CO 2 hydrate phase equilibrium was studied in simulated marine sediments. ► CO 2 hydrate equilibrium temperature in NaCl and submarine pore water was depressed. ► Coarse-grained silica sand does not affect CO 2 hydrate phase equilibrium. ► The relationship between equilibrium temperature and freezing point was discussed. - Abstract: The phase equilibrium of ocean carbon dioxide hydrate should be understood for ocean storage of carbon dioxide. In this paper, the isochoric multi-step heating dissociation method was employed to investigate the phase equilibrium of carbon dioxide hydrate in a variety of systems (NaCl solution, submarine pore water, silica sand + NaCl solution mixture). The experimental results show that the depression in the phase equilibrium temperature of carbon dioxide hydrate in NaCl solution is caused mainly by Cl − ion. The relationship between the equilibrium temperature and freezing point in NaCl solution was discussed. The phase equilibrium temperature of carbon dioxide hydrate in submarine pore water is shifted by −1.1 K to lower temperature region than that in pure water. However, the phase equilibrium temperature of carbon dioxide hydrate in mixture samples of coarsed-grained silica sand and NaCl solution is in agreement with that in NaCl solution with corresponding concentrations. The relationship between the equilibrium temperature and freezing point in mixture samples was also discussed.

  16. Model-independent determination of dissociation energies: method and applications

    International Nuclear Information System (INIS)

    Vogel, Manuel; Hansen, Klavs; Herlert, Alexander; Schweikhard, Lutz

    2003-01-01

    A number of methods are available for the purpose of extracting dissociation energies of polyatomic particles. Many of these techniques relate the rate of disintegration at a known excitation energy to the value of the dissociation energy. However, such a determination is susceptible to systematic uncertainties, mainly due to the unknown thermal properties of the particles and the potential existence of 'dark' channels, such as radiative cooling. These problems can be avoided with a recently developed procedure, which applies energy-dependent reactions of the decay products as an uncalibrated thermometer. Thus, it allows a direct measurement of dissociation energies, without any assumption on properties of the system or on details of the disintegration process. The experiments have been performed in a Penning trap, where both rate constants and branching ratios have been measured. The dissociation energies determined with different versions of the method yield identical values, within a small uncertainty

  17. Theoretical Studies of Aqueous Systems above 25 deg C. 1. Fundamental Concepts for Equilibrium Diagrams and some General Features of the Water System

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Derek

    1971-09-15

    The illustration of thermodynamic data on aqueous systems is discussed and diagrams are described that are useful for bringing together the large numbers of data that are relevant to technological problems such as corrosion, mass-transport and deposition. Two kinds of logarithmic equilibrium diagram are particularly useful, namely, diagrams depicting the variation with pH or pe of the concentrations of ionic species relative to that of a chosen reference ion and diagrams depicting the fields of conditions of pH and pe in which the various species in any given system predominate or are stable. Such diagrams clearly and concisely illustrate the data and greatly simplify the comparison of the states of a system at different temperatures. Estimates of the equilibrium constants for the redox and the acid-base dissociation of water up to 375 C are reported and some general features of aqueous systems at elevated temperatures are discussed

  18. Constant physics and characteristics of fundamental constant

    International Nuclear Information System (INIS)

    Tarrach, R.

    1998-01-01

    We present some evidence which supports a surprising physical interpretation of the fundamental constants. First, we relate two of them through the renormalization group. This leaves as many fundamental constants as base units. Second, we introduce and a dimensional system of units without fundamental constants. Third, and most important, we find, while interpreting the units of the a dimensional system, that is all cases accessible to experimentation the fundamental constants indicate either discretization at small values or boundedness at large values of the corresponding physical quantity. (Author) 12 refs

  19. Differential dissociation micromethod for the investigation of binding of metandrostenolone (Nerobol) to plasma proteins

    International Nuclear Information System (INIS)

    Bojadzsieva, Milka; Kocsar, Laszlo; Kremmer, Tibor

    1985-01-01

    A micromethod was developed to determine the binding of anabolic streoids to plasma proteins. The new procedure combines precipitation with ammonium sulphate and differential dissociation. The binding parameters (association constant, specific binding capacity) are calculated on the basis of dissociation curves of sup(3)H-metandrostenolone from the precipitated sexual binding globuline. (L.E.)

  20. Differential dissociation micromethod for the investigation of binding of metandrostenolone (Nerobol) to plasma proteins

    Energy Technology Data Exchange (ETDEWEB)

    Bojadzsieva, M.; Kocsar, L. (Orszagos Frederic Joliot-Curie Sugarbiologiai es Sugaregeszseguegyi Kutato Intezet, Budapest (Hungary)); Kremmer, T. (Orszagos Onkologiai Intezet, Budapest (Hungary))

    1985-01-01

    A micromethod was developed to determine the binding of anabolic steroids to plasma proteins. The new procedure combines precipitation with ammonium sulphate and differential dissociation. The binding parameters (association constant, specific binding capacity) are calculated on the basis of dissociation curves of sup(3)H-metandrostenolone from the precipitated sexual binding globuline.

  1. Equilibrium relationships in the system Ni-U-O

    International Nuclear Information System (INIS)

    Mansour, N.A.L.

    1980-01-01

    Phase relationships were established in air and in oxygen. Mixtures of NiO and U 3 O 8 oxidize to NiUO 4 . The results of analysis of NiUO 4 were identical to those previously published for NiU 3 O 10 . The uranate dissociates to NiO and U 3 O 8 at a temperature higher than that of their oxidation back to the uranate on cooling because of the difficulty of oxygen diffusion and uranate nucleation. Accordingly, dissociation temperature was taken to represent equilibrium and was used to calculate roughly ΔH and ΔS for the reaction of dissociation. In presence of NiO, U 3 O 8 melts partially and does not dissociate to the lower oxide. (orig.) [de

  2. Quantity Constrained General Equilibrium

    NARCIS (Netherlands)

    Babenko, R.; Talman, A.J.J.

    2006-01-01

    In a standard general equilibrium model it is assumed that there are no price restrictions and that prices adjust infinitely fast to their equilibrium values.In case of price restrictions a general equilibrium may not exist and rationing on net demands or supplies is needed to clear the markets.In

  3. [Dissociative disorders and affective disorders].

    Science.gov (United States)

    Montant, J; Adida, M; Belzeaux, R; Cermolacce, M; Pringuey, D; Da Fonseca, D; Azorin, J-M

    2014-12-01

    The phenomenology of dissociative disorders may be complex and sometimes confusing. We describe here two cases who were initially misdiagnosed. The first case concerned a 61 year-old woman, who was initially diagnosed as an isolated dissociative fugue and was actually suffering from severe major depressive episode. The second case concerned a 55 year-old man, who was suffering from type I bipolar disorder and polyvascular disease, and was initially diagnosed as dissociative fugue in a mooddestabilization context, while it was finally a stroke. Yet dissociative disorders as affective disorder comorbidity are relatively unknown. We made a review on this topic. Dissociative disorders are often studied through psycho-trauma issues. Litterature is rare on affective illness comorbid with dissociative disorders, but highlight the link between bipolar and dissociative disorders. The later comorbidity often refers to an early onset subtype with also comorbid panic and depersonalization-derealization disorder. Besides, unipolar patients suffering from dissociative symptoms have more often cyclothymic affective temperament. Despite the limits of such studies dissociative symptoms-BD association seems to correspond to a clinical reality and further works on this topic may be warranted. Copyright © 2014 L’Encéphale. Published by Elsevier Masson SAS.. All rights reserved.

  4. Multiphoton dissociation of polyatomic molecules

    International Nuclear Information System (INIS)

    Schulz, P.A.

    1979-10-01

    The dynamics of infrared multiphoton excitation and dissociation of SF 6 was investigated under collision free conditions by a crossed laser-molecular beam method. In order to understand the excitation mechanism and to elucidate the requirements of laser intensity and energy fluence, a series of experiments were carried out to measure the dissociation yield dependences on energy fluence, vibrational temperature of SF 6 , the pulse duration of the CO 2 laser and the frequency in both one and two laser experiments. Translational energy distributions of the SF 5 dissociation product measured by time of flight and angular distributions and the dissociation lifetime of excited SF 6 as inferred from the observation of secondary dissociation of SF 5 into SF 4 and F during the laser pulse suggest that the dynamics of dissociation of excited molecules is dominated by complete energy randomization and rapid intramolecular energy transfer on a nanosecond timescale, and can be adequately described by RRKM theory. An improved phenomenological model including the initial intensity dependent excitation, a rate equation describing the absorption and stimulated emission of single photons, and the unimolecular dissociation of excited molecules is constructed based on available experimental results. The model shows that the energy fluence of the laser determines the excitation of molecules in the quasi-continuum and the excess energy with which molecules dissociate after the laser pulse. The role played by the laser intensity in multiphoton dissociation is more significant than just that of overcoming the intensity dependent absorption in the lowest levels. 63 references

  5. Strong-field dissociation dynamics

    International Nuclear Information System (INIS)

    DiMauro, L.F.; Yang, Baorui.

    1993-01-01

    The strong-field dissociation behavior of diatomic molecules is examined under two distinctive physical scenarios. In the first scenario, the dissociation of the isolated hydrogen and deuterium molecular ions is discussed. The dynamics of above-threshold dissociation (ATD) are investigated over a wide range of green and infrared intensities and compared to a dressed-state model. The second situation arises when strong-field neutral dissociation is followed by ionization of the atomic fragments. The study results in a direct measure of the atomic fragment's ac-Stark shift by observing the intensity-dependent shifts in the electron or nuclear fragment kinetic energy. 8 figs., 14 refs

  6. Cosmological Hubble constant and nuclear Hubble constant

    International Nuclear Information System (INIS)

    Horbuniev, Amelia; Besliu, Calin; Jipa, Alexandru

    2005-01-01

    The evolution of the Universe after the Big Bang and the evolution of the dense and highly excited nuclear matter formed by relativistic nuclear collisions are investigated and compared. Values of the Hubble constants for cosmological and nuclear processes are obtained. For nucleus-nucleus collisions at high energies the nuclear Hubble constant is obtained in the frame of different models involving the hydrodynamic flow of the nuclear matter. Significant difference in the values of the two Hubble constant - cosmological and nuclear - is observed

  7. Dissociative State and Competence

    Directory of Open Access Journals (Sweden)

    Yu-Ju Lin

    2007-10-01

    Full Text Available This report presents the results of forensic evaluation of the civil competence of a case of alleged dissociative identity disorder (DID and discusses whether such dissociative states substantially jeopardize civil competence. A 40-year-old woman claimed that she had had many personalities since her college days. From the age of 37 to 40, she shopped excessively, which left her with millions of dollars of debt. She ascribed her shopping to a certain identity state, over which she had no control. (In this article, we use the term identity state to replace personality as an objective description of a mental state. She thus raised the petition of civil incompetence. During the forensic evaluation, it was found that the identity states were relatively stable and mutually aware of each other. The switch into another identity state was sometimes under voluntary control. The subject showed consistency and continuity in behavioral patterns across the different identity states, and no matter which identity state she was in, there was no evidence of impairment in her factual knowledge of social situations and her capacity for managing personal affairs. We hence concluded that she was civilly competent despite the claimed DID. Considering that the existence and diagnosis of DID are still under dispute and a diagnosis of DID alone is not sufficient to interdict a person's civil right, important clinical and forensic issues remain to be answered.

  8. Stability constants for silicate adsorbed to ferrihydrite

    DEFF Research Database (Denmark)

    Hansen, Hans Christian Bruun; Wetche, T.P.; Raulund-Rasmussen, Karsten

    1994-01-01

    Intrinsic surface acidity constants (K(a1)intr, K(a2)intr) and surface complexation constant for adsorption of orthosilicate onto synthetic ferrihydrite (K(Si) for the complex = FeOSi(OH)3) have been determined from acid/base titrations in 0.001-0.1 m NaClO4 electrolytes and silicate adsorption...... experiments in 0.01 m NaNO3 electrolyte (pH 3-6). The surface equilibrium constants were calculated according to the two-layer model by Dzombak & Morel (1990). Near equilibrium between protons/hydroxyls in solution and the ferrihydrite surface was obtained within minutes while equilibration with silicate...

  9. Hyperglycemia associated dissociative fugue (organic dissociative disorder) in an elderly.

    Science.gov (United States)

    Ram, Dushad; Ashoka, H G; Gowdappa, Basavnna

    2015-01-01

    Inadequate glycemic control in patients with diabetes is known to be associated with psychiatric disorders such as depression, anxiety disorder, and cognitive impairment. However, dissociative syndrome has not been reported so far. Here we are reporting a case of repeated dissociative fugue associated with hyperglycemia, in an elderly with type II diabetes. Possible neurobiological mechanism has been discussed.

  10. Hyperglycemia associated dissociative fugue (organic dissociative disorder) in an elderly

    OpenAIRE

    Ram, Dushad; Ashoka, H. G; Gowdappa, Basavnna

    2015-01-01

    Inadequate glycemic control in patients with diabetes is known to be associated with psychiatric disorders such as depression, anxiety disorder, and cognitive impairment. However, dissociative syndrome has not been reported so far. Here we are reporting a case of repeated dissociative fugue associated with hyperglycemia, in an elderly with type II diabetes. Possible neurobiological mechanism has been discussed.

  11. Hyperglycemia associated dissociative fugue (organic dissociative disorder in an elderly

    Directory of Open Access Journals (Sweden)

    Dushad Ram

    2015-01-01

    Full Text Available Inadequate glycemic control in patients with diabetes is known to be associated with psychiatric disorders such as depression, anxiety disorder, and cognitive impairment. However, dissociative syndrome has not been reported so far. Here we are reporting a case of repeated dissociative fugue associated with hyperglycemia, in an elderly with type II diabetes. Possible neurobiological mechanism has been discussed.

  12. Chemical equilibrium of glycerol carbonate synthesis from glycerol

    International Nuclear Information System (INIS)

    Li Jiabo; Wang Tao

    2011-01-01

    Research highlights: → Transesterification of glycerol with cyclic carbonates or alkyl carbonates is thermodynamically favourable for the preparation of glycerol carbonate from glycerol. → The reaction of glycerol and carbon dioxide is thermodynamically limited. → High temperature and low pressure is favourable to the reaction of glycerol and urea. → Increasing temperature can increase the chemical equilibrium constant for the reaction of glycerol and dimethyl carbonate. → For the reaction of glycerol and ethylene carbonate, increasing temperature can decrease the chemical equilibrium constant. - Abstract: In this paper, the chemical equilibrium for the glycerol carbonate preparation from glycerol was investigated. The chemical equilibrium constants were calculated for the reactions to produce glycerol carbonate from glycerol. The theoretical calculation was compared with the experimental results for the transesterification of glycerol with dimethyl carbonate. Transesterification of glycerol with cyclic carbonates or alkyl carbonates is thermodynamically favourable for producing glycerol carbonate from glycerol according to the equilibrium constant. Increasing temperature can increase the chemical equilibrium constant for the reaction of glycerol with dimethyl carbonate. For the reaction of glycerol with ethylene carbonate, increasing temperature can decrease the chemical equilibrium constant. The reaction of glycerol with carbon dioxide is thermodynamically limited. High temperature and low pressure are favourable to the reaction of glycerol and urea.

  13. A New Application for Radioimmunoassay: Measurement of Thermodynamic Constants.

    Science.gov (United States)

    Angstadt, Carol N.; And Others

    1983-01-01

    Describes a laboratory experiment in which an equilibrium radioimmunoassay (RIA) is used to estimate thermodynamic parameters such as equilibrium constants. The experiment is simple and inexpensive, and it introduces a technique that is important in the clinical chemistry and research laboratory. Background information, procedures, and results are…

  14. Affinity of hemoglobin for the cytoplasmic fragment of human erythrocyte membrane band 3. Equilibrium measurements at physiological pH using matrix-bound proteins: the effects of ionic strength, deoxygenation and of 2,3-diphosphoglycerate.

    Science.gov (United States)

    Chétrite, G; Cassoly, R

    1985-10-05

    The cytoplasmic fragment of band 3 protein isolated from the human erythrocyte membrane was linked to a CNBr-activated Sepharose matrix in an attempt to measure, in batch experiments, its equilibrium binding constant with oxy- and deoxyhemoglobin at physiological pH and ionic strength values and in the presence or the absence of 2,3-diphosphoglycerate. All the experiments were done at pH 7.2, and equilibrium constants were computed on the basis of one hemoglobin tetramer bound per monomer of fragment. In 10 mM-phosphate buffer, a dissociation constant KD = 2 X 10(-4)M was measured for oxyhemoglobin and was shown to increase to 8 X 10(-4)M in the presence of 50 mM-NaCl. Association could not be demonstrated at higher salt concentrations. Diphosphoglycerate-stripped deoxyhemoglobin was shown to associate more strongly with the cytoplasmic fragment of band 3. In 10 mM-bis-Tris (pH 7.2) and in the presence of 120 mM-NaCl, a dissociation constant KD = 4 X 10(-4)M was measured. Upon addition of increasing amounts of 2,3-diphosphoglycerate, the complex formed between deoxyhemoglobin and the cytoplasmic fragment of band 3 was dissociated. On the reasonable assumption that the hemoglobin binding site present on band 3 fragment was not modified upon linking the protein to the Sepharose matrix, the results indicated that diphosphoglycerate-stripped deoxyhemoglobin or partially liganded hemoglobin tetramers in the T state could bind band 3 inside the intact human red blood cell.

  15. Constants and thermodynamics of the acid-base equilibria of triglycine in water-ethanol solutions containing sodium perchlorate at 298 K

    Science.gov (United States)

    Pham Tkhi, L.; Usacheva, T. R.; Tukumova, N. V.; Koryshev, N. E.; Khrenova, T. M.; Sharnin, V. A.

    2016-02-01

    The acid-base equilibrium constants for glycyl-glycyl-glycine (triglycine) in water-ethanol solvents containing 0.0, 0.1, 0.3, and 0.5 mole fractions of ethanol are determined by potentiometric titration at 298.15 K and an ionic strength of 0.1, maintained with sodium perchlorate. It is established that an increase in the ethanol content in the solvent reduces the dissociation constant of the carboxyl group of triglycine (increases p K 1) and increases the dissociation constant of the amino group of triglycine (decreases p K 2). It is noted that the weakening of the acidic properties of a triglycinium ion upon an increase of the ethanol content in the solvent is due to the attenuation of the solvation shell of the zwitterionic form of triglycine, and to the increased solvation of triglycinium ions. It is concluded that the acid strength of triglycine increases along with a rise in the EtOH content in the solvent, due to the desolvation of the tripeptide zwitterion and the enhanced solvation of protons.

  16. Interfaces at equilibrium: A guide to fundamentals.

    Science.gov (United States)

    Marmur, Abraham

    2017-06-01

    The fundamentals of the thermodynamics of interfaces are reviewed and concisely presented. The discussion starts with a short review of the elements of bulk thermodynamics that are also relevant to interfaces. It continues with the interfacial thermodynamics of two-phase systems, including the definition of interfacial tension and adsorption. Finally, the interfacial thermodynamics of three-phase (wetting) systems is discussed, including the topic of non-wettable surfaces. A clear distinction is made between equilibrium conditions, in terms of minimizing energies (internal, Gibbs or Helmholtz), and equilibrium indicators, in terms of measurable, intrinsic properties (temperature, chemical potential, pressure). It is emphasized that the equilibrium indicators are the same whatever energy is minimized, if the boundary conditions are properly chosen. Also, to avoid a common confusion, a distinction is made between systems of constant volume and systems with drops of constant volume. Copyright © 2016 Elsevier B.V. All rights reserved.

  17. Thermochemical equilibrium modelling of a gasifying process

    International Nuclear Information System (INIS)

    Melgar, Andres; Perez, Juan F.; Laget, Hannes; Horillo, Alfonso

    2007-01-01

    This article discusses a mathematical model for the thermochemical processes in a downdraft biomass gasifier. The model combines the chemical equilibrium and the thermodynamic equilibrium of the global reaction, predicting the final composition of the producer gas as well as its reaction temperature. Once the composition of the producer gas is obtained, a range of parameters can be derived, such as the cold gas efficiency of the gasifier, the amount of dissociated water in the process and the heating value and engine fuel quality of the gas. The model has been validated experimentally. This work includes a parametric study of the influence of the gasifying relative fuel/air ratio and the moisture content of the biomass on the characteristics of the process and the producer gas composition. The model helps to predict the behaviour of different biomass types and is a useful tool for optimizing the design and operation of downdraft biomass gasifiers

  18. Dissociated dislocations in Ni: a computational study

    International Nuclear Information System (INIS)

    Szelestey, P.; Patriarca, M.; Kaski, K.

    2005-01-01

    A systematic computational study of the behavior of a (1/2) dissociated screw dislocation in fcc nickel is presented, in which atomic interactions are described through an embedded-atom potential. A suitable external stress is applied on the system, both for modifying the equilibrium separation distance d and moving the dislocation complex. The structure of the dislocation and its corresponding changes during the motion are studied in the framework of the two-dimensional Peierls model, for different values of the ratio d/a', where a' is the period of the Peierls potential. The distance between the edge and screw components of the partials, as well as their widths, undergo a modulation with period a', as the dislocation moves, and the amplitudes of such oscillations are shown to depend on d/a'. The stress profile acting on the dislocation complex is analyzed and the effective Peierls stress is estimated for different values of d/a'

  19. A storage ring study of dissociative excitation and recombination of D3+

    International Nuclear Information System (INIS)

    Le Padellec, A.; Larson, Aa.; Semaniak, J.; Stroemholm, C.; Larsson, M.; Rosen, S.; Danared, H.; Peterson, J.R.

    1998-01-01

    Dissociative recombination and excitation of D 3 + have been studied in CRYRING, a heavy-ion storage ring at the Manne Siegbahn laboratory at Stockholm University. The measured cross section for dissociative recombination was used to deduce a 300 K rate constant of 2.7 x 10 -8 cm 3 s -1 . This is a factor of four smaller than the corresponding value for H 3 + measured earlier in CRYRING. Dissociative excitation into both the D and 2D channels (D + D or D 2 ) were studied. The 2D channel occurs at energies below threshold for the ion's dissociative states, which indicates that resonant enhanced dissociative excitation via autoionizing resonances takes place. No measurable effect could be observed for the dissociative recombination cross sections when an electric field of 30 V/cm was applied to the electron-ion interaction region. (orig.)

  20. Dissociation: a developmental psychoneurobiological perspective

    African Journals Online (AJOL)

    Adele

    ... the stream of con- sciousness and memory.1 It is a frequent symptom of a range ... infant for long time spans in an extremely disturbed psycho- biological state that ... Advantage: Dissociation is adaptive in the short-term. Dissociation can be ...

  1. Dissipation and the relaxation to equilibrium

    International Nuclear Information System (INIS)

    Evans, Denis J; Williams, Stephen R; Searles, Debra J

    2009-01-01

    Using the recently derived dissipation theorem and a corollary of the transient fluctuation theorem (TFT), namely the second-law inequality, we derive the unique time independent, equilibrium phase space distribution function for an ergodic Hamiltonian system in contact with a remote heat bath. We prove under very general conditions that any deviation from this equilibrium distribution breaks the time independence of the distribution. Provided temporal correlations decay, we show that any nonequilibrium distribution that is an even function of the momenta eventually relaxes (not necessarily monotonically) to the equilibrium distribution. Finally we prove that the negative logarithm of the microscopic partition function is equal to the thermodynamic Helmholtz free energy divided by the thermodynamic temperature and Boltzmann's constant. Our results complement and extend the findings of modern ergodic theory and show the importance of dissipation in the process of relaxation towards equilibrium

  2. Phase equilibrium engineering

    CERN Document Server

    Brignole, Esteban Alberto

    2013-01-01

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

  3. Equilibrium and generators

    International Nuclear Information System (INIS)

    Balter, H.S.

    1994-01-01

    This work studies the behaviour of radionuclides when it produce a desintegration activity,decay and the isotopes stable creation. It gives definitions about the equilibrium between activity of parent and activity of the daughter, radioactive decay,isotope stable and transient equilibrium and maxim activity time. Some considerations had been given to generators that permit a disgregation of two radioisotopes in equilibrium and its good performance. Tabs

  4. Dissociative recombination of dications

    International Nuclear Information System (INIS)

    Seiersen, K.; Heber, O.; Jensen, M.J.; Safvan, C.P.; Andersen, L. H.

    2003-01-01

    Dissociative recombination (DR) of doubly-charged positive ions has been studied at the heavy ion storage ring ASTRID. Low-energy electrons were scattered on the dication of the N 2 molecule, and the absolute cross section was measured in the energy range of 10 -4 -50 eV. From the measured cross section, a thermal rate coefficient of 5.8x10 -7 cm 3 s -1 at 300 K was extracted. Furthermore, we present new results on the CO 2+ DR rate, and a summary and comparison of measured DR rate coefficients for both the singly and doubly-charged ions of CO, CO 2 , and N 2 is presented

  5. Quarkonium dissociation by anisotropy

    Science.gov (United States)

    Chernicoff, Mariano; Fernández, Daniel; Mateos, David; Trancanelli, Diego

    2013-01-01

    We compute the screening length for quarkonium mesons moving through an anisotropic, strongly coupled mathcal{N} = 4 super Yang-Mills plasma by means of its gravity dual. We present the results for arbitrary velocities and orientations of the mesons, as well as for arbitrary values of the anisotropy. The anisotropic screening length can be larger or smaller than the isotropic one, and this depends on whether the comparison is made at equal temperatures or at equal entropy densities. For generic motion we find that: (i) mesons dissociate above a certain critical value of the anisotropy, even at zero temperature; (ii) there is a limiting velocity for mesons in the plasma, even at zero temperature; (iii) in the ultra-relativistic limit the screening length scales as (1 - v 2)ɛ with ɛ = 1 /2, in contrast with the isotropic result ɛ = 1 /4.

  6. Dissociation - a preliminary contextual model

    Directory of Open Access Journals (Sweden)

    C Krüger

    2007-02-01

    Full Text Available Background. The Diagnostic and Statistical Manual of Mental Disorders (DSM system has certain limitations when applied to two South African examples of dissociation, because it is descriptive (non-explanatory and focuses on intrapsychic (non-communal processes. Even the existing Western explanatory models of dissociation fail to accommodate fully the communal aspects of dissociation in our South African context. Objectives and methods. The aim was to explore an expanded perspective on dissociation that does not limit it to an intrapsychic phenomenon, but that accounts for the interrelatedness of individuals within their social context. Auto-ethnography was used. In this article a collective, socially orientated, contextual hermeneutic was applied to two local examples of dissociation. Three existing Western models were expanded along multicontextual, collective lines, for them to be more useful in the pluralistic South African context. Results. This preliminary contextual model of dissociation includes a person’s interpersonal, socio-cultural, and spiritual contexts, in addition to the intrapsychic context. Dissociation is considered to be a normal information-processing tool that maintains balanced, coherent selves-in-society, i.e. individuals connected to each other. In the South African context dissociation appears mostly as a normal phenomenon and seldom as a sign of mental illness. Dissociation is pivotal for the normal construction of individual and communal identities in the face of conflicting sets of information from various contexts. Dissociation may help individuals or communities to survive in a world of conflicting messages, where conflict is often interpersonal/cultural/societal in nature, rather than primarily intrapsychic. Conclusions. This model should be developed and evaluated further. Such evaluation would require suitable new local terminology.

  7. Abacavir and warfarin modulate allosterically kinetics of NO dissociation from ferrous nitrosylated human serum heme-albumin

    International Nuclear Information System (INIS)

    Ascenzi, Paolo; Imperi, Francesco; Coletta, Massimo; Fasano, Mauro

    2008-01-01

    Human serum albumin (HSA) participates to heme scavenging, in turn HSA-heme binds gaseous diatomic ligands at the heme-Fe-atom. Here, the effect of abacavir and warfarin on denitrosylation kinetics of HSA-heme-Fe(II)-NO (i.e., k off ) is reported. In the absence of drugs, the value of k off is (1.3 ± 0.2) x 10 -4 s -1 . Abacavir and warfarin facilitate NO dissociation from HSA-heme-Fe(II)-NO, the k off value increases to (8.6 ± 0.9) x 10 -4 s -1 . From the dependence of k off on the drug concentration, values of the dissociation equilibrium constant for the abacavir and warfarin binding to HSA-heme-Fe(II)-NO (i.e., K = (1.2 ± 0.2) x 10 -3 M and (6.2 ± 0.7) x 10 -5 M, respectively) were determined. The increase of k off values reflects the stabilization of the basic form of HSA-heme-Fe by ligands (e.g., abacavir and warfarin) that bind to Sudlow's site I. This event parallels the stabilization of the six-coordinate derivative of the HSA-heme-Fe(II)-NO atom. Present data highlight the allosteric modulation of HSA-heme-Fe(II) reactivity by heterotropic effectors

  8. Formation of nitric acid hydrates - A chemical equilibrium approach

    Science.gov (United States)

    Smith, Roland H.

    1990-01-01

    Published data are used to calculate equilibrium constants for reactions of the formation of nitric acid hydrates over the temperature range 190 to 205 K. Standard enthalpies of formation and standard entropies are calculated for the tri- and mono-hydrates. These are shown to be in reasonable agreement with earlier calorimetric measurements. The formation of nitric acid trihydrate in the polar stratosphere is discussed in terms of these equilibrium constants.

  9. Fall Back Equilibrium

    NARCIS (Netherlands)

    Kleppe, J.; Borm, P.E.M.; Hendrickx, R.L.P.

    2008-01-01

    Fall back equilibrium is a refinement of the Nash equilibrium concept. In the underly- ing thought experiment each player faces the possibility that, after all players decided on their action, his chosen action turns out to be blocked. Therefore, each player has to decide beforehand on a back-up

  10. Dissociative symptomatology in cancer patients

    Science.gov (United States)

    Civilotti, Cristina; Castelli, Lorys; Binaschi, Luca; Cussino, Martina; Tesio, Valentina; Di Fini, Giulia; Veglia, Fabio; Torta, Riccardo

    2015-01-01

    Introduction: The utilization of the post-traumatic stress disorder (PTSD) diagnostic spectrum is currently being debated to categorize psychological adjustment in cancer patients. The aims of this study were to: (1) evaluate the presence of cancer-related traumatic dissociative symptomatology in a sample of cancer patients; (2) examine the correlation of cancer-related dissociation and sociodemographic and medical variables, anxiety, depression, and post-traumatic stress symptomatology; (3) investigate the predictors of cancer-related dissociation. Methods: Ninety-two mixed cancer patients (mean age: 58.94, ds = 10.13) recruited from two hospitals in northern Italy were administered a questionnaire on sociodemographic and medical characteristics, the Karnofsky Scale to measure the level of patient activity and medical care requirements, the Hospital Anxiety and Depression Scale (HADS) to evaluate the presence of anxiety and depression, the Impact of Event Scale Revised (IES-R) to assess the severity of intrusion, avoidance, and hypervigilance, and the Peritraumatic Dissociative Experiences Questionnaire (PDEQ) to quantify the traumatic dissociative symptomatology. Results: 31.5% of participants report a PDEQ score above the cutoff. The results indicated that dissociative symptomatology was positively correlated with HADS scores (HADS-Anxiety: r = 0.476, p dissociative symptomatology. The results converged on a three predictor model revealing that IES-R-Intrusion, IES-R-Avoidance, and IES-R-Hyperarousal accounted for 53.9% of the explained variance. Conclusion: These findings allow us to hypothesize a specific psychological reaction which may be ascribed to the traumatic spectrum within the context of cancer, emphasizing the close relationship between the origin of dissociative constituents which, according to the scientific literature, compose the traumatic experience. Our results have implications for understanding dissociative symptomatology in a cancer

  11. Small angle neutron scattering (SANS) under non-equilibrium conditions

    International Nuclear Information System (INIS)

    Oberthur, R.C.

    1984-01-01

    The use of small angle neutron scattering (SANS) for the study of systems under non-equilibrium conditions is illustrated by three types of experiments in the field of polymer research: - the relaxation of a system from an initial non-equilibrium state towards equilibrium, - the cyclic or repetitive installation of a series of non-equilibrium states in a system, - the steady non-equilibrium state maintained by a constant dissipation of energy within the system. Characteristic times obtained in these experiments with SANS are compared with the times obtained from quasi-elastic neutron and light scattering, which yield information about the equilibrium dynamics of the system. The limits of SANS applied to non-equilibrium systems for the measurement of relaxation times at different length scales are shown and compared to the limits of quasielastic neutron and light scattering

  12. Correlations between channel probabilities in collisional dissociation of D3+

    International Nuclear Information System (INIS)

    Abraham, S.; Nir, D.; Rosner, B.

    1984-01-01

    Measurements of the dissociation of D 3 + ions at 300--600 keV under single- and multiple-collision conditions in Ar- and H 2 -gas targets have been performed. A complete separation of all dissociation channels was achieved, including the neutral channels, which were resolved using a fine-mesh technique. Data analysis in the multiple-collision regime confirms the validity of the rate equations governing the charge exchange processes. In the single-collision region the analysis yields constant relations between channel probabilities. Data rearrangement shows probability factorization and suggests that collisional dissociation is a two-stage process, a fast electron exchange followed by rearrangement and branching to the exit channels

  13. GABA, depressants and chloride ions affect the rate of dissociation of 35S-t-butylbicyclophosphorothionate binding

    International Nuclear Information System (INIS)

    Maksay, G.; Ticku, M.K.

    1985-01-01

    The dissociation of 35 S-TBPS was studied from binding sites of rat cerebral cortex. Monophasic dissociation plots became polyphasic and accelerated in the presence of micromolar concentrations of GABA suggesting the involvement of low (or super-low) affinity GABA receptors. The presence of the depressants etazolate, R(-)MPPB and ethanol resulted in similarly accelerated dissociation patterns. In contrast, the convulsants S(+)MPPB and pentamethylenetetrazol did not significantly affect the dissociation of TBPS. Dissociation initiated by dilution was not affected either by an excess of picrotoxin or by varying the equilibrium occupancy of the TBPS sites. These findings rule out the possibility of a kinetic cooperativity for the binding of convulsants. The removal of chloride ions also enhanced the rate of TBPS dissociation. Kinetic heterogeneity of the TBPS binding sites can be interpreted with allosteric interactions mediated by various sites at the GABA receptor complex coupled to different states of the chloride ionophore. 15 references, 3 figures, 1 table

  14. Dissociative absorption: An empirically unique, clinically relevant, dissociative factor.

    Science.gov (United States)

    Soffer-Dudek, Nirit; Lassri, Dana; Soffer-Dudek, Nir; Shahar, Golan

    2015-11-01

    Research of dissociative absorption has raised two questions: (a) Is absorption a unique dissociative factor within a three-factor structure, or a part of one general dissociative factor? Even when three factors are found, the specificity of the absorption factor is questionable. (b) Is absorption implicated in psychopathology? Although commonly viewed as "non-clinical" dissociation, absorption was recently hypothesized to be specifically associated with obsessive-compulsive symptoms. To address these questions, we conducted exploratory and confirmatory factor analyses on 679 undergraduates. Analyses supported the three-factor model, and a "purified" absorption scale was extracted from the original inclusive absorption factor. The purified scale predicted several psychopathology scales. As hypothesized, absorption was a stronger predictor of obsessive-compulsive symptoms than of general psychopathology. In addition, absorption was the only dissociative scale that longitudinally predicted obsessive-compulsive symptoms. We conclude that absorption is a unique and clinically relevant dissociative tendency that is particularly meaningful to obsessive-compulsive symptoms. Copyright © 2015 Elsevier Inc. All rights reserved.

  15. The empirical equilibrium structure of diacetylene

    OpenAIRE

    Thorwirth, S.; Harding, M. E.; Muders, D.; Gauss, J.

    2008-01-01

    High-level quantum-chemical calculations are reported at the MP2 and CCSD(T) levels of theory for the equilibrium structure and the harmonic and anharmonic force fields of diacetylene, HCCCCH. The calculations were performed employing Dunning's hierarchy of correlation-consistent basis sets cc-pVXZ, cc-pCVXZ, and cc-pwCVXZ, as well as the ANO2 basis set of Almloef and Taylor. An empirical equilibrium structure based on experimental rotational constants for thirteen isotopic species of diacety...

  16. Equilibrium and non-equilibrium extraction separation of rare earth metals in presence of diethylenetriaminepentaacetic acid in aqueous phase

    International Nuclear Information System (INIS)

    Azis, Abdul; Teramoto, Masaaki; Matsuyama, Hideto.

    1995-01-01

    Equilibrium and non-equilibrium extraction separations of rare earth metals were carried out in the presence of chelating agent in the aqueous phase. The separation systems of the rare earth metal mixtures used were Y/Dy, Y/Ho, Y/Er and Y/Tm, and the chelating agent and the extractant were diethylenetriaminepentaacetic acid (DTPA) and bis (2,4,4-trimethylpentyl) phosphinic acid (CYANEXR 272), respectively. For Y/Dy and Y/Ho systems, higher selectivities were obtained in equilibrium separation compared with those in non-equilibrium separation. On the other hand, the selectivities in non-equilibrium separation were higher for Y/Er and Y/Tm systems. In the separation condition suitable to each system, the addition of DTPA to the aqueous phase was found to be very effective for obtaining higher selectivities. The distribution ratios of the rare earth metals and the selectivities in the equilibrium separations obtained experimentally were thoroughly analyzed by considering various equilibria such as the extraction equilibrium and the complex formation equilibrium between rare earth metals and DTPA in the aqueous phase. Moreover, the extraction rates and the selectivities in the non-equilibrium separations were also analyzed by the extraction model considering the dissociation reactions of the rare earth metal-DTPA complexes in the aqueous stagnant layer. Based on these analyses, we presented an index which is useful for selecting the optimum operation mode. Using this index, we can predict that the selectivities under equilibrium conditions are higher than those under non-equilibrium conditions for Y/Dy and Y/Ho systems, while for Y/Er and Y/Tm systems, higher selectivities are obtained under non-equilibrium conditions. The experimental results were in agreement with predictions by this index. Further, the selectivities in various systems including other chelating agents and extractants were discussed based on this index. (J.P.N.)

  17. Equilibrium and non equilibrium in fragmentation

    International Nuclear Information System (INIS)

    Dorso, C.O.; Chernomoretz, A.; Lopez, J.A.

    2001-01-01

    Full text: In this communication we present recent results regarding the interplay of equilibrium and non equilibrium in the process of fragmentation of excited finite Lennard Jones drops. Because the general features of such a potential resemble the ones of the nuclear interaction (fact that is reinforced by the similarity between the EOS of both systems) these studies are not only relevant from a fundamental point of view but also shed light on the problem of nuclear multifragmentation. We focus on the microscopic analysis of the state of the fragmenting system at fragmentation time. We show that the Caloric Curve (i e. the functional relationship between the temperature of the system and the excitation energy) is of the type rise plateau with no vapor branch. The usual rise plateau rise pattern is only recovered when equilibrium is artificially imposed. This result puts a serious question on the validity of the freeze out hypothesis. This feature is independent of the dimensionality or excitation mechanism. Moreover we explore the behavior of magnitudes which can help us determine the degree of the assumed phase transition. It is found that no clear cut criteria is presently available. (Author)

  18. Dissociation Energies of Diatomic Molecules

    International Nuclear Information System (INIS)

    Qun-Chao, Fan; Wei-Guo, Sun

    2008-01-01

    Molecular dissociation energies of 10 electronic states of alkali molecules of KH, 7 LiD, 7 LiH, 6 LiH, NaK, NaLi and NaRb are studied using the highest three accurate vibrational energies of each electronic state, and an improved parameter-free analytical formula which is obtained starting from the LeRoy–Bernstein vibrational energy expression near the dissociation limit. The results show that as long as the highest three vibrational energies are accurate, the current analytical formula will give accurate theoretical dissociation energies D e theory , which are in excellent agreement with the experimental dissociation energies D e expt . (atomic and molecular physics)

  19. Neural complexity, dissociation, and schizophrenia

    Czech Academy of Sciences Publication Activity Database

    Bob, P.; Šusta, M.; Chládek, Jan; Glaslová, K.; Fedor-Ferybergh, P.

    2007-01-01

    Roč. 13, č. 10 (2007), HY1-5 ISSN 1234-1010 Institutional research plan: CEZ:AV0Z20650511 Keywords : neural complexity * dissociation * schizophrenia Subject RIV: FH - Neurology Impact factor: 1.607, year: 2007

  20. Dissociative Tendencies and Traffic Incidents

    Directory of Open Access Journals (Sweden)

    Valle, Virginia

    2012-01-01

    Full Text Available This paper analyses the relationship between dissociative experiences and road traffic incidents (crashes and traffic tickets in drivers (n=295 from Mar del Plata (Argentina city. A self-report questionnaire was applied to assess traffic crash involvement and sociodemographic variables. Dissociative tendencies were assessed by a modified version of the DES scale. To examine differences in DES scores tests of the difference of means were applied. Drivers who reported to be previously involved in traffic incidents obtained higher puntuations in the dissociative experiences scale than drivers who did not report such events. This result is observed for the total scale and for the three sub-scales (absorption, amnesia and depersonalization. However, differences appeared mainly for minor damage collisions. Further studies are needed to evaluate the role of dissociative tendencies as a risk factor in road traffic safety.

  1. Atrioventricular Dissociation after Electroconvulsive Therapy

    Directory of Open Access Journals (Sweden)

    Siegfried William Yu

    2011-01-01

    Full Text Available Electroconvulsive therapy (ECT is increasingly used as a treatment for psychiatric disorders. Cardiac effects are the principal cause of medical complications in these patients. We report a case of atrioventricular (AV dissociation that occurred after ECT that was treated with pacemaker implantation. The mechanisms contributing to the onset of AV dissociation in this patient, and the management and rationale for device therapy, in light of the most recent guidelines, are reviewed.

  2. Equilibrium and non-equilibrium phenomena in arcs and torches

    NARCIS (Netherlands)

    Mullen, van der J.J.A.M.

    2000-01-01

    A general treatment of non-equilibrium plasma aspects is obtained by relating transport fluxes to equilibrium restoring processes in so-called disturbed Bilateral Relations. The (non) equilibrium stage of a small microwave induced plasma serves as case study.

  3. Dissociative disorders in DSM-5.

    Science.gov (United States)

    Spiegel, David; Lewis-Fernández, Roberto; Lanius, Ruth; Vermetten, Eric; Simeon, Daphne; Friedman, Matthew

    2013-01-01

    The rationale, research literature, and proposed changes to the dissociative disorders and conversion disorder in the fifth edition of the Diagnostic and Statistical Manual of Mental Disorders (DSM-5) are presented. Dissociative identity disorder will include reference to possession as well as identity fragmentation, to make the disorder more applicable to culturally diverse situations. Dissociative amnesia will include dissociative fugue as a subtype, since fugue is a rare disorder that always involves amnesia but does not always include confused wandering or loss of personality identity. Depersonalization disorder will include derealization as well, since the two often co-occur. A dissociative subtype of posttraumatic stress disorder (PTSD), defined by the presence of depersonalization or derealization in addition to other PTSD symptoms, is being recommended, based upon new epidemiological and neuroimaging evidence linking it to an early life history of adversity and a combination of frontal activation and limbic inhibition. Conversion disorder (functional neurological symptom disorder) will likely remain with the somatic symptom disorders, despite considerable dissociative comorbidity.

  4. A statistical method for evaluation of the experimental phase equilibrium data of simple clathrate hydrates

    DEFF Research Database (Denmark)

    Eslamimanesh, Ali; Gharagheizi, Farhad; Mohammadi, Amir H.

    2012-01-01

    We, herein, present a statistical method for diagnostics of the outliers in phase equilibrium data (dissociation data) of simple clathrate hydrates. The applied algorithm is performed on the basis of the Leverage mathematical approach, in which the statistical Hat matrix, Williams Plot, and the r......We, herein, present a statistical method for diagnostics of the outliers in phase equilibrium data (dissociation data) of simple clathrate hydrates. The applied algorithm is performed on the basis of the Leverage mathematical approach, in which the statistical Hat matrix, Williams Plot...... in exponential form is used to represent/predict the hydrate dissociation pressures for three-phase equilibrium conditions (liquid water/ice–vapor-hydrate). The investigated hydrate formers are methane, ethane, propane, carbon dioxide, nitrogen, and hydrogen sulfide. It is interpreted from the obtained results...

  5. Non-equilibrium Economics

    Directory of Open Access Journals (Sweden)

    Katalin Martinás

    2007-02-01

    Full Text Available A microeconomic, agent based framework to dynamic economics is formulated in a materialist approach. An axiomatic foundation of a non-equilibrium microeconomics is outlined. Economic activity is modelled as transformation and transport of commodities (materials owned by the agents. Rate of transformations (production intensity, and the rate of transport (trade are defined by the agents. Economic decision rules are derived from the observed economic behaviour. The non-linear equations are solved numerically for a model economy. Numerical solutions for simple model economies suggest that the some of the results of general equilibrium economics are consequences only of the equilibrium hypothesis. We show that perfect competition of selfish agents does not guarantee the stability of economic equilibrium, but cooperativity is needed, too.

  6. DIAGNOSIS OF FINANCIAL EQUILIBRIUM

    Directory of Open Access Journals (Sweden)

    SUCIU GHEORGHE

    2013-04-01

    Full Text Available The analysis based on the balance sheet tries to identify the state of equilibrium (disequilibrium that exists in a company. The easiest way to determine the state of equilibrium is by looking at the balance sheet and at the information it offers. Because in the balance sheet there are elements that do not reflect their real value, the one established on the market, they must be readjusted, and those elements which are not related to the ordinary operating activities must be eliminated. The diagnosis of financial equilibrium takes into account 2 components: financing sources (ownership equity, loaned, temporarily attracted. An efficient financial equilibrium must respect 2 fundamental requirements: permanent sources represented by ownership equity and loans for more than 1 year should finance permanent needs, and temporary resources should finance the operating cycle.

  7. Experimental determination of thermodynamic equilibrium in biocatalytic transamination.

    Science.gov (United States)

    Tufvesson, Pär; Jensen, Jacob S; Kroutil, Wolfgang; Woodley, John M

    2012-08-01

    The equilibrium constant is a critical parameter for making rational design choices in biocatalytic transamination for the synthesis of chiral amines. However, very few reports are available in the scientific literature determining the equilibrium constant (K) for the transamination of ketones. Various methods for determining (or estimating) equilibrium have previously been suggested, both experimental as well as computational (based on group contribution methods). However, none of these were found suitable for determining the equilibrium constant for the transamination of ketones. Therefore, in this communication we suggest a simple experimental methodology which we hope will stimulate more accurate determination of thermodynamic equilibria when reporting the results of transaminase-catalyzed reactions in order to increase understanding of the relationship between substrate and product molecular structure on reaction thermodynamics. Copyright © 2012 Wiley Periodicals, Inc.

  8. The Fine Structure Constant

    Indian Academy of Sciences (India)

    IAS Admin

    The article discusses the importance of the fine structure constant in quantum mechanics, along with the brief history of how it emerged. Al- though Sommerfelds idea of elliptical orbits has been replaced by wave mechanics, the fine struc- ture constant he introduced has remained as an important parameter in the field of ...

  9. Equilibrium statistical mechanics

    CERN Document Server

    Mayer, J E

    1968-01-01

    The International Encyclopedia of Physical Chemistry and Chemical Physics, Volume 1: Equilibrium Statistical Mechanics covers the fundamental principles and the development of theoretical aspects of equilibrium statistical mechanics. Statistical mechanical is the study of the connection between the macroscopic behavior of bulk matter and the microscopic properties of its constituent atoms and molecules. This book contains eight chapters, and begins with a presentation of the master equation used for the calculation of the fundamental thermodynamic functions. The succeeding chapters highlight t

  10. Computing Equilibrium Chemical Compositions

    Science.gov (United States)

    Mcbride, Bonnie J.; Gordon, Sanford

    1995-01-01

    Chemical Equilibrium With Transport Properties, 1993 (CET93) computer program provides data on chemical-equilibrium compositions. Aids calculation of thermodynamic properties of chemical systems. Information essential in design and analysis of such equipment as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical-processing equipment. CET93/PC is version of CET93 specifically designed to run within 640K memory limit of MS-DOS operating system. CET93/PC written in FORTRAN.

  11. Investigation of Chemical Equilibrium Kinetics by the Electromigration Method

    CERN Document Server

    Bozhikov, G A; Bontchev, G D; Maslov, O D; Milanov, M V; Dmitriev, S N

    2002-01-01

    Measurement of the chemical reaction rates for complex formation as well as hydrolysis type reactions by the method of horizontal zone electrophoresis is outlined. The correlation between chemical equilibrium kinetics and electrodiffusion processes in a constant d.c. electric field is described. In model electromigration experiments the reaction rate constant of the complex formation of Hf(IV) and DTPA is determined.

  12. Methane Hydrate Formation and Dissociation in the Presence of Silica Sand and Bentonite Clay

    Directory of Open Access Journals (Sweden)

    Kumar Saw V.

    2015-11-01

    Full Text Available The formation and dissociation of methane hydrates in a porous media containing silica sand of different sizes and bentonite clay were studied in the presence of synthetic seawater with 3.55 wt% salinity. The phase equilibrium of methane hydrate under different experimental conditions was investigated. The effects of the particle size of silica sand as well as a mixture of bentonite clay and silica sand on methane hydrate formation and its dissociation were studied. The kinetics of hydrate formation was studied under different subcooling conditions to observe its effects on the induction time of hydrate formation. The amount of methane gas encapsulated in hydrate was computed using a real gas equation. The Clausius-Clapeyron equation is used to estimate the enthalpy of hydrate dissociation with measured phase equilibrium data.

  13. Association/dissociation in dense gases and adsorption/desorption on surfaces

    International Nuclear Information System (INIS)

    Flannery, M.R.

    1984-01-01

    A new comprehensive theory is described for the time evolution towards equilibrium of association and dissociation in a dense gas. Expressions are formulated and are illustrated for the net probabilities of association to stable vibrational levels and dissociation to the continuum from an arbitrary bound vibrational level via collision with the thermal gas bath. A general variational principle emerges: The rate which corresponds to the overall direction of the process always adjusts itself to a minimum and the time evolution towards equilibrium is hindered. Analogy is established with Kirchhoff's Laws and Tellegen's Theorem for electrical networks, and with the Principle of Least Dissipation basic to thermodynamics, heat conduction, and fluid mechanics. The theory can also be modified to provide the first basic microscopic account of Associative Desorption of atoms from and Dissociative Chemisorption of molecules to surfaces

  14. Visuomotor Dissociation in Cerebral Scaling of Size.

    Science.gov (United States)

    Potgieser, Adriaan R E; de Jong, Bauke M

    2016-01-01

    Estimating size and distance is crucial in effective visuomotor control. The concept of an internal coordinate system implies that visual and motor size parameters are scaled onto a common template. To dissociate perceptual and motor components in such scaling, we performed an fMRI experiment in which 16 right-handed subjects copied geometric figures while the result of drawing remained out of sight. Either the size of the example figure varied while maintaining a constant size of drawing (visual incongruity) or the size of the examples remained constant while subjects were instructed to make changes in size (motor incongruity). These incongruent were compared to congruent conditions. Statistical Parametric Mapping (SPM8) revealed brain activations related to size incongruity in the dorsolateral prefrontal and inferior parietal cortex, pre-SMA / anterior cingulate and anterior insula, dominant in the right hemisphere. This pattern represented simultaneous use of a 'resized' virtual template and actual picture information requiring spatial working memory, early-stage attention shifting and inhibitory control. Activations were strongest in motor incongruity while right pre-dorsal premotor activation specifically occurred in this condition. Visual incongruity additionally relied on a ventral visual pathway. Left ventral premotor activation occurred in all variably sized drawing while constant visuomotor size, compared to congruent size variation, uniquely activated the lateral occipital cortex additional to superior parietal regions. These results highlight size as a fundamental parameter in both general hand movement and movement guided by objects perceived in the context of surrounding 3D space.

  15. Visuomotor Dissociation in Cerebral Scaling of Size.

    Directory of Open Access Journals (Sweden)

    Adriaan R E Potgieser

    Full Text Available Estimating size and distance is crucial in effective visuomotor control. The concept of an internal coordinate system implies that visual and motor size parameters are scaled onto a common template. To dissociate perceptual and motor components in such scaling, we performed an fMRI experiment in which 16 right-handed subjects copied geometric figures while the result of drawing remained out of sight. Either the size of the example figure varied while maintaining a constant size of drawing (visual incongruity or the size of the examples remained constant while subjects were instructed to make changes in size (motor incongruity. These incongruent were compared to congruent conditions. Statistical Parametric Mapping (SPM8 revealed brain activations related to size incongruity in the dorsolateral prefrontal and inferior parietal cortex, pre-SMA / anterior cingulate and anterior insula, dominant in the right hemisphere. This pattern represented simultaneous use of a 'resized' virtual template and actual picture information requiring spatial working memory, early-stage attention shifting and inhibitory control. Activations were strongest in motor incongruity while right pre-dorsal premotor activation specifically occurred in this condition. Visual incongruity additionally relied on a ventral visual pathway. Left ventral premotor activation occurred in all variably sized drawing while constant visuomotor size, compared to congruent size variation, uniquely activated the lateral occipital cortex additional to superior parietal regions. These results highlight size as a fundamental parameter in both general hand movement and movement guided by objects perceived in the context of surrounding 3D space.

  16. Scaling studies of spheromak formation and equilibrium

    International Nuclear Information System (INIS)

    Geddes, C.G.; Kornack, T.W.; Brown, M.R.

    1998-01-01

    Formation and equilibrium studies have been performed on the Swarthmore Spheromak Experiment (SSX). Spheromaks are formed with a magnetized coaxial plasma gun and equilibrium is established in both small (d small =0.16 m) and large (d large =3d small =0.50 m) copper flux conservers. Using magnetic probe arrays it has been verified that spheromak formation is governed solely by gun physics (in particular the ratio of gun current to flux, μ 0 I gun /Φ gun ) and is independent of the flux conserver dimensions. It has also been verified that equilibrium is well described by the force free condition ∇xB=λB (λ=constant), particularly early in decay. Departures from the force-free state are due to current profile effects described by a quadratic function λ=λ(ψ). Force-free SSX spheromaks will be merged to study magnetic reconnection in simple magnetofluid structures. copyright 1998 American Institute of Physics

  17. Kinetics and mechanism of the dissociation of chlorophyll and its metalloanalogues in proton-donating media

    International Nuclear Information System (INIS)

    Berezin, B.D.; Drobysheva, A.N.; Karmanova, L.P.

    1976-01-01

    The kinetics of the dissociation of chlorophyll a and its metalloanalogues (Zn 2+ and Cd 2+ complexes of chlorophyllic acid) have been investigated in t-butyl alcohol-trichloracetic acid mixtures. The dissociation reaction is kinetically firts-order with respect to the complex. The rate constants and the activation energies and entropies for the dissociation reaction have been calculated. In order to determine the order of the reaction with respect to the protogenic species, a study was made of the ionisation of m-nitroaniline in t-butyl alcohol at 25 0 C in the trichloroacetic acid concentration range from 0.15 to 4.75 M. The dissociation reaction of chlorophyll and its zinc-containing metalloanalogue has been shown to be of second order with respect to the solvated proton. The cadmium complex dissociates by a second-order reaction with respect to trichloroacetic acid

  18. First-principles study of H2 adsorption and dissociation on Zr(0 0 0 1)

    International Nuclear Information System (INIS)

    Zhang Peng; Wang Shuangxi; Zhao Jian; He Chaohui; Zhang Ping

    2011-01-01

    Highlights: → The stability of the equilibrium adsorption states is determined after the geometry optimization. → The origin of the stable chemisorbed state is analyzed by the electronic structure and charge redistribution calculation. → The dissociation energetics of H2 are investigated in details by the PES and CINEB calculation. - Abstract: The adsorption and dissociation of H 2 molecules on the Zr(0 0 0 1) surface are systematically investigated by using density functional theory within the generalized gradient approximation and a supercell approach. After geometry optimization, the most stable equilibrium adsorption state is found to be along the top-y entrance. By calculating the adiabatic potential energy surface, the chemisorbed molecular adsorption states are also identified to be along the parallel channel at the top site. The electronic properties of the stable chemisorbed molecular state are analyzed, which show that the interaction between the molecule and substrate is of covalent characteristic with a sizeable charge redistribution. On the other hand, the hcp site is turned out to be the most stable equilibrium adsorption site for hydrogen atom on Zr(0 0 0 1) surface after the dissociation of H 2 . The dissociation energetics of H 2 are studied by calculating the potential energy surface and the minimum energy path of the transition state is determined by using the climb image nudged elastic band method, wherein the fcc-y channel is found to be most stable and favorable for dissociative adsorption of H 2 among the five possible dissociative paths. Remarkably, we find that the adiabatic dissociation process of H 2 is an activated type but with a small energy barrier, which is well consistent with the macroscopic phenomenon that the zirconium metal is easily hydrogenated.

  19. Cosmological constants and variations

    International Nuclear Information System (INIS)

    Barrow, John D

    2005-01-01

    We review properties of theories for the variation of the gravitation and fine structure 'constants'. We highlight some general features of the cosmological models that exist in these theories with reference to recent quasar data that is consistent with time-variation in the fine structure 'constant' since a redshift of 3.5. The behaviour of a simple class of varying alpha cosmologies is outlined in the light of all the observational constraints. We also discuss some of the consequences of varying 'constants' for oscillating universes and show by means of exact solutions that they appear to evolve monotonically in time even though the scale factor of the universe oscillates

  20. The cosmological constant problem

    International Nuclear Information System (INIS)

    Dolgov, A.D.

    1989-05-01

    A review of the cosmological term problem is presented. Baby universe model and the compensating field model are discussed. The importance of more accurate data on the Hubble constant and the Universe age is stressed. 18 refs

  1. Immunity by equilibrium.

    Science.gov (United States)

    Eberl, Gérard

    2016-08-01

    The classical model of immunity posits that the immune system reacts to pathogens and injury and restores homeostasis. Indeed, a century of research has uncovered the means and mechanisms by which the immune system recognizes danger and regulates its own activity. However, this classical model does not fully explain complex phenomena, such as tolerance, allergy, the increased prevalence of inflammatory pathologies in industrialized nations and immunity to multiple infections. In this Essay, I propose a model of immunity that is based on equilibrium, in which the healthy immune system is always active and in a state of dynamic equilibrium between antagonistic types of response. This equilibrium is regulated both by the internal milieu and by the microbial environment. As a result, alteration of the internal milieu or microbial environment leads to immune disequilibrium, which determines tolerance, protective immunity and inflammatory pathology.

  2. [Dissociative identity disorder or schizophrenia?].

    Science.gov (United States)

    Tschöke, S; Steinert, T

    2010-01-01

    We present a case of dissociative identity disorder in which Schneiderian first rank symptoms were present besides of various states of consciousness. Thus the diagnosis of schizophrenia had to be considered. Formally, the symptoms met ICD-10 criteria for schizophrenia. However, taking into account the lack of formal thought disorder and of negative symptoms as well as a typical history of severe and prolonged traumatisation, we did not diagnose a co-morbid schizophrenic disorder. There is good evidence for the existence of psychotic symptoms among patients with dissociative disorders. However, in clinical practice this differential diagnosis is rarely considered.

  3. Diffraction dissociation at the LHC

    Energy Technology Data Exchange (ETDEWEB)

    Jenkovszky, Laszlo [Bogolyubov Institute for Theoretical Physics (BITP), Ukrainian National Academy of Sciences 14-b, Metrolohichna str., Kiev, 03680, Ukraine and Wigner Research Centre for Physics, Hungarian Academy of Sciences 1525 Budapest, POB 49 (Hungary); Orava, Risto [Institute of Physics, Division of Elementary Particle Physics, P.O. Box 64 (Gustaf Haellstroeminkatu 2a), FI-00014 University of Helsinki, Finland and CERN, CH-1211 Geneva 23 (Switzerland); Salii, Andrii [Bogolyubov Institute for Theoretical Physics (BITP), Ukrainian National Academy of Sciences 14-b, Metrolohichna str., Kiev, 03680 (Ukraine)

    2013-04-15

    We report on recent calculations of low missing mass single (SD) and double (DD) diffractive dissociation at LHC energies. The calculations are based on a dual-Regge model, dominated by a single Pomeron exchange. The diffractively excited states lie on the nucleon trajectory N*, appended by the isolated Roper resonance. Detailed predictions for the squared momentum transfer and missing mass dependence of the differential and integrated single-and double diffraction dissociation in the kinematical range of present and future LHC measurements are given.

  4. Diffraction dissociation at the LHC

    International Nuclear Information System (INIS)

    Jenkovszky, László; Orava, Risto; Salii, Andrii

    2013-01-01

    We report on recent calculations of low missing mass single (SD) and double (DD) diffractive dissociation at LHC energies. The calculations are based on a dual-Regge model, dominated by a single Pomeron exchange. The diffractively excited states lie on the nucleon trajectory N*, appended by the isolated Roper resonance. Detailed predictions for the squared momentum transfer and missing mass dependence of the differential and integrated single-and double diffraction dissociation in the kinematical range of present and future LHC measurements are given.

  5. Equilibrium shoreface profiles

    DEFF Research Database (Denmark)

    Aagaard, Troels; Hughes, Michael G

    2017-01-01

    Large-scale coastal behaviour models use the shoreface profile of equilibrium as a fundamental morphological unit that is translated in space to simulate coastal response to, for example, sea level oscillations and variability in sediment supply. Despite a longstanding focus on the shoreface...... profile and its relevance to predicting coastal response to changing environmental conditions, the processes and dynamics involved in shoreface equilibrium are still not fully understood. Here, we apply a process-based empirical sediment transport model, combined with morphodynamic principles to provide......; there is no tuning or calibration and computation times are short. It is therefore easily implemented with repeated iterations to manage uncertainty....

  6. Dissociative symptoms and dissociative disorders comorbidity in obsessive compulsive disorder: Symptom screening, diagnostic tools and reflections on treatment

    OpenAIRE

    Belli, Hasan

    2014-01-01

    Borderline personality disorder, conversion disorder and obsessive compulsive disorder frequently have dissociative symptoms. The literature has demonstrated that the level of dissociation might be correlated with the severity of obsessive compulsive disorder (OCD) and that those not responding to treatment had high dissociative symptoms. The structured clinical interview for DSM-IV dissociative disorders, dissociation questionnaire, somatoform dissociation questionnaire and dissociative expe...

  7. Dissociative symptoms and neuroendocrine dysregulation in depression.

    Science.gov (United States)

    Bob, Petr; Fedor-Freybergh, Peter; Jasova, Denisa; Bizik, Gustav; Susta, Marek; Pavlat, Josef; Zima, Tomas; Benakova, Hana; Raboch, Jiri

    2008-10-01

    Dissociative symptoms are traditionally attributed to psychological stressors that produce dissociated memories related to stressful life events. Dissociative disorders and dissociative symptoms including psychogenic amnesia, fugue, dissociative identity-disorder, depersonalization, derealization and other symptoms or syndromes have been reported as an epidemic psychiatric condition that may be coexistent with various psychiatric diagnoses such as depression, schizophrenia, borderline personality disorder or anxiety disorders. According to recent findings also the somatic components of dissociation may occur and influence brain, autonomic and neuroendocrine functions. At this time there are only few studies examining neuroendocrine response related to dissociative symptoms that suggest significant dysregulation of the hypothalamus-pituitary-adrenal (HPA) axis. The aim of the present study is to perform examination of HPA axis functioning indexed by basal cortisol and prolactin and test their relationship to psychic and somatoform dissociative symptoms. Basal cortisol and prolactin and psychic and somatoform dissociative symptoms were assessed in 40 consecutive inpatients with diagnosis of unipolar depression mean age 43.37 (SD=12.21). The results show that prolactin and cortisol as indices of HPA axis functioning manifest significant relationship to dissociative symptoms. Main results represent highly significant correlations obtained by simple regression between psychic dissociative symptoms (DES) and serum prolactin (R=0.55, p=0.00027), and between somatoform dissociation (SDQ-20) and serum cortisol (R=-0.38, p=0.015). These results indicate relationship between HPA-axis reactivity and dissociative symptoms in unipolar depressive patients that could reflect passive coping behavior and disengagement.

  8. Determination of protonation constants of hydroquinone and stability constants of Th(IV) hydroquinone complex

    International Nuclear Information System (INIS)

    Sawant, R.M.; Ramakumar, K.L.; Sharma, R.S.

    2003-01-01

    Protonation constants of hydroquinone and stability constants of thorium hydroquinone complexes were determined in 1 M NaClO 4 medium at 25 ± 0.5 degC, by varying concentration of thorium, using pH titration technique. Protonation constants of hydroquinone (β 1H = [HQ]/[H][Q] and β 2H = [H 2 Q]/[H] 2 [Q]) were found to be β 1H = 11.404 ± 0.014 and β 2H = 21.402 ± 0.012. The analysis of titration data of thorium-hydroquinone system appears to indicate the formation of species Th(H 2 Q) 3 (OH) and Th(H 2 O) 4 (OH). Equilibrium constants obtained for these species are -log β 13-I = 48.51 ± 0.67 and -log β 14-1 64.86 ± 1.25 respectively which are not reported in the literature. (author)

  9. Microeconomics : Equilibrium and Efficiency

    NARCIS (Netherlands)

    Ten Raa, T.

    2013-01-01

    Microeconomics: Equilibrium and Efficiency teaches how to apply microeconomic theory in an innovative, intuitive and concise way. Using real-world, empirical examples, this book not only covers the building blocks of the subject, but helps gain a broad understanding of microeconomic theory and

  10. Differential Equation of Equilibrium

    African Journals Online (AJOL)

    user

    ABSTRACT. Analysis of underground circular cylindrical shell is carried out in this work. The forth order differential equation of equilibrium, comparable to that of beam on elastic foundation, was derived from static principles on the assumptions of P. L Pasternak. Laplace transformation was used to solve the governing ...

  11. Comments on equilibrium, transient equilibrium, and secular equilibrium in serial radioactive decay

    International Nuclear Information System (INIS)

    Prince, J.R.

    1979-01-01

    Equations describing serial radioactive decay are reviewed along with published descriptions or transient and secular equilibrium. It is shown that terms describing equilibrium are not used in the same way by various authors. Specific definitions are proposed; they suggest that secular equilibrium is a subset of transient equilibrium

  12. Radiographic constant exposure technique

    DEFF Research Database (Denmark)

    Domanus, Joseph Czeslaw

    1985-01-01

    The constant exposure technique has been applied to assess various industrial radiographic systems. Different X-ray films and radiographic papers of two producers were compared. Special attention was given to fast film and paper used with fluorometallic screens. Radiographic image quality...... was tested by the use of ISO wire IQI's and ASTM penetrameters used on Al and Fe test plates. Relative speed and reduction of kilovoltage obtained with the constant exposure technique were calculated. The advantages of fast radiographic systems are pointed out...

  13. DISSOCIATIVE DISORDERS IN DSM-5

    NARCIS (Netherlands)

    Spiegel, David; Loewenstein, Richard J.; Lewis-Fernandez, Roberto; Sar, Vedat; Simeon, Daphne; Vermetten, Eric; Cardena, Etzel; Dell, Paul F.

    Background: We present recommendations for revision of the diagnostic criteria for the Dissociative Disorders (DDs) for DSM-5. The periodic revision of the DSM provides an opportunity to revisit the assumptions underlying specific diagnoses and the empirical support, or lack of it, for the defining

  14. Hydrogen dissociation on metal surfaces

    NARCIS (Netherlands)

    Wijzenbroek, M.

    2016-01-01

    Dissociative chemisorption is an important reaction step in many catalytic reactions. An example of such a reaction is the Haber-Bosch process, which is used commercially to produce ammonia, an important starting material in the production of fertilisers. In theoretical descriptions of such chemical

  15. Energy localization and molecular dissociation

    International Nuclear Information System (INIS)

    Takeno, S.; Tsironis, G.P.

    2005-01-01

    We study analytically as well as numerically the role that large-amplitude vibrations play during the process of molecular dissociation. Our model consists of a linear three-atom molecule composed of identical atoms interacting with their nearest neighbors by Morse potentials. We find a close relation between energy localization and bond breaking and evaluate numerically the corresponding reaction paths

  16. Development of a collision induced dissociation ion cyclotron resonance spectrometer

    International Nuclear Information System (INIS)

    Fan, Y.N.

    1982-01-01

    A transient analysis ion cyclotron resonance spectrometer is developed to investigate the phenomena of collision induced dissociation. The Fourier transform method and the modified maximum entropy spectral analysis or covariance least square method are implemented in measuring the mass spectrum of the ion ensemble. The Fourier transform method can be used in quantitative analysis while the maximum entropy method as developed here is useful for qualitative analysis only. The cyclotron resonance frequency, relaxation time constant, and the relative ion population are observable from the Fourier transform spectrum. These parameters are very important in investigating collision induced dissociation process and other topics in gas phase chemistry. The ion cyclotron resonance spectrometer is not only developed to study fragments and their abundance from a parent ion, but also to determine the threshold energy and reaction cross section in the collision induced dissociation process. When hard sphere model is used in the ion-molecule collision, the radius of acetone ion measured from the reactive cross section is 2.2 angstrom which is very close to the physical dimension of acetone. The threshold energy for acetone ion in collision induced dissociation process is 1.8 eV which is similar to the result obtained by the angle-resolved mass spectrometer

  17. Equilibrium isotope exchange kinetics of native and site-specific mutant forms of E. coli aspartate transcarbamoylase

    International Nuclear Information System (INIS)

    Wedler, F.C.; Hsuanyu, Y.; Kantrowitz, E.R.

    1987-01-01

    Isotope exchange kinetics at equilibrium (EIEK) have been used to probe the kinetic and regulatory mechanisms of native aspartate transcarbamoylase (ATCase) from E. coli at pH 7.0, 30 0 . Substrate saturation patterns were most consistent with a preferred order random kinetic mechanism: C-P prior to L-Asp, C-Asp released before Pi, with the Asp ↔ C-Asp exchange rate 5X faster than C-P ↔ Pi. Computer simulations allow one to fit the EIEK experimental data and to arrive at the best set of kinetic constants for a given enzyme state. These approaches have been applied to modified ATCase. Bound CTP and ATP were observed, respectively, to inhibit and activate differentially Asp ↔ C-Asp, but not C-P ↔ Pi, indicating that these modifiers alter the association-dissociation rates of L-Asp and C-Asp but not of C-P or Pi. Low levels of PALA activated both exchange rates (due to shifting the T-R equilibrium), but higher [PALA] completely blocked both exchanges. The effects of a site-specific mutation of Tyr240 Phe have been similarly probed by EIEK methods. The Phe240 mutant enzyme exhibited kinetic properties markedly different from native ATCase: the data indicate that Phe240 ATCase is much closer to an R-state enzyme than is native enzyme

  18. Kinetic and equilibrium studies of acrylonitrile binding to cytochrome c peroxidase and oxidation of acrylonitrile by cytochrome c peroxidase compound I.

    Science.gov (United States)

    Chinchilla, Diana; Kilheeney, Heather; Vitello, Lidia B; Erman, James E

    2014-01-03

    Ferric heme proteins bind weakly basic ligands and the binding affinity is often pH dependent due to protonation of the ligand as well as the protein. In an effort to find a small, neutral ligand without significant acid/base properties to probe ligand binding reactions in ferric heme proteins we were led to consider the organonitriles. Although organonitriles are known to bind to transition metals, we have been unable to find any prior studies of nitrile binding to heme proteins. In this communication we report on the equilibrium and kinetic properties of acrylonitrile binding to cytochrome c peroxidase (CcP) as well as the oxidation of acrylonitrile by CcP compound I. Acrylonitrile binding to CcP is independent of pH between pH 4 and 8. The association and dissociation rate constants are 0.32±0.16 M(-1) s(-1) and 0.34±0.15 s(-1), respectively, and the independently measured equilibrium dissociation constant for the complex is 1.1±0.2 M. We have demonstrated for the first time that acrylonitrile can bind to a ferric heme protein. The binding mechanism appears to be a simple, one-step association of the ligand with the heme iron. We have also demonstrated that CcP can catalyze the oxidation of acrylonitrile, most likely to 2-cyanoethylene oxide in a "peroxygenase"-type reaction, with rates that are similar to rat liver microsomal cytochrome P450-catalyzed oxidation of acrylonitrile in the monooxygenase reaction. CcP compound I oxidizes acrylonitrile with a maximum turnover number of 0.61 min(-1) at pH 6.0. Copyright © 2013 Elsevier Inc. All rights reserved.

  19. Global functioning and disability in dissociative disorders.

    Science.gov (United States)

    Mueller-Pfeiffer, Christoph; Rufibach, Kaspar; Perron, Noelle; Wyss, Daniela; Kuenzler, Cornelia; Prezewowsky, Cornelia; Pitman, Roger K; Rufer, Michael

    2012-12-30

    Dissociative disorders are frequent comorbid conditions of other mental disorders. Yet, there is controversy about their clinical relevance, and little systematic research has been done on how they influence global functioning. Outpatients and day care patients (N=160) of several psychiatric units in Switzerland were assessed with the Structured Clinical Interview for Diagnostic and Statistical Manual of Mental Disorders (DSM)-IV Axis I Disorders, Structured Clinical Interview for DSM-IV Dissociative Disorders, Global Assessment of Functioning Scale, and World Health Organization Disability Assessment Schedule-II. The association between subjects with a dissociative disorder (N=30) and functional impairment after accounting for non-dissociative axis I disorders was evaluated by linear regression models. We found a proportion of 18.8% dissociative disorders (dissociative amnesia=0%, dissociative fugue=0.6%, depersonalization disorder=4.4%, dissociative identity disorder=7.5%, dissociative disorder-not-otherwise-specified=6.3%) across treatment settings. Adjusted for other axis I disorders, subjects with a comorbid dissociative identity disorder or dissociative disorder-not-otherwise-specified had a median global assessment of functioning score that was 0.86 and 0.88 times, respectively, the score of subjects without a comorbid dissociative disorder. These findings support the hypothesis that complex dissociative disorders, i.e., dissociative identity disorder and dissociative disorder-not-otherwise-specified, contribute to functional impairment above and beyond the impact of co-existing non-dissociative axis I disorders, and that they qualify as "serious mental illness". Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

  20. On the cosmical constant

    International Nuclear Information System (INIS)

    Chandra, R.

    1977-01-01

    On the grounds of the two correspondence limits, the Newtonian limit and the special theory limit of Einstein field equations, a modification of the cosmical constant has been proposed which gives realistic results in the case of a homogeneous universe. Also, according to this modification an explanation for the negative pressure in the steady-state model of the universe has been given. (author)

  1. Cosmological constant problem

    International Nuclear Information System (INIS)

    Weinberg, S.

    1989-01-01

    Cosmological constant problem is discussed. History of the problem is briefly considered. Five different approaches to solution of the problem are described: supersymmetry, supergravity, superstring; anthropic approach; mechamism of lagrangian alignment; modification of gravitation theory and quantum cosmology. It is noted that approach, based on quantum cosmology is the most promising one

  2. The Yamabe constant

    International Nuclear Information System (INIS)

    O Murchadha, N.

    1991-01-01

    The set of riemannian three-metrics with positive Yamabe constant defines the space of independent data for the gravitational field. The boundary of this set is investigated, and it is shown that metrics close to the boundary satisfy the positive-energy theorem. (Author) 18 refs

  3. Dissociative Functions in the Normal Mourning Process.

    Science.gov (United States)

    Kauffman, Jeffrey

    1994-01-01

    Sees dissociative functions in mourning process as occurring in conjunction with integrative trends. Considers initial shock reaction in mourning as model of normal dissociation in mourning process. Dissociation is understood to be related to traumatic significance of death in human consciousness. Discerns four psychological categories of…

  4. Correlations in the hadronic double diffractive dissociation

    International Nuclear Information System (INIS)

    Goldegol, Alexandre.

    1991-05-01

    A given reaction of double diffractive dissociation is studied based on the three-component Deck Model. The correlations among the diffractive slope, the effective mass of the dissociated particle sub-system and the dissociation angle in the Gottfried-Jackson are studied based in this model. 9 refs, 19 figs

  5. Rate constant and thermochemistry for K + O2 + N2 = KO2 + N2

    DEFF Research Database (Denmark)

    Sorvajärvi, Tapio; Viljanen, Jan; Toivonen, Juha

    2015-01-01

    in the form of double exponential decays of [K], which yielded both kR1 and the equilibrium constant for KO2 formation. kR1 can be summarized as 1.07 × 10-30(T/1000 K)-0.733 cm6 molecule-2 s-1. Combination with literature values leads to a recommended kR1 of 5.5 × 10-26T-1.55 exp(-10/T) cm6 molecule-2 s-1...... over 250-1320 K, with an error limit of a factor of 1.5. A vant Hoff analysis constrained to fit the computed ΔS298 yields a K-O2 bond dissociation enthalpy of 184.2 ± 4.0 kJ mol-1 at 298 K and ΔfH298(KO2) = -95.2 ± 4.1 kJ mol-1. The corresponding D0 is 181.5 ± 4.0 kJ mol-1. This value compares well...

  6. Analysing chemical equilibrium conditions when studying butyl acetate synthesis

    OpenAIRE

    Álvaro Orjuela Londoño; Fernando Leiva Lenis; Luis Alejandro Boyacá Mendivelso; Gerardo Rodríguez Niño; Luis María Carballo Suárez

    2010-01-01

    This work studied the liquid phase of acetic acid and butyl alcohol esterification reaction (P atm = 560 mmHg),using an ion exchange resin (Lewatit K-2431) as catalyst. A set of assays were carried out for determining the effect of catalyst load, temperature and molar ratio (acid/alcohol) on chemical equilibrium constant. Components’ selective sorption on the resin matrix was noticed; its effect on equilibrium conditions was verified, by using different acid/alcohol starting ratios. A non-ide...

  7. Thermodynamics of ion exchange equilibrium for some uni ...

    African Journals Online (AJOL)

    The study on thermodynamics of ion exchange equilibrium for uni-univalent Cl-/I-, Cl-/Br-, and uni-divalent Cl-/SO42-, Cl-/C2O42- reaction systems was carried out using ion exchange resin Indion FF-IP. The equilibrium constant K was calculated by taking into account the activity coefficient of ions both in solution as well as ...

  8. Equilibrium and pre-equilibrium emissions in proton-induced ...

    Indian Academy of Sciences (India)

    necessary for the domain of fission-reactor technology for the calculation of nuclear transmutation ... tions occur in three stages: INC, pre-equilibrium and equilibrium (or compound. 344. Pramana ... In the evaporation phase of the reaction, the.

  9. Phase equilibrium modeling of gas hydrate systems for CO2 capture

    DEFF Research Database (Denmark)

    Herslund, Peter Jørgensen; Thomsen, Kaj; Abildskov, Jens

    2012-01-01

    to form from vapor phases with initial mole fractions of CO2 at or above 0.15.The two models are validated against mixed hydrate equilibrium data found in literature. Both dissociation pressures and hydrate compositions are considered in the validation process.With the fitted parameters, Model I predicts...

  10. Gated equilibrium bloodpool scintigraphy

    International Nuclear Information System (INIS)

    Reinders Folmer, S.C.C.

    1981-01-01

    This thesis deals with the clinical applications of gated equilibrium bloodpool scintigraphy, performed with either a gamma camera or a portable detector system, the nuclear stethoscope. The main goal has been to define the value and limitations of noninvasive measurements of left ventricular ejection fraction as a parameter of cardiac performance in various disease states, both for diagnostic purposes as well as during follow-up after medical or surgical intervention. Secondly, it was attempted to extend the use of the equilibrium bloodpool techniques beyond the calculation of ejection fraction alone by considering the feasibility to determine ventricular volumes and by including the possibility of quantifying valvular regurgitation. In both cases, it has been tried to broaden the perspective of the observations by comparing them with results of other, invasive and non-invasive, procedures, in particular cardiac catheterization, M-mode echocardiography and myocardial perfusion scintigraphy. (Auth.)

  11. Problems in equilibrium theory

    CERN Document Server

    Aliprantis, Charalambos D

    1996-01-01

    In studying General Equilibrium Theory the student must master first the theory and then apply it to solve problems. At the graduate level there is no book devoted exclusively to teaching problem solving. This book teaches for the first time the basic methods of proof and problem solving in General Equilibrium Theory. The problems cover the entire spectrum of difficulty; some are routine, some require a good grasp of the material involved, and some are exceptionally challenging. The book presents complete solutions to two hundred problems. In searching for the basic required techniques, the student will find a wealth of new material incorporated into the solutions. The student is challenged to produce solutions which are different from the ones presented in the book.

  12. Equilibrium statistical mechanics

    CERN Document Server

    Jackson, E Atlee

    2000-01-01

    Ideal as an elementary introduction to equilibrium statistical mechanics, this volume covers both classical and quantum methodology for open and closed systems. Introductory chapters familiarize readers with probability and microscopic models of systems, while additional chapters describe the general derivation of the fundamental statistical mechanics relationships. The final chapter contains 16 sections, each dealing with a different application, ordered according to complexity, from classical through degenerate quantum statistical mechanics. Key features include an elementary introduction t

  13. Volatility in Equilibrium

    DEFF Research Database (Denmark)

    Bollerslev, Tim; Sizova, Natalia; Tauchen, George

    Stock market volatility clusters in time, carries a risk premium, is fractionally inte- grated, and exhibits asymmetric leverage effects relative to returns. This paper develops a first internally consistent equilibrium based explanation for these longstanding empirical facts. The model is cast i......, and the dynamic cross-correlations of the volatility measures with the returns calculated from actual high-frequency intra-day data on the S&P 500 aggregate market and VIX volatility indexes....

  14. Molecular equilibrium with condensation

    International Nuclear Information System (INIS)

    Sharp, C.M.; Huebner, W.F.

    1990-01-01

    Minimization of the Gibbs energy of formation for species of chemical elements and compounds in their gas and condensed phases determines their relative abundances in a mixture in chemical equilibrium. The procedure is more general and more powerful than previous abundance determinations in multiphase astrophysical mixtures. Some results for astrophysical equations of state are presented, and the effects of condensation on opacity are briefly indicated. 18 refs

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

    Science.gov (United States)

    1976-01-01

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

  16. Production in constant evolution

    International Nuclear Information System (INIS)

    Lozano, T.

    2009-01-01

    The Cofrentes Nuclear Power Plant now has 25 years of operation behind it: a quarter century adding value and demonstrating the reasons why it is one of the most important energy producing facilities in the Spanish power market. Particularly noteworthy is the enterprising spirit of the plant, which has strived to continuously improve with the large number of modernization projects that it has undertaken over the past 25 years. The plant has constantly evolved thanks to the amount of investments made to improve safety and reliability and the perseverance to stay technologically up to date. Efficiency, training and teamwork have been key to the success of the plant over these 25 years of constant change and progress. (Author)

  17. Stabilized power constant alimentation

    International Nuclear Information System (INIS)

    Roussel, L.

    1968-06-01

    The study and realization of a stabilized power alimentation variable from 5 to 100 watts are described. In order to realize a constant power drift of Lithium compensated diodes, we have searched a 1 per cent precision of regulation and a response time minus than 1 sec. Recent components like Hall multiplicator and integrated amplifiers give this possibility and it is easy to use permutable circuits. (author) [fr

  18. Universe of constant

    Science.gov (United States)

    Yongquan, Han

    2016-10-01

    The ideal gas state equation is not applicable to ordinary gas, it should be applied to the Electromagnetic ``gas'' that is applied to the radiation, the radiation should be the ultimate state of matter changes or initial state, the universe is filled with radiation. That is, the ideal gas equation of state is suitable for the Singular point and the universe. Maybe someone consider that, there is no vessel can accommodate radiation, it is because the Ordinary container is too small to accommodate, if the radius of your container is the distance that Light through an hour, would you still think it can't accommodates radiation? Modern scientific determinate that the radius of the universe now is about 1027 m, assuming that the universe is a sphere whose volume is approximately: V = 4.19 × 1081 cubic meters, the temperature radiation of the universe (cosmic microwave background radiation temperature of the universe, should be the closest the average temperature of the universe) T = 3.15k, radiation pressure P = 5 × 10-6 N / m 2, according to the law of ideal gas state equation, PV / T = constant = 6 × 1075, the value of this constant is the universe, The singular point should also equal to the constant Author: hanyongquan

  19. Connecting Fundamental Constants

    International Nuclear Information System (INIS)

    Di Mario, D.

    2008-01-01

    A model for a black hole electron is built from three basic constants only: h, c and G. The result is a description of the electron with its mass and charge. The nature of this black hole seems to fit the properties of the Planck particle and new relationships among basic constants are possible. The time dilation factor in a black hole associated with a variable gravitational field would appear to us as a charge; on the other hand the Planck time is acting as a time gap drastically limiting what we are able to measure and its dimension will appear in some quantities. This is why the Planck time is numerically very close to the gravitational/electric force ratio in an electron: its difference, disregarding a π√(2) factor, is only 0.2%. This is not a coincidence, it is always the same particle and the small difference is between a rotating and a non-rotating particle. The determination of its rotational speed yields accurate numbers for many quantities, including the fine structure constant and the electron magnetic moment

  20. Equilibrium thermodynamics in modified gravitational theories

    International Nuclear Information System (INIS)

    Bamba, Kazuharu; Geng, C.-Q.; Tsujikawa, Shinji

    2010-01-01

    We show that it is possible to obtain a picture of equilibrium thermodynamics on the apparent horizon in the expanding cosmological background for a wide class of modified gravity theories with the Lagrangian density f(R,φ,X), where R is the Ricci scalar and X is the kinetic energy of a scalar field φ. This comes from a suitable definition of an energy-momentum tensor of the 'dark' component that respects to a local energy conservation in the Jordan frame. In this framework the horizon entropy S corresponding to equilibrium thermodynamics is equal to a quarter of the horizon area A in units of gravitational constant G, as in Einstein gravity. For a flat cosmological background with a decreasing Hubble parameter, S globally increases with time, as it happens for viable f(R) inflation and dark energy models. We also show that the equilibrium description in terms of the horizon entropy S is convenient because it takes into account the contribution of both the horizon entropy S in non-equilibrium thermodynamics and an entropy production term.

  1. Can elliptical galaxies be equilibrium systems

    Energy Technology Data Exchange (ETDEWEB)

    Caimmi, R [Padua Univ. (Italy). Ist. di Astronomia

    1980-08-01

    This paper deals with the question of whether elliptical galaxies can be considered as equilibrium systems (i.e., the gravitational + centrifugal potential is constant on the external surface). We find that equilibrium models such as Emden-Chandrasekhar polytropes and Roche polytropes with n = 0 can account for the main part of observations relative to the ratio of maximum rotational velocity to central velocity dispersion in elliptical systems. More complex models involving, for example, massive halos could lead to a more complete agreement. Models that are a good fit to the observed data are characterized by an inner component (where most of the mass is concentrated) and a low-density outer component. A comparison is performed between some theoretical density distributions and the density distribution observed by Young et al. (1978) in NGC 4473, but a number of limitations must be adopted. Alternative models, such as triaxial oblate non-equilibrium configurations with coaxial shells, involve a number of problems which are briefly discussed. We conclude that spheroidal oblate models describing elliptical galaxies cannot be ruled out until new analyses relative to more refined theoretical equilibrium models (involving, for example, massive halos) and more detailed observations are performed.

  2. Apparent formation constants of Pu(IV) and Th(IV) with humic acids determined by solvent extraction method

    Energy Technology Data Exchange (ETDEWEB)

    Sasaki, T.; Aoyama, S.; Yoshida, H.; Kobayashi, T.; Takagi, I. [Tokyo Univ. (Japan). Dept. of Nuclear Engineering; Kulyako, Y.; Samsonov, M.; Miyasoedov, B. [Russian Academy of Sciences, Moscow (Russian Federation). V. I. Vernadsky Institute of Geochemistry and Analytical Chemistry (GEOKHI); Moriyama, H. [Kyoto Univ. (Japan). Research Reactor Inst.

    2012-07-01

    Apparent formation constants of Pu(IV) and Th(IV) with two kinds of humic acids were determined in 0.1 M NaClO{sub 4} at 25 C using a solvent extraction method with thenoyltrifluoroacetone in xylene. The acid dissociation constants of humic acids were also measured by potentiometric titration and used as the degree of dissociation for calculating the formation constants. The effect of solution conditions, such as the pH, the initial metal and humic acid concentrations, and the ionic strength, on the formation constants was examined. The obtained data were compared with the ones in the literature. (orig.)

  3. Noncompact Equilibrium Points and Applications

    Directory of Open Access Journals (Sweden)

    Zahra Al-Rumaih

    2012-01-01

    Full Text Available We prove an equilibrium existence result for vector functions defined on noncompact domain and we give some applications in optimization and Nash equilibrium in noncooperative game.

  4. 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

  5. MHD equilibrium with toroidal rotation

    International Nuclear Information System (INIS)

    Li, J.

    1987-03-01

    The present work attempts to formulate the equilibrium of axisymmetric plasma with purely toroidal flow within ideal MHD theory. In general, the inertial term Rho(v.Del)v caused by plasma flow is so complicated that the equilibrium equation is completely different from the Grad-Shafranov equation. However, in the case of purely toroidal flow the equilibrium equation can be simplified so that it resembles the Grad-Shafranov equation. Generally one arbitrary two-variable functions and two arbitrary single variable functions, instead of only four single-variable functions, are allowed in the new equilibrium equations. Also, the boundary conditions of the rotating (with purely toroidal fluid flow, static - without any fluid flow) equilibrium are the same as those of the static equilibrium. So numerically one can calculate the rotating equilibrium as a static equilibrium. (author)

  6. Multiphoton dissociation and thermal unimolecular reactions induced by infrared lasers

    International Nuclear Information System (INIS)

    Dai, H.L.

    1981-04-01

    Multiphoton dissociation (MPD) of ethyl chloride was studied using a tunable 3.3 μm laser to excite CH stretches. The absorbed energy increases almost linearly with fluence, while for 10 μm excitation there is substantial saturation. Much higher dissociation yields were observed for 3.3 μm excitation than for 10 μm excitation, reflecting bottlenecking in the discrete region of 10 μm excitation. The resonant nature of the excitation allows the rate equations description for transitions in the quasicontinuum and continuum to be extended to the discrete levels. Absorption cross sections are estimated from ordinary ir spectra. A set of cross sections which is constant or slowly decreasing with increasing vibrational excitation gives good fits to both absorption and dissociation yield data. The rate equations model was also used to quantitatively calculate the pressure dependence of the MPD yield of SF 6 caused by vibrational self-quenching. Between 1000-3000 cm -1 of energy is removed from SF 6 excited to approx. > 60 kcal/mole by collision with a cold SF 6 molecule at gas kinetic rate. Calculation showed the fluence dependence of dissociation varies strongly with the gas pressure. Infrared multiphoton excitation was applied to study thermal unimolecular reactions. With SiF 4 as absorbing gas for the CO 2 laser pulse, transient high temperature pulses were generated in a gas mixture. IR fluorescence from the medium reflected the decay of the temperature. The activation energy and the preexponential factor of the reactant dissociation were obtained from a phenomenological model calculation. Results are presented in detail

  7. Radiative capture versus Coulomb dissociation

    International Nuclear Information System (INIS)

    Esbensen, H.; Physics

    2006-01-01

    Measurements of the Coulomb dissociation of 8 B have been used to infer the rate of the inverse radiative proton capture on 7 Be. The analysis is usually based on the assumptions that the two processes are related by detailed balance and described by E1 transitions. However, there are corrections to this relation. The Coulomb form factors for the two processes, for example, are not identical. There are also E2 transitions and higher-order effects in the Coulomb dissociation, and the nuclear induced breakup cannot always be ignored. While adding first-order E2 transitions enhances the decay energy spectrum, the other mechanisms cause a suppression at low relative energies. The net result may accidentally be close to the conventional first-order E1 calculation, but there are differences which cannot be ignored if accuracies of 10% or better are needed

  8. Radiative Capture versus Coulomb Dissociation

    International Nuclear Information System (INIS)

    Esbensen, Henning

    2006-01-01

    Measurements of the Coulomb dissociation of 8B have been used to infer the rate of the inverse radiative proton capture on 7Be. The analysis is usually based on the assumptions that the two processes are related by detailed balance and described by E1 transitions. However, there are corrections to this relation. The Coulomb form factors for the two processes, for example, are not identical. There are also E2 transitions and higher-order effects in the Coulomb dissociation, and the nuclear induced breakup cannot always be ignored. While adding first-order E2 transitions enhances the decay energy spectrum, the other mechanisms cause a suppression at low relative energies. The net result may accidentally be close to the conventional first-order E1 calculation, but there are differences which cannot be ignored if accuracies of 10% or better are needed

  9. Non-equilibrium plasma chemistry at high pressure and its applications

    International Nuclear Information System (INIS)

    Bai Xiyao; Zhang Zhitao; Bai Mindong; Zhu Qiaoying

    2000-01-01

    A review is presented of research and development of gas discharge and non-equilibrium plasma including, new ideas of non-equilibrium plasma at high gas pressure. With special technology, strong electric fields (>400 Td) can be achieved by which electrons are accelerated suddenly, becoming high energy electrons (> 10 eV) at high pressure. On impact with the electrons, the gas molecules dissociate into ions, atomic ions, atoms and free radicals, and new substances or molecules can be synthesized through custom design. Chemical reaction difficult to achieve by conventional method can be realized or accelerated. Non-equilibrium plasma chemistry at high pressure has wide application prospects

  10. Dissociation heat of mixed-gas hydrate composed of methane and ethane

    Energy Technology Data Exchange (ETDEWEB)

    Hachikubo, A.; Nakagawa, R.; Kubota, D.; Sakagami, H.; Takahashi, N.; Shoji, H. [Kitami Inst. of Technology, Kitami (Japan)

    2008-07-01

    Formation and dissociation processes of natural gas hydrates in permafrost, marine and lake sediments are highly controlled by their thermal properties. Dissociation heat of gas hydrates can be estimated from phase equilibrium data using the Clausius-Clapeyron equation. However, this method is applicable for pure gas hydrate and at a temperature of 0 degrees Celsius. Direct calorimetric measurements on gas hydrates using a calorimeter have been developed to obtain thermal properties of gas hydrates, including dissociation heat and heat capacity. Studies have shown that a structure 2 gas hydrate appears in appropriate gas composition of methane and ethane. This paper investigated the effect of ethane concentration on dissociation heat of mixed-gas (methane and ethane) hydrate. Raman spectroscopy was used to confirm the appearance of a structure 2 gas hydrate. The paper identified the experimental procedure and discussed sample preparation, Raman spectroscopy, and calorimetric measurements. A schematic diagram of the calorimeter was also presented. It was concluded that in most cases, two stages of dissociation were found at the dissociation process. 15 refs., 6 figs.

  11. Barrierless association of CF2 and dissociation of C2F4 by variational transition-state theory and system-specific quantum Rice–Ramsperger–Kassel theory

    Science.gov (United States)

    Bao, Junwei Lucas; Zhang, Xin

    2016-01-01

    Bond dissociation is a fundamental chemical reaction, and the first principles modeling of the kinetics of dissociation reactions with a monotonically increasing potential energy along the dissociation coordinate presents a challenge not only for modern electronic structure methods but also for kinetics theory. In this work, we use multifaceted variable-reaction-coordinate variational transition-state theory (VRC-VTST) to compute the high-pressure limit dissociation rate constant of tetrafluoroethylene (C2F4), in which the potential energies are computed by direct dynamics with the M08-HX exchange correlation functional. To treat the pressure dependence of the unimolecular rate constants, we use the recently developed system-specific quantum Rice–Ramsperger–Kassel theory. The calculations are carried out by direct dynamics using an exchange correlation functional validated against calculations that go beyond coupled-cluster theory with single, double, and triple excitations. Our computed dissociation rate constants agree well with the recent experimental measurements. PMID:27834727

  12. Hydrogen dissociation on metal surfaces

    OpenAIRE

    Wijzenbroek, M.

    2016-01-01

    Dissociative chemisorption is an important reaction step in many catalytic reactions. An example of such a reaction is the Haber-Bosch process, which is used commercially to produce ammonia, an important starting material in the production of fertilisers. In theoretical descriptions of such chemical processes often approximations need to be made in order to keep the computational cost feasible, such as fixing the surface atoms in place, rather than allowing them to vibrate. In this work, seve...

  13. Diffraction dissociation and elastic scattering

    International Nuclear Information System (INIS)

    Verebryusov, V.S.; Ponomarev, L.A.; Smorodinskaya, N.Ya.

    1987-01-01

    In the framework of Regge scheme with supercritical pomeron a model is suggested for the NN-scattering amplitude which takes into account the contribution introduced to the intermediate state by diffraction dissociation (DD) processes. The DD amplitude is written in terms of the Deck model which has been previously applied to describing the main DD features. The calculated NN cross sections are compared with those obtained experimentally. Theoretical predictions for higher energy are presented

  14. Dissociative Photoionization of Diethyl Ether.

    Science.gov (United States)

    Voronova, Krisztina; Mozaffari Easter, Chrissa M; Covert, Kyle J; Bodi, Andras; Hemberger, Patrick; Sztáray, Bálint

    2015-10-29

    The dissociative photoionization of internal energy selected diethyl ether ions was investigated by imaging photoelectron photoion coincidence spectroscopy. In a large, 5 eV energy range Et2O(+) cations decay by two parallel and three sequential dissociative photoionization channels, which can be modeled well using statistical theory. The 0 K appearance energies of the CH3CHOCH2CH3(+) (H-loss, m/z = 73) and CH3CH2O═CH2(+) (methyl-loss, m/z = 59) fragment ions were determined to be 10.419 ± 0.015 and 10.484 ± 0.008 eV, respectively. The reemergence of the hydrogen-loss ion above 11 eV is attributed to transition-state (TS) switching, in which the second, outer TS is rate-determining at high internal energies. At 11.81 ± 0.05 eV, a secondary fragment of the CH3CHOCH2CH3(+) (m/z = 73) ion, protonated acetaldehyde, CH3CH═OH(+) (m/z = 45) appears. On the basis of the known thermochemical onset of this fragment, a reverse barrier of 325 meV was found. Two more sequential dissociation reactions were examined, namely, ethylene and formaldehyde losses from the methyl-loss daughter ion. The 0 K appearance energies of 11.85 ± 0.07 and 12.20 ± 0.08 eV, respectively, indicate no reverse barrier in these processes. The statistical model of the dissociative photoionization can also be used to predict the fractional ion abundances in threshold photoionization at large temperatures, which could be of use in, for example, combustion diagnostics.

  15. Autonoesis and dissociative identity disorder.

    Science.gov (United States)

    Morton, John

    2018-01-01

    Dissociative identity disorder is characterised by the presence in one individual of two or more alternative personality states (alters). For such individuals, the memory representation of a particular event can have full episodic, autonoetic status for one alter, while having the status of knowledge or even being inaccessible to a second alter. This phenomenon appears to create difficulties for a purely representational theory and is presented to Mahr & Csibra (M&C) for their consideration.

  16. Dissociation behavior of Np(IV) from humic acid colloid

    Energy Technology Data Exchange (ETDEWEB)

    Iijima, K.; Tobitsuka, S. [Japan Nuclear Cycle Development Institute, 4-33 Muramatsu, Tokai, Naka-gun, Ibaraki 319-1194 (Japan); Kohara, Y. [Inspection Development Corporation, 4-33, Muramatsu, Tokai, Nakagun, Ibaraki 319-1112 (Japan)

    2005-07-01

    Full text of publication follows: Dissociation behavior of Np(IV) from humic colloid, which was prepared with purified Aldrich humic acid (PAHA) was investigated. The complexation experiments were carried out in 0.1 M NaClO{sub 4} - 0.05 M Na{sub 2}S{sub 2}O{sub 4} solution at pH 8 with PAHA concentration between 0 and 500 mg L-1 under anaerobic condition. Np-237 was added as Np(V) solution so that its concentration becomes 1.1 x 10-5 mol L-1. After shaking from 1 to 156 days, aliquots of experimental solution were filtered through the membranes with 50, 10 and 3 kD of MWCO to obtain the size distribution of colloid, followed by adding the filtrate into the 6 M HCl for dissociation. At the end of experiments for 596 days, 0.1 M NaHCO{sub 3} was used for dissociation solution. The concentration of Np released into this solution was evaluated by measuring a activity of Np-237. The concentration of Np becomes constant by 112 days. Since Eh of the solution has been kept between -300 and -100 mV vs. SHE during experimental duration, Np is presumed to be reduced into tetravalent. In the case of higher PAHA concentration than 50 mg L{sup -1}, the Np concentration is close to that of initially added Np. Since the size of the dissolved species of Np during complexation experiments varies from 3 to 50 kD, the Np is sorbed on humic acid colloid. In the dissociation experiments, the Np dissociated by 6 M HCl decreases with increasing complexation time and PAHA concentration. After 156 days complexation with 500 mg L{sup -1} of PAHA, 35% of Np can be dissociated from the colloid. Such a tendency, however, is not observed in case of the lowest PAHA concentration, 5 mg L{sup -1}. After 596 days complexation, the dissociation experiments were carried out by adding 0.1 M NaHCO{sub 3} solution to avoid the precipitation which might hinder the dissociation of Np in the aforementioned experiments with HCl. As a result, 50% of Np is dissociated in the presence of 50 and 100 mg L-1 of

  17. [Clinical Handling of Patients with Dissociative Disorders].

    Science.gov (United States)

    Okano, Kenichiro

    2015-01-01

    This paper discusses the way informed psychiatrists are expected to handle dissociative patients in clinical situations, with a specific focus on dissociative identity disorders and dissociative fugue. On the initial interview with dissociative patients, information on their history of trauma and any nascent dissociative symptoms in their childhood should be carefully obtained. Their level of stress in their current life should also be assessed in order to understand their symptomatology, as well as to predict their future clinical course. A psychoeducational approach is crucial; it might be helpful to give information on dissociative disorder to these patients as well as their family members in order to promote their adherence to treatment. Regarding the symptomatology of dissociative disorders, detailed symptoms and the general clinical course are presented. It was stressed that dissociative identity disorder and dissociative fugue, the most high-profile dissociative disorders, are essentially different in their etiology and clinical presentation. Dissociative disorders are often confused with and misdiagnosed as psychotic disorders, such as schizophrenia. Other conditions considered in terms of the differential diagnosis include borderline personality disorder as well as temporal lobe epilepsy. Lastly, the therapeutic approach to dissociative identity disorder is discussed. Each dissociative identity should be understood as potentially representing some traumatically stressful event in the past. The therapist should be careful not to excessively promote the creation or elaboration of any dissociative identities. Three stages are proposed in the individual psychotherapeutic process. In the initial stage, a secure environment and stabilization of symptoms should be sought. The second stage consists of aiding the "host" personality to make use of other more adaptive coping skills in their life. The third stage involves coaching as well as continuous awareness of

  18. Gyrokinetic Magnetohydrodynamics and the Associated Equilibrium

    Science.gov (United States)

    Lee, W. W.; Hudson, S. R.; Ma, C. H.

    2017-10-01

    A proposed scheme for the calculations of gyrokinetic MHD and its associated equilibrium is discussed related a recent paper on the subject. The scheme is based on the time-dependent gyrokinetic vorticity equation and parallel Ohm's law, as well as the associated gyrokinetic Ampere's law. This set of equations, in terms of the electrostatic potential, ϕ, and the vector potential, ϕ , supports both spatially varying perpendicular and parallel pressure gradients and their associated currents. The MHD equilibrium can be reached when ϕ -> 0 and A becomes constant in time, which, in turn, gives ∇ . (J|| +J⊥) = 0 and the associated magnetic islands. Examples in simple cylindrical geometry will be given. The present work is partially supported by US DoE Grant DE-AC02-09CH11466.

  19. Cosmic curvature from de Sitter equilibrium cosmology.

    Science.gov (United States)

    Albrecht, Andreas

    2011-10-07

    I show that the de Sitter equilibrium cosmology generically predicts observable levels of curvature in the Universe today. The predicted value of the curvature, Ω(k), depends only on the ratio of the density of nonrelativistic matter to cosmological constant density ρ(m)(0)/ρ(Λ) and the value of the curvature from the initial bubble that starts the inflation, Ω(k)(B). The result is independent of the scale of inflation, the shape of the potential during inflation, and many other details of the cosmology. Future cosmological measurements of ρ(m)(0)/ρ(Λ) and Ω(k) will open up a window on the very beginning of our Universe and offer an opportunity to support or falsify the de Sitter equilibrium cosmology.

  20. A generalized quantitative antibody homeostasis model: maintenance of global antibody equilibrium by effector functions.

    Science.gov (United States)

    Prechl, József

    2017-11-01

    The homeostasis of antibodies can be characterized as a balanced production, target-binding and receptor-mediated elimination regulated by an interaction network, which controls B-cell development and selection. Recently, we proposed a quantitative model to describe how the concentration and affinity of interacting partners generates a network. Here we argue that this physical, quantitative approach can be extended for the interpretation of effector functions of antibodies. We define global antibody equilibrium as the zone of molar equivalence of free antibody, free antigen and immune complex concentrations and of dissociation constant of apparent affinity: [Ab]=[Ag]=[AbAg]= K D . This zone corresponds to the biologically relevant K D range of reversible interactions. We show that thermodynamic and kinetic properties of antibody-antigen interactions correlate with immunological functions. The formation of stable, long-lived immune complexes correspond to a decrease of entropy and is a prerequisite for the generation of higher-order complexes. As the energy of formation of complexes increases, we observe a gradual shift from silent clearance to inflammatory reactions. These rules can also be applied to complement activation-related immune effector processes, linking the physicochemical principles of innate and adaptive humoral responses. Affinity of the receptors mediating effector functions shows a wide range of affinities, allowing the continuous sampling of antibody-bound antigen over the complete range of concentrations. The generation of multivalent, multicomponent complexes triggers effector functions by crosslinking these receptors on effector cells with increasing enzymatic degradation potential. Thus, antibody homeostasis is a thermodynamic system with complex network properties, nested into the host organism by proper immunoregulatory and effector pathways. Maintenance of global antibody equilibrium is achieved by innate qualitative signals modulating a

  1. The Hubble Constant

    Directory of Open Access Journals (Sweden)

    Neal Jackson

    2015-09-01

    Full Text Available I review the current state of determinations of the Hubble constant, which gives the length scale of the Universe by relating the expansion velocity of objects to their distance. There are two broad categories of measurements. The first uses individual astrophysical objects which have some property that allows their intrinsic luminosity or size to be determined, or allows the determination of their distance by geometric means. The second category comprises the use of all-sky cosmic microwave background, or correlations between large samples of galaxies, to determine information about the geometry of the Universe and hence the Hubble constant, typically in a combination with other cosmological parameters. Many, but not all, object-based measurements give H_0 values of around 72–74 km s^–1 Mpc^–1, with typical errors of 2–3 km s^–1 Mpc^–1. This is in mild discrepancy with CMB-based measurements, in particular those from the Planck satellite, which give values of 67–68 km s^–1 Mpc^–1 and typical errors of 1–2 km s^–1 Mpc^–1. The size of the remaining systematics indicate that accuracy rather than precision is the remaining problem in a good determination of the Hubble constant. Whether a discrepancy exists, and whether new physics is needed to resolve it, depends on details of the systematics of the object-based methods, and also on the assumptions about other cosmological parameters and which datasets are combined in the case of the all-sky methods.

  2. The inconstant solar constant

    International Nuclear Information System (INIS)

    Willson, R.C.; Hudson, H.

    1984-01-01

    The Active Cavity Radiometer Irradiance Monitor (ACRIM) of the Solar Maximum Mission satellite measures the radiant power emitted by the sun in the direction of the earth and has worked flawlessly since 1980. The main motivation for ACRIM's use to measure the solar constant is the determination of the extent to which this quantity's variations affect earth weather and climate. Data from the solar minimum of 1986-1987 is eagerly anticipated, with a view to the possible presence of a solar cycle variation in addition to that caused directly by sunspots

  3. Determination of complex association constants from gas chromatograhic data

    NARCIS (Netherlands)

    Ligny, C.L. de; Koole, N.J.; Nelson, H.D.; Nieuwdorp, G.H.E.

    1975-01-01

    Abstract The equilibrium constants for hydrogen bonding of a series of β-substituted alcohols with a number of monofunctional hexadecyl derivatives and dioctyl compounds have been measured by gas chromatography. For ethanol, propanol and butanol, the enthalpy and standard entropy of hydrogen

  4. 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

  5. Isotope anomalies in oxygen isotope exchange equilibrium systems

    International Nuclear Information System (INIS)

    Kotaka, M.

    1997-01-01

    The purpose of the present work is to elucidate the isotope anomalies in oxygen isotope exchange equilibrium systems, according to the calculations of the equilibrium constants for oxygen isotopic exchange reactions, and the calculations of the oxygen isotope separation factors between two phases. The equilibrium constants (K65, K67, K68 and K69) of 16 O- 15 O, 16 O 17 O, 16 O- 18 O, and 16 O- 19 O exchange reactions between diatomic oxides were calculated in a wide temperature range on the basis of quantum statistical mechanics. Many equilibrium constants showed the anomalous mass effects, and then had the crossover temperatures and the mass independent fractionation (MIF) temperatures which held K67 = K65, K67 = K68, or K67 = K69, etc. For example, the equilibrium constants for the reactions between OH and the other diatomic oxides (MO) showed the anomalous mass effects, when M was Li, Na, Mg, K, Fe, Al, Ge, Zr, Pt, etc. The 16 O 15 O, 16 O 17 O, 16 O- 18 O, and 16 O- 19 O oxygen isotope separation factors (S65, S67, S68 and S69) between two phases were calculated, when OH and CO were in the first phase, and SiO was in the second phase. Although the oxygen isotopic exchange equilibria in the two phases had no MIF and crossover temperatures, the separation factors showed the anomalous mass effects and had the temperatures. According to what is called the normal mass effects for the equilibrium constant of isotopic exchange reaction, the value of InK68/InK67 is 1.885. Therefore, the value of InS68/InS67 should be 1.885 too. The value calculated, however, widely changed. It can be concluded from the results obtained in the present work that some oxygen isotopic exchange equilibria cause the anomalous mass effects, the anomalous oxygen isotope separation factors, and then isotope anomalies

  6. A study on the equilibrium relationships in the system Ni-U-O in air and in oxygen

    International Nuclear Information System (INIS)

    Elmasry, M.A.A.; Younis, S.S.

    1996-01-01

    The phase relationships for the ternary system Ni-U-O were established in air and in oxygen. Mixtures of Ni O and U 3 O 8 were found to oxidize to Ni U O 4 that was identical to that previously published for Ni U 3 O 1 0. The nickel uranate dissociates to Ni O, U 3 O 8 and oxygen at a temperature higher than that of the oxidation. The dissociation products go back to the uranate when they are cooled because of the difficulty of oxygen diffusion and uranate nucleation. Accordingly dissociation temperature. 966 degree C was taken to represent equilibrium and was used to calculate roughly H and S for the dissociation reaction. In presence of Ni O, U 3 O 8 melts partially at 1470 degree C and does not dissociate to the lower oxide. 4 figs

  7. Thermal equilibrium of goats.

    Science.gov (United States)

    Maia, Alex S C; Nascimento, Sheila T; Nascimento, Carolina C N; Gebremedhin, Kifle G

    2016-05-01

    The effects of air temperature and relative humidity on thermal equilibrium of goats in a tropical region was evaluated. Nine non-pregnant Anglo Nubian nanny goats were used in the study. An indirect calorimeter was designed and developed to measure oxygen consumption, carbon dioxide production, methane production and water vapour pressure of the air exhaled from goats. Physiological parameters: rectal temperature, skin temperature, hair-coat temperature, expired air temperature and respiratory rate and volume as well as environmental parameters: air temperature, relative humidity and mean radiant temperature were measured. The results show that respiratory and volume rates and latent heat loss did not change significantly for air temperature between 22 and 26°C. In this temperature range, metabolic heat was lost mainly by convection and long-wave radiation. For temperature greater than 30°C, the goats maintained thermal equilibrium mainly by evaporative heat loss. At the higher air temperature, the respiratory and ventilation rates as well as body temperatures were significantly elevated. It can be concluded that for Anglo Nubian goats, the upper limit of air temperature for comfort is around 26°C when the goats are protected from direct solar radiation. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Reaction constants, in cyclohexane, of lauryl-amines with tetrabromo-phenolphthalein magenta E acid

    International Nuclear Information System (INIS)

    Perez, J.J.

    1966-11-01

    Trilauryl amine is an extracting agent used for plutonium purification. Its main degradation product is di-laurylamine. The titration of this impurity is carried out by spectro-colorimetry in cyclohexane using bromophtalein Magenta E as coloured acid indicator. The reported dissociation constants for alcoylammonium salts are too closed to lead to a discrimination between secondary and tertiary amines. The present spectrophotometric study shows that the ratios of various dissociation constants for bromophtalein Magenta E salts are notably different from those for salts of simple coloured acids like 2,4 dinitro phenol. The structural changes accompanying the colorations are discussed in order to explain this phenomenon. (author) [fr

  9. Theoretical and experimental investigation of the destruction of graphites in a flow of dissociated air

    Science.gov (United States)

    Bovina, T. A.; Zviagin, Y. V.; Markelov, N. V.; Chudetskiy, Y. V.

    1986-01-01

    A method is presented for calculating the heating and erosion of blunt bodies made of graphite in a high-enthalpy flow of dissociated air, assuming chemical equilibrium on the surface and taking account of the thermal effects of combustion and sublimation of graphite. The analysis involves the use of a finite difference scheme to solve an equation of unsteady heat conduction. Attention is given to the equilibrium vaporization of C, C2 and C3 molecules. The calculations agree well with experimental data for a wide range of temperatures and stagnation pressures.

  10. Rate coefficients for low-energy electron dissociative attachment to molecular hydrogen

    International Nuclear Information System (INIS)

    Horacek, J.; Houfek, K.; Cizek, M.; Murakami, I.; Kato, T.

    2003-02-01

    Calculation of rate constants for dissociative electron attachment to molecular hydrogen is reported. The calculation is based on an improved nonlocal resonance model of Cizek, Horacek and Domcke which takes fully into account the nonlocality of the resonance dynamics and uses potentials with correct asymptotic forms. The rate constants are calculated for all quantum numbers v and J of the target molecules and for electron temperature in the range 0-30000 K. (author)

  11. Experimentally-induced dissociation impairs visual memory.

    Science.gov (United States)

    Brewin, Chris R; Mersaditabari, Niloufar

    2013-12-01

    Dissociation is a phenomenon common in a number of psychological disorders and has been frequently suggested to impair memory for traumatic events. In this study we explored the effects of dissociation on visual memory. A dissociative state was induced experimentally using a mirror-gazing task and its short-term effects on memory performance were investigated. Sixty healthy individuals took part in the experiment. Induced dissociation impaired visual memory performance relative to a control condition; however, the degree of dissociation was not associated with lower memory scores in the experimental group. The results have theoretical and practical implications for individuals who experience frequent dissociative states such as patients with posttraumatic stress disorder (PTSD). Copyright © 2013 Elsevier Inc. All rights reserved.

  12. Diffractive dissociation and new quarks

    International Nuclear Information System (INIS)

    White, A.R.

    1983-04-01

    We argue that the chiral limit of QCD can be identified with the strong (diffractive dissociation) coupling limit of reggeon field theory. Critical Pomeron scaling at high energy must then be directly related to an infra-red fixed-point of massless QCD and so requires a large number of flavors. This gives a direct argument that the emergence of diffraction-peak scaling, KNO scaling etc. at anti p-p colliders are evidence of a substantial quark structure still to be discovered

  13. [Characteristics of Bacillus cereus dissociants].

    Science.gov (United States)

    Doroshenko, E V; Loĭko, N G; Il'inskaia, O N; Kolpakov, A I; Gornova, I B; Klimanova, E V; El'-Registan, G I

    2001-01-01

    The autoregulation of the phenotypic (populational) variability of the Bacillus cereus strain 504 was studied. The isolated colonial morphotypes of this bacterium were found to differ in their growth characteristics and the synthesis of extracellular proteases. The phenotypic variabilities of vegetative proliferating cells and those germinated from endospores and cystlike refractory cells were different. Bacterial variants also differed in the production of the d1 and d2 factors (the autoinducers of dormancy and autolysis, respectively) and sensitivity to them. The possible role of these factors in the dissociation of microorganisms is discussed.

  14. Experimental investigation of gas heating and dissociation in a microwave plasma torch at atmospheric pressure

    International Nuclear Information System (INIS)

    Su, Liu; Kumar, Rajneesh; Ogungbesan, Babajide; Sassi, Mohamed

    2014-01-01

    Highlights: • Atmospheric-pressure microwave plasma torch. • Gas heating and dissociation. • Parametric studies of plasma operating conditions. • Local thermal equilibrium plasma. - Abstract: Experimental investigations are made to understand gas heating and dissociation in a microwave (MW) plasma torch at atmospheric pressure. The MW induced plasma torch operates at 2.45 GHz frequency and up to 2 kW power. Three different gas mixtures are injected in the form of axial flow and swirl flow in a quartz tube plasma torch to experimentally investigate the MW plasma to gas energy transfer. Air–argon, air–air and air–nitrogen plasmas are formed and their operational ranges are determined in terms of gas flow rates and MW power. Visual observations, optical emission spectroscopy and K-type thermocouple measurements are used to characterize the plasma. The study reveals that the plasma structure is highly dependent on the carrier gas type, gas flow rate, and MW power. However, the plasma gas temperature is shown not to vary much with these parameters. Further spectral and analytical analysis show that the plasma is in thermal equilibrium and presents very good energy coupling between the microwave power and gas heating and dissociation. The MW plasma torch outlet temperature is also measured and found to be suitable for many thermal heating and chemical dissociation applications

  15. Aggregation-induced chemical reactions: acid dissociation in growing water clusters.

    Science.gov (United States)

    Forbert, Harald; Masia, Marco; Kaczmarek-Kedziera, Anna; Nair, Nisanth N; Marx, Dominik

    2011-03-23

    Understanding chemical reactivity at ultracold conditions, thus enabling molecular syntheses via interstellar and atmospheric processes, is a key issue in cryochemistry. In particular, acid dissociation and proton transfer reactions are ubiquitous in aqueous microsolvation environments. Here, the full dissociation of a HCl molecule upon stepwise solvation by a small number of water molecules at low temperatures, as relevant to helium nanodroplet isolation (HENDI) spectroscopy, is analyzed in mechanistic detail. It is found that upon successive aggregation of HCl with H(2)O molecules, a series of cyclic heteromolecular structures, up to and including HCl(H(2)O)(3), are initially obtained before a precursor state for dissociation, HCl(H(2)O)(3)···H(2)O, is observed upon addition of a fourth water molecule. The latter partially aggregated structure can be viewed as an "activated species", which readily leads to dissociation of HCl and to the formation of a solvent-shared ion pair, H(3)O(+)(H(2)O)(3)Cl(-). Overall, the process is mostly downhill in potential energy, and, in addition, small remaining barriers are overcome by using kinetic energy released as a result of forming hydrogen bonds due to aggregation. The associated barrier is not ruled by thermal equilibrium but is generated by athermal non-equilibrium dynamics. These "aggregation-induced chemical reactions" are expected to be of broad relevance to chemistry at ultralow temperature much beyond HENDI spectroscopy.

  16. Collision-induced dissociation of diatomic ions

    International Nuclear Information System (INIS)

    Los, J.; Govers, T.R.

    1978-01-01

    An attempt is made to illustrate how mass spectrometric studies of dissociation in diatomic molecular ions can provide information on the dynamics of these collisions and on the predissociative states involved. Restriction is made to primary beam energies of the order of at least keV. The review covers the dynamics of dissociation, experimental techniques, direct dissociation in heavy-particle collisions, and translational spectroscopy. 120 references

  17. Mirror Writing and a Dissociative Identity Disorder

    OpenAIRE

    Le, Catherine; Smith, Joyce; Cohen, Lewis

    2009-01-01

    Individuals with dissociative identity disorder (DID) have been known to show varied skills and talents as they change from one dissociative state to another. For example, case reports have described people who have changed their handedness or have spoken foreign languages during their dissociative states. During an interview with a patient with DID, a surprising talent emerged when she wrote a sentence for the Folstein Mini-Mental State Exam—mirror writing. It is not known whether her mirror...

  18. Predictions of hydrate plug dissociation with electrical heating

    Energy Technology Data Exchange (ETDEWEB)

    Davies, S.R.; Ivanic, J.; Sloan, E.D.

    2005-07-01

    The rate of dissociation for cylindrical hydrate plugs by the application of radial electrical heating was investigated for structure I and structure II hydrates for pressures of 7 MPa (1000 psia) and 14 MPa (2000 psia). Heating rates of 2.3 kWm{sup -3}, 4.5 kWm-3 and 6.8 kWm{sup -3} were investigated for a plug 91.4 cm (36 inches) in length and 2.54 cm (1 inch) in diameter. A heat transfer model was developed in cylindrical coordinates based on Fourier's Law with a boundary condition of constant heat flux at the pipe wall. The equation set was solved numerically using a finite difference grid and the standard explicit scheme. The model was found to replicate well the experimental observations with no fitted parameters. A computer program was formulated to allow the practicing engineer to simulate the dissociation of industrial hydrates with minimal complexity. This program was incorporated into the latest version of our CSMPlug program which has been used by a number of energy companies to predict hydrate plug dissociation rates in the field. (Author)

  19. Mirror Writing and a Dissociative Identity Disorder

    Directory of Open Access Journals (Sweden)

    Catherine Le

    2009-01-01

    Full Text Available Individuals with dissociative identity disorder (DID have been known to show varied skills and talents as they change from one dissociative state to another. For example, case reports have described people who have changed their handedness or have spoken foreign languages during their dissociative states. During an interview with a patient with DID, a surprising talent emerged when she wrote a sentence for the Folstein Mini-Mental State Exam—mirror writing. It is not known whether her mirror writing had a deeper level of meaning; however, it does emphasize the idiosyncratic nature of dissociative identity disorder.

  20. Mirror writing and a dissociative identity disorder.

    Science.gov (United States)

    Le, Catherine; Smith, Joyce; Cohen, Lewis

    2009-01-01

    Individuals with dissociative identity disorder (DID) have been known to show varied skills and talents as they change from one dissociative state to another. For example, case reports have described people who have changed their handedness or have spoken foreign languages during their dissociative states. During an interview with a patient with DID, a surprising talent emerged when she wrote a sentence for the Folstein Mini-Mental State Exam-mirror writing. It is not known whether her mirror writing had a deeper level of meaning; however, it does emphasize the idiosyncratic nature of dissociative identity disorder.

  1. Direct observation of characteristic dissociation behaviors of hydrate-bearing cores by rapid-scanning X-ray CT imaging

    Energy Technology Data Exchange (ETDEWEB)

    Ebinuma, T.; Oyama, H.; Utiumi, T.; Nagao, J.; Narita, H. [National Inst. of Advanced Industrial Science and Technology, Toyohiraku, Sapporo (Japan)

    2008-07-01

    Methane hydrate has significant potential as a new source of energy. Major considerations in developing production methods of methane from hydrates are the fundamental properties of hydrate-bearing sediments, and the dissociation behavior of methane hydrate and the gas and water flow generated by its dissociation in sediments. Marine methane hydrates occur several hundred meters below the sea floor, in a variety of forms. The pore-space filling-type is considered to be the most suited to exploitation, as it is contained within the pore spaces of sandy sediments, and has relatively larger gas permeability compared to other forms. However, shallow sandy sediments are not usually consolidated, and methane hydrate is unstable at normal pressure and temperature. Therefore, common methods are not suitable, and new experimental methods have been developed to study the properties of hydrate-bearing sediment and its dissociation process. This paper presented the results of an experimental study involving the dissociation of artificial methane-hydrate-bearing sediments. The experiment was performed using X-ray computed tomography in order to directly observe dissociation behavior in the sediments and the gas and water flows generated by dissociation. The paper described the depressurization process and presented a schematic diagram of rapid scanning X-ray computed tomography scanner and core holder with tri-axial structure. The experimental apparatus for dissociation of methane hydrate was also illustrated. The thermal stimulation process and hot water injection process were explained. It was concluded that dissociation by depressurization demonstrated that the temperature reduction induced by depressurization depended on the phase equilibrium state of methane hydrate, and that dissociation preferentially occurred at the periphery of the core. This behavior was due to the heat flux from the outside of the core, where the heat flux controlled the dissociation rate. 10 refs

  2. Dissociative symptoms and dissociative disorder comorbidity in patients with obsessive-compulsive disorder.

    Science.gov (United States)

    Belli, Hasan; Ural, Cenk; Vardar, Melek Kanarya; Yesılyurt, Sema; Oncu, Fatıh

    2012-10-01

    The present study attempted to assess the dissociative symptoms and overall dissociative disorder comorbidity in patients with obsessive-compulsive disorder (OCD). In addition, we examined the relationship between the severity of obsessive-compulsive symptoms and dissociative symptoms. All patients admitted for the first time to the psychiatric outpatient unit were included in the study. Seventy-eight patients had been diagnosed as having OCD during the 2-year study period. Patients had to meet the Diagnostic and Statistical Manual of Mental Disorders, Fourth Edition criteria for OCD. Most (76.9%; n = 60) of the patients were female, and 23.1% (n = 18) of the patients were male. Dissociation Questionnaire was used to measure dissociative symptoms. The Structured Clinical Interview for Diagnostic and Statistical Manual of Mental Disorders, Fourth Edition Dissociative Disorders interviews and Yale-Brown Obsessive Compulsive Checklist and Severity Scale were used. Eleven (14%) of the patients with OCD had comorbid dissociative disorder. The most prevalent disorder in our study was dissociative depersonalization disorder. Dissociative amnesia and dissociative identity disorder were common as well. The mean Yale-Brown score was 23.37 ± 7.27 points. Dissociation Questionnaire scores were between 0.40 and 3.87 points, and the mean was 2.23 ± 0.76 points. There was a statistically significant positive correlation between Yale-Brown points and Dissociation Questionnaire points. We conclude that dissociative symptoms among patients with OCD should alert clinicians for the presence of a chronic and complex dissociative disorder. Clinicians may overlook an underlying dissociative process in patients who have severe symptoms of OCD. However, a lack of adequate response to cognitive-behavioral and drug therapy may be a consequence of dissociative process. Copyright © 2012 Elsevier Inc. All rights reserved.

  3. Dissociative identity disorder: Medicolegal challenges.

    Science.gov (United States)

    Farrell, Helen M

    2011-01-01

    Persons with dissociative identity disorder (DID) often present in the criminal justice system rather than the mental health system and perplex experts in both professions. DID is a controversial diagnosis with important medicolegal implications. Defendants have claimed that they committed serious crimes, including rape or murder, while they were in a dissociated state. Asserting that their alter personality committed the bad act, defendants have pleaded not guilty by reason of insanity (NGRI). In such instances, forensic experts are asked to assess the defendant for DID and provide testimony in court. Debate continues over whether DID truly exists, whether expert testimony should be allowed into evidence, and whether it should exculpate defendants for their criminal acts. This article reviews historical and theoretical perspectives on DID, presents cases that illustrate the legal implications and controversies of raising an insanity defense based on multiple personalities, and examines the role of forensic experts asked to comment on DID with the goal of assisting clinicians in the medicolegal assessment of DID in relation to crimes.

  4. Equilibrium models and variational inequalities

    CERN Document Server

    Konnov, Igor

    2007-01-01

    The concept of equilibrium plays a central role in various applied sciences, such as physics (especially, mechanics), economics, engineering, transportation, sociology, chemistry, biology and other fields. If one can formulate the equilibrium problem in the form of a mathematical model, solutions of the corresponding problem can be used for forecasting the future behavior of very complex systems and, also, for correcting the the current state of the system under control. This book presents a unifying look on different equilibrium concepts in economics, including several models from related sciences.- Presents a unifying look on different equilibrium concepts and also the present state of investigations in this field- Describes static and dynamic input-output models, Walras, Cassel-Wald, spatial price, auction market, oligopolistic equilibrium models, transportation and migration equilibrium models- Covers the basics of theory and solution methods both for the complementarity and variational inequality probl...

  5. Potential constants and centrifugal distortion constants of octahedral hexafluoride molecules

    Energy Technology Data Exchange (ETDEWEB)

    Manivannan, G [Government Thirumagal Mill' s Coll., Gudiyattam, Tamil Nadu (India)

    1981-04-01

    The kinetic constants method outlined by Thirugnanasambandham (1964) based on Wilson's (1955) group theory has been adapted in evaluating the potential constants for SF/sub 6/, SeF/sub 6/, WF/sub 6/, IrF/sub 6/, UF/sub 6/, NpF/sub 6/, and PuF/sub 6/ using the experimentally observed vibrational frequency data. These constants are used to calculate the centrifugal distortion constants for the first time.

  6. A New Equilibrium State for Singly Synchronous Binary Asteroids

    Science.gov (United States)

    Golubov, Oleksiy; Unukovych, Vladyslav; Scheeres, Daniel J.

    2018-04-01

    The evolution of rotation states of small asteroids is governed by the Yarkovsky–O’Keefe–Radzievskii–Paddack (YORP) effect, nonetheless some asteroids can stop their YORP evolution by attaining a stable equilibrium. The same is true for binary asteroids subjected to the binary YORP (BYORP) effect. Here we discuss a new type of equilibrium that combines these two, which is possible in a singly synchronous binary system. This equilibrium occurs when the normal YORP, the tangential YORP, and the BYORP compensate each other, and tidal torques distribute the angular momentum between the components of the system and dissipate energy. If unperturbed, such a system would remain singly synchronous in perpetuity with constant spin and orbit rates, as the tidal torques dissipate the incoming energy from impinging sunlight at the same rate. The probability of the existence of this kind of equilibrium in a binary system is found to be on the order of a few percent.

  7. Universal relation between spectroscopic constants

    Indian Academy of Sciences (India)

    , viz., ∆ 2 2re has been obtained for the ... G depends on anharmonicityωexe, (ii) ∆ is governed by the dissociation energy,De and (iii) the nature of the outer ..... solid state edited by P O Löwdin (Academic Press, New York, 1996) p. 231. [12] K P ...

  8. Mental Equilibrium and Rational Emotions

    OpenAIRE

    Eyal Winter; Ignacio Garcia-Jurado; Jose Mendez-Naya; Luciano Mendez-Naya

    2009-01-01

    We introduce emotions into an equilibrium notion. In a mental equilibrium each player "selects" an emotional state which determines the player's preferences over the outcomes of the game. These preferences typically differ from the players' material preferences. The emotional states interact to play a Nash equilibrium and in addition each player's emotional state must be a best response (with respect to material preferences) to the emotional states of the others. We discuss the concept behind...

  9. Para-equilibrium phase diagrams

    International Nuclear Information System (INIS)

    Pelton, Arthur D.; Koukkari, Pertti; Pajarre, Risto; Eriksson, Gunnar

    2014-01-01

    Highlights: • A rapidly cooled system may attain a state of para-equilibrium. • In this state rapidly diffusing elements reach equilibrium but others are immobile. • Application of the Phase Rule to para-equilibrium phase diagrams is discussed. • A general algorithm to calculate para-equilibrium phase diagrams is described. - Abstract: If an initially homogeneous system at high temperature is rapidly cooled, a temporary para-equilibrium state may result in which rapidly diffusing elements have reached equilibrium but more slowly diffusing elements have remained essentially immobile. The best known example occurs when homogeneous austenite is quenched. A para-equilibrium phase assemblage may be calculated thermodynamically by Gibbs free energy minimization under the constraint that the ratios of the slowly diffusing elements are the same in all phases. Several examples of calculated para-equilibrium phase diagram sections are presented and the application of the Phase Rule is discussed. Although the rules governing the geometry of these diagrams may appear at first to be somewhat different from those for full equilibrium phase diagrams, it is shown that in fact they obey exactly the same rules with the following provision. Since the molar ratios of non-diffusing elements are the same in all phases at para-equilibrium, these ratios act, as far as the geometry of the diagram is concerned, like “potential” variables (such as T, pressure or chemical potentials) rather than like “normal” composition variables which need not be the same in all phases. A general algorithm to calculate para-equilibrium phase diagrams is presented. In the limit, if a para-equilibrium calculation is performed under the constraint that no elements diffuse, then the resultant phase diagram shows the single phase with the minimum Gibbs free energy at any point on the diagram; such calculations are of interest in physical vapor deposition when deposition is so rapid that phase

  10. From dissociation to trauma? Individual differences in dissociation as predictor of 'trauma' perception

    NARCIS (Netherlands)

    Rassin, Eric; van Rootselaar, Anne-Fleur

    2006-01-01

    In clinical literature, dissociative complaints are generally considered to be the result of traumatic experiences. However, it has been argued that dissociative complaints, in turn, may indulge over-reporting of traumatic experiences. Hence, correlations between dissociation and self-reported

  11. Dissociation in patients with dissociative seizures: relationships with trauma and seizure symptoms.

    Science.gov (United States)

    Pick, S; Mellers, J D C; Goldstein, L H

    2017-05-01

    This study aimed to extend the current understanding of dissociative symptoms experienced by patients with dissociative (psychogenic, non-epileptic) seizures (DS), including psychological and somatoform types of symptomatology. An additional aim was to assess possible relationships between dissociation, traumatic experiences, post-traumatic symptoms and seizure manifestations in this group. A total of 40 patients with DS were compared with a healthy control group (n = 43), matched on relevant demographic characteristics. Participants completed several self-report questionnaires, including the Multiscale Dissociation Inventory (MDI), Somatoform Dissociation Questionnaire-20, Traumatic Experiences Checklist and the Post-Traumatic Diagnostic Scale. Measures of seizure symptoms and current emotional distress (Hospital Anxiety and Depression Scale) were also administered. The clinical group reported significantly more psychological and somatoform dissociative symptoms, trauma, perceived impact of trauma, and post-traumatic symptoms than controls. Some dissociative symptoms (i.e. MDI disengagement, MDI depersonalization, MDI derealization, MDI memory disturbance, and somatoform dissociation scores) were elevated even after controlling for emotional distress; MDI depersonalization scores correlated positively with trauma scores while seizure symptoms correlated with MDI depersonalization, derealization and identity dissociation scores. Exploratory analyses indicated that somatoform dissociation specifically mediated the relationship between reported sexual abuse and DS diagnosis, along with depressive symptoms. A range of psychological and somatoform dissociative symptoms, traumatic experiences and post-traumatic symptoms are elevated in patients with DS relative to healthy controls, and seem related to seizure manifestations. Further studies are needed to explore peri-ictal dissociative experiences in more detail.

  12. Dissociation behavior of methane--ethane mixed gas hydrate coexisting structures I and II.

    Science.gov (United States)

    Kida, Masato; Jin, Yusuke; Takahashi, Nobuo; Nagao, Jiro; Narita, Hideo

    2010-09-09

    Dissociation behavior of methane-ethane mixed gas hydrate coexisting structures I and II at constant temperatures less than 223 K was studied with use of powder X-ray diffraction and solid-state (13)C NMR techniques. The diffraction patterns at temperatures less than 203 K showed both structures I and II simultaneously convert to Ih during the dissociation, but the diffraction pattern at temperatures greater than 208 K showed different dissociation behavior between structures I and II. Although the diffraction peaks from structure II decreased during measurement at constant temperatures greater than 208 K, those from structure I increased at the initial step of dissociation and then disappeared. This anomalous behavior of the methane-ethane mixed gas hydrate coexisting structures I and II was examined by using the (13)C NMR technique. The (13)C NMR spectra revealed that the anomalous behavior results from the formation of ethane-rich structure I. The structure I hydrate formation was associated with the dissociation rate of the initial methane-ethane mixed gas hydrate.

  13. Mean flow structure of non-equilibrium boundary layers with adverse ...

    Indian Academy of Sciences (India)

    According to them, an equilibrium boundary layer might exist if the pressure ... of adverse pressure gradient on the turbulent boundary layer at the flat plate for ..... of a constant-pressure turbulent layer to the sudden application of an sudden.

  14. Stabilization of third-order bilinear systems using constant controls

    Directory of Open Access Journals (Sweden)

    A. E. Golubev

    2014-01-01

    Full Text Available This paper deals with the zero equilibrium stabilization for dynamical systems that have control input singularities. A dynamical system with scalar control input is called nonregular if the coefficient of input becomes null on a subset of the phase space that contains the origin. One of the classes of nonregular dynamical systems is represented by bilinear systems. In case of second-order bilinear systems the necessary and sufficient conditions for the zero equilibrium stabilizability are known in the literature. However, in general case the stabilization problem in the presence of control input singularities has not been solved yet.In this note we solve the problem of the zero equilibrium stabilization for the third-order bilinear dynamical systems given in a canonical form. The solution is found in the class of constant controls. The necessary and sufficient conditions are obtained for the zero equilibrium stabilizability of the bilinear systems in question.The dependence of the zero equilibrium stabilizability on system parameter values is analyzed. The general criteria of stabilizability by means of constant controls are given for the bilinear systems in question. In case when all the system parameters have nonzero values the necessary and sufficient stabilizability conditions are proved. The case when some of the parameters are equal to zero is also considered.Further research can be focused on extending the obtained results to a higher-order case of bilinear and affine dynamical systems. The solution of the considered stabilization problem should also be found not only within constant controls but also in a class of state feedbacks, particularly, in the case when stabilizing constant control does not exist.One of the potential application areas for the obtained theoretical results is automatic control of technical plants like unmanned aerial vehicles and mobile robots.

  15. Effects of chirping on the dissociation dynamics of H2 in a two-frequency laser field

    International Nuclear Information System (INIS)

    Datta, Avijit; Bhattacharyya, S.S.; Kim, Bongsoo

    2002-01-01

    We present the effects of frequency chirping of laser pulses on (1+1)-photon resonance-enhanced dissociation dynamics of H 2 . The dissociation occurs via two closely spaced nonadiabatically coupled intermediate levels which are in one-photon resonance or near resonance with the initial level. Predissociating levels embedded into continua are considered. When the first laser field is sufficiently intense and suitably chirped, the dissociation probability is enhanced by adiabatic rapid passage through the avoided crossing arising from the frequency swept radiative interaction. The whole population of the ground level can be effectively transferred to the intermediate levels by this technique facilitating the dissociation process by the second field. We also report the effect of frequency detuning and chirp width on the dissociation probability. Widths of the two peaks of the dissociation line shape increase with an increase in chirp width, resulting in the possibility of control in the dissociation yield. When the first field is a laser pulse of low intensity and constant frequency and the second laser frequency is chirped, predissociating levels take important parts in the dissociation dynamics and we obtain a signature of the nonadiabatic effect of the first step on the second step of photodissociation dynamics. This feature is due to the presence of the predissociating levels and the nonadiabatic mixing of two intermediate levels. All these results can be explained in terms of the adiabatic dressed levels

  16. Beyond the Hubble Constant

    Science.gov (United States)

    1995-08-01

    about the distances to galaxies and thereby about the expansion rate of the Universe. A simple way to determine the distance to a remote galaxy is by measuring its redshift, calculate its velocity from the redshift and divide this by the Hubble constant, H0. For instance, the measured redshift of the parent galaxy of SN 1995K (0.478) yields a velocity of 116,000 km/sec, somewhat more than one-third of the speed of light (300,000 km/sec). From the universal expansion rate, described by the Hubble constant (H0 = 20 km/sec per million lightyears as found by some studies), this velocity would indicate a distance to the supernova and its parent galaxy of about 5,800 million lightyears. The explosion of the supernova would thus have taken place 5,800 million years ago, i.e. about 1,000 million years before the solar system was formed. However, such a simple calculation works only for relatively ``nearby'' objects, perhaps out to some hundred million lightyears. When we look much further into space, we also look far back in time and it is not excluded that the universal expansion rate, i.e. the Hubble constant, may have been different at earlier epochs. This means that unless we know the change of the Hubble constant with time, we cannot determine reliable distances of distant galaxies from their measured redshifts and velocities. At the same time, knowledge about such change or lack of the same will provide unique information about the time elapsed since the Universe began to expand (the ``Big Bang''), that is, the age of the Universe and also its ultimate fate. The Deceleration Parameter q0 Cosmologists are therefore eager to determine not only the current expansion rate (i.e., the Hubble constant, H0) but also its possible change with time (known as the deceleration parameter, q0). Although a highly accurate value of H0 has still not become available, increasing attention is now given to the observational determination of the second parameter, cf. also the Appendix at the

  17. Association constants of telluronium salts

    International Nuclear Information System (INIS)

    Kovach, N.A.; Rivkin, B.B.; Sadekov, T.D.; Shvajka, O.P.

    1996-01-01

    Association constants in acetonitrile of triphenyl telluronium salts, which are dilute electrolytes, are determined through the conductometry method. Satisfactory correlation dependence of constants of interion association and threshold molar electroconductivity on the Litvinenko-Popov constants for depositing groups is identified. 6 refs

  18. Anisotropic constant-roll inflation

    Energy Technology Data Exchange (ETDEWEB)

    Ito, Asuka; Soda, Jiro [Kobe University, Department of Physics, Kobe (Japan)

    2018-01-15

    We study constant-roll inflation in the presence of a gauge field coupled to an inflaton. By imposing the constant anisotropy condition, we find new exact anisotropic constant-roll inflationary solutions which include anisotropic power-law inflation as a special case. We also numerically show that the new anisotropic solutions are attractors in the phase space. (orig.)

  19. Quintessence and the cosmological constant

    International Nuclear Information System (INIS)

    Doran, M.; Wetterich, C.

    2003-01-01

    Quintessence -- the energy density of a slowly evolving scalar field -- may constitute a dynamical form of the homogeneous dark energy in the universe. We review the basic idea in the light of the cosmological constant problem. Cosmological observations or a time variation of fundamental 'constants' can distinguish quintessence from a cosmological constant

  20. Dissociation and the Development of Psychopathology.

    Science.gov (United States)

    Putnam, Frank W.; Trickett, Penelope K.

    This paper reviews the research on dissociation and the development of psychopathology in children and adolescents. Definitions and dimensions of dissociation are addressed, noting its range from normative daydreaming to the extremes found in individuals with multiple personality disorder. Memory dysfunctions, disturbances of identity, passive…

  1. Inflight dissociation of zircon in air plasma

    Energy Technology Data Exchange (ETDEWEB)

    Yugeswaran, S; Selvarajan, V [Bharathiar University, Coimbatore 641046 (India); Ananthapadmanabhan, P V; Thiyagarajan, T K [Laser and Plasma Technology Division, Bhabha Atomic Research Centre, Mumbai - 400 085 (India); Nair, Janardhanan [Ion Arc Technologies Pvt Ltd, Coimbatore (India)

    2010-02-01

    Thermal dissociation of zircon can be conveniently carried out in a plasma reactor, which is characterized by high temperature, high energy density and high quench rate. Zirconia is recovered from this partially dissociated zircon by alkali leaching. Dissociation of zircon has been conventionally carried out in argon gas, which is expensive. The present paper reports experimental results on thermal dissociation of zircon in air plasma medium. Process simulation for 'inflight' dissociation of zircon in air plasma medium is also presented. The experimental system consists of a central hollow graphite electrode, which acts as the cathode and a graphite anode. The material to be processed is fed centrally through the cathode. The unique feature of the system is that it uses air as the working gas to generate the thermal plasma. The system has been used to study in-flight dissociation of zircon in the thermal plasma jet. Dissociation was carried out over 10-25 kW power range. Results of the study indicate that complete dissociation of zircon to ZrO{sub 2} and silica could be accomplished at 25 kW in air plasma.

  2. Inflight dissociation of zircon in air plasma

    International Nuclear Information System (INIS)

    Yugeswaran, S; Selvarajan, V; Ananthapadmanabhan, P V; Thiyagarajan, T K; Nair, Janardhanan

    2010-01-01

    Thermal dissociation of zircon can be conveniently carried out in a plasma reactor, which is characterized by high temperature, high energy density and high quench rate. Zirconia is recovered from this partially dissociated zircon by alkali leaching. Dissociation of zircon has been conventionally carried out in argon gas, which is expensive. The present paper reports experimental results on thermal dissociation of zircon in air plasma medium. Process simulation for 'inflight' dissociation of zircon in air plasma medium is also presented. The experimental system consists of a central hollow graphite electrode, which acts as the cathode and a graphite anode. The material to be processed is fed centrally through the cathode. The unique feature of the system is that it uses air as the working gas to generate the thermal plasma. The system has been used to study in-flight dissociation of zircon in the thermal plasma jet. Dissociation was carried out over 10-25 kW power range. Results of the study indicate that complete dissociation of zircon to ZrO 2 and silica could be accomplished at 25 kW in air plasma.

  3. Coulomb dissociation of N-20,N-21

    NARCIS (Netherlands)

    Roeder, Marko; Adachi, Tatsuya; Aksyutina, Yulia; Alcantara, Juan; Altstadt, Sebastian; Alvarez-Pol, Hector; Ashwood, Nicholas; Atar, Leyla; Aumann, Thomas; Avdeichikov, Vladimir; Barr, M.; Beceiro, Saul; Bemmerer, Daniel; Benlliure, Jose; Bertulani, Carlos; Boretzky, Konstanze; Borge, Maria J. G.; Burgunder, G.; Caamano, Manuel; Caesar, Christoph; Casarejos, Enrique; Catford, Wilton; Cederkall, Joakim; Chakraborty, S.; Chartier, Marielle; Chulkov, Leonid; Cortina-Gil, Dolores; Crespo, Raquel; Pramanik, Ushasi Datta; Diaz-Fernandez, Paloma; Dillmann, Iris; Elekes, Zoltan; Enders, Joachim; Ershova, Olga; Estrade, A.; Farinon, F.; Fraile, Luis M.; Freer, Martin; Freudenberger, M.; Fynbo, Hans; Galaviz, Daniel; Geissel, Hans; Gernhaeuser, Roman; Goebel, Kathrin; Kalantar-Nayestanaki, Nasser; Najafi, Mohammad Ali; Rigollet, Catherine; Stoica, V.; Streicher, Branislav; Van de Walle, J.

    2016-01-01

    Neutron-rich light nuclei and their reactions play an important role in the creation of chemical elements. Here, data from a Coulomb dissociation experiment on N-20,N-21 are reported. Relativistic N-20,N-21 ions impinged on a lead target and the Coulomb dissociation cross section was determined in a

  4. Dissociative depression among women in the community.

    Science.gov (United States)

    Sar, Vedat; Akyüz, Gamze; Oztürk, Erdinç; Alioğlu, Firdevs

    2013-01-01

    This study screened the prevalence and correlates of dissociative disorders among depressive women in the general population. The Dissociative Disorders Interview Schedule and the posttraumatic stress disorder (PTSD) and borderline personality disorder sections of the Structured Clinical Interview for DSM-IV were administered to 628 women in 500 homes. The prevalence of current major depressive episode was 10.0%. Of the women, 26 (40.6%) had the lifetime diagnosis of a DSM-IV, dissociative disorder, yielding a prevalence of 4.1% for dissociative depression. This group was younger (mean age = 30.7 years) than the nondissociative depression women (mean age = 39.6 years). There was no difference between the 2 groups on comorbid somatization disorder, PTSD, or borderline personality disorder. Besides suicide attempts, the dissociative group was characterized by secondary features of dissociative identity disorder; Schneiderian symptoms; borderline personality disorder criteria; and extrasensory perceptions, including possession experiences. They reported suicidality, thoughts of guilt and worthlessness, diminished concentration and indecisiveness, and appetite and weight changes more frequently than the nondissociative group. Early cessation of school education and childhood sexual abuse were frequently reported by the dissociative depression group. With its distinct features, the concept of dissociative depression may facilitate understanding of treatment resistance in, development of better psychotherapy strategies for, and new thinking on the neurobiology and pharmacotherapy of depressive disorders.

  5. Dissociation kinetics of acyclic and macrocyclic polyaminopolycarboxylate complexes of yttrium

    International Nuclear Information System (INIS)

    Pathak, P.N.; Manchanda, V.K.

    2000-01-01

    Dissociation kinetics of Y III complexes of a linear as well as two macrocyclic polyaminopolycarboxylates, ethylenediamine diacetic acid (EDDA), 1,7-diaza-4,10,13-trioxacyclopentadecane-N,N'-diacetic acid (K21DA) and 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane-N,N'-diacetic acid (K22DA) have been studied at a constant ionic strength (0.1 M) under varying (H + ) and temperatures. Cu II ion acts as the scavenger of the free ligand. Dissociation rate of Y III -K21DA is insensitive to Cu II and acetate (used as buffer anion) concentrations. Kinetic stability of the three complexes follow the order : Y III -K22DA>Y III -K21DA>Y III -EDDA. Enthalpies of activation for K21DA and K22DA complexes of Y III are also evaluated. Thermodynamic stability constant (log K) for Y III -K22DA complex is 10.81 ± 0.04. (author)

  6. Dissociation of ethane by electron impact

    International Nuclear Information System (INIS)

    Winters, H.F.

    1979-01-01

    The absolute total dissociation cross section for ethane is reported for electron energies between 10 and 600 eV. A maximum value of 7.6 X 10 -16 cm 2 occurs at 80 eV while the apparent threshold is approximately 10 eV. Dissociative ionization is more probable than dissociation into neutral fragments at all energies except in the threshold region. The data indicates that fragmentation involving methane elimination (e - +C 2 H 6 → CH 4 + CH 2 ) occurs in less than 2% of the dissociative events for 50 < E < 600 eV. Arguments are presented which suggest that some of the lower excited states of ethane are stable against dissociation. (Auth.)

  7. Dissociation of polycyclic aromatic hydrocarbons: molecular dynamics studies

    Science.gov (United States)

    Simon, A.; Rapacioli, M.; Rouaut, G.; Trinquier, G.; Gadéa, F. X.

    2017-03-01

    We present dynamical studies of the dissociation of polycyclic aromatic hydrocarbon (PAH) radical cations in their ground electronic states with significant internal energy. Molecular dynamics simulations are performed, the electronic structure being described on-the-fly at the self-consistent-charge density functional-based tight binding (SCC-DFTB) level of theory. The SCC-DFTB approach is first benchmarked against DFT results. Extensive simulations are achieved for naphthalene , pyrene and coronene at several energies. Such studies enable one to derive significant trends on branching ratios, kinetics, structures and hints on the formation mechanism of the ejected neutral fragments. In particular, dependence of branching ratios on PAH size and energy were retrieved. The losses of H and C2H2 (recognized as the ethyne molecule) were identified as major dissociation channels. The H/C2H2 ratio was found to increase with PAH size and to decrease with energy. For , which is the most interesting PAH from the astrophysical point of view, the loss of H was found as the quasi-only channel for an internal energy of 30 eV. Overall, in line with experimental trends, decreasing the internal energy or increasing the PAH size will favour the hydrogen loss channels with respect to carbonaceous fragments. This article is part of the themed issue 'Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces'.

  8. Mechanisms of Coupled Vibrational Relaxation and Dissociation in Carbon Dioxide.

    Science.gov (United States)

    Armenise, Iole; Kustova, Elena

    2018-05-21

    A complete vibrational state-specific kinetic scheme describing dissociating carbon dioxide mixtures is proposed. CO 2 symmetric, bending and asymmetric vibrations and dissociation-recombination are strongly coupled through inter-mode vibrational energy transfers. Comparative study of state-resolved rate coefficients is carried out; the effect of different transitions may vary considerably with temperature. A non-equilibrium 1-D boundary layer flow typical to hypersonic planetary entry is studied in the state-to-state approach. To assess the sensitivity of fluid-dynamic variables and heat transfer to various vibrational transitions and chemical reactions, corresponding processes are successively included to the kinetic scheme. It is shown that vibrational-translational (VT) transitions in the symmetric and asymmetric modes do not alter the flow and can be neglected whereas the VT 2 exchange in the bending mode is the main channel of vibrational relaxation. Inter-mode vibrational exchanges affect the flow implicitly, through energy redistribution enhancing VT relaxation; the dominating role belongs to near-resonant transitions between symmetric and bending modes as well as between CO molecules and CO 2 asymmetric mode. Strong coupling between VT 2 relaxation and chemical reactions is emphasized. While vibrational distributions and average vibrational energy show strong dependence on the kinetic scheme, the heat flux is more sensitive to chemical reactions.

  9. Force and Stress along Simulated Dissociation Pathways of Cucurbituril-Guest Systems.

    Science.gov (United States)

    Velez-Vega, Camilo; Gilson, Michael K

    2012-03-13

    The field of host-guest chemistry provides computationally tractable yet informative model systems for biomolecular recognition. We applied molecular dynamics simulations to study the forces and mechanical stresses associated with forced dissociation of aqueous cucurbituril-guest complexes with high binding affinities. First, the unbinding transitions were modeled with constant velocity pulling (steered dynamics) and a soft spring constant, to model atomic force microscopy (AFM) experiments. The computed length-force profiles yield rupture forces in good agreement with available measurements. We also used steered dynamics with high spring constants to generate paths characterized by a tight control over the specified pulling distance; these paths were then equilibrated via umbrella sampling simulations and used to compute time-averaged mechanical stresses along the dissociation pathways. The stress calculations proved to be informative regarding the key interactions determining the length-force profiles and rupture forces. In particular, the unbinding transition of one complex is found to be a stepwise process, which is initially dominated by electrostatic interactions between the guest's ammoniums and the host's carbonyl groups, and subsequently limited by the extraction of the guest's bulky bicyclooctane moiety; the latter step requires some bond stretching at the cucurbituril's extraction portal. Conversely, the dissociation of a second complex with a more slender guest is mainly driven by successive electrostatic interactions between the different guest's ammoniums and the host's carbonyl groups. The calculations also provide information on the origins of thermodynamic irreversibilities in these forced dissociation processes.

  10. Fundamental functions in equilibrium thermodynamics

    NARCIS (Netherlands)

    Horst, H.J. ter

    In the standard presentations of the principles of Gibbsian equilibrium thermodynamics one can find several gaps in the logic. For a subject that is as widely used as equilibrium thermodynamics, it is of interest to clear up such questions of mathematical rigor. In this paper it is shown that using

  11. Is the dissociative adult suggestible? A test of the trauma and fantasy models of dissociation.

    Science.gov (United States)

    Kluemper, Nicole S; Dalenberg, Constance

    2014-01-01

    Psychologists have long assumed a connection between traumatic experience and psychological dissociation. This hypothesis is referred to as the trauma model of dissociation. In the past decade, a series of papers have been published that question this traditional causal link, proposing an alternative fantasy model of dissociation. In the present research, the relationship among dissociation, suggestibility, and fantasy proneness was examined. Suggestibility was measured through the Gudjonsson Scale of Interrogative Suggestibility (GSS) as well as an autobiographically based version of this measure based on the events of September 11, 2001. Consistent with prior research and with the trauma model, dissociation correlated positively with trauma severity (r = .32, p suggestibility measure. Although some participants did become quite emotional during the procedure, the risk/benefit ratio was perceived by almost all participants to be positive, with more reactive individuals evaluating the procedure more positively. The results consistently support the trauma model of dissociation and fail to support the fantasy model of dissociation.

  12. Dissociation and Memory Fragmentation in Posttraumatic Stress Disorder: An Evaluation of the Dissociative Encoding Hypothesis

    Science.gov (United States)

    Bedard-Gilligan, Michele; Zoellner, Lori A.

    2012-01-01

    Several prominent theories of posttraumatic stress disorder (PTSD) posit that peritraumatic dissociation results in insufficient encoding of the trauma memory and that persistent dissociation prevents memory elaboration, resulting in memory fragmentation and PTSD. In this review, we summarize the empirical literature on peritraumatic and trait dissociation and trauma narrative fragmentation as measured by meta-memory and rater/objective coding. Across 16 studies to date, the association between dissociation and fragmentation was most prominent when examining peritraumatic dissociation and patient's own ratings of memory fragmentation. This relationship did not hold when examining trait dissociation or rater-coded or computer-generated measures of fragmentation. Thus, initial evidence points more toward a strong self-reported association between constructs that is not supported on more objective fragmentation coding. Measurement overlap, construct ambiguity, and exclusion of potential confounds may underlie lack of a strong association between dissociation and objective-rated fragmentation. PMID:22348400

  13. The Shutdown Dissociation Scale (Shut-D)

    Science.gov (United States)

    Schalinski, Inga; Schauer, Maggie; Elbert, Thomas

    2015-01-01

    The evolutionary model of the defense cascade by Schauer and Elbert (2010) provides a theoretical frame for a short interview to assess problems underlying and leading to the dissociative subtype of posttraumatic stress disorder. Based on known characteristics of the defense stages “fright,” “flag,” and “faint,” we designed a structured interview to assess the vulnerability for the respective types of dissociation. Most of the scales that assess dissociative phenomena are designed as self-report questionnaires. Their items are usually selected based on more heuristic considerations rather than a theoretical model and thus include anything from minor dissociative experiences to major pathological dissociation. The shutdown dissociation scale (Shut-D) was applied in several studies in patients with a history of multiple traumatic events and different disorders that have been shown previously to be prone to symptoms of dissociation. The goal of the present investigation was to obtain psychometric characteristics of the Shut-D (including factor structure, internal consistency, retest reliability, predictive, convergent and criterion-related concurrent validity). A total population of 225 patients and 68 healthy controls were accessed. Shut-D appears to have sufficient internal reliability, excellent retest reliability, high convergent validity, and satisfactory predictive validity, while the summed score of the scale reliably separates patients with exposure to trauma (in different diagnostic groups) from healthy controls. The Shut-D is a brief structured interview for assessing the vulnerability to dissociate as a consequence of exposure to traumatic stressors. The scale demonstrates high-quality psychometric properties and may be useful for researchers and clinicians in assessing shutdown dissociation as well as in predicting the risk of dissociative responding. PMID:25976478

  14. The Shutdown Dissociation Scale (Shut-D

    Directory of Open Access Journals (Sweden)

    Inga Schalinski

    2015-05-01

    Full Text Available The evolutionary model of the defense cascade by Schauer and Elbert (2010 provides a theoretical frame for a short interview to assess problems underlying and leading to the dissociative subtype of posttraumatic stress disorder. Based on known characteristics of the defense stages “fright,” “flag,” and “faint,” we designed a structured interview to assess the vulnerability for the respective types of dissociation. Most of the scales that assess dissociative phenomena are designed as self-report questionnaires. Their items are usually selected based on more heuristic considerations rather than a theoretical model and thus include anything from minor dissociative experiences to major pathological dissociation. The shutdown dissociation scale (Shut-D was applied in several studies in patients with a history of multiple traumatic events and different disorders that have been shown previously to be prone to symptoms of dissociation. The goal of the present investigation was to obtain psychometric characteristics of the Shut-D (including factor structure, internal consistency, retest reliability, predictive, convergent and criterion-related concurrent validity.A total population of 225 patients and 68 healthy controls were accessed. Shut-D appears to have sufficient internal reliability, excellent retest reliability, high convergent validity, and satisfactory predictive validity, while the summed score of the scale reliably separates patients with exposure to trauma (in different diagnostic groups from healthy controls.The Shut-D is a brief structured interview for assessing the vulnerability to dissociate as a consequence of exposure to traumatic stressors. The scale demonstrates high-quality psychometric properties and may be useful for researchers and clinicians in assessing shutdown dissociation as well as in predicting the risk of dissociative responding.

  15. A Multiperiod Equilibrium Pricing Model

    Directory of Open Access Journals (Sweden)

    Minsuk Kwak

    2014-01-01

    Full Text Available We propose an equilibrium pricing model in a dynamic multiperiod stochastic framework with uncertain income. There are one tradable risky asset (stock/commodity, one nontradable underlying (temperature, and also a contingent claim (weather derivative written on the tradable risky asset and the nontradable underlying in the market. The price of the contingent claim is priced in equilibrium by optimal strategies of representative agent and market clearing condition. The risk preferences are of exponential type with a stochastic coefficient of risk aversion. Both subgame perfect strategy and naive strategy are considered and the corresponding equilibrium prices are derived. From the numerical result we examine how the equilibrium prices vary in response to changes in model parameters and highlight the importance of our equilibrium pricing principle.

  16. Non-equilibrium phase transitions

    CERN Document Server

    Henkel, Malte; Lübeck, Sven

    2009-01-01

    This book describes two main classes of non-equilibrium phase-transitions: (a) static and dynamics of transitions into an absorbing state, and (b) dynamical scaling in far-from-equilibrium relaxation behaviour and ageing. The first volume begins with an introductory chapter which recalls the main concepts of phase-transitions, set for the convenience of the reader in an equilibrium context. The extension to non-equilibrium systems is made by using directed percolation as the main paradigm of absorbing phase transitions and in view of the richness of the known results an entire chapter is devoted to it, including a discussion of recent experimental results. Scaling theories and a large set of both numerical and analytical methods for the study of non-equilibrium phase transitions are thoroughly discussed. The techniques used for directed percolation are then extended to other universality classes and many important results on model parameters are provided for easy reference.

  17. Determination of acidity constants and ionic mobilities of polyprotic peptide hormones by CZE

    Czech Academy of Sciences Publication Activity Database

    Šolínová, Veronika; Kašička, Václav

    2013-01-01

    Roč. 34, č. 18 (2013), s. 2655-2665 ISSN 0173-0835 R&D Projects: GA ČR(CZ) GAP206/12/0453; GA ČR(CZ) GA13-17224S Institutional support: RVO:61388963 Keywords : acid dissociation constant * gonadotropin-releasing hormones * ionization constant * peptides * pK(a) Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 3.161, year: 2013

  18. Synthesis, Acidity Constants and Tautomeric Structure of the Diazonium Coupling Products of 2-(Benzylsulfanyl)-7H-purin-6-one in Its Ground and Excited States

    OpenAIRE

    Darwish, Elham S.; Mosselhi, Mosselhi A.; Altalbawy, Farag M.; Saad, Hosam A.

    2011-01-01

    A series of new 8-arylhydrazono-2-(benzylsulfanyl)-7H-purin-6-ones 6 were synthesized, their electronic absorption spectra in different organic solvents of varying polarities were investigated and their acid dissociation constants in both the ground and excited states were determined spectrophotometrically. The tautomeric structures of such products were elucidated by spectral analyses and correlation of their acid dissociation constants with the Hammett equation. The results indicated that t...

  19. Psychotherapy and Pharmacotherapy for Patients with Dissociative Identity Disorder

    OpenAIRE

    Gentile, Julie P.; Dillon, Kristy S.; Gillig, Paulette Marie

    2013-01-01

    There is a wide variety of what have been called “dissociative disorders,” including dissociative amnesia, dissociative fugue, depersonalization disorder, dissociative identity disorder, and forms of dissociative disorder not otherwise specified. Some of these diagnoses, particularly dissociative identity disorder, are controversial and have been questioned by many clinicians over the years. The disorders may be under-diagnosed or misdiagnosed, but many persons who have experienced trauma rep...

  20. Heterogeneous equilibrium in mplybdenum-iodine system

    International Nuclear Information System (INIS)

    Klinkova, L.A.

    1983-01-01

    Heterogeneous equilibrium in the Mo-J system is studied to reveal regions of existence of molybdenum iodides, is studied. The investigation is performed for atomic ratio I/Mo=0.02-7.5 in the temperature range of 300-1370 K using methods of thermographic, X-ray phase, chemical and optical analyses of phases quenched after isothermal annealing. It is shown that higher molybdenum iodides (Mo1 4 , MoJ 5 , MoJ 6 ) are thermally unstable compounds and exist in the Mo-J system at low temperatures (360-490 K). Above 470 K higher iodides dissociate up to molybdenum triiodide. MoJ 3 under the pressure of iodine vapors is stable up to 970 K. Molybdenum diiodide is the product of triiodide decomposition and forms in the Mo-J system in the 700-1270 K range. At the J/Mo>>3 ratio the product of triiodide decomposition is MoJsub(2.87) which is thermally unstable up to 570 K, while in iodine atmosphere - up to 1170 K

  1. Estimation of acidity constants, ionic mobilities and charges of antimicrobial peptides by capillary electrophoresis

    Czech Academy of Sciences Publication Activity Database

    Tůmová, Tereza; Monincová, Lenka; Čeřovský, Václav; Kašička, Václav

    2016-01-01

    Roč. 37, 23/24 (2016), s. 3186-3195 ISSN 0173-0835 R&D Projects: GA ČR(CZ) GA15-01948S Institutional support: RVO:61388963 Keywords : acid dissociation constant * antimicrobial peptides * capillary electrophoresis * charge * mobility * Pka Subject RIV: CB - Analytical Chemistry , Separation Impact factor: 2.744, year: 2016

  2. Analysis of equilibrium and topology of tokamak plasmas

    International Nuclear Information System (INIS)

    Milligen, B.P. van.

    1991-01-01

    In a tokamak, the plasma is confined by means of a magnetic field. There exists an equilibrium between outward forces due to the pressure gradient in plasma and inward forces due to the interaction between currents flowing inside the plasma and the magnetic field. The equilibrium magnetic field is characterized by helical field lines that lie on nested toroidal surfaces of constant flux. The equilibrium yields values for global and local plasma parameters (e.g. plasma position, total current, local pressure). Thus, precise knowledge of the equilibrium is essential for plasma control, for the understanding of many phenomena occurring in the plasma (in particular departures from the ideal equilibrium involving current filamentation on the flux surfaces that lead to the formation of islands, i.e. nested helical flux surfaces), and for the interpretation of many different types of measurements (e.g. the translation of line integrated electron density measurements made by laser beams probing the plasma into a local electron density on a flux surface). The problem of determining the equilibrium magnetic field from external magnetic field measurements has been studied extensively in literature. The problem is 'ill-posed', which means that the solution is unstable to small changes in the measurement data, and the solution has to be constrained in order to stabilize it. Various techniques for handling this problem have been suggested in literature. Usually ad-hoc restrictions are imposed on the equilibrium solution in order to stabilize it. More equilibrium solvers are not able to handle very dissimilar measurement data which means information on the equilibrium is lost. The generally do not allow a straightforward error estimate of the obtained results to be made, and they require large amounts of computing time. This problems are addressed in this thesis. (author). 104 refs.; 42 figs.; 6 tabs

  3. Dissociative Part-Dependent Resting-State Activity in Dissociative Identity Disorder : A Controlled fMRI Perfusion Study

    NARCIS (Netherlands)

    Schlumpf, Yolanda R.; Reinders, Antje A. T. S.; Nijenhuis, Ellert R. S.; Luechinger, Roger; van Osch, Matthias J. P.; Jaencke, Lutz

    2014-01-01

    Background: In accordance with the Theory of Structural Dissociation of the Personality (TSDP), studies of dissociative identity disorder (DID) have documented that two prototypical dissociative subsystems of the personality, the "Emotional Part'' (EP) and the "Apparently Normal Part'' (ANP), have

  4. Income- and energy-taxation for redistribution in general equilibrium

    International Nuclear Information System (INIS)

    FitzRoy, F.R.

    1993-01-01

    In a 3-factor General Equilibrium (GE)-model with a continuum of ability, the employed choose optimal labour supply, and equilibrium unemployment is determined by benefits funded by wage- and energy-taxes. Aggregate labour and the net wage may increase or decrease with taxation (and unemployment), and conditions for a reduction in redistributive wage-taxes to be Pareto-improving are derived. A small energy tax always raises the net wage, providing the wage tax is reduced to maintain constant employment and a balanced budget. High ability households prefer higher energy taxes when externalities are uniformly distributed and non-distorting. (author)

  5. Magnetohydrodynamic equilibrium with spheroidal plasma-vacuum interface

    International Nuclear Information System (INIS)

    Kaneko, Shobu; Chiyoda, Katsuji; Hirota, Isao.

    1983-01-01

    The Grad-Shafranov equations for an oblate and a prolate spheroidal plasmas are solved analytically under the assumptions, Bsub(phi) = 0 and dp/dpsi = constant. Here Bsub(phi) is the toroidal magnetic field, p is the kinetic pressure, and psi is the magnetic flux function. The plasmas in magnetohydrodynamic equilibrium are shown to be toroidal. The equilibrium magnetic-field configurations outside the spheroidal plasmas are considerably different from that of a spherical plasma. A line cusp or two point cusps appear outside the oblate or the prolate spheroidal plasma, respectively. (author)

  6. From state dissociation to status dissociatus.

    Science.gov (United States)

    Antelmi, Elena; Ferri, Raffaele; Iranzo, Alex; Arnulf, Isabelle; Dauvilliers, Yves; Bhatia, Kailash P; Liguori, Rocco; Schenck, Carlos H; Plazzi, Giuseppe

    2016-08-01

    The states of being are conventionally defined by the simultaneous occurrence of behavioral, neurophysiological and autonomic descriptors. State dissociation disorders are due to the intrusion of features typical of a different state into an ongoing state. Disorders related to these conditions are classified according to the ongoing main state and comprise: 1) Dissociation from prevailing wakefulness as seen in hypnagogic or hypnopompic hallucinations, automatic behaviors, sleep drunkenness, cataplexy and sleep paralysis 2) Dissociation from rapid eye movement (REM) sleep as seen in REM sleep behavior disorder and lucid dreaming and 3) Dissociation from NREM sleep as seen in the disorders of arousal. The extreme expression of states dissociation is characterized by the asynchronous occurrence of the various components of the different states that prevents the recognition of any state of being. This condition has been named status dissociatus. According to the underlying disorders/diseases and to their severity, among status dissociatus we may recognize disorders in which such an extreme dissociation occurs only at night time or intermittently (i.e., autoimmune encephalopathies, narcolepsy type 1 and IgLON5 parasomnia), and others in which it occurs nearly continuously with complete loss of any conventionally defined state of being, and of the circadian pattern (agrypnia excitata). Here, we render a comprehensive review of all diseases/disorders associated with state dissociation and status dissociatus and propose a critical classification of this complex scenario. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. Non-equilibrium supramolecular polymerization.

    Science.gov (United States)

    Sorrenti, Alessandro; Leira-Iglesias, Jorge; Markvoort, Albert J; de Greef, Tom F A; Hermans, Thomas M

    2017-09-18

    Supramolecular polymerization has been traditionally focused on the thermodynamic equilibrium state, where one-dimensional assemblies reside at the global minimum of the Gibbs free energy. The pathway and rate to reach the equilibrium state are irrelevant, and the resulting assemblies remain unchanged over time. In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) structures that heavily depend on the method of preparation (i.e., pathway complexity), and where the assembly rates are of key importance. Kinetic models have greatly improved our understanding of competing pathways, and shown how to steer supramolecular polymerization in the desired direction (i.e., pathway selection). The most recent innovation in the field relies on energy or mass input that is dissipated to keep the system away from the thermodynamic equilibrium (or from other non-dissipative states). This tutorial review aims to provide the reader with a set of tools to identify different types of self-assembled states that have been explored so far. In particular, we aim to clarify the often unclear use of the term "non-equilibrium self-assembly" by subdividing systems into dissipative, and non-dissipative non-equilibrium states. Examples are given for each of the states, with a focus on non-dissipative non-equilibrium states found in one-dimensional supramolecular polymerization.

  8. Spontaneity and Equilibrium: Why "?G Equilibrium" Are Incorrect

    Science.gov (United States)

    Raff, Lionel M.

    2014-01-01

    The fundamental criteria for chemical reactions to be spontaneous in a given direction are generally incorrectly stated as ?G equilibrium are also misstated as being ?G = 0 or ?A = 0. Following a brief review of the…

  9. Dissociation in Psychiatric Disorders: A Meta-Analysis of Studies Using the Dissociative Experiences Scale.

    Science.gov (United States)

    Lyssenko, Lisa; Schmahl, Christian; Bockhacker, Laura; Vonderlin, Ruben; Bohus, Martin; Kleindienst, Nikolaus

    2018-01-01

    Dissociation is a complex, ubiquitous construct in psychopathology. Symptoms of dissociation are present in a variety of mental disorders and have been connected to higher burden of illness and poorer treatment response, and not only in disorders with high levels of dissociation. This meta-analysis offers a systematic and evidence-based study of the prevalence and distribution of dissociation, as assessed by the Dissociative Experiences Scale, within different categories of mental disorders, and it updates an earlier meta-analysis. More than 1,900 original publications were screened, and 216 were included in the meta-analysis, comprising 15,219 individuals in 19 diagnostic categories. The largest mean dissociation scores were found in dissociative disorders (mean scores >35), followed by posttraumatic stress disorder, borderline personality disorder, and conversion disorder (mean scores >25). Somatic symptom disorder, substance-related and addictive disorders, feeding and eating disorders, schizophrenia, anxiety disorder, OCD, and most affective disorders also showed mean dissociation scores >15. Bipolar disorders yielded the lowest dissociation scores (mean score, 14.8). The findings underline the importance of careful psychopathological assessment of dissociative symptoms in the entire range of mental disorders.

  10. Energy distribution in dissociations of polyatomic molecules

    International Nuclear Information System (INIS)

    Koernig, S.A.

    1989-01-01

    In this thesis studies are reported of fragmentation processes in polyatomic molecules. In order to find out which dessocaciation reactions take place, how they are brought about by the internal energy of the reactant, and to investigate the structure of the dissociating 'transition state', the fragment mass and the corresponding kinetic energy release (KER) are determined by differential translational spectroscopy using a position and time sensitive two-particle coincidence detector. The results are interpreted using the statistical theory of unimolecular dissociation. It turns out that the standard assumptions of the theory, especially in calculating KER-distributions, are not realistic in all molecules considered. Dissociation is induced by the neutralization with alkali metal vapour. In ch. 2 the experimental method and the analysis of the data (dissociation pathways, branching ratios and ε-d-distributions) are introduced and exemplified by measurements of cyclohexane, which represents the upper limit in precursor and fragment mass accessible in the apparatus. In ch. 3 a study is reported of the molecules methylchloride (CH 3 Cl) and the acetylradical (CH 3 CO). In spite of their similar geometric structures, completely different dissociation mechanisms have been found. Methylchloride dissociates via a repulsive state; acetyl radicals show energy scrambling. The energy distribution from dissociating acetyl exemplifies dynamical effects in the dissociation. In ch. 4 an investigation of a number of prototype hydrocarbons is presented. The dissociation pathways of several small linear alkanes indicate that neutralization takes place to unknown repulsive potentials, of which the position and steepness are determined from the kinetic energy release. (author). 118 refs.; 40 figs.; 5 tabs

  11. Helical axis stellarator equilibrium model

    International Nuclear Information System (INIS)

    Koniges, A.E.; Johnson, J.L.

    1985-02-01

    An asymptotic model is developed to study MHD equilibria in toroidal systems with a helical magnetic axis. Using a characteristic coordinate system based on the vacuum field lines, the equilibrium problem is reduced to a two-dimensional generalized partial differential equation of the Grad-Shafranov type. A stellarator-expansion free-boundary equilibrium code is modified to solve the helical-axis equations. The expansion model is used to predict the equilibrium properties of Asperators NP-3 and NP-4. Numerically determined flux surfaces, magnetic well, transform, and shear are presented. The equilibria show a toroidal Shafranov shift

  12. Dissociative identity disorder: a controversial diagnosis.

    Science.gov (United States)

    Gillig, Paulette Marie

    2009-03-01

    A brief description of the controversies surrounding the diagnosis of dissociative identity disorder is presented, followed by a discussion of the proposed similarities and differences between dissociative identity disorder and borderline personality disorder. The phenomenon of autohypnosis in the context of early childhood sexual trauma and disordered attachment is discussed, as is the meaning of alters or alternate personalities. The author describes recent neurosciences research that may relate the symptoms of dissociative identity disorder to demonstrable disordered attention and memory processes. A clinical description of a typical patient presentation is included, plus some recommendations for approaches to treatment.

  13. Dissociative recombination of molecular ions H2+

    International Nuclear Information System (INIS)

    Abarenov, A.V.; Marchenko, V.S.

    1989-01-01

    The total cross sections of dissociation and dissociative recombination of slow electrons and molecular ions H 2 + have been calculated in terms of the quasiclassical and dipole approximations. In the calculations allowance was made for the quantum nature of vibrational motion of heavy particles and presence of autoionization of divergence states of the H 2 (Σ u , nl) molecules. It is shown that the H 2 + ion dissociation cross sections are dominant in increase of the electron energy in the ε >or approx. 2-3 eV region for H 2 + (v) ion distribution over the vibrational levels characteristic for the beam experiments. 15 refs.; 5 figs

  14. Wavepacket theory of collisional dissociation in molecules

    International Nuclear Information System (INIS)

    Kulander, K.

    1980-01-01

    An explicit integration scheme is used to solve the time dependent Schroedinger equation for wavepackets which model collisions in the collinear H + H 2 system. A realistic LEPS-type potential energy surface is used. Collision energies considered are above the dissociation threshold and probabilities for collision induced dissociation are reported. Also quantum mechanical state-to-state transition probabilities are generated. These results are compared to extensive classical trajectory calculations performed on this same system. The time evolution of the wavepacket densities is studied to understand the dynamics of the collinear collisional dissociation process

  15. Rate constant for reaction of hydroxyl radicals with bicarbonate ions

    International Nuclear Information System (INIS)

    Buxton, G.V.; Elliot, A.J.

    1986-01-01

    The rate constant for reaction of hydroxyl radicals with the bicarbonate ion has been determined to be 8.5 x 10 6 dm 3 mol -1 s -1 . This value was calculated from: the measured rate of formation of the CO 3 - radical in pulsed electron irradiation of bicarbonate solutions over the pH range 7.0 to 9.4; the pK for the equilibrium HCO 3 - = CO 3 2- + H + ; and the rate constant for hydroxyl radicals reacting with the carbonate ion. (author)

  16. General concept of a gas engine for a hybrid vehicle, operating on methanol dissociation products

    International Nuclear Information System (INIS)

    Tartakovsky, L.; Aleinikov, Y.; Fainberg, V.; Garbar, A.; Gutman, M.; Hetsroni, G.; Schindler, Y.; Zvirin, Y.

    1998-01-01

    The paper presents a general concept of a hybrid propulsion system, based on an SI internal combustion engine fueled by methanol dissociation products (MDP). The proposed hybrid propulsion scheme is a series hybrid, which allows the engine to be operated in an on-off mode at constant optimal regime. The engine is fed by gaseous products of methanol dissociation (mainly hydrogen and carbon monoxide) emerging from an on-board catalytic reformer. The general scheme and base operation features of the propulsion system are described. The benefits that may be achieved by combining the well-known idea of on-board methanol dissociation with the hybrid vehicle concept are discussed. The proposed scheme is compared with those of systems operating on gasoline, liquid methanol, hydrogen and also with the multi-regime (not hybrid) engine fed by MDP

  17. Model, First-Principle Calculation of Ammonia Dissociation on Si(100 Surface. Importance of Proton Tunneling

    Directory of Open Access Journals (Sweden)

    Marek Z. Zgierski

    2003-06-01

    Full Text Available Abstract: The dissociation of an ammonia molecule on a cluster of Si atoms simulating the 100 silicon crystal structure with two Si dimers has been investigated by means of the DFT and an approximate instanton methods. The model corresponds to the low coverage limit of the surface. Absolute rate constants of two different dissociation paths are evaluated together with deuterium isotope effects. It is demonstrated that, even at room temperatures, the process is dominated by tunneling and that dissociation to a silicon atom of the adjacent dimer, rather than a silicon within the same dimer, is the prevailing mechanism. This leads to creation of a metastable structure which will slowly decay through a two-step hydrogen atom migration towards the absolute minimum on the potential energy surface corresponding to the NH2 group and the hydrogen atom residing in the same dimer.

  18. Theoretical investigation of shock stand-off distance for non-equilibrium flows over spheres

    KAUST Repository

    Shen, Hua

    2018-02-20

    We derived a theoretical solution of the shock stand-off distance for a non-equilibrium flow over spheres based on Wen and Hornung’s solution and Olivier’s solution. Compared with previous approaches, the main advantage of the present approach is allowing an analytic solution without involving any semi-empirical parameter for the whole non-equilibrium flow regimes. The effects of some important physical quantities therefore can be fully revealed via the analytic solution. By combining the current solution with Ideal Dissociating Gas (IDG) model, we investigate the effects of free stream kinetic energy and free stream dissociation level (which can be very different between different facilities) on the shock stand-off distance.

  19. Increased bone calcium dissociation in lead-exposed rats

    Directory of Open Access Journals (Sweden)

    Eko Suhartono

    2012-12-01

    Full Text Available Background Lead is still a major environmental and occupational health hazard, since it is extensively used in the production of paints, gasoline and cosmetics. This causes the metal to be ubiquitous in the environment, being found in the air, soil, and water, from which it can enter the human body by inhalation or ingestion. Absorbed lead is capable of altering the calcium levels in bone. The aim of this study was to demonstrate the effect of lead on bone calcium levels by measuring the reaction constant, Gibbs free energy, and enthalpy. Methods This study was of pure experimental design using 100 male albino rats (Rattus norvegicus. The experimental animals were assigned by simple randomization to two groups, one group receiving lead acetate orally at a dosage of 100 mg/kgBW, while the other group did not receive lead acetate. The intervention was given for 4 weeks and the rats were observed weekly for measurement of bone calcium levels by the permanganometric method. Results This study found that k1 (hydroxyapatite dissociation rate constant was 0.90 x 10-3 dt-1, and that k2 (hydroxyapatite association rate constant was 6.16 x 10-3 dt-1 for the control group, whereas for the intervention group k1 = 26.20 x 10-3 dt-1 and k2 = 16.75 x 10-3 dt-1. Thermodynamically, the overall reaction was endergonic and endothermic (DG > 0 and DH > 0. ConclusionS Lead exposure results in increased dissociation rate of bone in comparison with its association rate. Overall, the reaction was endergonic and endothermic (DG > 0 and DH > 0.

  20. Increased bone calcium dissociation in lead-exposed rats

    Directory of Open Access Journals (Sweden)

    Eko Suhartono

    2015-12-01

    Full Text Available BACKGROUND Lead is still a major environmental and occupational health hazard, since it is extensively used in the production of paints, gasoline and cosmetics. This causes the metal to be ubiquitous in the environment, being found in the air, soil, and water, from which it can enter the human body by inhalation or ingestion. Absorbed lead is capable of altering the calcium levels in bone. The aim of this study was to demonstrate the effect of lead on bone calcium levels by measuring the reaction constant, Gibbs free energy, and enthalpy. METHODS This study was of pure experimental design using 100 male albino rats (Rattus norvegicus. The experimental animals were assigned by simple randomization to two groups, one group receiving lead acetate orally at a dosage of 100 mg/ kgBW, while the other group did not receive lead acetate. The intervention was given for 4 weeks and the rats were observed weekly for measurement of bone calcium levels by the permanganometric method. RESULTS This study found that k1 (hydroxyapatite dissociation rate constant was 0.90 x 10-3 dt-1, and that k2 (hydroxyapatite association rate constant was 6.16 x 10-3 dt-1 for the control group, whereas for the intervention group k1 = 26.20 x 10-3 dt-1 and k2 = 16.75 x 10-3 dt-1. Thermodynamically, the overall reaction was endergonic and endothermic (ΔG > 0 and ΔH > 0. CONCLUSIONS Lead exposure results in increased dissociation rate of bone in comparison with its association rate. Overall, the reaction was endergonic and endothermic (ΔG > 0 and ΔH > 0.

  1. Global stability of an SEIR epidemic model with constant immigration

    Energy Technology Data Exchange (ETDEWEB)

    Li Guihua [Key Laboratory of Eco-environments in Three Gorges Reservoir Region (Ministry of Education), Faculty of Life Science, Southwest China Normal University, Chongqing 400715 (China) and Department of Mathematics, Southwest China Normal University, Chongqing 400715 (China) and Department of Mathematics, North University of China, Taiyuan Shanxi 030051 (China)]. E-mail: liguihua@nuc.edu.cn; Wang Wendi [Department of Mathematics, Southwest China Normal University, Chongqing 400715 (China); Jin Zhen [Department of Mathematics, North University of China, Taiyuan Shanxi 030051 (China)

    2006-11-15

    An SEIR epidemic model with the infectious force in the latent (exposed), infected and recovered period is studied. It is assumed that susceptible and exposed individuals have constant immigration rates. The model exhibits a unique endemic state if the fraction p of infectious immigrants is positive. If the basic reproduction number R is greater than 1, sufficient conditions for the global stability of the endemic equilibrium are obtained by the compound matrix theory.

  2. Global stability of an SEIR epidemic model with constant immigration

    International Nuclear Information System (INIS)

    Li Guihua; Wang Wendi; Jin Zhen

    2006-01-01

    An SEIR epidemic model with the infectious force in the latent (exposed), infected and recovered period is studied. It is assumed that susceptible and exposed individuals have constant immigration rates. The model exhibits a unique endemic state if the fraction p of infectious immigrants is positive. If the basic reproduction number R is greater than 1, sufficient conditions for the global stability of the endemic equilibrium are obtained by the compound matrix theory

  3. Elongational flow of polymer melts at constant strain rate, constant stress and constant force

    Science.gov (United States)

    Wagner, Manfred H.; Rolón-Garrido, Víctor H.

    2013-04-01

    Characterization of polymer melts in elongational flow is typically performed at constant elongational rate or rarely at constant tensile stress conditions. One of the disadvantages of these deformation modes is that they are hampered by the onset of "necking" instabilities according to the Considère criterion. Experiments at constant tensile force have been performed even more rarely, in spite of the fact that this deformation mode is free from necking instabilities and is of considerable industrial relevance as it is the correct analogue of steady fiber spinning. It is the objective of the present contribution to present for the first time a full experimental characterization of a long-chain branched polyethylene melt in elongational flow. Experiments were performed at constant elongation rate, constant tensile stress and constant tensile force by use of a Sentmanat Extensional Rheometer (SER) in combination with an Anton Paar MCR301 rotational rheometer. The accessible experimental window and experimental limitations are discussed. The experimental data are modelled by using the Wagner I model. Predictions of the steady-start elongational viscosity in constant strain rate and creep experiments are found to be identical, albeit only by extrapolation of the experimental data to Hencky strains of the order of 6. For constant stress experiments, a minimum in the strain rate and a corresponding maximum in the elongational viscosity is found at a Hencky strain of the order of 3, which, although larger than the steady-state value, follows roughly the general trend of the steady-state elongational viscosity. The constitutive analysis also reveals that constant tensile force experiments indicate a larger strain hardening potential than seen in constant elongation rate or constant tensile stress experiments. This may be indicative of the effect of necking under constant elongation rate or constant tensile stress conditions according to the Considère criterion.

  4. Determination of equilibrium structures of bromothymol blue revealed by using quantum chemistry with an aid of multivariate analysis of electronic absorption spectra.

    Science.gov (United States)

    Shimada, Toru; Hasegawa, Takeshi

    2017-10-05

    The pH dependent chemical structures of bromothymol blue (BTB), which have long been under controversy, are determined by employing a combined technique of multivariate analysis of electronic absorption spectra and quantum chemistry. Principle component analysis (PCA) of the pH dependent spectra apparently reveals that only two chemical species are adequate to fully account for the color changes, with which the spectral decomposition is readily performed by using augmented alternative least-squares (ALS) regression analysis. The quantity variation by the ALS analysis also reveals the practical acid dissociation constant, pK a '. The determination of pK a ' is performed for various ionic strengths, which reveals the thermodynamic acid constant (pK a =7.5) and the number of charge on each chemical species; the yellow form is negatively charged species of -1 and the blue form that of -2. On this chemical information, the quantum chemical calculation is carried out to find that BTB molecules take the pure quinoid form in an acid solution and the quinoid-phenolate form in an alkaline solution. The time-dependent density functional theory (TD-DFT) calculations for the theoretically determined chemical structures account for the peak shift of the electronic spectra. In this manner, the structures of all the chemical species appeared in equilibrium have finally been confirmed. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Determination of equilibrium structures of bromothymol blue revealed by using quantum chemistry with an aid of multivariate analysis of electronic absorption spectra

    Science.gov (United States)

    Shimada, Toru; Hasegawa, Takeshi

    2017-10-01

    The pH dependent chemical structures of bromothymol blue (BTB), which have long been under controversy, are determined by employing a combined technique of multivariate analysis of electronic absorption spectra and quantum chemistry. Principle component analysis (PCA) of the pH dependent spectra apparently reveals that only two chemical species are adequate to fully account for the color changes, with which the spectral decomposition is readily performed by using augmented alternative least-squares (ALS) regression analysis. The quantity variation by the ALS analysis also reveals the practical acid dissociation constant, pKa‧. The determination of pKa‧ is performed for various ionic strengths, which reveals the thermodynamic acid constant (pKa = 7.5) and the number of charge on each chemical species; the yellow form is negatively charged species of - 1 and the blue form that of - 2. On this chemical information, the quantum chemical calculation is carried out to find that BTB molecules take the pure quinoid form in an acid solution and the quinoid-phenolate form in an alkaline solution. The time-dependent density functional theory (TD-DFT) calculations for the theoretically determined chemical structures account for the peak shift of the electronic spectra. In this manner, the structures of all the chemical species appeared in equilibrium have finally been confirmed.

  6. Numerical Verification Of Equilibrium Chemistry

    International Nuclear Information System (INIS)

    Piro, Markus; Lewis, Brent; Thompson, William T.; Simunovic, Srdjan; Besmann, Theodore M.

    2010-01-01

    A numerical tool is in an advanced state of development to compute the equilibrium compositions of phases and their proportions in multi-component systems of importance to the nuclear industry. The resulting software is being conceived for direct integration into large multi-physics fuel performance codes, particularly for providing boundary conditions in heat and mass transport modules. However, any numerical errors produced in equilibrium chemistry computations will be propagated in subsequent heat and mass transport calculations, thus falsely predicting nuclear fuel behaviour. The necessity for a reliable method to numerically verify chemical equilibrium computations is emphasized by the requirement to handle the very large number of elements necessary to capture the entire fission product inventory. A simple, reliable and comprehensive numerical verification method is presented which can be invoked by any equilibrium chemistry solver for quality assurance purposes.

  7. Equilibrium ignition for ICF capsules

    International Nuclear Information System (INIS)

    Lackner, K.S.; Colgate, S.A.; Johnson, N.L.; Kirkpatrick, R.C.; Menikoff, R.; Petschek, A.G.

    1993-01-01

    There are two fundamentally different approaches to igniting DT fuel in an ICF capsule which can be described as equilibrium and hot spot ignition. In both cases, a capsule which can be thought of as a pusher containing the DT fuel is imploded until the fuel reaches ignition conditions. In comparing high-gain ICF targets using cryogenic DT for a pusher with equilibrium ignition targets using high-Z pushers which contain the radiation. The authors point to the intrinsic advantages of the latter. Equilibrium or volume ignition sacrifices high gain for lower losses, lower ignition temperature, lower implosion velocity and lower sensitivity of the more robust capsule to small fluctuations and asymmetries in the drive system. The reduction in gain is about a factor of 2.5, which is small enough to make the more robust equilibrium ignition an attractive alternative

  8. On the local equilibrium condition

    International Nuclear Information System (INIS)

    Hessling, H.

    1994-11-01

    A physical system is in local equilibrium if it cannot be distinguished from a global equilibrium by ''infinitesimally localized measurements''. This should be a natural characterization of local equilibrium, but the problem is to give a precise meaning to the qualitative phrase ''infinitesimally localized measurements''. A solution is suggested in form of a Local Equilibrium Condition (LEC), which can be applied to linear relativistic quantum field theories but not directly to selfinteracting quantum fields. The concept of local temperature resulting from LEC is compared to an old approach to local temperature based on the principle of maximal entropy. It is shown that the principle of maximal entropy does not always lead to physical states if it is applied to relativistic quantum field theories. (orig.)

  9. Isotope exchange study of the dissociation of metal-humic complexes

    International Nuclear Information System (INIS)

    Mizera, J.; Jansova, A.; Hvozdova, I.; Benes, P.

    2002-01-01

    Prediction of the migration of toxic metals and radionuclides in the environment requires knowledge of equilibrium and kinetic parameters characterising their interaction with humic substance (HS). In this work, isotope exchange of Eu and Co in the systems containing HS has been used to study dissociation of the cations from their complexes with HS under quasi-stationary conditions. In the experimental arrangement of the so-called diaphragm method, a dialysis membrane divides two compartments containing solutions of metal and HS, identical in both half-cells but for radiolabeling ( 152 Eu and 60 Co) applied only in one cell. The membrane is permeable for free metal cation but not for the metal-HS complex. The slow dissociation of metal cation from HS is reflected by retardation (compared to a reference system in the absence of HS) of the rate of the isotope exchange between the two compartments. However, only an apparent dissociation rate can be observed, as detection of fast dissociation is limited by the rate of diffusion of dissociated cations through membrane and by their recombination with available binding sites of HS. The rate of isotope exchange of Eu and Co in the systems with HS (Aldrich sodium humate, soil humic and fulvic acid) was monitored as function of pH (4 and 6), ionic strength (0.01 and 0.1 M), and the degree of HS loading with metal ([M] 0 = 10 -7 - 2x10 -5 M at 10 mg/L HS). For Co, the rate of 60 Co 2+ diffusion through the membrane showed up to control the rate of the isotope exchange indicating that the Co-HS dissociation is too fast to be followed by the diaphragm method, and that the abundance of non-complexed Co is not negligible. The apparent rate of Eu-HS dissociation was found to be enhanced by decreasing pH value, increasing ionic strength, and increasing metal loading (i.e., metal/HS ratio). For interpretation of the experimental kinetic data, a discrete 2-component model (bi-exponential decay function) was applied. Based on

  10. Thermodynamic evolution far from equilibrium

    Science.gov (United States)

    Khantuleva, Tatiana A.

    2018-05-01

    The presented model of thermodynamic evolution of an open system far from equilibrium is based on the modern results of nonequilibrium statistical mechanics, the nonlocal theory of nonequilibrium transport developed by the author and the Speed Gradient principle introduced in the theory of adaptive control. Transition to a description of the system internal structure evolution at the mesoscopic level allows a new insight at the stability problem of non-equilibrium processes. The new model is used in a number of specific tasks.

  11. Hypnotic suggestibility, cognitive inhibition, and dissociation.

    Science.gov (United States)

    Dienes, Zoltán; Brown, Elizabeth; Hutton, Sam; Kirsch, Irving; Mazzoni, Giuliana; Wright, Daniel B

    2009-12-01

    We examined two potential correlates of hypnotic suggestibility: dissociation and cognitive inhibition. Dissociation is the foundation of two of the major theories of hypnosis and other theories commonly postulate that hypnotic responding is a result of attentional abilities (including inhibition). Participants were administered the Waterloo-Stanford Group Scale of Hypnotic Susceptibility, Form C. Under the guise of an unrelated study, 180 of these participants also completed: a version of the Dissociative Experiences Scale that is normally distributed in non-clinical populations; a latent inhibition task, a spatial negative priming task, and a memory task designed to measure negative priming. The data ruled out even moderate correlations between hypnotic suggestibility and all the measures of dissociation and cognitive inhibition overall, though they also indicated gender differences. The results are a challenge for existing theories of hypnosis.

  12. The co-occurrence of PTSD and dissociation: differentiating severe PTSD from dissociative-PTSD.

    Science.gov (United States)

    Armour, Cherie; Karstoft, Karen-Inge; Richardson, J Don

    2014-08-01

    A dissociative-posttraumatic stress disorder (PTSD) subtype has been included in the DSM-5. However, it is not yet clear whether certain socio-demographic characteristics or psychological/clinical constructs such as comorbid psychopathology differentiate between severe PTSD and dissociative-PTSD. The current study investigated the existence of a dissociative-PTSD subtype and explored whether a number of trauma and clinical covariates could differentiate between severe PTSD alone and dissociative-PTSD. The current study utilized a sample of 432 treatment seeking Canadian military veterans. Participants were assessed with the Clinician Administered PTSD Scale (CAPS) and self-report measures of traumatic life events, depression, and anxiety. CAPS severity scores were created reflecting the sum of the frequency and intensity items from each of the 17 PTSD and 3 dissociation items. The CAPS severity scores were used as indicators in a latent profile analysis (LPA) to investigate the existence of a dissociative-PTSD subtype. Subsequently, several covariates were added to the model to explore differences between severe PTSD alone and dissociative-PTSD. The LPA identified five classes: one of which constituted a severe PTSD group (30.5 %), and one of which constituted a dissociative-PTSD group (13.7 %). None of the included, demographic, trauma, or clinical covariates were significantly predictive of membership in the dissociative-PTSD group compared to the severe PTSD group. In conclusion, a significant proportion of individuals report high levels of dissociation alongside their PTSD, which constitutes a dissociative-PTSD subtype. Further investigation is needed to identify which factors may increase or decrease the likelihood of membership in a dissociative-PTSD subtype group compared to a severe PTSD only group.

  13. Relevance of equilibrium in multifragmentation

    International Nuclear Information System (INIS)

    Furuta, Takuya; Ono, Akira

    2009-01-01

    The relevance of equilibrium in a multifragmentation reaction of very central 40 Ca + 40 Ca collisions at 35 MeV/nucleon is investigated by using simulations of antisymmetrized molecular dynamics (AMD). Two types of ensembles are compared. One is the reaction ensemble of the states at each reaction time t in collision events simulated by AMD, and the other is the equilibrium ensemble prepared by solving the AMD equation of motion for a many-nucleon system confined in a container for a long time. The comparison of the ensembles is performed for the fragment charge distribution and the excitation energies. Our calculations show that there exists an equilibrium ensemble that well reproduces the reaction ensemble at each reaction time t for the investigated period 80≤t≤300 fm/c. However, there are some other observables that show discrepancies between the reaction and equilibrium ensembles. These may be interpreted as dynamical effects in the reaction. The usual static equilibrium at each instant is not realized since any equilibrium ensemble with the same volume as that of the reaction system cannot reproduce the fragment observables

  14. Achieving Chemical Equilibrium: The Role of Imposed Conditions in the Ammonia Formation Reaction

    Science.gov (United States)

    Tellinghuisen, Joel

    2006-01-01

    Under conditions of constant temperature T and pressure P, chemical equilibrium occurs in a closed system (fixed mass) when the Gibbs free energy G of the reaction mixture is minimized. However, when chemical reactions occur under other conditions, other thermodynamic functions are minimized or maximized. For processes at constant T and volume V,…

  15. A consistent set of thermodynamic constants for americium (III) species with hydroxyl and carbonate

    International Nuclear Information System (INIS)

    Kerrisk, J.F.; Silva, R.J.

    1986-01-01

    A consistent set of thermodynamic constants for aqueous species, and compounds of Am(III) with hydroxyl and carbonate ligands has been developed. The procedure used to develop these constants involved establishing a value for one formation constant at a time in a sequential order, starting with the hydrolysis products and hydroxide solids, and then proceeding to carbonate species. The EQ3NR chemical-equilibrium model was used to test the constants developed. These constants are consistent with most of the experimental data that form their basis; however, considerable uncertainty still exists in some aspects of the Am(III) data

  16. Dissociation of NF3 in shock waves

    International Nuclear Information System (INIS)

    Breshears, W.D.; Bird, P.F.

    1978-01-01

    The thermal dissociation rate of NF 3 in mixtures of 5% and 10%NF 3 in Ar has been measured behind incident shock waves over the temperature range 1330-2000 K. Dissociation rates were determined from postshock density gradients measured by laser beam deflection. The second order rate coefficient determined for NF 3 -Ar collisions is k/sub d/=2.31 x 10 15 exp(-20500/T) cm 3 mole sec

  17. Dissociation and decay of ultracold sodium molecules

    International Nuclear Information System (INIS)

    Mukaiyama, T.; Abo-Shaeer, J.R.; Xu, K.; Chin, J.K.; Ketterle, W.

    2004-01-01

    The dissociation of ultracold molecules was studied by ramping an external magnetic field through a Feshbach resonance. The observed dissociation energies directly yielded the strength of the atom-molecule coupling. They showed nonlinear dependence on the ramp speed. This was explained by a Wigner threshold law which predicts that the decay rate of the molecules above threshold increases with the density of states. In addition, inelastic molecule-molecule and molecule-atom collisions were characterized

  18. Schizophrenia masquerading as Dissociative Identity Disorder

    OpenAIRE

    Jegan Yogaratnam; Rajesh Jacob

    2012-01-01

    Dissociative symptoms can dominate the clinical picture in many psychiatric conditions and possess a huge challenge to the clinicians in management. We present a case report of a female with a strong family history of schizophrenia who initially presented with features suggestive of dissociative identity disorder, which is itself a rare clinical entity, was later diagnosed to have schizophrenia. Authors would like to emphasise that clinicians should have a high index of suspicion for schizoph...

  19. Equilibrium figures for beta Lyrae type disks

    International Nuclear Information System (INIS)

    Wilson, R.E.

    1981-01-01

    Accumulated evidence for a geometrically and optically thick disk in the β Lyrae system has now established the disk's basic external configuration. Since the disk has been constant in its main properties over the historical interval of β Lyrae observations and also seems to have a basically well-defined photosphere, it is now time to being consideration of its sturcture. Here, we compute equilibrium figures for self-gravitating disks around stars in binary systems as a start toward eventual computation of complete disk models. A key role is played by centrifugally limited rotation of the central star, which would naturally arise late in the rapid phase of mass transfer. Beta Lyrae is thus postulated to be a double-contact binary, which makes possible nonarbitrary separation of star and disk into separate structures. The computed equilibrium figures are three-dimensional, as the gravitation of the second star is included. Under the approximation that the gravitational potential of the disk is that of a thin wire and that the local disk angular velocity is proportional to u/sup n/ (u = distance from rotation axis), we comptue the total potential and locate equipotential surfaces. The centrifugal potential is written in a particularly convenient form which permits one to change the rotation law discontinuously (for example, at the star-disk coupling point) while ensuring that centrifugal potential and centrifigual force are continuous functions of position. With such a one-parameter rotation law, one can find equilibrium disk figures with dimensions very similar to those found in β Lyrae, but considerations of internal consistency demand at least a two-parameter law

  20. [Screening for major dissociative disorders with the FDS, the German version of the Dissociative Experience Scale].

    Science.gov (United States)

    Rodewald, Frauke; Gast, Ursula; Emrich, Hinderk M

    2006-06-01

    The prevalence of major dissociative disorders (dissociative identity disorder, DID and similar forms of dissociative disorder not otherwise specified, DDNOS) in clinical samples is about 5 %. Despite their frequency, major dissociative disorders are often overseen for a long time. Screening-scales have proved to be effective to support clinical diagnosis. The aim of this study was to test, whether the Fragebogen für dissoziative Symptome (FDS), the German version of the Dissociative Experiences Scale (DES), differentiates between patients with dissociative disorders, non-dissociative disorders and non-clinical controls. Additionally, an optimal FDS-cutoff for a more detailed differential-diagnostic evaluation of the dissociative symptomatology should be identified. 150 participants with DID (group DID: n = 44), DDNOS (DDNOS: n = 22), posttraumatic disorders (TRAUMA: n = 20), other non-dissociative disorders (non-TRAUMA: n = 34) and non-clinical controls (KG: n = 30) completed the FDS. In the five diagnostic groups, mean values were calculated and compared for the FDS, DES and FDS-20. Via receiver-operating-curves the cutoff-scores, which differentiated best between participants with and without major dissociative disorders, were identified. FDS, DES and FDS-20 differentiate significantly between patients with and without major dissociative disorders. For all scales, there were significant differences between the diagnostic groups, with mean-scores decreasing continuously from the groups DID to DDNOS and TRAUMA. Between the groups non-TRAUMA and KG tendencies were found in the predicted direction. The optimal cutoff-scores to differentiate between participants with and without major dissociative disorders were 13 (FDS/FDS-20) and 15 (DES). Using these cutoff-scores, at least 90 % of the patients with major dissociative disorders could be identified correctly (sensitivity). The specifity of the scales was 0.89 to 0.90. Screening for major dissociative disorders

  1. The Off-rate of Monomers Dissociating from Amyloid-β Protofibrils*

    Science.gov (United States)

    Grüning, Clara S. R.; Klinker, Stefan; Wolff, Martin; Schneider, Mario; Toksöz, Küpra; Klein, Antonia N.; Nagel-Steger, Luitgard; Willbold, Dieter; Hoyer, Wolfgang

    2013-01-01

    The interconversion of monomers, oligomers, and amyloid fibrils of the amyloid-β peptide (Aβ) has been implicated in the pathogenesis of Alzheimer disease. The determination of the kinetics of the individual association and dissociation reactions is hampered by the fact that forward and reverse reactions to/from different aggregation states occur simultaneously. Here, we report the kinetics of dissociation of Aβ monomers from protofibrils, prefibrillar high molecular weight oligomers previously shown to possess pronounced neurotoxicity. An engineered binding protein sequestering specifically monomeric Aβ was employed to follow protofibril dissociation by tryptophan fluorescence, precluding confounding effects of reverse or competing reactions. Aβ protofibril dissociation into monomers follows exponential decay kinetics with a time constant of ∼2 h at 25 °C and an activation energy of 80 kJ/mol, values typical for high affinity biomolecular interactions. This study demonstrates the high kinetic stability of Aβ protofibrils toward dissociation into monomers and supports the delineation of the Aβ folding and assembly energy landscape. PMID:24247242

  2. Stability of plasma in static equilibrium

    Energy Technology Data Exchange (ETDEWEB)

    Krusiial, M D; Oberman, N R [Project Matterhorn, Princeton University, Princeton, NJ (United States)

    1958-07-01

    Our purpose is to derive from the Boltzmann equation in the small m/e limit, criteria useful in the discussion of stability of plasmas in static equilibrium. At first we ignore collisions but later show their effects may be taken into account. Our approach yields a generalization of the usual energy principles for investigating the stability of hydromagnetic systems to situations where the effect of heat flow along magnetic lines is not negligible, and hence to situations where the strictly hydrodynamic approach is inapplicable. In the first two sections we characterize our general method of approach and delineate the properties of the small m/e limit which we use to determine the constants of the motion and the condition for static equilibrium. In the next two sections we calculate the first and second variations of the energy and conclude with a statement of the general stability criterion. In the final three sections we state several theorems which relate our stability criterion to those of ordinary hydromagnetic theory, we show how to take into account the effect of collisions, and briefly discuss the remaining problem of incorporating the charge neutrality condition into the present stability theory. (author)

  3. The empirical equilibrium structure of diacetylene

    Science.gov (United States)

    Thorwirth, Sven; Harding, Michael E.; Muders, Dirk; Gauss, Jürgen

    2008-09-01

    High-level quantum-chemical calculations are reported at the MP2 and CCSD(T) levels of theory for the equilibrium structure and the harmonic and anharmonic force fields of diacetylene, H sbnd C tbnd C sbnd C tbnd C sbnd H. The calculations were performed employing Dunning's hierarchy of correlation-consistent basis sets cc-pV XZ, cc-pCV XZ, and cc-pwCV XZ, as well as the ANO2 basis set of Almlöf and Taylor. An empirical equilibrium structure based on experimental rotational constants for 13 isotopic species of diacetylene and computed zero-point vibrational corrections is determined (reemp:r=1.0615 Å,r=1.2085 Å,r=1.3727 Å) and in good agreement with the best theoretical structure (CCSD(T)/cc-pCV5Z: r=1.0617 Å, r=1.2083 Å, r=1.3737 Å). In addition, the computed fundamental vibrational frequencies are compared with the available experimental data and found in satisfactory agreement.

  4. Development of chemical equilibrium analysis code 'CHEEQ'

    International Nuclear Information System (INIS)

    Nagai, Shuichiro

    2006-08-01

    'CHEEQ' code which calculates the partial pressure and the mass of the system consisting of ideal gas and pure condensed phase compounds, was developed. Characteristics of 'CHEEQ' code are as follows. All the chemical equilibrium equations were described by the formation reactions from the mono-atomic gases in order to simplify the code structure and input preparation. Chemical equilibrium conditions, Σν i μ i =0 for the gaseous compounds and precipitated condensed phase compounds and Σν i μ i > 0 for the non-precipitated condensed phase compounds, were applied. Where, ν i and μ i are stoichiometric coefficient and chemical potential of component i. Virtual solid model was introduced to perform the calculation of constant partial pressure condition. 'CHEEQ' was consisted of following 3 parts, (1) analysis code, zc132. f. (2) thermodynamic data base, zmdb01 and (3) input data file, zindb. 'CHEEQ' code can calculate the system which consisted of elements (max.20), condensed phase compounds (max.100) and gaseous compounds. (max.200). Thermodynamic data base, zmdb01 contains about 1000 elements and compounds, and 200 of them were Actinide elements and their compounds. This report describes the basic equations, the outline of the solution procedure and instructions to prepare the input data and to evaluate the calculation results. (author)

  5. Dissociative Spectrum Disorders in the Primary Care Setting

    OpenAIRE

    Elmore, James L.

    2000-01-01

    Dissociative disorders have a lifetime prevalence of about 10%. Dissociative symptoms may occur in acute stress disorder, posttraumatic stress disorder, somatization disorder, substance abuse, trance and possession trance, Ganser's syndrome, and dissociative identity disorder, as well as in mood disorders, psychoses, and personality disorders. Dissociative symptoms and disorders are observed frequently among patients attending our rural South Carolina community mental health center. Given the...

  6. Fast kinetics of calcium dissociation from calsequestrin

    Directory of Open Access Journals (Sweden)

    MARIANELA BELTRÁN

    2006-01-01

    Full Text Available We measured the kinetics of calcium dissociation from calsequestrin in solution or forming part of isolated junctional sarcoplasmic reticulum membranes by mixing calsequestrin equilibrated with calcium with calcium-free solutions in a stopped-flow system. In parallel, we measured the kinetics of the intrinsic fluorescence changes that take place following calcium dissociation from calsequestrin. We found that at 25ºC calcium dissociation was 10-fold faster for calsequestrin attached to junctional membranes (k = 109 s-1 than in solution. These results imply that calcium dissociation from calsequestrin in vivo is not rate limiting during excitation-contraction coupling. In addition, we found that the intrinsic fluorescence decrease for calsequestrin in solution or forming part of junctional membranes was significantly slower than the rates of calcium dissociation. The kinetics of intrinsic fluorescence changes had two components for calsequestrin associated to junctional membranes and only one for calsequestrin in solution; the faster component was 8-fold faster (k = 54.1 s-1 than the slower component (k = 6.9 s-1, which had the same k value as for calsequestrin in solution. These combined results suggest that the presence of calsequestrin at high concentrations in a restricted space, such as when bound to the junctional membrane, accelerates calcium dissociation and the resulting structural changes, presumably as a result of cooperative molecular interactions.

  7. Shape characteristics of equilibrium and non-equilibrium fractal clusters.

    Science.gov (United States)

    Mansfield, Marc L; Douglas, Jack F

    2013-07-28

    It is often difficult in practice to discriminate between equilibrium and non-equilibrium nanoparticle or colloidal-particle clusters that form through aggregation in gas or solution phases. Scattering studies often permit the determination of an apparent fractal dimension, but both equilibrium and non-equilibrium clusters in three dimensions frequently have fractal dimensions near 2, so that it is often not possible to discriminate on the basis of this geometrical property. A survey of the anisotropy of a wide variety of polymeric structures (linear and ring random and self-avoiding random walks, percolation clusters, lattice animals, diffusion-limited aggregates, and Eden clusters) based on the principal components of both the radius of gyration and electric polarizability tensor indicates, perhaps counter-intuitively, that self-similar equilibrium clusters tend to be intrinsically anisotropic at all sizes, while non-equilibrium processes such as diffusion-limited aggregation or Eden growth tend to be isotropic in the large-mass limit, providing a potential means of discriminating these clusters experimentally if anisotropy could be determined along with the fractal dimension. Equilibrium polymer structures, such as flexible polymer chains, are normally self-similar due to the existence of only a single relevant length scale, and are thus anisotropic at all length scales, while non-equilibrium polymer structures that grow irreversibly in time eventually become isotropic if there is no difference in the average growth rates in different directions. There is apparently no proof of these general trends and little theoretical insight into what controls the universal anisotropy in equilibrium polymer structures of various kinds. This is an obvious topic of theoretical investigation, as well as a matter of practical interest. To address this general problem, we consider two experimentally accessible ratios, one between the hydrodynamic and gyration radii, the other

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

    Science.gov (United States)

    Sousa, Tânia; Domingos, Tiago

    2006-11-01

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

  9. Spectral Quasi-Equilibrium Manifold for Chemical Kinetics.

    Science.gov (United States)

    Kooshkbaghi, Mahdi; Frouzakis, Christos E; Boulouchos, Konstantinos; Karlin, Iliya V

    2016-05-26

    The Spectral Quasi-Equilibrium Manifold (SQEM) method is a model reduction technique for chemical kinetics based on entropy maximization under constraints built by the slowest eigenvectors at equilibrium. The method is revisited here and discussed and validated through the Michaelis-Menten kinetic scheme, and the quality of the reduction is related to the temporal evolution and the gap between eigenvalues. SQEM is then applied to detailed reaction mechanisms for the homogeneous combustion of hydrogen, syngas, and methane mixtures with air in adiabatic constant pressure reactors. The system states computed using SQEM are compared with those obtained by direct integration of the detailed mechanism, and good agreement between the reduced and the detailed descriptions is demonstrated. The SQEM reduced model of hydrogen/air combustion is also compared with another similar technique, the Rate-Controlled Constrained-Equilibrium (RCCE). For the same number of representative variables, SQEM is found to provide a more accurate description.

  10. Investigation of chemical equilibrium kinetics by the electromigration method

    International Nuclear Information System (INIS)

    Bozhikov, G.A.; Ivanov, P.I.; Maslov, O.D.; Dmitriev, S.N.; Bontchev, G.D.; Milanov, M.V.

    2003-01-01

    The measurement of the chemical reaction rates for complex formation as well as hydrolysis type reactions by the method of horizontal zone electrophoresis is outlined. The correlation between chemical equilibrium kinetics and electrodiffusion processes in a constant d.c. electric field is described. In model electromigration experiments the reaction rate constant of the formation a complex by Hf(IV) and diethylenetriaminepentaacetic acid (DTPA) is determined. The electrophoretic mobility, diffusion coefficient and stability constant of the [HfDTPA] - complex are calculated, taking into account experimental electrophoretic data obtained at 298.15±0.05 K and constant ionic strength. No-carrier-added 175 Hf radionuclide was used in electromigration experiments at concentrations of 10 -10 -10 -11 M. (orig.)

  11. Derivatives of imidopyrophosphoric acids as extractants. Part I. The preparation and fundamental constants of tetraalkylimidopyrophosphoric acids

    International Nuclear Information System (INIS)

    Preez, J.G.H. du; Knabl, K.U.; Krueger, L.; Brecht, B.J.A.M. van

    1992-01-01

    Improved methods for the preparation of imidotetraalkylpyrophosphates are reported. The dissociation constant of the water soluble tetraethyl analogue was determined by potentiometric titration. The values for the partition constant and aggregation constant of the tetradodecyl analogue were determined by two phase EMF potentiometric titration of which the data were processed through a sophisticated general optimization technique. The application of this method also made it possible to obtain a species distribution curve of the organic phase in terms of variation of pH in the aqueous phase. 17 refs., 7 figs., 4 tabs

  12. Measurements of some basic constants of 68Ga(BAT-TECH) as an imaging agent

    International Nuclear Information System (INIS)

    Chen Huawei; Liu Boli

    1994-01-01

    The kinetic properties of a new myocardial imaging agent 68 Ga(BAT-TECH) are investigated and its thermodynamic constants are measured. The results are as follows: Citrate→BAT-TECH exchange reaction order is second-order; reaction rate k = 0.50 l/mol·s; activation energy E a = 56.6 kJ/mol; the stability constant of 68 Ga(BAT-TECH) lgβ = 14.9; the acid dissociation constants of BAT-TECH pK 1 = 4.62, pK 2 = 7.68, pK-3 = 8.68, pK 4 = 11.2

  13. Simulations of NMR pulse sequences during equilibrium and non-equilibrium chemical exchange

    International Nuclear Information System (INIS)

    Helgstrand, Magnus; Haerd, Torleif; Allard, Peter

    2000-01-01

    The McConnell equations combine the differential equations for a simple two-state chemical exchange process with the Bloch differential equations for a classical description of the behavior of nuclear spins in a magnetic field. This equation system provides a useful starting point for the analysis of slow, intermediate and fast chemical exchange studied using a variety of NMR experiments. The McConnell equations are in the mathematical form of an inhomogeneous system of first-order differential equations. Here we rewrite the McConnell equations in a homogeneous form in order to facilitate fast and simple numerical calculation of the solution to the equation system. The McConnell equations can only treat equilibrium chemical exchange. We therefore also present a homogeneous equation system that can handle both equilibrium and non-equilibrium chemical processes correctly, as long as the kinetics is of first-order. Finally, the same method of rewriting the inhomogeneous form of the McConnell equations into a homogeneous form is applied to a quantum mechanical treatment of a spin system in chemical exchange. In order to illustrate the homogeneous McConnell equations, we have simulated pulse sequences useful for measuring exchange rates in slow, intermediate and fast chemical exchange processes. A stopped-flow NMR experiment was simulated using the equations for non-equilibrium chemical exchange. The quantum mechanical treatment was tested by the simulation of a sensitivity enhanced 15 N-HSQC with pulsed field gradients during slow chemical exchange and by the simulation of the transfer efficiency of a two-dimensional heteronuclear cross-polarization based experiment as a function of both chemical shift difference and exchange rate constants

  14. Local Equilibrium and Retardation Revisited.

    Science.gov (United States)

    Hansen, Scott K; Vesselinov, Velimir V

    2018-01-01

    In modeling solute transport with mobile-immobile mass transfer (MIMT), it is common to use an advection-dispersion equation (ADE) with a retardation factor, or retarded ADE. This is commonly referred to as making the local equilibrium assumption (LEA). Assuming local equilibrium, Eulerian textbook treatments derive the retarded ADE, ostensibly exactly. However, other authors have presented rigorous mathematical derivations of the dispersive effect of MIMT, applicable even in the case of arbitrarily fast mass transfer. We resolve the apparent contradiction between these seemingly exact derivations by adopting a Lagrangian point of view. We show that local equilibrium constrains the expected time immobile, whereas the retarded ADE actually embeds a stronger, nonphysical, constraint: that all particles spend the same amount of every time increment immobile. Eulerian derivations of the retarded ADE thus silently commit the gambler's fallacy, leading them to ignore dispersion due to mass transfer that is correctly modeled by other approaches. We then present a particle tracking simulation illustrating how poor an approximation the retarded ADE may be, even when mobile and immobile plumes are continually near local equilibrium. We note that classic "LEA" (actually, retarded ADE validity) criteria test for insignificance of MIMT-driven dispersion relative to hydrodynamic dispersion, rather than for local equilibrium. Published 2017. This article is a U.S. Government work and is in the public domain in the USA.

  15. Dissociation behavior of pellet shaped mixed gas hydrate samples that contain propane as a guest

    International Nuclear Information System (INIS)

    Kawamura, Taro; Sakamoto, Yasuhide; Ohtake, Michika; Yamamoto, Yoshitaka; Komai, Takeshi; Haneda, Hironori; Yoon, Ji-Ho; Ohga, Kotaro

    2006-01-01

    The dissociation kinetics of mixed gas hydrates that contain propane as a guest molecule have been investigated. The mixed gas hydrates used in this work were artificially prepared using the binary gas mixture of methane-propane and the ternary gas mixture of methane-ethane-propane. The crystal structures and the guest compositions of the mixed hydrates were clearly identified by using Raman spectroscopy and gas chromatography. The dissociation rates of the gas hydrates observed under several isothermal and isobaric conditions were discussed with an analytical model. The isobaric conditions were achieved by pressurizing with mixed gases using buffer cylinders, which had similar compositions to those of the initial gases used for synthesizing each hydrate sample. Interestingly, the calculated result agreed well with the experimentally observed results only when the composition of the vapor phase was assumed to be identical with that of the hydrate phase instead of the bulk (equilibrium) gas composition

  16. Generating functional analysis of complex formation and dissociation in large protein interaction networks

    International Nuclear Information System (INIS)

    Coolen, A C C; Rabello, S

    2009-01-01

    We analyze large systems of interacting proteins, using techniques from the non-equilibrium statistical mechanics of disordered many-particle systems. Apart from protein production and removal, the most relevant microscopic processes in the proteome are complex formation and dissociation, and the microscopic degrees of freedom are the evolving concentrations of unbound proteins (in multiple post-translational states) and of protein complexes. Here we only include dimer-complexes, for mathematical simplicity, and we draw the network that describes which proteins are reaction partners from an ensemble of random graphs with an arbitrary degree distribution. We show how generating functional analysis methods can be used successfully to derive closed equations for dynamical order parameters, representing an exact macroscopic description of the complex formation and dissociation dynamics in the infinite system limit. We end this paper with a discussion of the possible routes towards solving the nontrivial order parameter equations, either exactly (in specific limits) or approximately.

  17. Composition and thermochemistry of the equilibrium vapour of the systems NaI-FeI2 and NaI-PbI2

    International Nuclear Information System (INIS)

    Hilpert, K.; Gerads, H.; Koberts, D.; Miller, M.

    1987-01-01

    The vaporization of NaI/FeI 2 and NaI/PbI 2 samples of equimolar composition was investigated was investigated in the temperature ranges between 574 to 683 K and 562 to 669 K, respectively, by using the mass spectrometric Knudsen effusion method. The gaseous species I, I 2 , NaI, (NaI) 2 , FeI 2 , (FeI 2 ) 2 , FeI 3 , NaFeI 3 , and Na 2 FeI 4 (NaI-FeI 2 system) as well as NaI, (NaI) 2 , PbI 2 , (PbI 2 ) 2 , and NaPbI 3 (NaI-PbI 2 system) are present in the equilibrium vapours. The equilibrium partial pressures of these species were determined with the exception of I, I 2 , and FeI 3 . Enthalpies and entropies of dissociation resulted for the reactions NaFeI 3 (g) ↔ NaI(g)+FeI 2 (g) (1), Na 2 FeI 4 (g) ↔ 2NaI(g)+FeI 2 (g) and (2) NaPbI 3 (g) ↔ NaI(g)+PbI 2 (g) (3) as Δ d H 298 0 (Eq. (1)) = 184±5 kJ mol -1 , Δ d S 298 0 (Eq. (1)) = 143±8 J mol -1 K -1 ; Δ d H 298 0 (Eq. (2)) = 333±9 kJ mol -1 , Δ d S 298 0 (Eq. (2)) = 274±14 J mol -1 K -1 ; and Δ d H 298 0 (Eq. (3)) = 168±5 kJ mol -1 , Δ d S 298 0 (Eq. (3)) = 151±9 J mol -1 K -1 . Equilibrium constants for these reactions are additionally given. The pressures of NaFeI 3 (g) and NaPbI 3 (g) as all as their enthalpies of dissociation are discussed with respect to their significance of semi empirical rules. (orig.)

  18. Coulomb dissociation in relativistic heavy ion reactions

    International Nuclear Information System (INIS)

    Mercier, M.T.

    1982-01-01

    Targets of 12 C, 59 Co, 89 Y, 197 Au and 238 U were bombarded by 2.1 GeV/A 1 H, 12 C and 20 Ne projectiles using the SuperHILAC and BEVATRON facilities at Lawrence Berkeley Laboratory (LBL). The beam flux was calculated by monitoring the decay of 11 C produced from the 12 C(projectile,projectile n) 11 C reaction. Residual gamma-ray activity from the Co, Y, Au and U targets was collected in order to trace the decay of several reaction products. The experiment focused on the calculation of cross sections for the formation of products with one neutron removed from the various target nuclei. Corrections to the saturation activity of each product were made for detector efficiency, gamma-ray absorption in the target, gamma-ray branching, beam geometry and secondary reactions. These date are shown to be inconsistent with a geometrical form given by sigma varies as (A/sub p/sup 1/3/ + A/sub t/sup 1/3/ - b) where b is a universal constant. In fact the data indicates the b = A/sub t/sup 1/3/. Instead the data can be fit quite well by a simple empirical relation, sigma/sub emp/ = 12.0 mb A/sub p/sup 1/3/ A/sub t/sup 1/3/. It is demonstrated that an empirical fit which varies as A/sub t/sup 1/3/ is also consistent with projectile fragmentation data measured by a group at LBL. In addition these data are compared to a theoretical prediction which is the sum of a renormalized Glauber term and a term which represents the contribution due to Coulomb or electromagnetic dissociation (ED). The theoretical predictions are quite low for the 12 C projectile data and high for the 20 Ne projectile data. The systematic trends from the comparison seem to indicate that theoretical prediction for the ED contribution is rising too fast as a function of projectile for a given target

  19. Dissociations between developmental dyslexias and attention deficits

    Science.gov (United States)

    Lukov, Limor; Friedmann, Naama; Shalev, Lilach; Khentov-Kraus, Lilach; Shalev, Nir; Lorber, Rakefet; Guggenheim, Revital

    2014-01-01

    We examine whether attention deficits underlie developmental dyslexia, or certain types of dyslexia, by presenting double dissociations between the two. We took into account the existence of distinct types of dyslexia and of attention deficits, and focused on dyslexias that may be thought to have an attentional basis: letter position dyslexia (LPD), in which letters migrate within words, attentional dyslexia (AD), in which letters migrate between words, neglect dyslexia, in which letters on one side of the word are omitted or substituted, and surface dyslexia, in which words are read via the sublexical route. We tested 110 children and adults with developmental dyslexia and/or attention deficits, using extensive batteries of reading and attention. For each participant, the existence of dyslexia and the dyslexia type were tested using reading tests that included stimuli sensitive to the various dyslexia types. Attention deficit and its type was established through attention tasks assessing sustained, selective, orienting, and executive attention functioning. Using this procedure, we identified 55 participants who showed a double dissociation between reading and attention: 28 had dyslexia with normal attention and 27 had attention deficits with normal reading. Importantly, each dyslexia with suspected attentional basis dissociated from attention: we found 21 individuals with LPD, 13 AD, 2 neglect dyslexia, and 12 surface dyslexia without attention deficits. Other dyslexia types (vowel dyslexia, phonological dyslexia, visual dyslexia) also dissociated from attention deficits. Examination of 55 additional individuals with both a specific dyslexia and a certain attention deficit found no attention function that was consistently linked with any dyslexia type. Specifically, LPD and AD dissociated from selective attention, neglect dyslexia dissociated from orienting, and surface dyslexia dissociated from sustained and executive attention. These results indicate that

  20. Kinetic and equilibrium studies of acrylonitrile binding to cytochrome c peroxidase and oxidation of acrylonitrile by cytochrome c peroxidase compound I

    Energy Technology Data Exchange (ETDEWEB)

    Chinchilla, Diana, E-mail: Diana_Chinchilla@yahoo.com; Kilheeney, Heather, E-mail: raindropszoo@yahoo.com; Vitello, Lidia B., E-mail: lvitello@niu.edu; Erman, James E., E-mail: jerman@niu.edu

    2014-01-03

    Highlights: •Cytochrome c peroxidase (CcP) binds acrylonitrile in a pH-independent fashion. •The spectrum of the CcP/acrylonitrile complex is that of a 6c–ls ferric heme. •The acrylonitrile/CcP complex has a K{sub D} value of 1.1 ± 0.2 M. •CcP compound I oxidizes acrylonitrile with a maximum turnover rate of 0.61 min{sup −1}. -- Abstract: Ferric heme proteins bind weakly basic ligands and the binding affinity is often pH dependent due to protonation of the ligand as well as the protein. In an effort to find a small, neutral ligand without significant acid/base properties to probe ligand binding reactions in ferric heme proteins we were led to consider the organonitriles. Although organonitriles are known to bind to transition metals, we have been unable to find any prior studies of nitrile binding to heme proteins. In this communication we report on the equilibrium and kinetic properties of acrylonitrile binding to cytochrome c peroxidase (CcP) as well as the oxidation of acrylonitrile by CcP compound I. Acrylonitrile binding to CcP is independent of pH between pH 4 and 8. The association and dissociation rate constants are 0.32 ± 0.16 M{sup −1} s{sup −1} and 0.34 ± 0.15 s{sup −1}, respectively, and the independently measured equilibrium dissociation constant for the complex is 1.1 ± 0.2 M. We have demonstrated for the first time that acrylonitrile can bind to a ferric heme protein. The binding mechanism appears to be a simple, one-step association of the ligand with the heme iron. We have also demonstrated that CcP can catalyze the oxidation of acrylonitrile, most likely to 2-cyanoethylene oxide in a “peroxygenase”-type reaction, with rates that are similar to rat liver microsomal cytochrome P450-catalyzed oxidation of acrylonitrile in the monooxygenase reaction. CcP compound I oxidizes acrylonitrile with a maximum turnover number of 0.61 min{sup −1} at pH 6.0.

  1. Equilibrium Arrival Times to Queues

    DEFF Research Database (Denmark)

    Breinbjerg, Jesper; Østerdal, Lars Peter

    We consider a non-cooperative queueing environment where a finite number of customers independently choose when to arrive at a queueing system that opens at a given point in time and serves customers on a last-come first-serve preemptive-resume (LCFS-PR) basis. Each customer has a service time...... requirement which is identically and independently distributed according to some general probability distribution, and they want to complete service as early as possible while minimizing the time spent in the queue. In this setting, we establish the existence of an arrival time strategy that constitutes...... a symmetric (mixed) Nash equilibrium, and show that there is at most one symmetric equilibrium. We provide a numerical method to compute this equilibrium and demonstrate by a numerical example that the social effciency can be lower than the effciency induced by a similar queueing system that serves customers...

  2. Varying Constants, Gravitation and Cosmology

    Directory of Open Access Journals (Sweden)

    Jean-Philippe Uzan

    2011-03-01

    Full Text Available Fundamental constants are a cornerstone of our physical laws. Any constant varying in space and/or time would reflect the existence of an almost massless field that couples to matter. This will induce a violation of the universality of free fall. Thus, it is of utmost importance for our understanding of gravity and of the domain of validity of general relativity to test for their constancy. We detail the relations between the constants, the tests of the local position invariance and of the universality of free fall. We then review the main experimental and observational constraints that have been obtained from atomic clocks, the Oklo phenomenon, solar system observations, meteorite dating, quasar absorption spectra, stellar physics, pulsar timing, the cosmic microwave background and big bang nucleosynthesis. At each step we describe the basics of each system, its dependence with respect to the constants, the known systematic effects and the most recent constraints that have been obtained. We then describe the main theoretical frameworks in which the low-energy constants may actually be varying and we focus on the unification mechanisms and the relations between the variation of different constants. To finish, we discuss the more speculative possibility of understanding their numerical values and the apparent fine-tuning that they confront us with.

  3. Multiscale measures of equilibrium on finite dynamic systems

    International Nuclear Information System (INIS)

    Bigerelle, M.; Iost, A.

    2004-01-01

    This article presents a new method for the study of the evolution of dynamic systems based on the notion of quantity of information. The system is divided into elementary cells and the quantity of information is studied with respect to the cell size. We have introduced an analogy between quantity of information and entropy, and defined the intrinsic entropy as the entropy of the whole system independent of the size of the cells. It is shown that the intrinsic entropy follows a Gaussian probability density function (PDF) and thereafter, the time needed by the system to reach equilibrium is a random variable. For a finite system, statistical analyses show that this entropy converges to a state of equilibrium and an algorithmic method is proposed to quantify the time needed to reach equilibrium for a given confidence interval level. A Monte-Carlo simulation of diffusion of A* atoms in A is then provided to illustrate the proposed simulation. It follows that the time to reach equilibrium for a constant error probability, t e , depends on the number, n, of elementary cells as: t e ∝n 2.22 ±0.06 . For an infinite system size (n infinite), the intrinsic entropy obtained by statistical modelling is a pertinent characteristic number of the system at the equilibrium

  4. The Importance of the Dissociation Rate in Ion Channel Blocking

    Directory of Open Access Journals (Sweden)

    Hugo Zeberg

    2018-02-01

    Full Text Available Understanding the relationships between the rates and dynamics of current wave forms under voltage clamp conditions is essential for understanding phenomena such as state-dependence and use-dependence, which are fundamental for the action of drugs used as anti-epileptics, anti-arrhythmics, and anesthetics. In the present study, we mathematically analyze models of blocking mechanisms. In previous experimental studies of potassium channels we have shown that the effect of local anesthetics can be explained by binding to channels in the open state. We therefore here examine models that describe the effect of a blocking drug that binds to a non-inactivating channel in its open state. Such binding induces an inactivation-like current decay at higher potential steps. The amplitude of the induced peak depends on voltage and concentration of blocking drug. In the present study, using analytical methods, we (i derive a criterion for the existence of a peak in the open probability time evolution for a model with an arbitrary number of closed states, (ii derive formula for the relative height of the peak amplitude, and (iii determine the voltage dependence of the relative peak height. Two findings are apparent: (1 the dissociation (unbinding rate constant is important for the existence of a peak in the current waveform, while the association (binding rate constant is not, and (2 for a peak to exist it suffices that the dissociation rate must be smaller than the absolute value of all eigenvalues to the kinetic matrix describing the model.

  5. Selectivity and stoichiometry boosting of beta-cyclodextrin in cationic/anionic surfactant systems: when host-guest equilibrium meets biased aggregation equilibrium.

    Science.gov (United States)

    Jiang, Lingxiang; Yu, Caifang; Deng, Manli; Jin, Changwen; Wang, Yilin; Yan, Yun; Huang, Jianbin

    2010-02-18

    Cationic surfactant/anionic surfactant/beta-CD ternary aqueous systems provide a platform for the coexistence of the host-guest (beta-CD/surfactant) equilibrium and the biased aggregation (monomeric/aggregated surfactants) equilibrium. We report here that the interplay between the two equilibria dominates the systems as follows. (1) The biased aggregation equilibrium imposes an apparent selectivity on the host-guest equilibrium, namely, beta-CD has to always selectively bind the major surfactant (molar fraction > 0.5) even if binding constants of beta-CD to the pair of surfactants are quite similar. (2) In return, the host-guest equilibrium amplifies the bias of the aggregation equilibrium, that is, the selective binding partly removes the major surfactant from the aggregates and leaves the aggregate composition approaching the electroneutral mixing stoichiometry. (3) This composition variation enhances electrostatic attractions between oppositely charged surfactant head groups, thus resulting in less-curved aggregates. In particular, the present apparent host-guest selectivity is of remarkably high values, and the selectivity stems from the bias of the aggregation equilibrium rather than the difference in binding constants. Moreover, beta-CD is defined as a "stoichiometry booster" for the whole class of cationic/anionic surfactant systems, which provides an additional degree of freedom to directly adjust aggregate compositions of the systems. The stoichiometry boosting of the compositions can in turn affect or even determine microstructures and macroproperties of the systems.

  6. The co-occurrence of PTSD and dissociation: differentiating severe PTSD from dissociative-PTSD

    DEFF Research Database (Denmark)

    Armour, C.; Karstoft, K. I.; Richardson, J. D.

    2014-01-01

    A dissociative-posttraumatic stress disorder (PTSD) subtype has been included in the DSM-5. However, it is not yet clear whether certain socio-demographic characteristics or psychological/clinical constructs such as comorbid psychopathology differentiate between severe PTSD and dissociative-PTSD....... The current study investigated the existence of a dissociative-PTSD subtype and explored whether a number of trauma and clinical covariates could differentiate between severe PTSD alone and dissociative-PTSD. The current study utilized a sample of 432 treatment seeking Canadian military veterans. Participants...... were assessed with the Clinician Administered PTSD Scale (CAPS) and self-report measures of traumatic life events, depression, and anxiety. CAPS severity scores were created reflecting the sum of the frequency and intensity items from each of the 17 PTSD and 3 dissociation items. The CAPS severity...

  7. Spontaneity and Equilibrium: Why "?G Equilibrium" Are Incorrect

    Science.gov (United States)

    Raff, Lionel M.

    2014-01-01

    The fundamental criteria for chemical reactions to be spontaneous in a given direction are generally incorrectly stated as ?G chemistry textbooks and even in some more advanced texts. Similarly, the criteria for equilibrium are also misstated as being ?G = 0 or ?A = 0. Following a brief review of the…

  8. Equilibrium problems for Raney densities

    Science.gov (United States)

    Forrester, Peter J.; Liu, Dang-Zheng; Zinn-Justin, Paul

    2015-07-01

    The Raney numbers are a class of combinatorial numbers generalising the Fuss-Catalan numbers. They are indexed by a pair of positive real numbers (p, r) with p > 1 and 0 0 and similarly use both methods to identify the equilibrium problem for (p, r) = (θ/q + 1, 1/q), θ > 0 and q \\in Z+ . The Wiener-Hopf method is used to extend the latter to parameters (p, r) = (θ/q + 1, m + 1/q) for m a non-negative integer, and also to identify the equilibrium problem for a family of densities with moments given by certain binomial coefficients.

  9. Equilibrium in a Production Economy

    Energy Technology Data Exchange (ETDEWEB)

    Chiarolla, Maria B., E-mail: maria.chiarolla@uniroma1.it [Universita di Roma ' La Sapienza' , Dipartimento di Metodi e Modelli per l' Economia, il Territorio e la Finanza, Facolta di Economia (Italy); Haussmann, Ulrich G., E-mail: uhaus@math.ubc.ca [University of British Columbia, Department of Mathematics (Canada)

    2011-06-15

    Consider a closed production-consumption economy with multiple agents and multiple resources. The resources are used to produce the consumption good. The agents derive utility from holding resources as well as consuming the good produced. They aim to maximize their utility while the manager of the production facility aims to maximize profits. With the aid of a representative agent (who has a multivariable utility function) it is shown that an Arrow-Debreu equilibrium exists. In so doing we establish technical results that will be used to solve the stochastic dynamic problem (a case with infinite dimensional commodity space so the General Equilibrium Theory does not apply) elsewhere.

  10. Incentives in Supply Function Equilibrium

    DEFF Research Database (Denmark)

    Vetter, Henrik

    2014-01-01

    The author analyses delegation in homogenous duopoly under the assumption that the firm-managers compete in supply functions. In supply function equilibrium, managers’ decisions are strategic complements. This reverses earlier findings in that the author finds that owners give managers incentives...... to act in an accommodating way. As a result, optimal delegation reduces per-firm output and increases profits to above-Cournot profits. Moreover, in supply function equilibrium the mode of competition is endogenous. This means that the author avoids results that are sensitive with respect to assuming...

  11. Equilibrium in a Production Economy

    International Nuclear Information System (INIS)

    Chiarolla, Maria B.; Haussmann, Ulrich G.

    2011-01-01

    Consider a closed production-consumption economy with multiple agents and multiple resources. The resources are used to produce the consumption good. The agents derive utility from holding resources as well as consuming the good produced. They aim to maximize their utility while the manager of the production facility aims to maximize profits. With the aid of a representative agent (who has a multivariable utility function) it is shown that an Arrow-Debreu equilibrium exists. In so doing we establish technical results that will be used to solve the stochastic dynamic problem (a case with infinite dimensional commodity space so the General Equilibrium Theory does not apply) elsewhere.

  12. The Equilibrium Rule--A Personal Discovery

    Science.gov (United States)

    Hewitt, Paul G.

    2016-01-01

    Examples of equilibrium are evident everywhere and the equilibrium rule provides a reasoned way to view all things, whether in static (balancing rocks, steel beams in building construction) or dynamic (airplanes, bowling balls) equilibrium. Interestingly, the equilibrium rule applies not just to objects at rest but whenever any object or system of…

  13. Non equilibrium atomic processes and plasma spectroscopy

    International Nuclear Information System (INIS)

    Kato, Takako

    2003-01-01

    Along with the technical progress in plasma spectroscopy, non equilibrium ionization processes have been recently observed. We study non local thermodynamic equilibrium and non ionization equilibrium for various kinds of plasmas. Specifically we discuss non equilibrium atomic processes in magnetically confined plasmas, solar flares and laser produced plasmas using a collisional radiative model based on plasma spectroscopic data. (author)

  14. Isotope separation by photoselective dissociative electron

    International Nuclear Information System (INIS)

    Stevens, C.G.

    1978-01-01

    A method of separating isotopes based on photoselective electron capture dissociation of molecules having an electron capture cross section dependence on the vibrational state of the molecule is described. A molecular isotope source material is irradiated to selectively excite those molecules containing a desired isotope to a predetermined vibrational state having associated therewith an electron capture energy region substantially non-overlapping with the electron capture energy ranges associated with the lowest vibration states of the molecules. The isotope source is also subjected to electrons having an energy corresponding to the non-overlapping electron capture region whereby the selectively excited molecules preferentially capture electrons and dissociate into negative ions and neutrals. The desired isotope may be in the negative ion product or in the neutral product depending upon the mechanism of dissociation of the particular isotope source used. The dissociation product enriched in the desired isotope is then separated from the reaction system by conventional means. Specifically, 235 UF 6 is separated from a UF 6 mixture by selective excitation followed by dissociative electron capture into 235 UF 5 - and F

  15. Rapid separation of pure 144Ce fraction from fuel dissolver solution for demonstration experiment on secular equilibrium

    International Nuclear Information System (INIS)

    Ashok Kumar, G.V.S.; Kumar, R.; Venkata Subramani, C.R.

    2015-01-01

    Radioactive equilibrium is a condition in which the activity ratio of parent to its daughter is maintained constant with time which occurs only when the parent half-life is greater than daughter half-life. It is transient equilibrium in the case of the ratio of their half-lives of parent to daughter being less than an order whereas it becomes secular equilibrium when it is more than an order. In the case of secular equilibrium, the ratio of the activities becomes unity whereas the same depends on the decay constants of the parent and daughter nuclide for the transient equilibrium. 144 Ce- 144 Pr pair is a good example for the demonstration of secular equilibrium

  16. Stabilized power constant alimentation; Alimentation regulee a puissance constante

    Energy Technology Data Exchange (ETDEWEB)

    Roussel, L [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1968-06-01

    The study and realization of a stabilized power alimentation variable from 5 to 100 watts are described. In order to realize a constant power drift of Lithium compensated diodes, we have searched a 1 per cent precision of regulation and a response time minus than 1 sec. Recent components like Hall multiplicator and integrated amplifiers give this possibility and it is easy to use permutable circuits. (author) [French] On decrit l'etude et la realisation d'une alimentation a puissance constante reglable dans une gamme de 5 a 100 watts. Prevue pour le drift a puissance constante des diodes compensees au lithium, l'etude a ete menee en vue d'obtenir une precision de regulation de 1 pour cent et un temps de reponse inferieur a la seconde. Des systemes recents tels que multiplicateurs a effet Hall et circuits integres ont permis d'atteindre ce but tout en facilitant l'emploi de modules interchangeables. (auteur)

  17. From the Rydberg constant to the fundamental constants metrology

    International Nuclear Information System (INIS)

    Nez, F.

    2005-06-01

    This document reviews the theoretical and experimental achievements of the author since the beginning of his scientific career. This document is dedicated to the spectroscopy of hydrogen, deuterium and helium atoms. The first part is divided into 6 sub-sections: 1) the principles of hydrogen spectroscopy, 2) the measurement of the 2S-nS/nD transitions, 3) other optical frequency measurements, 4) our contribution to the determination of the Rydberg constant, 5) our current experiment on the 1S-3S transition, 6) the spectroscopy of the muonic hydrogen. Our experiments have improved the accuracy of the Rydberg Constant by a factor 25 in 15 years and we have achieved the first absolute optical frequency measurement of a transition in hydrogen. The second part is dedicated to the measurement of the fine structure constant and the last part deals with helium spectroscopy and the search for optical references in the near infrared range. (A.C.)

  18. Psychotherapy and pharmacotherapy for patients with dissociative identity disorder.

    Science.gov (United States)

    Gentile, Julie P; Dillon, Kristy S; Gillig, Paulette Marie

    2013-02-01

    There is a wide variety of what have been called "dissociative disorders," including dissociative amnesia, dissociative fugue, depersonalization disorder, dissociative identity disorder, and forms of dissociative disorder not otherwise specified. Some of these diagnoses, particularly dissociative identity disorder, are controversial and have been questioned by many clinicians over the years. The disorders may be under-diagnosed or misdiagnosed, but many persons who have experienced trauma report "dissociative" symptoms. Prevalence of dissociative disorders is unknown, but current estimates are higher than previously thought. This paper reviews clinical, phenomenological, and epidemiological data regarding diagnosis in general, and illustrates possible treatment interventions for dissociative identity disorder, with a focus on psychotherapy interventions and a review of current psychopharmacology recommendations as part of a comprehensive multidisciplinary treatment plan.

  19. Learning Read-constant Polynomials of Constant Degree modulo Composites

    DEFF Research Database (Denmark)

    Chattopadhyay, Arkadev; Gavaldá, Richard; Hansen, Kristoffer Arnsfelt

    2011-01-01

    Boolean functions that have constant degree polynomial representation over a fixed finite ring form a natural and strict subclass of the complexity class \\textACC0ACC0. They are also precisely the functions computable efficiently by programs over fixed and finite nilpotent groups. This class...... is not known to be learnable in any reasonable learning model. In this paper, we provide a deterministic polynomial time algorithm for learning Boolean functions represented by polynomials of constant degree over arbitrary finite rings from membership queries, with the additional constraint that each variable...

  20. Reconsidering the autohypnotic model of the dissociative disorders.

    Science.gov (United States)

    Dell, Paul F

    2018-03-22

    The dissociative disorders field and the hypnosis field currently reject the autohypnotic model of the dissociative disorders, largely because many correlational studies have shown hypnotizability and dissociation to be minimally related (r = .12). Curiously, it is also widely accepted that dissociative patients are highly hypnotizable. If dissociative patients are highly hypnotizable because only highly hypnotizable individuals can develop a dissociative disorder - as the author proposes - then the methodology of correlational studies of hypnotizability and dissociation in random clinical and community samples would necessarily be constitutively unable to detect, and statistically unable to reflect, that fact. That is, the autohypnotic, dissociative distancing of that small subset of highly hypnotizable individuals who repeatedly encountered intolerable circumstances is statistically lost among the data of (1) the highly hypnotizable subjects who do not dissociate and (2) subjects (of all levels of hypnotizability) who manifest other kinds of dissociation. The author proposes that, when highly hypnotizable individuals repeatedly engage in autohypnotic distancing from intolerable circumstances, they develop an overlearned, highly-motivated, automatized pattern of dissociative self-protection (i.e., a dissociative disorder). The author urges that theorists of hypnosis and the dissociative disorders explicitly include in their theories (a) the trait of high hypnotizability, (b) the phenomena of autohypnosis, and (c) the manifestations of systematized, autohypnotic pathology. Said differently, the author is suggesting that autohypnosis and autohypnotic pathology are unacknowledged nodes in the nomothetic networks of both hypnosis and dissociation.

  1. Deviations from thermal equilibrium in plasmas

    International Nuclear Information System (INIS)

    Burm, K.T.A.L.

    2004-01-01

    A plasma system in local thermal equilibrium can usually be described with only two parameters. To describe deviations from equilibrium two extra parameters are needed. However, it will be shown that deviations from temperature equilibrium and deviations from Saha equilibrium depend on one another. As a result, non-equilibrium plasmas can be described with three parameters. This reduction in parameter space will ease the plasma describing effort enormously

  2. Non-equilibrium fluctuation-induced interactions

    International Nuclear Information System (INIS)

    Dean, David S

    2012-01-01

    We discuss non-equilibrium aspects of fluctuation-induced interactions. While the equilibrium behavior of such interactions has been extensively studied and is relatively well understood, the study of these interactions out of equilibrium is relatively new. We discuss recent results on the non-equilibrium behavior of systems whose dynamics is of the dissipative stochastic type and identify a number of outstanding problems concerning non-equilibrium fluctuation-induced interactions.

  3. Thermal dissociation of molten KHSO4: Temperature dependence of Raman spectra and thermodynamics

    DEFF Research Database (Denmark)

    Knudsen, Christian B.; Kalampounias, Angelos G.; Fehrmann, Rasmus

    2008-01-01

    Raman spectroscopy is used to study the thermal dissociation of molten KHSO4 at temperatures of 240-450 degrees C under static equilibrium conditions. Raman spectra obtained at 10 different temperatures for the molten phase and for the vapors thereof exhibit vibrational wavenumbers and relative...... process taking place to a significant extent in the temperature range of the investigation and for determining its enthalpy to be Delta H degrees = 64.9 +/- 2.9 kJ mol(-1). The importance of these findings for the understanding of the performance of the industrially important sulfuric acid catalyst. under...

  4. Studies of neutron dissociation at Fermilab energies

    International Nuclear Information System (INIS)

    Ferbel, T.

    1975-01-01

    The latest results obtained in a continuing investigation of neutron dissociation in (pπ - ) systems in neutron--nucleus collisions between 50 and 300 GeV/c are summarized. The nuclear coherent dissociation data are discussed first; then new measurements of total cross sections of neutrons on nuclei in the Fermilab momentum range are presented; finally, neutron dissociation using a hydrogen target is considered, and the hydrogen data are compared with expectations from simple Deck models. A substantial correlation was observed between the mass and the t of the system produced. The spin structure of the pπ - amplitudes at low mass was described surprisingly well by the simple Deck mechanism. The t-channel helicity amplitudes contained comparable contributions from flip and nonflip terms, and the states produced were not restricted to those expected on the basis of the Morrison rule. (19 figures, 2 tables) (U.S.)

  5. Dissociation in virtual reality: depersonalization and derealization

    Science.gov (United States)

    Garvey, Gregory P.

    2010-01-01

    This paper looks at virtual worlds such as Second Life7 (SL) as possible incubators of dissociation disorders as classified by the Diagnostic and Statistical Manual of Mental Disorders, 4th Edition3 (also known as the DSM-IV). Depersonalization is where "a person feels that he or she has changed in some way or is somehow unreal." Derealization when "the same beliefs are held about one's surroundings." Dissociative Identity Disorder (DID), previously known as multiple personality disorder fits users of Second Life who adopt "in-world" avatars and in effect, enact multiple distinct identities or personalities (known as alter egos or alters). Select questions from the Structured Clinical Interview for Depersonalization (SCI-DER)8 will be discussed as they might apply to the user's experience in Second Life. Finally I would like to consider the hypothesis that rather than a pathological disorder, dissociation is a normal response to the "artificial reality" of Second Life.

  6. Understanding Thermal Equilibrium through Activities

    Science.gov (United States)

    Pathare, Shirish; Huli, Saurabhee; Nachane, Madhura; Ladage, Savita; Pradhan, Hemachandra

    2015-01-01

    Thermal equilibrium is a basic concept in thermodynamics. In India, this concept is generally introduced at the first year of undergraduate education in physics and chemistry. In our earlier studies (Pathare and Pradhan 2011 "Proc. episteme-4 Int. Conf. to Review Research on Science Technology and Mathematics Education" pp 169-72) we…

  7. Thermodynamic theory of equilibrium fluctuations

    International Nuclear Information System (INIS)

    Mishin, Y.

    2015-01-01

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

  8. Equilibrium theory : A salient approach

    NARCIS (Netherlands)

    Schalk, S.

    1999-01-01

    Whereas the neoclassical models in General Equilibrium Theory focus on the existence of separate commodities, this thesis regards 'bundles of trade' as the unit objects of exchange. Apart from commodities and commodity bundles in the neoclassical sense, the term `bundle of trade' includes, for

  9. Essays in general equilibrium theory

    NARCIS (Netherlands)

    Konovalov, A.

    2001-01-01

    The thesis focuses on various issues of general equilibrium theory and can approximately be divided into three parts. The first part of the thesis studies generalized equilibria in the Arrow-Debreu model in the situation where the strong survival assumption is not satisfied. Chapter four deals with

  10. Financial equilibrium with career concerns

    Directory of Open Access Journals (Sweden)

    Amil Dasgupta

    2006-03-01

    Full Text Available What are the equilibrium features of a financial market where a sizeable proportion of traders face reputational concerns? This question is central to our understanding of financial markets, which are increasingly dominated by institutional investors. We construct a model of delegated portfolio management that captures key features of the US mutual fund industry and embed it in an asset pricing framework. We thus provide a formal model of financial equilibrium with career concerned agents. Fund managers differ in their ability to understand market fundamentals, and in every period investors choose a fund. In equilibrium, the presence of career concerns induces uninformed fund managers to churn, i.e., to engage in trading even when they face a negative expected return. Churners act as noise traders and enhance the level of trading volume. The equilibrium relationship between fund return and net fund flows displays a skewed shape that is consistent with stylized facts. The robustness of our core results is probed from several angles.

  11. Equilibrium with arbitrary market structure

    DEFF Research Database (Denmark)

    Grodal, Birgit; Vind, Karl

    2005-01-01

    . The complete market predicted by this theory is clearly unrealistic, and Radner [10] formulated and proved existence of equilibrium in a multiperiod model with incomplete markets. In this paper the Radner result is extended. Radner assumed a specific structure of markets, independence of preferences...

  12. Nash equilibrium with lower probabilities

    DEFF Research Database (Denmark)

    Groes, Ebbe; Jacobsen, Hans Jørgen; Sloth, Birgitte

    1998-01-01

    We generalize the concept of Nash equilibrium in mixed strategies for strategic form games to allow for ambiguity in the players' expectations. In contrast to other contributions, we model ambiguity by means of so-called lower probability measures or belief functions, which makes it possible...

  13. Study of photoionization and dissociative photoionization of carbon monoxide from ionization threshold to 38 eV by using synchrotron radiation

    International Nuclear Information System (INIS)

    Zhao, Yujie; Cao, Maoqi; Li, Yuquan; Shan, Xiaobin; Liu, Fuyi; Sheng, Liusi; Li, Li; Liu, Wanfang

    2014-01-01

    Highlights: • The high resolution photoionization spectrum of carbon monoxide has been investigated using tunable synchrotron radiation. • This work has investigated comprehensively almost all kinds of photo excitation processes of CO in wide photon region. • The mechanisms of photoionization and dissociative photoionization of CO have been researched in detail. - Abstract: The vacuum-ultraviolet photoionization and dissociative photoionization of carbon monoxide in a region 14–38 eV have been investigated with time-of-flight (TOF) photoionization mass spectrometry (PIMS) using tunable synchrotron radiation (SR). The adiabatic ionization energy (IE) of carbon monoxide and appearance energies (AE) for its fragment ions in different states are determined by measurements of photoionization efficiency spectra (PIES). Ab initio calculations have been performed to investigate the reaction mechanism of dissociative photoionization of carbon monoxide. On the basis of experimental and predicted theoretical results, the mechanisms of photoionization and dissociative photoionization of molecular CO are discussed, and sixteen dissociative photoionization processes are proposed. The equilibrium geometries and harmonic vibrational frequencies of CO molecule, and its parent cation were calculated by using MP2 (full) method. The differences of configurations between them are also discussed on the basis of theoretical calculations. According to our results, the experimental IE of CO molecule, and dissociation energies (E d ) of possible dissociative channels are in reasonable agreement with the calculated values of the proposed photodissociation channels

  14. Dissociative amnesia: a case with management challenges

    Directory of Open Access Journals (Sweden)

    Priti Singh

    2015-07-01

    Full Text Available A case of dissociative amnesia with regressed behaviour was diagnosed applying the existing criteria for dissociative disorder in the tenth revision of the International Statistical Classification of Diseases and Related Health Problems (ICD-10. Though there are number of cases of such condition, but when coupled with regressed behaviour it adds to new dimension in the management. An applied strategy in lines with both pharmacological and non pharmacological was used, and we found that it helped our patient to gradually improve her behaviour. This is one of the few cases reported and we hope more such cases should be reported in understanding the psychopathology.

  15. Coulomb dissociation of N 20,21

    OpenAIRE

    Röder, Marko; Adachi, Tatsuya; Aksyutina, Yulia; Alcantara, Juan; Altstadt, Sebastian; Alvarez-Pol, Hector; Ashwood, Nicholas; Atar, Leyla; Aumann, Thomas; Avdeichikov, Vladimir; Barr, M.; Beceiro, Saul; Bemmerer, Daniel; Benlliure, Jose; Bertulani, Carlos

    2016-01-01

    Neutron-rich light nuclei and their reactions play an important role in the creation of chemical elements. Here, data from a Coulomb dissociation experiment on N20,21 are reported. Relativistic N20,21 ions impinged on a lead target and the Coulomb dissociation cross section was determined in a kinematically complete experiment. Using the detailed balance theorem, the N19(n,γ)N20 and N20(n,γ)N21 excitation functions and thermonuclear reaction rates have been determined. The N19(n,γ)N20 rate is...

  16. From the Rydberg constant to the fundamental constants metrology; De la constante de Rydberg a la metrologie des constantes fondamentales

    Energy Technology Data Exchange (ETDEWEB)

    Nez, F

    2005-06-15

    This document reviews the theoretical and experimental achievements of the author since the beginning of his scientific career. This document is dedicated to the spectroscopy of hydrogen, deuterium and helium atoms. The first part is divided into 6 sub-sections: 1) the principles of hydrogen spectroscopy, 2) the measurement of the 2S-nS/nD transitions, 3) other optical frequency measurements, 4) our contribution to the determination of the Rydberg constant, 5) our current experiment on the 1S-3S transition, 6) the spectroscopy of the muonic hydrogen. Our experiments have improved the accuracy of the Rydberg Constant by a factor 25 in 15 years and we have achieved the first absolute optical frequency measurement of a transition in hydrogen. The second part is dedicated to the measurement of the fine structure constant and the last part deals with helium spectroscopy and the search for optical references in the near infrared range. (A.C.)

  17. Systematics of constant roll inflation

    Science.gov (United States)

    Anguelova, Lilia; Suranyi, Peter; Wijewardhana, L. C. R.

    2018-02-01

    We study constant roll inflation systematically. This is a regime, in which the slow roll approximation can be violated. It has long been thought that this approximation is necessary for agreement with observations. However, recently it was understood that there can be inflationary models with a constant, and not necessarily small, rate of roll that are both stable and compatible with the observational constraint ns ≈ 1. We investigate systematically the condition for such a constant-roll regime. In the process, we find a whole new class of inflationary models, in addition to the known solutions. We show that the new models are stable under scalar perturbations. Finally, we find a part of their parameter space, in which they produce a nearly scale-invariant scalar power spectrum, as needed for observational viability.

  18. Objective documentation of child abuse and dissociation in 12 murderers with dissociative identity disorder.

    Science.gov (United States)

    Lewis, D O; Yeager, C A; Swica, Y; Pincus, J H; Lewis, M

    1997-12-01

    The skepticism regarding the existence of dissociative identity disorder as well as the abuse that engenders it persists for lack of objective documentation. This is doubly so for the disorder in murderers because of issues of suspected malingering. This article presents objective verification of both dissociative symptoms and severe abuse during childhood in a series of adult murderers with dissociative identity disorder. This study consisted of a review of the clinical records of 11 men and one woman with DSM-IV-defined dissociative identity disorder who had committed murder. Data were gathered from medical, psychiatric, social service, school, military, and prison records and from records of interviews with subjects' family members and others. Handwriting samples were also examined. Data were analyzed qualitatively. Signs and symptoms of dissociative identity disorder in childhood and adulthood were corroborated independently and from several sources in all 12 cases; objective evidence of severe abuse was obtained in 11 cases. The subjects had amnesia for most of the abuse and underreported it. Marked changes in writing style and/or signatures were documented in 10 cases. This study establishes, once and for all, the linkage between early severe abuse and dissociative identity disorder. Further, the data demonstrate that the disorder can be distinguished from malingering and from other disorders. The study shows that it is possible, with great effort, to obtain objective evidence of both the symptoms of dissociative identity disorder and the abuse that engenders it.

  19. Adsorption and dissociation of H2O on Al(1 1 1) surface by density functional theory calculation

    International Nuclear Information System (INIS)

    Guo, F.Y.; Long, C.G.; Zhang, J.; Zhang, Z.; Liu, C.H.; Yu, K.

    2015-01-01

    Highlights: • O 2 on Al(1 1 1) surface can spontaneously dissociate, but H 2 O can not. • H 2 O, OH and H on top sites are favorable on Al(1 1 1) surface. • O on the hollow (fcc) site is preferred. • O which plays a key role in the dissociate reaction of H 2 O. - Abstract: Using the first-principles calculations method based on the density functional theory, we systematically study the adsorption behavior of a single molecular H 2 O on a clean and a pre-adsorbed O atom Al(1 1 1) surface, and also its corresponding dissociation reactions. The equilibrium configuration on top, bridge, and hollow (fcc and hcp) site were determined by relaxation of the system relaxation. The adsorptions of H 2 O, OH and H on top sites are favorable on the Al(1 1 1) surface, while that of O on the hollow (fcc) site is preferred. The results show that the hydrogen atom dissociating from H 2 O needs a 248.32 kJ/mol of energy on clean Al(1 1 1) surface, while the dissociating energy decreases to 128.53 kJ/mol with the aid of the O absorption. On the other hand, these phenomena indicate that the dehydrogenated reaction energy barrier of the pre-adsorbed O on metal surface is lower than that of on a clean one, because O can promote the dehydrogenation of H 2 O

  20. Strain fluctuations and elastic constants

    Energy Technology Data Exchange (ETDEWEB)

    Parrinello, M.; Rahman, A.

    1982-03-01

    It is shown that the elastic strain fluctuations are a direct measure of elastic compliances in a general anisotropic medium; depending on the ensemble in which the fluctuation is measured either the isothermal or the adiabatic compliances are obtained. These fluctuations can now be calculated in a constant enthalpy and pressure, and hence, constant entropy, ensemble due to recent develpments in the molecular dynamics techniques. A calculation for a Ni single crystal under uniform uniaxial 100 tensile or compressive load is presented as an illustration of the relationships derived between various strain fluctuations and the elastic modulii. The Born stability criteria and the behavior of strain fluctuations are shown to be related.