A comparative study of the adsorption equilibrium of progesterone by a carbon black and a commercial activated carbon

NASA Astrophysics Data System (ADS)

Valenzuela-Calahorro, Cristóbal; Navarrete-Guijosa, Antonio; Stitou, Mostafa; Cuerda-Correa, Eduardo M.

2007-04-01

In this paper the adsorption process of a natural steroid hormone (progesterone) by a carbon black and a commercial activated carbon has been studied. The corresponding equilibrium isotherms have been analyzed according to a previously proposed model which establishes a kinetic law satisfactorily fitting the C versus t isotherms. The analysis of the experimental data points out the existence of two well-defined sections in the equilibrium isotherms. A general equation including these two processes has been proposed, the global adsorption process being fitted to such equation. From the values of the kinetic equilibrium constant so obtained, values of standard average adsorption enthalpy ( ΔH°) and entropy ( ΔS°) have been calculated. Finally, information related to variations of differential adsorption enthalpy ( ΔH) and entropy ( ΔS) with the surface coverage fraction ( θ) was obtained by using the corresponding Clausius-Clapeyron equations.

Equilibrium 2H/1H fractionation in organic molecules: III. Cyclic ketones and hydrocarbons

NASA Astrophysics Data System (ADS)

Wang, Ying; Sessions, Alex L.; Nielsen, Robert J.; Goddard, William A.

2013-04-01

Quantitative interpretation of stable hydrogen isotope ratios (2H/1H) in organic compounds is greatly aided by knowledge of the relevant equilibrium fractionation factors (ɛeq). Previous efforts have combined experimental measurements and hybrid Density Functional Theory (DFT) calculations to accurately predict equilibrium fractionations in linear (acyclic) organic molecules (Wang et al., 2009a,b), but the calibration produced by that study is not applicable to cyclic compounds. Here we report experimental measurements of equilibrium 2H/1H fractionation in six cyclic ketones, and use those data to evaluate DFT calculations of fractionation in diverse monocyclic and polycyclic compounds commonly found in sedimentary organic matter and petroleum. At 25, 50, and 75 °C, the experimentally measured ɛeq values for secondary and tertiary Hα in isotopic equilibrium with water are in the ranges of -130‰ to -150‰ and +10‰ to -40‰ respectively. Measured data are similar to DFT calculations of ɛeq for axial Hα but not equatorial Hα. In tertiary Cα positions with methyl substituents, this can be understood as a result of the methyl group forcing Hα atoms into a dominantly axial position. For secondary Cα positions containing both axial and equatorial Hα atoms, we propose that axial Hα exchanges with water significantly faster than the equatorial Hα does, due to the hyperconjugation-stabilized transition state. Interconversion of axial and equatorial positions via ring flipping is much faster than isotopic exchange at either position, and as a result the steady-state isotopic composition of both H's is strongly weighted toward that of axial Hα. Based on comparison with measured ɛeq values, a total uncertainty of 10-30‰ remains for theoretical ɛeq values. Using DFT, we systematically estimated the ɛeq values for individual H positions in various cyclic structures. By summing over all individual H positions, the molecular equilibrium fractionation was estimated to be -75‰ to -95‰ for steroids, -90‰ to -105‰ for hopanoids, and -65‰ to -100‰ for typical cycloparaffins between 0 and 100 °C relative to water. These are distinct from the typical biosynthetic fractionations of -150‰ to -300‰, but are similar to equilibrium fractionations for linear hydrocarbons (Wang et al., 2009b). Thus post-burial H exchange will generally remove the ˜50-100‰ biosynthetic fractionations between cyclic isoprenoid and n-alkyl lipid molecules, which can be used to evaluate the extent of H exchange in sedimentary organic matter and oils.

Variability of radon and thoron equilibrium factors in indoor environment of Garhwal Himalaya.

PubMed

Prasad, Mukesh; Rawat, Mukesh; Dangwal, Anoop; Kandari, Tushar; Gusain, G S; Mishra, Rosaline; Ramola, R C

2016-01-01

The measurements of radon, thoron and their progeny concentrations have been carried out in the dwellings of Uttarkashi and Tehri districts of Garhwal Himalaya, India using LR-115 detector based pin-hole dosimeter and DRPS/DTPS techniques. The equilibrium factors for radon, thoron and their progeny were calculated by using the values measured with these techniques. The average values of equilibrium factor between radon and its progeny have been found to be 0.44, 0.39, 0.39 and 0.28 for rainy, autumn, winter and summer seasons, respectively. For thoron and its progeny, the average values of equilibrium factor have been found to be 0.04, 0.04, 0.04 and 0.03 for rainy, autumn, winter and summer seasons, respectively. The equilibrium factor between radon and its progeny has been found to be dependent on the seasonal changes. However, the equilibrium factor for thoron and progeny has been found to be same for rainy, autumn and winter seasons but slightly different for summer season. The annual average equilibrium factors for radon and thoron have been found to vary from 0.23 to 0.80 with an average of 0.42 and from 0.01 to 0.29 with an average of 0.07, respectively. The detailed discussion of the measurement techniques and the explanation for the results obtained is given in the paper. Copyright © 2015 Elsevier Ltd. All rights reserved.

Zirconium-nickel crystals—hydrogen accumulators: Dissolution and penetration of hydrogen atoms in alloys

NASA Astrophysics Data System (ADS)

Matysina, Z. A.; Zaginaichenko, S. Yu.; Shchur, D. V.; Gabdullin, M. T.; Kamenetskaya, E. A.

2016-07-01

The calculation of the free energy, thermodynamic equilibrium equations, and kinetic equations of the intermetallic compound Zr2NiH x has been carried out based on molecular-kinetic concepts. The equilibrium hydrogen concentration depending on the temperature, pressure, and energy parameters has been calculated. The absorption-desorption of hydrogen has been studied, and the possibility of the realization of the hysteresis effect has been revealed. The kinetics of the dissolution and permeability of hydrogen is considered, the time dependence of these values has been found, and conditions for the extremum character of their time dependence have been determined. Relaxation times of the dissolution and permeability of hydrogen into the alloy have been calculated. The calculation results are compared with the experimental data available in the literature.

Using Triple Oxygen Isotope Analyses of Biogenic Carbonate to Reconstruct Early Triassic Ocean Oxygen Isotopic Values and Temperatures

NASA Astrophysics Data System (ADS)

Gibbons, J. A.; Sharp, Z. D.; Atudorei, V.

2017-12-01

The calcite-water triple oxygen isotope fractionation is used to determine isotopic equilibrium and ancient ocean oxygen isotopic values and temperatures. Unlike conventional δ18O analysis where the formation water's isotopic value is assumed, paired δ17O-δ18O measurements allow for the water's isotopic composition to be calculated because there is only one unique solution for equilibrium fractionation using Δ17O-δ18O values (where Δ17O=δ17O-0.528δ18O). To a first approximation, the calcite-water equilibrium fractionation factor, θ (where θ=ln17α/ln18α), varies with temperature by 0.00001/°. The calcite-water equilibrium fractionation line was determined at two temperatures, 30° and 0°, by using modern carbonate samples that formed in ocean water with a δ18O value of 0‰. The θ values for the 30° and 0° samples are 0.52515 and 0.52486, respectively. Oxygen values were measured using complete fluorination in nickel tubes with BrF5 as the reaction reagent. We calibrated all oxygen values to the SMOW-SLAP scale by measuring SMOW, SLAP, San Carlos olivine, NBS-18, NBS-19, and PDB. The triple oxygen isotope calcite-water equilibrium fractionation line was applied to well preserved Early Triassic ammonite shells from the Western United States. Based on paired δ17O-δ18O measurements, the samples did not form in equilibrium with an ice-free ocean with an oxygen isotopic value of -1‰ or the modern ocean value of 0‰. Assuming the calcite is still primary and formed in equilibrium with the ocean water, our data indicate that the δ18O value of the ocean in the early Triassic was 3-5‰ lower than modern. Samples from the Smithian thermal maximum formed in water 10° warmer than samples from after the thermal maximum. Paired δ17O-δ18O measurements of pristine ancient carbonates may provide a better understanding of past ocean conditions during climate change events.

Complications in Determining Oxygen Fugacities From Olivine-Melt Equilibrium Illustrated by the Pu'u'O'o Lavas, Hawaii

NASA Astrophysics Data System (ADS)

McCann, V. E.; Barton, M.; Thornber, C. R.

2005-12-01

We have shown previously that oxygen fugacities calculated from olivine-melt equilibrium using rim compositions agree well with those calculated from analyzed Fe3+/σFe for MORB and for Icelandic OIB (MORB - average ΔFMQ -0.72 versus -0.70, Iceland average ΔFMQ -0.49 versus -0.58). The agreement between oxygen fugacities calculated from Ol-melt equilibrium and those calculated from analyzed Fe3+/σFe is excellent for individual samples of MORB from the FAMOUS region and Blanco Trough ( difference in calculated ΔFMQ < 0.30). Published analyses of Fe3+/σFe yield oxygen fugacilties of ΔFMQ= -0.72±0.43 for lavas from Kilauea and Mauna Loa, and ΔFMQ=0.91±0.72 for Loihi, very close to those for MORB. Oxygen fugacities determined using carefully selected Ol-melt analyses (ΔFMQ= -0.43±0.32) are in reasonable agreement with those determined from Fe3+/σFe for Kilauea and Mauna Loa, and agreement between fO2 calculated from Ol-melt equilibrium (ΔFMQ= -0.26) and that calculated from Fe3+/σFe (ΔFMQ= -0.64) is excellent for one sample from Kilauea. However, olivine-melt pairs from some samples, including those from the Pu'u'O'o lavas, yield anomalously high or low estimates of fO2 (average ΔFMQ =-0.6907, range -4.07 to +0.34). We suggest that these anomalous values reflect the complex history of olivines in these lavas, in particular the effects of magma mixing. Some olivines in the Pu'u'O'o lavas clearly have rims that are anomalously rich in Fa, whereas others have rims that are anomalously rich in Fo and do not appear to have equilibrium compositions. Given the dependence of olivine composition on melt Fe3+/σFe, there is no simple method to determine the equilibrium composition of olivine for a particular melt. However, detailed zoning profiles and analyses of microphenocrysts allow probable equilibrium compositions to be identified. We suggest that the average fO2 of Hawaiian lavas lies close to (ΔFMQ= -1) based on published results using spinel-melt equilibrium and Fe-Ni exchange between olivine and sulfide liquid. Olivine-glass inclusion data for Koolau samples also suggest (ΔFMQ= ~-1).

Kinetics and equilibrium modelling of lead uptake by algae Gelidium and algal waste from agar extraction industry.

PubMed

Vilar, Vítor J P; Botelho, Cidália M S; Boaventura, Rui A R

2007-05-08

Pb(II) biosorption onto algae Gelidium, algal waste from agar extraction industry and a composite material was studied. Discrete and continuous site distribution models were used to describe the biosorption equilibrium at different pH (5.3, 4 and 3), considering competition among Pb(II) ions and protons. The affinity distribution function of Pb(II) on the active sites was calculated by the Sips distribution. The Langmuir equilibrium constant was compared with the apparent affinity calculated by the discrete model, showing higher affinity for lead ions at higher pH values. Kinetic experiments were conducted at initial Pb(II) concentrations of 29-104 mgl(-1) and data fitted to pseudo-first Lagergren and second-order models. The adsorptive behaviour of biosorbent particles was modelled using a batch mass transfer kinetic model, which successfully predicts Pb(II) concentration profiles at different initial lead concentration and pH, and provides significant insights on the biosorbents performance. Average values of homogeneous diffusivity, D(h), are 3.6 x 10(-8); 6.1 x 10(-8) and 2.4 x 10(-8)cm(2)s(-1), respectively, for Gelidium, algal waste and composite material. The concentration of lead inside biosorbent particles follows a parabolic profile that becomes linear near equilibrium.

Metastable equilibria among dicarboxylic acids and the oxidation state during aqueous alteration on the CM2 chondrite parent body

NASA Astrophysics Data System (ADS)

McAlister, Jason A.; Kettler, Richard M.

2008-01-01

Linear saturated dicarboxylic acids are present in carbonaceous chondrite samples at concentrations that suggest aqueous alteration under conditions of metastable equilibrium. In this study, previously published values of dicarboxylic acid concentrations measured in Murchison, Yamato-791198, and Tagish Lake carbonaceous chondrites are converted to aqueous activities during aqueous alteration assuming water:rock ratios that range from 1:10 to 10:1. Logarithmic plots of the aqueous activities of any two dicarboxylic acids are proximal to lines whose slope is fixed by the stoichiometry of reactions describing the oxidation-reduction equilibrium between the two species. The precise position of any line is controlled by the equilibrium constant of the reaction relating the species and the hydrogen fugacity for the reaction of interest. Reactions among succinic (C4), glutaric (C5), and adipic (C6) acids obtained from CM2 chondrites show evidence of metastable equilibrium and yield logf values that agree to within 0.3 log units at 298.15 K and 0.6 log units at 473.15 K. At a water:rock ratio of 1:1, metastable equilibrium among succinic, glutaric, and adipic acids results in calculated logf values during aqueous alteration that range from -6.2 at 298.15 K to -3.3 at 373.15 K. These values are consistent with those obtained in previous work on carbonaceous chondrites and with metastable equilibrium at temperatures ranging from 300 to 355 K in contact with cronstedtite + magnetite.

Seasonal variability of equilibrium factor and unattached fractions of radon and thoron in different regions of Punjab, India.

PubMed

Saini, Komal; Singh, Parminder; Singh, Prabhjot; Bajwa, B S; Sahoo, B K

2017-02-01

A survey was conducted to estimate equilibrium factor and unattached fractions of radon and thoron in different regions of Punjab state, India. Pin hole based twin cup dosimeters and direct progeny sensor techniques have been utilized for estimation of concentration level of radon, thoron and their progenies. Equilibrium factor calculated from radon, thoron and their progenies concentration has been found to vary from 0.15 to 0.80 and 0.008 to 0.101 with an average value of 0.44 and 0.036 for radon and thoron respectively. Equilibrium factor for radon has found to be highest in winter season and lowest in summer season whereas for thoron highest value is observed in winter and rainy season and lowest in summer. Unattached fractions of radon and thoron have been found to vary from 0.022 to 0.205 and 0.013 to 0.212 with an average value of 0.099 and 0.071 respectively. Unattached fractions have found to be highest in winter season and lowest in rainy and summer season. Copyright © 2016 Elsevier Ltd. All rights reserved.

Electronic structure and linear optical properties of ZnSe and ZnSe:Mn.

PubMed

Su, Kang; Wang, Yuhua

2010-03-01

As an important wide band-gap II-VI semiconductor, ZnSe has attracted much attention for its various applications in photo-electronic devices such as blue light-emitting diodes and blue-green diode lasers. Mn-doped ZnSe is an excellent quantum dot material. The electronic structures of the sphalerite ZnSe and ZnSe:Mn were calculated using the Vienna ab initio Simulation Package with ultra-soft pseudo potentials and Material Studio. The calculated equilibrium lattice constants agree well with the experimental values. Using the optimized equilibrium lattice constants, the densities of states and energy band structures were further calculated. By analyzing the partial densities of states, the contributions of different electron states in different atoms were estimated. The p states of Zn mostly contribute to the top of the valence band, and the s states of Zn and the s states of Se have major effects on the bottom of the conduction band. The calculated results of ZnSe:Mn show the band gap was changed from 2.48 to 1.1 eV. The calculated linear optical properties, such as refractive index and absorption spectrum, are in good agreement with experimental values.

Bioconcentration of lipophilic compounds by some aquatic organisms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hawker, D.W.; Connell, D.W.

1986-04-01

With nondegradable, lipophilic compounds having log P values ranging from 2 to 6, direct linear relationships have been found between the logarithms of the equilibrium bioconcentration factors, and also reciprocal clearance rate constants, with log P for daphnids and molluscs. These relationships permit calculation of the times required for equilibrium and significant bioconcentration of lipophilic chemicals. Compared with fish, these time periods are successively shorter for molluscs, then daphnids. The equilibrium biotic concentration was found to decrease with increasing chemical hydrophobicity for both molluscs and daphnids. Also, new linear relationships between the logarithm of the bioconcentration factor and log Pmore » were found for compounds not attaining equilibrium within finite exposure times.« less

Comment on “Hydromagnesite solubility product and growth kinetics in aqueous solution from 25 to 75 °C” by Gautier, Q., Benezeth, P., Mavromatis, V., and Schott, J

DOE PAGES

Xiong, Yongliang

2016-04-16

Here, Gautier et al. (2014) recently published their determination of hydromagnesite solubility constant and hydromagnesite growth kinetics. Although their raw data appear to be of high quality, there is an oversight in their calculations of the hydromagnesite solubility constants given the solution compositions in their experiments. The oversight lies in the fact that they did not consider the constraint of simultaneous equilibrium with brucite. This oversight causes their newly calculated equilibrium constant for hydromagnesite to be discordant with the literature values (Königsberger et al., 1992 and Xiong, 2011).

On exchange rate misalignments in the Eurozone's peripheral countries

NASA Astrophysics Data System (ADS)

Grochová, Ladislava; Plecitá, Klára

2013-10-01

In this paper we model equilibrium exchange rates for the Eurozone's countries on the basis of the Behavioural Equilibrium Exchange Rate approach, which assumes, that equilibrium exchange rates are in the long run affected by economic fundamentals. To assess the degree of exchange rate misalignment for the Eurozone's peripheral countries - Portugal, Ireland, Greece and Spain - the gap between the actual and the modelled equilibrium exchange rate value is calculated. Our results show that Spain, Portugal and Ireland had their real exchange rates in equilibrium when they joined the Eurozone; however their real exchange rates have been persistently overvalued since the beginning of the 2000s. Greece, on the other hand, has experienced diminishing undervaluation at the beginning of its membership in the Eurozone and since 2009 has exhibited an overvalued real exchange rate.

An extension of ASM2d including pH calculation.

PubMed

Serralta, J; Ferrer, J; Borrás, L; Seco, A

2004-11-01

This paper presents an extension of the Activated Sludge Model No. 2d (ASM2d) including a chemical model able to calculate the pH value in biological processes. The developed chemical model incorporates the complete set of chemical species affecting the pH value to ASM2d describing non-equilibrium biochemical processes. It considers the system formed by one aqueous phase, in which biochemical processes take place, and one gaseous phase, and is based on the assumptions of instantaneous chemical equilibrium under liquid phase and kinetically governed mass transport between the liquid and gas phase. The ASM2d enlargement comprises the addition of every component affecting the pH value and an ion-balance for the calculation of the pH value and the dissociation species. The significant pH variations observed in a sequencing batch reactor operated for enhanced biological phosphorus removal were used to verify the capability of the extended model for predicting the dynamics of pH jointly with concentrations of acetic acid and phosphate. A pH inhibition function for polyphosphate accumulating bacteria has also been included in the model to simulate the behaviour observed. Experimental data obtained in four different experiments (with different sludge retention time and influent phosphorus concentrations) were accurately reproduced.

Equilibrium Droplets on Deformable Substrates: Equilibrium Conditions.

PubMed

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.

Catalytic supercritical water gasification of primary paper sludge using a homogeneous and heterogeneous catalyst: Experimental vs thermodynamic equilibrium results.

PubMed

Louw, Jeanne; Schwarz, Cara E; Burger, Andries J

2016-02-01

H2, CH4, CO and CO2 yields were measured during supercritical water gasification (SCWG) of primary paper waste sludge (PWS) at 450°C. Comparing these yields with calculated thermodynamic equilibrium values offer an improved understanding of conditions required to produce near-equilibrium yields. Experiments were conducted at different catalyst loads (0-1g/gPWS) and different reaction times (15-120min) in a batch reactor, using either K2CO3 or Ni/Al2O3-SiO2 as catalyst. K2CO3 up to 1g/gPWS increased the H2 yield significantly to 7.5mol/kgPWS. However, these yields and composition were far from equilibrium values, with carbon efficiency (CE) and energy recovery (ER) of only 29% and 20%, respectively. Addition of 0.5-1g/gPWS Ni/Al2O3-SiO2 resulted in high H2 and CH4 yields (6.8 and 14.8mol/kgPWS), CE of 84-90%, ER of 83% and a gas composition relatively close to the equilibrium values (at hold times of 60-120min). Copyright © 2015 Elsevier Ltd. All rights reserved.

Ozone chemical equilibrium in the extended mesopause under the nighttime conditions

NASA Astrophysics Data System (ADS)

Belikovich, M. V.; Kulikov, M. Yu.; Grygalashvyly, M.; Sonnemann, G. R.; Ermakova, T. S.; Nechaev, A. A.; Feigin, A. M.

2018-01-01

For retrieval of atomic oxygen and atomic hydrogen via ozone observations in the extended mesopause region (∼70-100 km) under nighttime conditions, an assumption on photochemical equilibrium of ozone is often used in research. In this work, an assumption on chemical equilibrium of ozone near mesopause region during nighttime is proofed. We examine 3D chemistry-transport model (CTM) annual calculations and determine the ratio between the correct (modeled) distributions of the O3 density and its equilibrium values depending on the altitude, latitude, and season. The results show that the retrieval of atomic oxygen and atomic hydrogen distributions using an assumption on ozone chemical equilibrium may lead to large errors below ∼81-87 km. We give simple and clear semi-empirical criterion for practical utilization of the lower boundary of the area with ozone's chemical equilibrium near mesopause.

How the flow affects the phase behaviour and microstructure of polymer nanocomposites.

PubMed

Stephanou, Pavlos S

2015-02-14

We address the issue of flow effects on the phase behaviour of polymer nanocomposite melts by making use of a recently reported Hamiltonian set of evolution equations developed on principles of non-equilibrium thermodynamics. To this end, we calculate the spinodal curve, by computing values for the nanoparticle radius as a function of the polymer radius-of-gyration for which the second derivative of the generalized free energy of the system becomes zero. Under equilibrium conditions, we recover the phase diagram predicted by Mackay et al. [Science 311, 1740 (2006)]. Under non-equilibrium conditions, we account for the extra terms in the free energy due to changes in the conformations of polymer chains by the shear flow. Overall, our model predicts that flow enhances miscibility, since the corresponding miscibility window opens up for non-zero shear rate values.

Effect of Sediment Availability in Bedload-Dominated Rivers on Fluvial Geomorphic Equilibrium

NASA Astrophysics Data System (ADS)

Marti, M.

2016-12-01

Channels are known to compensate for changes in sediment supply via covariate changes in channel properties, yet the timescale for adjustment remains poorly constrained. We propose that reductions in sediment flux inhibit equilibrium re-establishment and thus impact the timescale of system adjustment. Using run-of-river dams as natural experiments, this study quantifies the geomorphic response of channels to sediment supply reduction. Channel traits that facilitate increased sediment trapping behind the dam, such as large reservoir storage capacity relative to annual inflow and low slope, were expected to inhibit a channel's ability to re-establish equilibrium following impoundment, lengthening the equilibrium establishment timescale to tens or hundreds of years. Reaches associated with increased trapping were therefore anticipated to exhibit non-equilibrium forms. Channel equilibrium was evaluated downstream of 8 ROR dams in New England with varying degrees of sediment trapping. Sites cover a range of watershed sizes (3-155 km2), channel slopes (.05-5%), 2-year discharges (1.5-60 m3/s) and storage capacity volumes. Because equilibrium channel form is just sufficient to mobilize grains under bankfull conditions in bedload-dominated rivers, the Shields parameter was used to assess equilibrium form. Unregulated, upstream Shields values and regulated, downstream values were calculated at 14 total cross-sections extending 300-450 m upstream and downstream of each dam. Sediment trapping was estimated using Brune's curve (1953). On the Charles Brown Brook (VT), a marginally significant (p=0.08) increase in Shields values from a mean of 0.14 upstream to 0.41 downstream of a 100+ year old dam was observed. In contrast, reaches downstream of the 100+ year old Pelham dam (MA) exhibit significantly lower Shields values. This suggests that trapping behind the dam inhibits the downstream channel from reaching an equilibrium state, but not always in the same way. Better understanding of geomorphic response to reduced sediment flux as a control on equilibrium establishment will broaden the knowledge of geomorphic equilibrium and aid in management of regulated, bedload-dominated rivers.

General equilibrium second-order hydrodynamic coefficients for free quantum fields

NASA Astrophysics Data System (ADS)

Buzzegoli, M.; Grossi, E.; Becattini, F.

2017-10-01

We present a systematic calculation of the corrections of the stress-energy tensor and currents of the free boson and Dirac fields up to second order in thermal vorticity, which is relevant for relativistic hydrodynamics. These corrections are non-dissipative because they survive at general thermodynamic equilibrium with non vanishing mean values of the conserved generators of the Lorentz group, i.e. angular momenta and boosts. Their equilibrium nature makes it possible to express the relevant coefficients by means of correlators of the angular-momentum and boost operators with stress-energy tensor and current, thus making simpler to determine their so-called "Kubo formulae". We show that, at least for free fields, the corrections are of quantum origin and we study several limiting cases and compare our results with previous calculations. We find that the axial current of the free Dirac field receives corrections proportional to the vorticity independently of the anomalous term.

Computer codes for the evaluation of thermodynamic and transport properties for equilibrium air to 30000 K

NASA Technical Reports Server (NTRS)

Thompson, Richard A.; Lee, Kam-Pui; Gupta, Roop N.

1991-01-01

The computer codes developed here provide self-consistent thermodynamic and transport properties for equilibrium air for temperatures from 500 to 30000 K over a temperature range of 10 (exp -4) to 10 (exp -2) atm. These properties are computed through the use of temperature dependent curve fits for discrete values of pressure. Interpolation is employed for intermediate values of pressure. The curve fits are based on mixture values calculated from an 11-species air model. Individual species properties used in the mixture relations are obtained from a recent study by the present authors. A review and discussion of the sources and accuracy of the curve fitted data used herein are given in NASA RP 1260.

Emergence of currents as a transient quantum effect in nonequilibrium systems

NASA Astrophysics Data System (ADS)

Granot, Er'El; Marchewka, Avi

2011-09-01

Most current calculations are based on equilibrium or semi-equilibrium models. However, except for very special scenarios (like ring configuration), the current cannot exist in equilibrium. Moreover, unlike with equilibrium scenarios, there is no generic approach to confront out-of-equilibrium currents. In this paper we used recent studies on transient quantum mechanics to solve the current, which appears in the presence of very high density gradients and fast transients. It shows that the emerging current appears instantaneously, and although the density beyond the discontinuity is initially negligible the currents there have a finite value, and remain constant for a finite period. It is shown that this nonequilibrium effect can be measured in real experiments (such as cooled rubidium atoms), where the discontinuity is replaced with a finite width (hundreds of nanometers) gradient.

Electronic structure and magnetic ordering in manganese hydride

NASA Astrophysics Data System (ADS)

Magnitskaya, M. V.; Kulikov, N. I.

1991-03-01

The self-consistent electron energy bands of antiferromagnetic (AFM) and non-magnetic manganese hydride are calculated using the linear muffintin orbital method (LMTO). The calculated values of equilibrium volume and of magnetic moment on the manganese site are in good agreement with experiment. The Fermi surface of paramagnetic MnH contains two nesting parts, and their superposition gives rise to AFM gap.

Calculation of boron-isotope fractionation between B(OH) 3(aq) and B(OH)4-(aq)

NASA Astrophysics Data System (ADS)

Rustad, James R.; Bylaska, Eric J.; Jackson, Virgil E.; Dixon, David A.

2010-05-01

Density functional and correlated molecular orbital calculations (MP2) are carried out on B(OH) 3· nH 2O clusters ( n = 0, 6, 32), and B(OH)4-· nH 2O ( n = 0, 8, 11, 32) to estimate the equilibrium distribution of 10B and 11B isotopes between boric acid and borate in aqueous solution. For the large 32-water clusters, multiple conformations are generated from ab initio molecular dynamics simulations to account for the effect of solvent fluctuations on the isotopic fractionation. We provide an extrapolated value of the equilibrium constant α34 for the isotope exchange reaction 10B(OH) 3(aq) + 11B(OH)4- (aq) = 11B(OH) 3(aq) + 11B(OH)4- (aq) of 1.026-1.028 near the MP2 complete basis set limit with 32 explicit waters of solvation. With some exchange-correlation functionals we find potentially important contributions from a tetrahedral neutral B(OH) 3·H 2O Lewis acid-base complex. The extrapolations presented here suggest that DFT calculations give a value for 10 3ln α34 about 15% higher than the MP2 calculations.

Calculation of individual isotope equilibrium constants for implementation in geochemical models

USGS Publications Warehouse

Thorstenson, Donald C.; Parkhurst, David L.

2002-01-01

Theory is derived from the work of Urey to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by , where is n the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example and , and to include the effects of nonideality. The equilibrium constants of the isotope exchange reactions provide a basis for calculating the individual isotope equilibrium constants for the geochemical modeling reactions. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors. Equilibrium constants are calculated for all species that can be formed from and selected species containing , in the molecules and the ion pairs with where the subscripts g, aq, l, and s refer to gas, aqueous, liquid, and solid, respectively. These equilibrium constants are used in the geochemical model PHREEQC to produce an equilibrium and reaction-transport model that includes these isotopic species. Methods are presented for calculation of the individual isotope equilibrium constants for the asymmetric bicarbonate ion. An example calculates the equilibrium of multiple isotopes among multiple species and phases.

Calculation of the vibrational spectra of betaine hydrochloride

NASA Astrophysics Data System (ADS)

Szafran, Miroslaw; Koput, Jacek

1997-02-01

The molecular geometries of betaine hydrochloride, BET·HCl, and free protonated betaine, BET·H +, were calculated with the 6-31G(d,p) basis set at the SCF, MP2 and DFT levels of theory. At the SCF level, the minimum energy corresponds to the ionic pair, B +Htctdot;A -, however, the equilibrium Otctdot;Cl distance is 0.14 Å shorter than the X-ray value. Inclusion of the correlation effects, both at the MP2 and DFT levels, predicts a minimum energy for the molecular complex, Btctdot;H-A, with the equilibrium Otctdot;Cl distance close to the experimental value. The frequencies and intensities of the vibrational bands of BET·HCl, BET·DCl and BET·H + were calculated at the SCF and DFT levels and compared with the solid IR spectra. All measured IR bands were interpreted in term of the calculated vibrational modes. The rms deviations between the experimental and calculated SCF frequencies were 21 and 29 cm -1 for BET·HCl and BET·DCl, respectively. The computed band intensities agree qualitatively with the experimental data. The coupling of the CO stretching and OH bending modes are discussed. The summation bands are probably enhanced in intensity by Fermi resonance with the fundamentals responsible for the main ν(OH) (ν(OD) absorption region.

From Urey To The Ocean's Glacial Ph: News From The Boron-11 Paleo-acidimetry.

NASA Astrophysics Data System (ADS)

Zeebe, R. E.; Wolf-Gladrow, D. A.; Bijma, J.

Boron paleo-acidimetry is based on the stable boron isotope composition of foraminiferal shells which has been shown to be a function of seawater pH. It is cur- rently one of the most promising paleo-carbonate chemistry proxies. One important parameter of the proxy is the equilibrium fractionation between the dissolved boron species B(OH)3 and B(OH)- which was calculated to be 19 per mil at 25C by Kak- 4 ihana and Kotaka (1977), based on Urey's theory. The calculated equilibrium frac- tionation, however, depends on the vibrational frequencies of the molecules for which different values have been reported in the literature. We have recalculated the equilib- rium fractionation and find that it may be distinctly different from 19 per mil (this is the bad news). The good news is that - theoretically - the use of 11B as a paleo-pH indicator is not compromised through vital effects in planktonic foraminifera. We de- rive this conclusion by the use of a diffusion-reaction model that calculates pH profiles and 11B values in the vicinity of a foraminifer.

Reduced Equations for Calculating the Combustion Rates of Jet-A and Methane Fuel

NASA Technical Reports Server (NTRS)

Molnar, Melissa; Marek, C. John

2003-01-01

Simplified kinetic schemes for Jet-A and methane fuels were developed to be used in numerical combustion codes, such as the National Combustor Code (NCC) that is being developed at Glenn. These kinetic schemes presented here result in a correlation that gives the chemical kinetic time as a function of initial overall cell fuel/air ratio, pressure, and temperature. The correlations would then be used with the turbulent mixing times to determine the limiting properties and progress of the reaction. A similar correlation was also developed using data from NASA's Chemical Equilibrium Applications (CEA) code to determine the equilibrium concentration of carbon monoxide as a function of fuel air ratio, pressure, and temperature. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates and the values obtained from the equilibrium correlations were then used to calculate the necessary chemical kinetic times. Chemical kinetic time equations for fuel, carbon monoxide, and NOx were obtained for both Jet-A fuel and methane.

Non-equilibrium transport in the quantum dot: quench dynamics and non-equilibrium steady state

NASA Astrophysics Data System (ADS)

Culver, Adrian; Andrei, Natan

We calculate the non-equilibrium current driven by a voltage drop across a quantum dot. The system is described by the two lead Anderson model at zero temperature with on-site Coulomb repulsion and non-interacting, linearized leads. We prepare the system in an initial state consisting of a free Fermi sea in each lead with the voltage drop given as the difference between the two Fermi levels. We quench the system by coupling the dot to the leads at t =0 and following the time evolution of the wavefunction. In the long time limit a new type of Bethe Ansatz wavefunction emerges, which satisfies the Lippmann-Schwinger equation with the two Fermi seas serving as the boundary conditions. The solution describes the non-equilibrium steady state of the system. We use this solution to compute the infinite time limit of the expectation value of the current operator at a given voltage, yielding the I-V characteristic. The calculation is non-perturbative and exact. Research supported by NSF Grant DMR 1410583.

Constraints on the photolysis and the equilibrium constant of ClO-dimer from airborne and balloon-borne measurements of chlorine compounds

NASA Astrophysics Data System (ADS)

Kleinboehl, A.; Canty, T. P.; Salawitch, R. J.; Khosravi, M.; Urban, J.; Toon, G. C.; Kuellmann, H.; Notholt, J.

2011-12-01

Significant differences exist between different laboratory measurements of the photolysis cross-sections of ClO-dimer, and the rate constant controlling the thermal equilibrium between ClO-dimer and ClO. This leads to uncertainties in the calculations of stratospheric ozone loss in the winter polar regions. One way to constrain the plausibility of these parameters is the measurement of ClO across the terminator in the activated polar vortex. Here we analyze measurements of ClO taken by the airborne submillimeter radiometer ASUR in the Arctic winter of 1999/2000. We use measured ClO at low solar zenith angles (SZA) to estimate the total active chlorine (ClOx). We estimate total available inorganic chlorine (Cly) using ASUR measurements of N2O in January 2000 and a N2O-Cly correlation established by a balloon measurement of the MarkIV interferometer in December 1999. We compare the ClOx estimates based on different photolysis rates of ClO-Dimer. Our results show that cross-sections leading to fast photolysis rates like the ones by Burkholder et al. [1990] or Papanastasiou et al. [2009] give ClOx mixing ratios that overlap with our estimated range of available Cly. Slower photolysis rates like the ones by von Hobe et al. [2009] and Pope et al. [2007] lead to ClOx values that are significantly higher than the available Cly. We use the calculated ClOx from low SZA to estimate the ClO in darkness with different equilibrium constants, and compare it with ASUR ClO measurements before sunrise (SZA > 95). We find that calculations with equilibrium constants published in the JPL evaluation of the last few years all give good agreement with observed ClO mixing ratios. The equilibrium constant estimated by von Hobe et al. [2005] yields ClO values that are higher than the ones observed.

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.

PubMed

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.

Simulating equilibrium processes in the Ga(NO3)3-H2O-NaOH system

NASA Astrophysics Data System (ADS)

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

2016-06-01

Equilibrium processes in the Ga(NO3)3-H2O-NaOH system are simulated with allowance for the formation of precipitates of various compositions using experimental data from potentiometric titration and theoretical studies. The values of the instability constants are calculated along with the stoichiometric compositions of the resulting compounds. It is found that pH ranges of 1.0 to 4.3 and 12.0 to 14.0 are best for the deposition of gallium chalcogenide films.

Graphical tests for Hardy-Weinberg equilibrium based on the ternary plot.

PubMed

Graffelman, Jan; Camarena, Jair Morales

2008-01-01

We design a graphical test for Hardy-Weinberg equilibrium. This can circumvent the calculation of p values and the statistical (non)significance of a large number of bi-allelic markers can be inferred from their position in a graph. By rewriting expressions for the chi(2) statistic (with and without continuity correction) in terms of the heterozygote frequency an acceptance region for Hardy-Weinberg equilibrium is obtained that can be depicted in a ternary plot. We obtain equations for curves in the ternary plot that separate markers that are out of Hardy-Weinberg equilibrium from those that are in equilibrium. The curves depend on the chosen significance level, the sample size and on a continuity correction parameter. Some examples of graphical tests using a set of 106 SNPs on the long arm of human chromosome 22 are described. Significant markers and poor markers with a lot of missing values are easily identified in the proposed plots. R software for making the diagrams is provided. The proposed graphs can be used as control charts for spotting problematic markers in large scale genotyping studies, and constitute an excellent tool for the graphical exploration of bi-allelic marker data. (c) 2007 S. Karger AG, Basel.

An extensive study of Bose-Einstein condensation in liquid helium using Tsallis statistics

NASA Astrophysics Data System (ADS)

Guha, Atanu; Das, Prasanta Kumar

2018-05-01

Realistic scenario can be represented by general canonical ensemble way better than the ideal one, with proper parameter sets involved. We study the Bose-Einstein condensation phenomena of liquid helium within the framework of Tsallis statistics. With a comparatively high value of the deformation parameter q(∼ 1 . 4) , the theoretically calculated value of the critical temperature (Tc) of the phase transition of liquid helium is found to agree with the experimentally determined value (Tc = 2 . 17 K), although they differs from each other for q = 1 (undeformed scenario). This throws a light on the understanding of the phenomenon and connects temperature fluctuation(non-equilibrium conditions) with the interactions between atoms qualitatively. More interactions between atoms give rise to more non-equilibrium conditions which is as expected.

pK(a) Values of Titrable Amino Acids at the Water/Membrane Interface.

PubMed

Teixeira, Vitor H; Vila-Viçosa, Diogo; Reis, Pedro B P S; Machuqueiro, Miguel

2016-03-08

Peptides and proteins protonation equilibrium is strongly influenced by its surrounding media. Remarkably, until now, there have been no quantitative and systematic studies reporting the pK(a) shifts in the common titrable amino acids upon lipid membrane insertion. Here, we applied our recently developed CpHMD-L method to calculate the pK(a) values of titrable amino acid residues incorporated in Ala-based pentapeptides at the water/membrane interface. We observed that membrane insertion leads to desolvation and a clear stabilization of the neutral forms, and we quantified the increases/decreases of the pK(a) values in the anionic/cationic residues along the membrane normal. This work highlights the importance of properly modeling the protonation equilibrium in peptides and proteins interacting with membranes using molecular dynamics simulations.

Evaluation of mineral-aqueous chemical equilibria of felsic reservoirs with low-medium temperature: A comparative study in Yangbajing geothermal field and Guangdong geothermal fields

NASA Astrophysics Data System (ADS)

Li, Jiexiang; Sagoe, Gideon; Yang, Guang; Lu, Guoping

2018-02-01

Classical geothermometers are useful tools for estimating reservoir temperatures of geothermal systems. However, their application to low-medium temperature reservoirs is limited because large variations of temperatures calculated by different classical geothermometers are usually observed. In order to help choose the most appropriate classical geothermometer for calculating the temperatures of low-medium temperature reservoirs, this study evaluated the mineral-aqueous equilibria of typical low-medium temperature felsic reservoirs in the Yangbajing geothermal field and Guangdong geothermal fields. The findings of this study support that reservoirs in the Guangdong geothermal fields have no direct magma influence. Also, natural reservoirs may represent the intermediate steady state before reaching full equilibrium, which rarely occurs. For the low-medium temperature geothermal systems without the influence of magma, even with seawater intrusion, the process of minerals reaching mineral-aqueous equilibrium is sequential: chlorite and chalcedony are the first, then followed by K-feldspar, kaolinite and K-mica. Chlorite may reach equilibrium at varying activity values, and the equilibrium between K-feldspar and kaolinite or K-feldspar and K-mica can fix the contents of K and Al in the solutions. Although the SiO2 and Al attain equilibrium state, albite and laumontite remain unsaturated and thus may affect low-medium temperature calculations. In this study, the chalcedony geothermometer was found to be the most suitable geothermometer for low-medium temperature reservoirs. The results of K-Mg geothermometer may be useful to complement that of the chalcedony geothermometer in low-medium temperature reservoir systems. Na-K geothermometer will give unreliable results at low-medium temperatures; and Na-K-Ca will also be unsuitable to calculate reservoir temperatures lower than 180 °C, probably caused by the chemical imbalance of laumontite.

Theoretical performance of liquid hydrogen and liquid fluorine as a rocket propellant

NASA Technical Reports Server (NTRS)

Gordon, Sanford; Huff, Vearl N

1953-01-01

Theoretical values of performance parameters for liquid hydrogen and liquid fluorine as a rocket propellant were calculated on the assumption of equilibrium composition during the expansion process for a wide range of fuel-oxidant and expansion ratios. The parameters included were specific impulse, combustion-chamber temperature, nozzle-exit temperature, equilibrium composition, mean molecular weight, characteristic velocity, coefficient of thrust, ration of nozzle-exit area to throat area, specific heat at constant pressure, coefficient of viscosity, and coefficient of thermal conductivity. The maximum value of specific impulse was 364.6 pound-seconds per pound for a chamber pressure of 300 pounds per square inch absolute (20.41 atm) and an exit pressure of 1 atmosphere.

Theoretical performance of liquid ammonia and liquid fluorine as a rocket propellant

NASA Technical Reports Server (NTRS)

Gordon, Sanford; Huff, Vearl N

1953-01-01

Theoretical values of performance parameters for liquid ammonia and liquid fluorine as a rocket propellant were calculated on the assumption of equilibrium composition during the expansion process for a wide range of fuel-oxidant and expansion ratios. The parameters included were specific impulse, combustion chamber temperature, nozzle-exit temperature, equilibrium composition, mean molecular weight, characteristic velocity, coefficient of thrust, ratio of nozzle-exit area to throat area, specific heat at constant pressure, coefficient of viscosity, and coefficient of thermal conductivity. The maximum value of specific impulse was 311.5 pound-seconds per pound for a chamber pressure of 300 pounds per square inch absolute (20.41 atm) and an exit pressure of 1 atmosphere.

Calculation of individual isotope equilibrium constants for geochemical reactions

USGS Publications Warehouse

Thorstenson, D.C.; Parkhurst, D.L.

2004-01-01

Theory is derived from the work of Urey (Urey H. C. [1947] The thermodynamic properties of isotopic substances. J. Chem. Soc. 562-581) to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by ?? = (Kex)1/n, where n is the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example 13C16O18O and 1H2H18O. The equilibrium constants of the isotope exchange reactions can be expressed as ratios of individual isotope equilibrium constants for geochemical reactions. Knowledge of the equilibrium constant for the dominant isotopic species can then be used to calculate the individual isotope equilibrium constants. Individual isotope equilibrium constants are calculated for the reaction CO2g = CO2aq for all species that can be formed from 12C, 13C, 16O, and 18O; for the reaction between 12C18 O2aq and 1H218Ol; and among the various 1H, 2H, 16O, and 18O species of H2O. This is a subset of a larger number of equilibrium constants calculated elsewhere (Thorstenson D. C. and Parkhurst D. L. [2002] Calculation of individual isotope equilibrium constants for implementation in geochemical models. Water-Resources Investigation Report 02-4172. U.S. Geological Survey). Activity coefficients, activity-concentration conventions for the isotopic variants of H2O in the solvent 1H216Ol, and salt effects on isotope fractionation have been included in the derivations. The effects of nonideality are small because of the chemical similarity of different isotopic species of the same molecule or ion. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors. The derivations can be extended to calculation of individual isotope equilibrium constants for ion pairs and equilibrium constants for isotopic species of other chemical elements. The individual isotope approach calculates the same phase isotopic compositions as existing methods, but also provides concentrations of individual species, which are needed in calculations of mass-dependent effects in transport processes. The equilibrium constants derived in this paper are used to calculate the example of gas-water equilibrium for CO2 in an acidic aqueous solution. ?? 2004 Elsevier Ltd.

Equilibrium mass-dependent fractionation relationships for triple oxygen isotopes

NASA Astrophysics Data System (ADS)

Cao, Xiaobin; Liu, Yun

2011-12-01

With a growing interest in small 17O-anomaly, there is a pressing need for the precise ratio, ln 17α/ln 18α, for a particular mass-dependent fractionation process (MDFP) (e.g., for an equilibrium isotope exchange reaction). This ratio (also denoted as " θ") can be determined experimentally, however, such efforts suffer from the demand of well-defined process or a set of processes in addition to high precision analytical capabilities. Here, we present a theoretical approach from which high-precision ratios for MDFPs can be obtained. This approach will complement and serve as a benchmark for experimental studies. We use oxygen isotope exchanges in equilibrium processes as an example. We propose that the ratio at equilibrium, θE ≡ ln 17α/ln 18α, can be calculated through the equation below: θa-bE=κa+(κa-κb){ln18βb}/{ln18α} where 18βb is the fractionation factor between a compound "b" and the mono-atomic ideal reference material "O", 18αa-b is the fractionation factor between a and b and it equals to 18βa/ 18βb and κ is a new concept defined in this study as κ ≡ ln 17β/ln 18β. The relationship between θ and κ is similar to that between α and β. The advantages of using κ include the convenience in documenting a large number of θ values for MDFPs and in estimating any θ values using a small data set due to the fact that κ values are similar among O-bearing compounds with similar chemical groups. Frequency scaling factor, anharmonic corrections and clumped isotope effects are found insignificant to the κ value calculation. However, the employment of the rule of geometric mean (RGM) can significantly affect the κ value. There are only small differences in κ values among carbonates and the structural effect is smaller than that of chemical compositions. We provide κ values for most O-bearing compounds, and we argue that κ values for Mg-bearing and S-bearing compounds should be close to their high temperature limitation (i.e., 0.5210 for Mg and 0.5159 for S). We also provide θ values for CO 2(g)-water, quartz-water and calcite-water oxygen isotope exchange reactions at temperature from 0 to 100 °C.

Oxygen transport properties estimation by DSMC-CT simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruno, Domenico; Frezzotti, Aldo; Ghiroldi, Gian Pietro

Coupling DSMC simulations with classical trajectories calculations is emerging as a powerful tool to improve predictive capabilities of computational rarefied gas dynamics. The considerable increase of computational effort outlined in the early application of the method (Koura,1997) can be compensated by running simulations on massively parallel computers. In particular, GPU acceleration has been found quite effective in reducing computing time (Ferrigni,2012; Norman et al.,2013) of DSMC-CT simulations. The aim of the present work is to study rarefied Oxygen flows by modeling binary collisions through an accurate potential energy surface, obtained by molecular beams scattering (Aquilanti, et al.,1999). The accuracy ofmore » the method is assessed by calculating molecular Oxygen shear viscosity and heat conductivity following three different DSMC-CT simulation methods. In the first one, transport properties are obtained from DSMC-CT simulations of spontaneous fluctuation of an equilibrium state (Bruno et al, Phys. Fluids, 23, 093104, 2011). In the second method, the collision trajectory calculation is incorporated in a Monte Carlo integration procedure to evaluate the Taxman’s expressions for the transport properties of polyatomic gases (Taxman,1959). In the third, non-equilibrium zero and one-dimensional rarefied gas dynamic simulations are adopted and the transport properties are computed from the non-equilibrium fluxes of momentum and energy. The three methods provide close values of the transport properties, their estimated statistical error not exceeding 3%. The experimental values are slightly underestimated, the percentage deviation being, again, few percent.« less

Turboexpander calculations using a generalized equation of state correlation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, M.S.; Starling, K.E.

1975-01-01

A generalized method for predicting the thermodynamic properties of natural gas fluids has been developed and tested. The results of several comparisons between thermodynamic property values predicted by the method and experimental data are presented. Comparisons of predicted and experimental vapor-liquid equilibrium are presented. These comparisons indicate that the generalized correlation can be used to predict many thermodynamic properties of natural gas and LNG. Turboexpander calculations are presented to show the utility of the generalized correlation for process design calculations.

Fundamental Study of Three-dimensional Fast Spin-echo Imaging with Spoiled Equilibrium Pulse.

PubMed

Ogawa, Masashi; Kaji, Naoto; Tsuchihashi, Toshio

2017-01-01

Three-dimensional fast spin-echo (3D FSE) imaging with variable refocusing flip angle has been recently applied to pre- or post-enhanced T 1 -weighted imaging. To reduce the acquisition time, this sequence requires higher echo train length (ETL), which potentially causes decreased T 1 contrast. Spoiled equilibrium (SpE) pulse consists of a resonant +90° radiofrequency (RF) pulse and is applied at the end of the echo train. This +90° RF pulse brings residual transverse magnetization to the negative longitudinal axis, which makes it possible to increase T 1 contrast. The purpose of our present study was to examine factors that influence the effect of spoiled equilibrium pulse and the relationship between T 1 contrast improvement and imaging parameters and to understand the characteristics of spoiled equilibrium pulse. Phantom studies were conducted using an magnetic resonance imaging (MRI) phantom made of polyvinyl alcohol gel. To evaluate the effect of spoiled equilibrium pulse with changes in repetition time (TR), ETL, and refocusing flip angle, we measured the signal-to-noise ratio and contrast-to-noise ratio (CNR). The effect of spoiled equilibrium pulse was evaluated by calculating the enhancement rate of CNR. The factors that influence the effect of spoiled equilibrium pulse are TR, ETL, and relaxation time of tissues. Spoiled equilibrium pulse is effective with increasing TR and decreasing ETL. The shorter the T 1 value, the better the spoiled equilibrium pulse functions. However, for tissues in which the T 1 value is long (>600 ms), at a TR of 600 ms, improvement in T 1 contrast by applying spoiled equilibrium pulse cannot be expected.

Research and application of method of oxygen isotope of inorganic phosphate in Beijing agricultural soils.

PubMed

Tian, Liyan; Guo, Qingjun; Zhu, Yongguan; He, Huijun; Lang, Yunchao; Hu, Jian; Zhang, Han; Wei, Rongfei; Han, Xiaokun; Peters, Marc; Yang, Junxing

2016-12-01

Phosphorus (P) in agricultural ecosystems is an essential and limited element for plants and microorganisms. However, environmental problems caused by P accumulation as well as by P loss have become more and more serious. Oxygen isotopes of phosphate can trace the sources, migration, and transformation of P in agricultural soils. In order to use the isotopes of phosphate oxygen, appropriate extraction and purification methods for inorganic phosphate from soils are necessary. Here, we combined two different methods to analyze the oxygen isotopic composition of inorganic phosphate (δ 18 O P ) from chemical fertilizers and different fractions (Milli-Q water, 0.5 mol L -1 NaHCO 3 (pH = 8.5), 0.1 mol L -1 NaOH and 1 mol L -1 HCl) of agricultural soils from the Beijing area. The δ 18 O P results of the water extracts and NaHCO 3 extracts in most samples were close to the calculated equilibrium value. These phenomena can be explained by rapid P cycling in soils and the influence of chemical fertilizers. The δ 18 O P value of the water extracts and NaHCO 3 extracts in some soil samples below the equilibrium value may be caused by the hydrolysis of organic P fractions mediated by extracellular enzymes. The δ 18 O P values of the NaOH extracts were above the calculated equilibrium value reflecting the balance state between microbial uptake of phosphate and the release of intracellular phosphate back to the soil. The HCl extracts with the lowest δ 18 O P values and highest phosphate concentrations indicated that the HCl fraction was affected by microbial activity. Hence, these δ 18 O p values likely reflected the oxygen isotopic values of the parent materials. The results suggested that phosphate oxygen isotope analyses could be an effective tool in order to trace phosphate sources, transformation processes, and its utilization by microorganisms in agricultural soils.

A partition-limited model for the plant uptake of organic contaminants from soil and water

USGS Publications Warehouse

Chiou, C.T.; Sheng, G.; Manes, M.

2001-01-01

In dealing with the passive transport of organic contaminants from soils to plants (including crops), a partition-limited model is proposed in which (i) the maximum (equilibrium) concentration of a contaminant in any location in the plant is determined by partition equilibrium with its concentration in the soil interstitial water, which in turn is determined essentially by the concentration in the soil organic matter (SOM) and (ii) the extent of approach to partition equilibrium, as measured by the ratio of the contaminant concentrations in plant water and soil interstitial water, ??pt (??? 1), depends on the transport rate of the contaminant in soil water into the plant and the volume of soil water solution that is required for the plant contaminant level to reach equilibrium with the external soil-water phase. Through reasonable estimates of plant organic-water compositions and of contaminant partition coefficients with various plant components, the model accounts for calculated values of ??pt in several published crop-contamination studies, including near-equilibrium values (i.e., ??pt ??? 1) for relatively water-soluble contaminants and lower values for much less soluble contaminants; the differences are attributed to the much higher partition coefficients of the less soluble compounds between plant lipids and plant water, which necessitates much larger volumes of the plant water transport for achieving the equilibrium capacities. The model analysis indicates that for plants with high water contents the plant-water phase acts as the major reservoir for highly water-soluble contaminants. By contrast, the lipid in a plant, even at small amounts, is usually the major reservoir for highly water-insoluble contaminants.

Experimental and Theoretical Studies of Interstellar Grains. Ph.D. Thesis - Maryland Univ., College Park, 1982

NASA Technical Reports Server (NTRS)

Nuth, J. A., III

1981-01-01

Steady state vibrational populations of SiO and CO in dilute black body radiation fields were calculated as a function of total pressure, kinetic temperature and chemical composition of the gas. Approximate calculations for polyatomic molecules are presented. Vibrational disequilibrium becomes increasingly significant as total pressure and radiation density decrease. Many regions of postulated grain formation are found to be far from thermal equilibrium before the onset of nucleation. Calculations based upon classical nucleation theory or equilibrium thermodynamics are expected to be of dubious value in such regions. Laboratory measurements of the extinction of small iron and magnetite grains were made from 195 nm to 830 nm and found to be consistent with predictions based upon published optical constants. This implies that small iron particles are not responsible for the 220 nm interstellar extinction features. Additional measurements are discussed.

Stability properties and fast ion confinement of hybrid tokamak plasma configurations

NASA Astrophysics Data System (ADS)

Graves, J. P.; Brunetti, D.; Pfefferle, D.; Faustin, J. M. P.; Cooper, W. A.; Kleiner, A.; Lanthaler, S.; Patten, H. W.; Raghunathan, M.

2015-11-01

In hybrid scenarios with flat q just above unity, extremely fast growing tearing modes are born from toroidal sidebands of the near resonant ideal internal kink mode. New scalings of the growth rate with the magnetic Reynolds number arise from two fluid effects and sheared toroidal flow. Non-linear saturated 1/1 dominant modes obtained from initial value stability calculation agree with the amplitude of the 1/1 component of a 3D VMEC equilibrium calculation. Viable and realistic equilibrium representation of such internal kink modes allow fast ion studies to be accurately established. Calculations of MAST neutral beam ion distributions using the VENUS-LEVIS code show very good agreement of observed impaired core fast ion confinement when long lived modes occur. The 3D ICRH code SCENIC also enables the establishment of minority RF distributions in hybrid plasmas susceptible to saturated near resonant internal kink modes.

A systematic and feasible method for computing nuclear contributions to electrical properties of polyatomic molecules

NASA Astrophysics Data System (ADS)

Luis, Josep M.; Duran, Miquel; Andrés, José L.

1997-08-01

An analytic method to evaluate nuclear contributions to electrical properties of polyatomic molecules is presented. Such contributions control changes induced by an electric field on equilibrium geometry (nuclear relaxation contribution) and vibrational motion (vibrational contribution) of a molecular system. Expressions to compute the nuclear contributions have been derived from a power series expansion of the potential energy. These contributions to the electrical properties are given in terms of energy derivatives with respect to normal coordinates, electric field intensity or both. Only one calculation of such derivatives at the field-free equilibrium geometry is required. To show the useful efficiency of the analytical evaluation of electrical properties (the so-called AEEP method), results for calculations on water and pyridine at the SCF/TZ2P and the MP2/TZ2P levels of theory are reported. The results obtained are compared with previous theoretical calculations and with experimental values.

Silicon Oxysulfide, OSiS: Rotational Spectrum, Quantum-Chemical Calculations, and Equilibrium Structure.

PubMed

Thorwirth, Sven; Mück, Leonie Anna; Gauss, Jürgen; Tamassia, Filippo; Lattanzi, Valerio; McCarthy, Michael C

2011-06-02

Silicon oxysulfide, OSiS, and seven of its minor isotopic species have been characterized for the first time in the gas phase at high spectral resolution by means of Fourier transform microwave spectroscopy. The equilibrium structure of OSiS has been determined from the experimental data using calculated vibration-rotation interaction constants. The structural parameters (rO-Si = 1.5064 Å and rSi-S = 1.9133 Å) are in very good agreement with values from high-level quantum chemical calculations using coupled-cluster techniques together with sophisticated additivity and extrapolation schemes. The bond distances in OSiS are very short in comparison with those in SiO and SiS. This unexpected finding is explained by the partial charges calculated for OSiS via a natural population analysis. The results suggest that electrostatic effects rather than multiple bonding are the key factors in determining bonding in this triatomic molecule. The data presented provide the spectroscopic information needed for radio astronomical searches for OSiS.

Metastable and equilibrium phase diagrams of unconjugated bilirubin IXα as functions of pH in model bile systems: Implications for pigment gallstone formation.

PubMed

Berman, Marvin D; Carey, Martin C

2015-01-01

Metastable and equilibrium phase diagrams for unconjugated bilirubin IXα (UCB) in bile are yet to be determined for understanding the physical chemistry of pigment gallstone formation. Also, UCB is a molecule of considerable biomedical importance because it is a potent antioxidant and an inhibitor of atherogenesis. We employed principally a titrimetric approach to obtain metastable and equilibrium UCB solubilities in model bile systems composed of taurine-conjugated bile salts, egg yolk lecithin (mixed long-chain phosphatidylcholines), and cholesterol as functions of total lipid concentration, biliary pH values, and CaCl2 plus NaCl concentrations. Metastable and equilibrium precipitation pH values were obtained, and average pKa values of the two carboxyl groups of UCB were calculated. Added lecithin and increased temperature decreased UCB solubility markedly, whereas increases in bile salt concentrations and molar levels of urea augmented solubility. A wide range of NaCl and cholesterol concentrations resulted in no specific effects, whereas added CaCl2 produced large decreases in UCB solubilities at alkaline pH values only. UV-visible absorption spectra were consistent with both hydrophobic and hydrophilic interactions between UCB and bile salts that were strongly influenced by pH. Reliable literature values for UCB compositions of native gallbladder biles revealed that biles from hemolytic mice and humans with black pigment gallstones are markedly supersaturated with UCB and exhibit more acidic pH values, whereas biles from nonstone control animals and patients with cholesterol gallstone are unsaturated with UCB. Copyright © 2015 the American Physiological Society.

Metastable and equilibrium phase diagrams of unconjugated bilirubin IXα as functions of pH in model bile systems: Implications for pigment gallstone formation

PubMed Central

Berman, Marvin D.

2014-01-01

Metastable and equilibrium phase diagrams for unconjugated bilirubin IXα (UCB) in bile are yet to be determined for understanding the physical chemistry of pigment gallstone formation. Also, UCB is a molecule of considerable biomedical importance because it is a potent antioxidant and an inhibitor of atherogenesis. We employed principally a titrimetric approach to obtain metastable and equilibrium UCB solubilities in model bile systems composed of taurine-conjugated bile salts, egg yolk lecithin (mixed long-chain phosphatidylcholines), and cholesterol as functions of total lipid concentration, biliary pH values, and CaCl2 plus NaCl concentrations. Metastable and equilibrium precipitation pH values were obtained, and average pKa values of the two carboxyl groups of UCB were calculated. Added lecithin and increased temperature decreased UCB solubility markedly, whereas increases in bile salt concentrations and molar levels of urea augmented solubility. A wide range of NaCl and cholesterol concentrations resulted in no specific effects, whereas added CaCl2 produced large decreases in UCB solubilities at alkaline pH values only. UV-visible absorption spectra were consistent with both hydrophobic and hydrophilic interactions between UCB and bile salts that were strongly influenced by pH. Reliable literature values for UCB compositions of native gallbladder biles revealed that biles from hemolytic mice and humans with black pigment gallstones are markedly supersaturated with UCB and exhibit more acidic pH values, whereas biles from nonstone control animals and patients with cholesterol gallstone are unsaturated with UCB. PMID:25359538

Calculation of the vibration-rotational transition intensities of water molecules trapped in an argon matrix: stretching O-H vibrations spectral region

NASA Astrophysics Data System (ADS)

Pitsevich, George; Shalamberidze, Elena; Malevich, Alex; Sablinskas, Valdas; Balevicius, Vytautas; Pettersson, Lars G. M.

2017-10-01

The frequencies and intensities of vibration-rotational transitions of water molecules in an argon matrix were calculated for temperatures of 6 and 30 K. The rigid asymmetric top approximation was used with available literature values of the effective rotational constants in the ground and excited vibrational states. The calculations were carried out by taking into account the existence of a non-equilibrium population distribution between the rotational levels of ortho- and para-water isomers. It was assumed that the temperature relaxation of the population of rotational levels is independent of the ortho- and para-isomers. Comparison of the results of the theoretical calculations with experimental literature data shows good agreement for the majority of the rotational structure lines for symmetric and antisymmetric stretching vibrations both in the frequency values and in the values of the relative intensities.

Diffusion coefficients in systems with inclusion compounds. 1. alpha. -Cyclodextrin-L-phenylalanine-water at 25 degree C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paduano, L.; Sartorio, R.; Vitagliano, V.

Diffusion coefficients in the ternary system {alpha}-cyclodextrin (at one concentration)-L-phenylalanine (at four concentrations)-water have been measured by using the Gouy interferometric technique. The effect of the inclusion equilibrium on the cross-term diffusion coefficients was observed. The measured diffusion coefficients in the ternary systems were used to calculate values of the binding constants. These values are in good agreement with the value obtained from calorimetric studies.

Quasi-equilibria in reduced Liouville spaces.

PubMed

Halse, Meghan E; Dumez, Jean-Nicolas; Emsley, Lyndon

2012-06-14

The quasi-equilibrium behaviour of isolated nuclear spin systems in full and reduced Liouville spaces is discussed. We focus in particular on the reduced Liouville spaces used in the low-order correlations in Liouville space (LCL) simulation method, a restricted-spin-space approach to efficiently modelling the dynamics of large networks of strongly coupled spins. General numerical methods for the calculation of quasi-equilibrium expectation values of observables in Liouville space are presented. In particular, we treat the cases of a time-independent Hamiltonian, a time-periodic Hamiltonian (with and without stroboscopic sampling) and powder averaging. These quasi-equilibrium calculation methods are applied to the example case of spin diffusion in solid-state nuclear magnetic resonance. We show that there are marked differences between the quasi-equilibrium behaviour of spin systems in the full and reduced spaces. These differences are particularly interesting in the time-periodic-Hamiltonian case, where simulations carried out in the reduced space demonstrate ergodic behaviour even for small spins systems (as few as five homonuclei). The implications of this ergodic property on the success of the LCL method in modelling the dynamics of spin diffusion in magic-angle spinning experiments of powders is discussed.

Sorption equilibrium, thermodynamics and pH-indicator properties of cresyl violet dye/bentonite composite system.

PubMed

Georgieva, Nedyalka; Yaneva, Zvezdelina; Dermendzhieva, Diyana

2017-09-01

The aim of the present study was to develop cresyl violet (CV)/bentonite composite system, to investigate the equilibrium sorption of the fluorescent dye on bentonite, to determine the characteristic equilibrium and thermodynamic parameters of the system by appropriate empirical isotherm models and to assess its pH-indicator properties. The absorption characteristics of CV solutions were investigated by UV/VIS spectrophotometer. Equilibrium experiments were conducted and the experimental data were modelled by six mathematical isotherm models. The analyses of the experimental data showed that bentonite exhibited significantly high capacity - 169.92 mg/g, towards CV. The encapsulation efficiency was 85%. The Langmuir, Flory-Huggins and El-Awady models best represented the experimental results. The free Gibbs energy of adsorption (ΔG o ) was calculated on the basis of the values of the equilibrium coefficients determined by the proposed models. The values of ΔG determined by the Langmuir, Temkin and Flory-Huggins models are within the range -20 to -40 kJ/mol, which indicates that the adsorption process is spontaneous and chemisorption takes place due to charge sharing or transfer from the dye molecules to the sorbent surface as a coordinate type of bond. The investigations of the obtained CV/bentonite hybrid systems for application as pH-markers showed satisfactory results.

Quantification of metabotropic glutamate subtype 5 receptors in the brain by an equilibrium method using 18F-SP203.

PubMed

Kimura, Yasuyuki; Siméon, Fabrice G; Zoghbi, Sami S; Zhang, Yi; Hatazawa, Jun; Pike, Victor W; Innis, Robert B; Fujita, Masahiro

2012-02-01

A new PET ligand, 3-fluoro-5-(2-(2-(18)F-(fluoromethyl)-thiazol-4-yl)ethynyl)benzonitrile (18F-SP203) can quantify metabotropic glutamate subtype 5 receptors (mGluR5) in human brain by a bolus injection and kinetic modeling. As an alternative approach to a bolus injection, binding can simply be measured as a ratio of tissue to metabolite-corrected plasma at a single time point under equilibrium conditions achieved by administering the radioligand with a bolus injection followed by a constant infusion. The purpose of this study was to validate the equilibrium method as an alternative to the standard kinetic method for measuring 18F-SP203 binding in the brain. Nine healthy subjects were injected with 18F-SP203 using a bolus plus constant infusion for 300 min. A single ratio of bolus-to-constant infusion (the activity of bolus equaled to that of infusion over 219 min) was applied to all subjects to achieve equilibrium in approximately 120 min. As a measure of ligand binding, we compared total distribution volume (VT) calculated by the equilibrium and kinetic methods in each scan. The equilibrium method calculated VT by the ratio of radioactivity in the brain to the concentration of 18F-SP203 in arterial plasma at 120 min, and the kinetic method calculated VT by a two-tissue compartment model using brain and plasma dynamic data from 0 to 120 min. VT obtained via the equilibrium method was highly correlated with VT obtained via kinetic modeling. Inter-subject variability of VT obtained via the equilibrium method was slightly smaller than VT obtained via the kinetic method. VT obtained via the equilibrium method was ~10% higher than VT obtained via the kinetic method, indicating a small difference between the measurements. Taken together, the results of this study show that using the equilibrium method is an acceptable alternative to the standard kinetic method when using 18F-SP203 to measure mGluR5. Although small differences in the measurements obtained via the equilibrium and kinetic methods exist, both methods consistently measured mGluR5 as indicated by the highly correlated VT values; the equilibrium method was slightly more precise, as indirectly measured by the smaller coefficient of variability across subjects. In addition, when using 18F-SP203, the equilibrium method is more efficient because it requires much less data. Copyright © 2011. Published by Elsevier Inc.

Methane on Mars: Thermodynamic Equilibrium and Photochemical Calculations

NASA Technical Reports Server (NTRS)

Levine, J. S.; Summers, M. E.; Ewell, M.

2010-01-01

The detection of methane (CH4) in the atmosphere of Mars by Mars Express and Earth-based spectroscopy is very surprising, very puzzling, and very intriguing. On Earth, about 90% of atmospheric ozone is produced by living systems. A major question concerning methane on Mars is its origin - biological or geological. Thermodynamic equilibrium calculations indicated that methane cannot be produced by atmospheric chemical/photochemical reactions. Thermodynamic equilibrium calculations for three gases, methane, ammonia (NH3) and nitrous oxide (N2O) in the Earth s atmosphere are summarized in Table 1. The calculations indicate that these three gases should not exist in the Earth s atmosphere. Yet they do, with methane, ammonia and nitrous oxide enhanced 139, 50 and 12 orders of magnitude above their calculated thermodynamic equilibrium concentration due to the impact of life! Thermodynamic equilibrium calculations have been performed for the same three gases in the atmosphere of Mars based on the assumed composition of the Mars atmosphere shown in Table 2. The calculated thermodynamic equilibrium concentrations of the same three gases in the atmosphere of Mars is shown in Table 3. Clearly, based on thermodynamic equilibrium calculations, methane should not be present in the atmosphere of Mars, but it is in concentrations approaching 30 ppbv from three distinct regions on Mars.

Breakdown and Limit of Continuum Diffusion Velocity for Binary Gas Mixtures from Direct Simulation

NASA Astrophysics Data System (ADS)

Martin, Robert Scott; Najmabadi, Farrokh

2011-05-01

This work investigates the breakdown of the continuum relations for diffusion velocity in inert binary gas mixtures. Values of the relative diffusion velocities for components of a gas mixture may be calculated using of Chapman-Enskog theory and occur not only due to concentration gradients, but also pressure and temperature gradients in the flow as described by Hirschfelder. Because Chapman-Enskog theory employs a linear perturbation around equilibrium, it is expected to break down when the velocity distribution deviates significantly from equilibrium. This breakdown of the overall flow has long been an area of interest in rarefied gas dynamics. By comparing the continuum values to results from Bird's DS2V Monte Carlo code, we propose a new limit on the continuum approach specific to binary gases. To remove the confounding influence of an inconsistent molecular model, we also present the application of the variable hard sphere (VSS) model used in DS2V to the continuum diffusion velocity calculation. Fitting sample asymptotic curves to the breakdown, a limit, Vmax, that is a fraction of an analytically derived limit resulting from the kinetic temperature of the mixture is proposed. With an expected deviation of only 2% between the physical values and continuum calculations within ±Vmax/4, we suggest this as a conservative estimate on the range of applicability for the continuum theory.

Solid solution partitioning of Sr2+, Ba2+, and Cd2+ to calcite

USGS Publications Warehouse

Tesoriero, A.J.; Pankow, J.F.

1996-01-01

Although solid solutions play important roles in controlling the concentrations of minor metal ions in natural waters, uncertainties regarding their compositions, thermodynamics, and kinetics usually prevent them from being considered. A range of precipitation rates was used here to study the nonequilibrium and equilibrium partitioning behaviors of Sr2+, Ba2+, and Cd2+ to calcite (CaCO3(s)). The distribution coefficient of a divalent metal ion Me2+ for partitioning from an aqueous solution into calcite is given by DMe = (XMeCO3(s)/[Me2+])/(XCaCO3(s)/[Ca 2+]). The X values are solid-phase mole fractions; the bracketed values are the aqueous molal concentrations. In agreement with prior work, at intermediate to high precipitation rates R (nmol/mg-min), DSr, DBa, and DCd were found to depend strongly on R. At low R, the values of DSr, DBa, and DCd became constant with R. At 25??C, the equilibrium values for DSr, DBa, and DCd for dilute solid solutions were estimated to be 0.021 ?? 0.003, 0.012 ?? 0.005, and 1240 ?? 300, respectively. Calculations using these values were made to illustrate the likely importance of partitioning of these ions to calcite in groundwater systems. Due to its large equilibrium DMe value, movement of Cd2+ will be strongly retarded in aquifers containing calcite; Sr2+ and Ba2+ will not be retarded nearly as much.

Determination of the partition coefficient between dissolved organic carbon and seawater using differential equilibrium kinetics.

PubMed

Kim, Du Yung; Kwon, Jung-Hwan

2018-05-04

Because the freely dissolved fraction of highly hydrophobic organic chemicals is bioavailable, knowing the partition coefficient between dissolved organic carbon and water (K DOCw ) is crucial to estimate the freely dissolved fraction from the total concentration. A kinetic method was developed to obtain K DOCw that required a shorter experimental time than equilibrium methods. The equilibrium partition coefficients of four polychlorinated biphenyls (PCBs) (2,4,4'-trichlorobiphenyl (PCB 28), 2,2',3,5'-tetrachlorobiphenyl (PCB 44), 2,2',4,5,5'-pentachlorobiphenyl (PCB 101), and 2,2',4,4',5,5'-hexachlorobiphenyl (PCB 153)) between dissolved organic carbon and seawater (K DOCsw ) were determined using seawater samples from the Korean coast. The log K DOCsw values of PCB 28 were measured by equilibrating PCB 28, the least hydrophobic congener, with seawater samples, and the values ranged from 6.60 to 7.20. For the more hydrophobic PCBs (PCB 44, PCB 101, and PCB 153), kinetic experiments were conducted to determine the sorption rate constants (k 2 ) and their log K DOCsw values were obtained by comparing their k 2 with that of PCB 28. The calculated log K DOCsw values were 6.57-7.35 for PCB 44, 6.23-7.44 for PCB 101, and 6.35-7.73 for PCB 153. The validity of the proposed method was further confirmed using three less hydrophobic polycyclic aromatic hydrocarbons. This kinetic method shortened the experimental time to obtain the K DOCsw values of the more hydrophobic PCBs, which did not reach phase equilibrium. Copyright © 2018 Elsevier Ltd. All rights reserved.

Thermal equilibrium concentrations and effects of negatively charged Ga vacancies in n-type GaAs

NASA Astrophysics Data System (ADS)

Tan, T. Y.; You, H.-M.; Gösele, U. M.

1993-03-01

We have calculated the thermal equilibrium concentrations of the various negatively charged Ga vacancy species in GaAs. The triply-negatively-charged Ga vacancy, V {Ga/3-}, has been emphasized, since it dominates Ga self-diffusion and Ga-Al interdiffusion under intrinsic and n-doping conditions, as well as the diffusion of Si donor atoms occupying Ga sites. Under strong n-doping conditions, the thermal equilibrium V {Ga/3-}concentration, C_{V_{_{Ga} }^{3 - } }^{eq} (n), has been found to exhibit a temperature independence or a negative temperature dependence, i.e., the C_{V_{_{Ga} }^{3 - } }^{eq} (n) value is either unchanged or increases as the temperature is lowered. This is quite contrary to the normal point defect behavior for which the point defect thermal equilibrium concentration decreases as the temperature is lowered. This C_{V_{_{Ga} }^{3 - } }^{eq} (n) property provides explanations to a number of outstanding experimental results, either requiring the interpretation that V {Ga/3-}has attained its thermal equilibrium concentration at the onset of each experiment, or requiring mechanisms involving point defect non-equilibrium phenomena.

Biochemical thermodynamics: applications of Mathematica.

PubMed

Alberty, Robert A

2006-01-01

The most efficient way to store thermodynamic data on enzyme-catalyzed reactions is to use matrices of species properties. Since equilibrium in enzyme-catalyzed reactions is reached at specified pH values, the thermodynamics of the reactions is discussed in terms of transformed thermodynamic properties. These transformed thermodynamic properties are complicated functions of temperature, pH, and ionic strength that can be calculated from the matrices of species values. The most important of these transformed thermodynamic properties is the standard transformed Gibbs energy of formation of a reactant (sum of species). It is the most important because when this function of temperature, pH, and ionic strength is known, all the other standard transformed properties can be calculated by taking partial derivatives. The species database in this package contains data matrices for 199 reactants. For 94 of these reactants, standard enthalpies of formation of species are known, and so standard transformed Gibbs energies, standard transformed enthalpies, standard transformed entropies, and average numbers of hydrogen atoms can be calculated as functions of temperature, pH, and ionic strength. For reactions between these 94 reactants, the changes in these properties can be calculated over a range of temperatures, pHs, and ionic strengths, and so can apparent equilibrium constants. For the other 105 reactants, only standard transformed Gibbs energies of formation and average numbers of hydrogen atoms at 298.15 K can be calculated. The loading of this package provides functions of pH and ionic strength at 298.15 K for standard transformed Gibbs energies of formation and average numbers of hydrogen atoms for 199 reactants. It also provides functions of temperature, pH, and ionic strength for the standard transformed Gibbs energies of formation, standard transformed enthalpies of formation, standard transformed entropies of formation, and average numbers of hydrogen atoms for 94 reactants. Thus loading this package makes available 774 mathematical functions for these properties. These functions can be added and subtracted to obtain changes in these properties in biochemical reactions and apparent equilibrium constants.

An update on 11B,10B fractionation in the fundamental reaction: 10B(OH)3 + 11B(OH)4- = 11B(OH)3 + 10B(OH)4-

NASA Astrophysics Data System (ADS)

Klochko, K.; Tossell, J. A.

2007-12-01

It has recently been demonstrated experimentally by Byrne, et al. (2006) and Klochko, et al. (2006) that the equilibrium constant for the isotopic exchange reaction: 10B(OH)3 + 11B(OH)4- = 11B(OH)3 + 10B(OH)4- (1) has a value around 1.027 for seawater at 25°C, for total B concentrations from 0.01 to 0.05 molal. These experimental studies involved essentially the accurate determination of the small pKa difference between the 11B and 10B isotopomers of boric acid. This new equilibrium constant value is significantly higher than the traditional value of 1.0194 from Kakihana, et al. (1977). This result has been obscured in recent controversies (Honisch, et al., 2007). The new value agrees well with the ab initio quantum cluster calculated values of Liu and Tossell (2005) and with the ab initio MD harmonic values of Rustad and Bylaska (2007). We will present additional calculations supporting and extending the study of Liu and Tossell (2005) and will discuss the general unsuitability of methods such as Sanchez-Valle, et al. (2005) which employ experimental spectral data. We have also established that polyborate formation in solutions as concentrated as 0.50 molal total B has little effect on the equilibrium constant. A mechanism is also presented for the interaction of B(OH)3 and B(OH)4- with HCO3- species occurring on the calcite surface. References: Byrne, et al. Deep-Sea Research I (2006) 53, 684-688. Honisch, et al. Geochim. Cosmochim. Acta (2007) 71, 1636-1641. Kakihana, et al. Bull. Chem. Soc. Jpn. (1977) 50, 158-163. Klochko, et al. Earth Planet. Sci. Lett. (2006) 248, 276-285. Liu and Tossell Geochim. Cosmochim. Acta (2005) 69, 3995-4006. Rustad and Bylaska J. Am. Chem. Soc. (2007) 129, 2222-2223. Sanchez-Valle, et al. Geochim. Cosmochim. Acta (2005) 69, 4301-4313.

Coupled phase and aqueous species equilibrium of the H 2O-CO 2-NaCl-CaCO 3 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to saturation of halite

NASA Astrophysics Data System (ADS)

Duan, Zhenhao; Li, Dedong

2008-10-01

A model is developed for the calculation of coupled phase and aqueous species equilibrium in the H 2O-CO 2-NaCl-CaCO 3 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to saturation of halite. The vapor-liquid-solid (calcite, halite) equilibrium together with the chemical equilibrium of H +, Na +, Ca 2+, CaHCO3+, Ca(OH) +, OH -, Cl -, HCO3-, CO32-, CO 2(aq) and CaCO 3(aq) in the aqueous liquid phase as a function of temperature, pressure, NaCl concentrations, CO 2(aq) concentrations can be calculated, with accuracy close to those of experiments in the stated T- P- m range, hence calcite solubility, CO 2 gas solubility, alkalinity and pH values can be accurately calculated. The merit and advantage of this model is its predictability, the model was generally not constructed by fitting experimental data. One of the focuses of this study is to predict calcite solubility, with accuracy consistent with the works in previous experimental studies. The resulted model reproduces the following: (1) as temperature increases, the calcite solubility decreases. For example, when temperature increases from 273 to 373 K, calcite solubility decreases by about 50%; (2) with the increase of pressure, calcite solubility increases. For example, at 373 K changing pressure from 10 to 500 bar may increase calcite solubility by as much as 30%; (3) dissolved CO 2 can increase calcite solubility substantially; (4) increasing concentration of NaCl up to 2 m will increase calcite solubility, but further increasing NaCl solubility beyond 2 m will decrease its solubility. The functionality of pH value, alkalinity, CO 2 gas solubility, and the concentrations of many aqueous species with temperature, pressure and NaCl (aq) concentrations can be found from the application of this model. Online calculation is made available on www.geochem-model.org/models/h2o_co2_nacl_caco3/calc.php.

A Heuristic Approach to Examining Volatile Equilibrium at Titan's Surface

NASA Technical Reports Server (NTRS)

Samuelson, Robert E.

1999-01-01

R. D. Lorenz, J. I. Lunine, and C. P. McKay have shown in a manuscript accepted for publication that, for a given ethane abundance and surface temperature, the nitrogen and methane abundances in Titan's atmosphere can be calculated, yielding a surface pressure that can be compared with the observed value. This is potentially a very valuable tool for examining the evolution of Titan's climatology. Its validity does depend on two important assumptions, however: 1) that the atmosphere of Titan is in global radiative equilibrium, and 2) that volatiles present are in vapor equilibrium with the surface. The former assumption has been shown to be likely, but the latter has not. Water vapor in the Earth's atmosphere, in fact, is generally not very close to equilibrium in a global sense. In the present work a heuristic approach is used to examine the likelihood that methane vapor is in equilibrium with Titan's surface. Plausible climate scenerios are examined that are consistent with methane vapor abundances derived from Voyager IRIS data. Simple precipitation and surface diffusion models are incorporated into the analysis. It is tentatively inferred that methane may be in surface equilibrium near the poles, but that equilibrium at low latitudes is more difficult to establish.

Equilibrium nuclear ensembles taking into account vaporization of hot nuclei in dense stellar matter

NASA Astrophysics Data System (ADS)

Furusawa, Shun; Mishustin, Igor

2018-02-01

We investigate the high-temperature effect on the nuclear matter that consists of mixture of nucleons and all nuclei in the dense and hot stellar environment. The individual nuclei are described within the compressible-liquid-drop model that is based on Skyrme interactions for bulk energies and that takes into account modifications of the surface and Coulomb energies at finite temperatures and densities. The free-energy density is minimized with respect to the individual equilibrium densities of all heavy nuclei and the nuclear composition. We find that their optimized equilibrium densities become smaller and smaller at high temperatures because of the increase in thermal contributions to bulk free energies and the reduction of surface energies. The neutron-rich nuclei become unstable and disappear one after another at given temperatures. The calculations are performed for two sets of model parameters leading to different values of the slope parameter in the nuclear-symmetry energy. It is found that the larger slope parameter reduces the equilibrium densities and the melting temperatures. We also compare the proposed model with some other approaches and find that the mass fractions of heavy nuclei in the previous calculations that omit vaporization are underestimated at T ≲10 MeV and overestimated at T ≳10 MeV. The further sophistication of calculations of nuclear vaporization and of light clusters would be required to construct the equation of state for explosive astrophysical phenomena.

Semi-experimental equilibrium structure of pyrazinamide from gas-phase electron diffraction. How much experimental is it?

NASA Astrophysics Data System (ADS)

Tikhonov, Denis S.; Vishnevskiy, Yury V.; Rykov, Anatolii N.; Grikina, Olga E.; Khaikin, Leonid S.

2017-03-01

A semi-experimental equilibrium structure of free molecules of pyrazinamide has been determined for the first time using gas electron diffraction method. The refinement was carried using regularization of geometry by calculated quantum chemical parameters. It is discussed to which extent is the final structure experimental. A numerical approach for estimation of the amount of experimental information in the refined parameters is suggested. The following values of selected internuclear distances were determined (values are in Å with 1σ in the parentheses): re(Cpyrazine-Cpyrazine)av = 1.397(2), re(Npyrazine-Cpyrazine)av = 1.332(3), re(Cpyrazine-Camide) = 1.493(1), re(Namide-Camide) = 1.335(2), re(Oamide-Camide) = 1.219(1). The given standard deviations represent pure experimental uncertainties without the influence of regularization.

Voltage Quench Dynamics of a Kondo System.

PubMed

Antipov, Andrey E; Dong, Qiaoyuan; Gull, Emanuel

2016-01-22

We examine the dynamics of a correlated quantum dot in the mixed valence regime. We perform numerically exact calculations of the current after a quantum quench from equilibrium by rapidly applying a bias voltage in a wide range of initial temperatures. The current exhibits short equilibration times and saturates upon the decrease of temperature at all times, indicating Kondo behavior both in the transient regime and in the steady state. The time-dependent current saturation temperature connects the equilibrium Kondo temperature to a substantially increased value at voltages outside of the linear response. These signatures are directly observable by experiments in the time domain.

Determination of acidity constants of curcumin in aqueous solution and apparent rate constant of its decomposition

NASA Astrophysics Data System (ADS)

Bernabé-Pineda, Margarita; Ramírez-Silva, María. Teresa; Romero-Romo, Mario; González-Vergara, Enrique; Rojas-Hernández, Alberto

2004-04-01

The stability of curcumin (H 3Cur) in aqueous media is improved when the systems in which it is present are at high pH values (higher than 11.7), fitting a model describable by a pseudo-zero order with a rate constant k' for the disappearance of the Cur 3- species of 1.39 (10 -9) M min -1. There were three acidity constants measured for the curcumin as follows: p KA3=10.51±0.01 corresponding to the equilibrium HCur 2-=Cur 3-+H +, a p KA2=9.88±0.02 corresponding to the equilibrium H 2Cur -=HCur -2+H +. These p KA values were attributed to the hydrogen of the phenol part of the curcumin, while the p KA1=8.38±0.04 corresponds to the equilibrium H 3Cur=H 2Cur -+H + and is attributed the acetylacetone type group. Formation of quinoid structures play an important role in the tautomeric forms of the curcumin in aqueous media, which makes the experimental values differ from the theoretically calculated ones, depending on the conditions adopted in the study.

Vibrational density of states and Lindemann melting law

NASA Astrophysics Data System (ADS)

Luo, Sheng-Nian; Strachan, Alejandro; Swift, Damian C.

2005-05-01

We examine the Lindemann melting law at different pressures using the vibrational density of states (DOS), equilibrium melting curve, and Lindemann parameter δL (fractional root-mean-squared displacement, rmsd, at equilibrium melting) calculated independently from molecular dynamics simulations of the Lennard-Jones system. The DOS is obtained using spectra analysis of atomic velocities and accounts for anharmonicity. The increase of δL with pressure is non-negligible: δL is about 0.116 and 0.145 at ambient and extreme pressures, respectively. If the component of rmsd normal to a reflecting plane as in the Debye-Waller-factor-type measurements using x rays is adopted for δL, these values are about 0.067(±0.002) and 0.084(±0.003), and are comparable with experimental and calculated values for face-centered-cubic elements. We find that the Lindemann relation holds accurately at ambient and high pressures. The non-negligible pressure dependence of δL suggests that caution should be exerted in applying the Lindemann law to obtaining the high pressure melting curve anchored at ambient pressure.

Conversion rate of para-hydrogen to ortho-hydrogen by oxygen: implications for PHIP gas storage and utilization.

PubMed

Wagner, Shawn

2014-06-01

To determine the storability of para-hydrogen before reestablishment of the room temperature thermal equilibrium mixture. Para-hydrogen was produced at near 100% purity and mixed with different oxygen quantities to determine the rate of conversion to the thermal equilibrium mixture of 75: 25% (ortho: para) by detecting the ortho-hydrogen (1)H nuclear magnetic resonance using a 9.4 T imager. The para-hydrogen to ortho-hydrogen velocity constant, k, near room temperature (292 K) was determined to be 8.27 ± 1.30 L/mol · min(-1). This value was calculated utilizing four different oxygen fractions. Para-hydrogen conversion to ortho-hydrogen by oxygen can be minimized for long term storage with judicious removal of oxygen contamination. Prior calculated velocity rates were confirmed demonstrating a dependence on only the oxygen concentration.

Protonation equilibrium and lipophilicity of olamufloxacin (HSR-903), a newly synthesized fluoroquinolone antibacterial.

PubMed

Sun, Jin; Sakai, Shigeko; Tauchi, Yoshihiko; Deguchi, Yoshiharu; Cheng, Gang; Chen, Jimin; Morimoto, Kazuhiro

2003-09-01

This study was performed to characterize the protonation equilibrium at the molecular level and pH-dependent lipophilicity of olamufloxacin. The deprotonation fraction of the carboxyl group as a function of pH was specifically calculated at the critical wavelength 294 nm, where UV pH-dependent absorbance of olamufloxacin was independent of the ionized state of the aminopyrrolidinyl amino group but heavily depended on that of the carboxyl moiety. Accordingly, micro-protonation equilibrium could be described using a nonlinear least-squares regression program MULTI. In contrast, macro-protonation equilibrium was depicted at most wavelengths where olamufloxacin absorbance was influenced by ionized states of both proton-binding groups, results coinciding with the former. Furthermore, distribution features of four microspecies in aqueous phase were assessed. The apparent partition coefficient versus pH profile of olamufloxacin showed a parabolic curve in n-octanol/buffer system which reached peak near pH 8, agreeing with the above determined isoelectric point (pI). Ion-pair effect was observed for olamufloxacin under an acidic condition, eliciting experimental values higher than those theoretically calculated, which was similar to ciprofloxacin but not levofloxacin due to amino group type. Moreover, olamufloxacin was moderately lipophilic in comparison with other quinolones, with an apparent partition coefficient of 1.95 at pH 7.4.

A dynamical stabilizer in the climate system: a mechanism suggested by a simple model

NASA Astrophysics Data System (ADS)

Bates, J. R.

1999-05-01

A simple zonally averaged hemispheric model of the climate system is constructed, based on energy equations for two ocean basins separated at 30° latitude with the surface fluxes calculated explicitly. A combination of empirical input and theoretical calculation is used to determine an annual mean equilibrium climate for the model and to study its stability with respect to small perturbations. The insolation, the mean albedos and the equilibrium temperatures for the two model zones are prescribed from observation. The principal agent of interaction between the zones is the vertically integrated poleward transport of atmospheric angular momentum across their common boundary. This is parameterized using an empirical formula derived from a multiyear atmospheric data set. The surface winds are derived from the angular momentum transport assuming the atmosphere to be in a state of dynamic balance on the climatic timescales of interest. A further assumption that the air sea temperature difference and low level relative humidity remain fixed at their mean observed values then allows the surface fluxes of latent and sensible heat to be calculated. Results from a radiative model, which show a positive lower tropospheric water vapour/infrared radiative feedback on SST perturbations in both zones, are used to calculate the net upward infrared radiative fluxes at the surface. In the model's equilibrium climate, the principal processes balancing the solar radiation absorbed at the surface are evaporation in the tropical zone and net infrared radiation in the extratropical zone. The stability of small perturbations about the equilibrium is studied using a linearized form of the ocean energy equations. Ice-albedo and cloud feedbacks are omitted and attention is focussed on the competing effects of the water vapour/infrared radiative feedback and the turbulent surface flux and oceanic heat transport feedbacks associated with the angular momentum cycle. The perturbation equations involve inter-zone coupling and have coefficients dependent on the values of the equilibrium fluxes and the sensitivity of the angular momentum transport. Analytical solutions for the perturbations are obtained. These provide criteria for the stability of the equilibrium climate. If the evaporative feedback on SST perturbations is omitted, the equilibrium climate is unstable due to the influence of the water vapour/infrared radiative feedback, which dominates over the effects of the sensible heat and ocean heat transport feedbacks. The inclusion of evaporation gives a negative feedback which is of sufficient strength to stabilize the system. The stabilizing mechanism involves wind and humidity factors in the evaporative fluxes that are of comparable magnitude. Both factors involve the angular momentum transport. In including angular momentum and calculating the surface fluxes explicitly, the model presented here differs from the many simple climate models based on the Budyko Sellers formulation. In that formulation, an atmospheric energy balance equation is used to eliminate surface fluxes in favour of top-of-the-atmosphere radiative fluxes and meridional atmospheric energy transports. In the resulting models, infrared radiation appears as a stabilizing influence on SST perturbations and the dynamical stabilizing mechanism found here cannot be identified.

The sensitivity of tokamak magnetohydrodynamics stability on the edge equilibrium

NASA Astrophysics Data System (ADS)

Zheng, L. J.; Kotschenreuther, M. T.; Valanju, P.

2017-10-01

Due to the X-point singularity, the safety factor tends to infinity as approaching to the last closed flux surface. The numerical treatments of the near X-point behavior become challenging both for equilibrium and stability. The usual solution is to cut off a small fraction of edge region for system stability evaluation or simply use an up-down symmetric equilibrium without X-point as an approximation. In this work, we assess the sensitivity of this type of equilibrium treatments on the stability calculation. It is found that the system stability can depend strongly on the safety factor value (qa) at the edge after the cutting-off. When the edge safety factor value falls in the vicinity of a rational mode number (referred to as the resonant gap), the system becomes quite unstable due to the excitation of the peeling type modes. Instead, when the edge safety factor is outside the resonant gaps, the system is much more stable and the predominant modes become the usual external kink (or ballooning and infernal) type. It is also found that the resonant gaps become smaller and smaller as qa increases. The ideal magnetohydrodynamic peeling ballooning stability diagram is widely used to explain the experimental observations, and the current results indicate that the conventional peeling ballooning stability diagram based on the simplified equilibrium needs to be reexamined.

MINTEQA2

EPA Science Inventory

MINTEQA2 is a equilibrium speciation model that can be used to calculate the equilibrium composition of dilute aqueous solutions in the laboratory or in natural aqueous systems. The model is useful for calculating the equilibrium mass distribution among dissolved species, adsorb...

The production of O(1S) from dissociative recombination of O2(+). [in earth upper atmosphere

NASA Technical Reports Server (NTRS)

Guberman, Steven L.

1987-01-01

The first theoretical calculations of the rate coefficient alpha for dissociative recombination of O2(+) leading to O(1S) are reported for a wide range of temperatures. The findings are discussed in terms of the potential energy curves for the ground state of O2(+) and for the dissociative 1Sigma(u) state calculated here. Values of alpha for the equilibrium case in which the electron and vibrational temperatures are identical are shown.

Hysteresis of Contact Angle of Sessile Droplets on Smooth Homogeneous Solid Substrates via Disjoining/Conjoining Pressure.

PubMed

Kuchin, I; Starov, V

2015-05-19

A theory of contact angle hysteresis of liquid droplets on smooth, homogeneous solid substrates is developed in terms of the shape of the disjoining/conjoining pressure isotherm and quasi-equilibrium phenomena. It is shown that all contact angles, θ, in the range θr < θ < θa, which are different from the unique equilibrium contact angle θ ≠ θe, correspond to the state of slow "microscopic" advancing or receding motion of the liquid if θe < θ < θa or θr < θ < θe, respectively. This "microscopic" motion almost abruptly becomes fast "macroscopic" advancing or receding motion after the contact angle reaches the critical values θa or θr, correspondingly. The values of the static receding, θr, and static advancing, θa, contact angles in cylindrical capillaries were calculated earlier, based on the shape of disjoining/conjoining pressure isotherm. It is shown now that (i) both advancing and receding contact angles of a droplet on a on smooth, homogeneous solid substrate can be calculated based on shape of disjoining/conjoining pressure isotherm, and (ii) both advancing and receding contact angles depend on the drop volume and are not unique characteristics of the liquid-solid system. The latter is different from advancing/receding contact angles in thin capillaries. It is shown also that the receding contact angle is much closer to the equilibrium contact angle than the advancing contact angle. The latter conclusion is unexpected and is in a contradiction with the commonly accepted view that the advancing contact angle can be taken as the first approximation for the equilibrium contact angle. The dependency of hysteresis contact angles on the drop volume has a direct experimental confirmation.

Non-equilibrium calculations of atmospheric processes initiated by electron impact.

NASA Astrophysics Data System (ADS)

Campbell, L.; Brunger, M. J.

2007-05-01

Electron impact in the atmosphere produces ionisation, dissociation, electronic excitation and vibrational excitation of atoms and molecules. The products can then take part in chemical reactions, recombination with electrons, or radiative or collisional deactivation. While most such processes are fast, some longer--lived species do not reach equilibrium. The electron source (photoelectrons or auroral electrons) also varies over time and longer-lived species can move substantially in altitude by molecular, ambipolar or eddy diffusion. Hence non-equilibrium calculations are required in some circumstances. Such time-step calculations need to have sufficiently short steps so that the fastest processes are still calculated correctly, but this can lead to computation times that are too large. Hence techniques to allow for longer time steps by incorporating equilibrium calculations are described. Examples are given for results of atmospheric non-equilibrium calculations, including the populations of the vibrational levels of ground state N2, the electron density and its dependence on vibrationally excited N2, predictions of nitric oxide density, and detailed processes during short duration auroral events.

Relationship between δ 18O values for skeletal apatite from reindeer and foxes and yearly mean δ 18O values of environmental water

NASA Astrophysics Data System (ADS)

Iacumin, Paola; Longinelli, Antonio

2002-07-01

The oxygen isotope composition of bone and tooth phosphate of 50 fox specimens and 30 reindeer specimens from various locations with different climatic and environmental conditions was measured. The existing relationship between these values and the mean oxygen isotope composition of local meteoric water has been calculated. In the case of foxes, specimens belonging to two genera ( Vulpes and Alopex) and three different species were measured. The samples fit a straight line whose equation can be used for paleoclimatological studies either in Arctic or in temperate regions. For reindeer ( Rangifer), a relatively large range of isotopic values was obtained from each location, suggesting imperfect equilibrium conditions with environmental water. The calculated equation can be used for semi-quantitative information on local paleowaters at high latitudes only.

Water adsorption isotherms of carboxymethyl cellulose, guar, locust bean, tragacanth and xanthan gums.

PubMed

Torres, María D; Moreira, Ramón; Chenlo, Francisco; Vázquez, María J

2012-06-20

Water adsorption isotherms of carboxymethyl cellulose (CMC), guar gum (GG), locust bean gum (LBG), tragacanth gum (TG) and xanthan gum (XG) were determined at different temperatures (20, 35, 50, and 65°C) using a gravimetric method. Several saturated salt solutions were selected to obtain different water activities in the range from 0.09 to 0.91. Water adsorption isotherms of tested hydrocolloids were classified like type II isotherms. In all cases, equilibrium moisture content decreased with increasing temperature at each water activity value. Three-parameter Guggenheim-Anderson-de Boer (GAB) model was employed to fit the experimental data in the water activity range and statistical analysis indicated that this model gave satisfactory results. CMC and GG were the most and the least hygroscopic gums, respectively. Sorption heats decreased with increasing moisture content. Monolayer moisture content evaluated with GAB model was consistent with equilibrium conditions of maximum stability calculated from thermodynamic analysis of net integral entropy. Values of equilibrium relative humidity at 20°C are proposed to storage adequately the tested gums. Copyright © 2012 Elsevier Ltd. All rights reserved.

Thermodynamic and structure-property study of liquid-vapor equilibrium for aroma compounds.

PubMed

Tromelin, Anne; Andriot, Isabelle; Kopjar, Mirela; Guichard, Elisabeth

2010-04-14

Thermodynamic parameters (T, DeltaH degrees , DeltaS degrees , K) were collected from the literature and/or calculated for five esters, four ketones, two aldehydes, and three alcohols, pure compounds and compounds in aqueous solution. Examination of correlations between these parameters and the range values of DeltaH degrees and DeltaS degrees puts forward the key roles of enthalpy for vaporization of pure compounds and of entropy in liquid-vapor equilibrium of compounds in aqueous solution. A structure-property relationship (SPR) study was performed using molecular descriptors on aroma compounds to better understand their vaporization behavior. In addition to the role of polarity for vapor-liquid equilibrium of compounds in aqueous solution, the structure-property study points out the role of chain length and branching, illustrated by the correlation between the connectivity index CHI-V-1 and the difference between T and log K for vaporization of pure compounds and compounds in aqueous solution. Moreover, examination of the esters' enthalpy values allowed a probable conformation adopted by ethyl octanoate in aqueous solution to be proposed.

Reversible uptake of molecular oxygen by heteroligand Co(II)-L-α-amino acid-imidazole systems: equilibrium models at full mass balance.

PubMed

Pająk, Marek; Woźniczka, Magdalena; Vogt, Andrzej; Kufelnicki, Aleksander

2017-09-19

The paper examines Co(II)-amino acid-imidazole systems (where amino acid = L-α-amino acid: alanine, asparagine, histidine) which, when in aqueous solutions, activate and reversibly take up dioxygen, while maintaining the structural scheme of the heme group (imidazole as axial ligand and O 2 uptake at the sixth, trans position) thus imitating natural respiratory pigments such as myoglobin and hemoglobin. The oxygenated reaction shows higher reversibility than for Co(II)-amac systems with analogous amino acids without imidazole. Unlike previous investigations of the heteroligand Co(II)-amino acid-imidazole systems, the present study accurately calculates all equilibrium forms present in solution and determines the [Formula: see text]equilibrium constants without using any simplified approximations. The equilibrium concentrations of Co(II), amino acid, imidazole and the formed complex species were calculated using constant data obtained for analogous systems under oxygen-free conditions. Pehametric and volumetric (oxygenation) studies allowed the stoichiometry of O 2 uptake reaction and coordination mode of the central ion in the forming oxygen adduct to be determined. The values of dioxygen uptake equilibrium constants [Formula: see text] were evaluated by applying the full mass balance equations. Investigations of oxygenation of the Co(II)-amino acid-imidazole systems indicated that dioxygen uptake proceeds along with a rise in pH to 9-10. The percentage of reversibility noted after acidification of the solution to the initial pH ranged within ca 30-60% for alanine, 40-70% for asparagine and 50-90% for histidine, with a rising tendency along with the increasing share of amino acid in the Co(II): amino acid: imidazole ratio. Calculations of the share of the free Co(II) ion as well as of the particular complex species existing in solution beside the oxygen adduct (regarding dioxygen bound both reversibly and irreversibly) indicated quite significant values for the systems with alanine and asparagine-in those cases the of oxygenation reaction is right shifted to a relatively lower extent. The experimental results indicate that the "active" complex, able to take up dioxygen, is a heteroligand CoL 2 L'complex, where L = amac (an amino acid with a non-protonated amine group) while L' = Himid, with the N1 nitrogen protonated within the entire pH range under study. Moreover, the corresponding log  [Formula: see text] value at various initial total Co(II), amino acid and imidazole concentrations was found to be constant within the limits of error, which confirms those results. The highest log [Formula: see text] value, 14.9, occurs for the histidine system; in comparison, asparagine is 7.8 and alanine is 9.7. This high value is most likely due to the participation of the additional effective N3 donor of the imidazole side group of histidine. The Co(II)-amac-Himid systems formed by using a [Co(imid) 2 ] n polymer as starting material demonstrate that the reversible uptake of molecular oxygen occurs by forming dimeric μ-peroxy adducts. The essential impact on the electron structure of the dioxygen bridge, and therefore, on the reversibility of O 2 uptake, is due to the imidazole group at axial position (trans towards O 2 ). However, the results of reversibility measurements of O 2 uptake, unequivocally indicate a much higher effectiveness of dioxygenation than in systems in which the oxygen adducts are formed in equilibrium mixtures during titration of solutions containing Co(II) ions, the amino acid and imidazole, separately.

Half-life of Th232 and the branching ratio of Bi212

USGS Publications Warehouse

Senftle, F.E.; Farley, T.A.; Lazar, N.

1956-01-01

The half-life of Th232 has been calculated by determining an absolute gamma-disintegration rate for Tl208 in equilibrium with Th232 for three old thorium nitrate salts and one natural thorite sample. The branching ratio, ??(??+??), for Bi212, a necessary parameter in the calculation, was also measured. The half-life of Th232 was found to be 1.42??1010 years within an estimated error of 5%, which is essentially in agreement with the presently accepted value. The branching ratio, ??(??+??), of Bi212 was found to be 0.362??0.006, about 7.4% higher than the currently accepted value. ?? 1956 The American Physical Society.

Sparse Partial Equilibrium Tables in Chemically Resolved Reactive Flow

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vitello, P; Fried, L E; Pudliner, B

2003-07-14

The detonation of an energetic material is the result of a complex interaction between kinetic chemical reactions and hydrodynamics. Unfortunately, little is known concerning the detailed chemical kinetics of detonations in energetic materials. CHEETAH uses rate laws to treat species with the slowest chemical reactions, while assuming other chemical species are in equilibrium. CHEETAH supports a wide range of elements and condensed detonation products and can also be applied to gas detonations. A sparse hash table of equation of state values, called the ''cache'' is used in CHEETAH to enhance the efficiency of kinetic reaction calculations. For large-scale parallel hydrodynamicmore » calculations, CHEETAH uses MPI communication to updates to the cache. We present here details of the sparse caching model used in the CHEETAH. To demonstrate the efficiency of modeling using a sparse cache model we consider detonations in energetic materials.« less

Sparse Partial Equilibrium Tables in Chemically Resolved Reactive Flow

NASA Astrophysics Data System (ADS)

Vitello, Peter; Fried, Laurence E.; Pudliner, Brian; McAbee, Tom

2004-07-01

The detonation of an energetic material is the result of a complex interaction between kinetic chemical reactions and hydrodynamics. Unfortunately, little is known concerning the detailed chemical kinetics of detonations in energetic materials. CHEETAH uses rate laws to treat species with the slowest chemical reactions, while assuming other chemical species are in equilibrium. CHEETAH supports a wide range of elements and condensed detonation products and can also be applied to gas detonations. A sparse hash table of equation of state values is used in CHEETAH to enhance the efficiency of kinetic reaction calculations. For large-scale parallel hydrodynamic calculations, CHEETAH uses parallel communication to updates to the cache. We present here details of the sparse caching model used in the CHEETAH coupled to an ALE hydrocode. To demonstrate the efficiency of modeling using a sparse cache model we consider detonations in energetic materials.

Fluctuation Pressure Assisted Ejection of DNA From Bacteriophage

NASA Astrophysics Data System (ADS)

Harrison, Michael J.

2011-03-01

The role of thermal pressure fluctuations excited within tightly packaged DNA while it is ejected from protein capsid shells is discussed in a model calculation. At equilibrium before ejection we assume the DNA is folded many times into a bundle of parallel segments that forms an equilibrium conformation at minimum free energy, which presses tightly against capsid walls. Using a canonical ensemble at temperature T we calculate internal pressure fluctuations against a slowly moving or static capsid mantle for an elastic continuum model of the folded DNA bundle. It is found that fluctuating pressures on the capsid from thermal excitation of longitudinal acoustic vibrations in the bundle whose wavelengths are exceeded by the bend persistence length may have root-mean-square values that are several tens of atmospheres for typically small phage dimensions. Comparisons are given with measured data on three mutants of lambda phage with different base pair lengths and total genome ejection pressures.

57Fe Mössbauer spectroscopy of mineral assemblages in mantle spinel lherzolites from Cenozoic alkali basalt, eastern China: Petrological applications

NASA Astrophysics Data System (ADS)

Hao, Xi-Luo; Li, Yi-Liang

2013-01-01

Mineral assemblages in spinel lherzolite xenoliths from the Cenozoic alkali basalt of eastern China were analyzed by 57Fe Mössbauer spectroscopy for Fe3+/ΣFe and distribution of Fe2+/Fe3+ in non-equivalent crystal cites. Orthopyroxene, clinopyroxene and spinel have 0.08-0.13, 0.19-0.31 and 0.13-0.23 Fe3+/ΣFe, respectively. The cation-exchange equilibrium temperatures, Fe3+ partition coefficient and oxygen fugacity of the upper mantle peridotites were calculated. The equilibrium temperatures are between 1103 K and 1405 K consistent with those reported elsewhere. The oxygen fugacities of spinel lherzolites calculated with olivine-orthopyroxene-spinel (ΔlogƒO2 from - 1.1 to 0) and clinopyroxene-olivine-orthopyroxene oxybarometers (ΔlogƒO2 from - 2.0 to 0.7) are consistent with previously reported upper mantle values.

Equilibrium structure and atomic vibrations of Nin clusters

NASA Astrophysics Data System (ADS)

Borisova, Svetlana D.; Rusina, Galina G.

2017-12-01

The equilibrium bond lengths and binding energy, second differences in energy and vibrational frequencies of free clusters Nin (2 ≤ n ≤ 20) were calculated with the use of the interaction potential obtained in the tight-binding approximation (TBA). The results show that the minimum vibration frequency plays a significant role in the evaluation of the dynamic stability of the clusters. A nonmonotonic dependence of the minimum vibration frequency of clusters on their size and the extreme values for the number of atoms in a cluster n = 4, 6, 13, and 19 are demonstrated. This result agrees with the theoretical and experimental data on stable structures of small metallic clusters.

The magnetic non-equilibrium of buoyant flux tubes in the solar corona

NASA Technical Reports Server (NTRS)

Browning, P. K.; Priest, E. R.

1984-01-01

The magnetic field in the convection zone and photosphere of the sun exists mostly as concentrated tubes of magnetic flux. It is, therefore, necessary to study the basic properties of magnetic flux tubes to obtain a basis for understanding the behavior of the sun's magnetic field. The present investigation is concerned with the global equilibrium shape of a flux tube in the stratified solar atmosphere. A fundamental property of isolated flux tubes is magnetic buoyancy. Attention is given to flux tubes with external field, and twisted flux tubes. It is shown that the analysis of Parker (1975, 1979) and Spruit (1981) for calculating the equilibrium of a slender flux tube in a stratified atmosphere may be extended to more general situations. The slender tube approximation provides a method of solving the problem of modeling the overall curvature of flux tubes. It is found that for a twisted flux tube, there can be two possible equilibrium values of the height.

Monte Carlo calculations of diatomic molecule gas flows including rotational mode excitation

NASA Technical Reports Server (NTRS)

Yoshikawa, K. K.; Itikawa, Y.

1976-01-01

The direct simulation Monte Carlo method was used to solve the Boltzmann equation for flows of an internally excited nonequilibrium gas, namely, of rotationally excited homonuclear diatomic nitrogen. The semi-classical transition probability model of Itikawa was investigated for its ability to simulate flow fields far from equilibrium. The behavior of diatomic nitrogen was examined for several different nonequilibrium initial states that are subjected to uniform mean flow without boundary interactions. A sample of 1000 model molecules was observed as the gas relaxed to a steady state starting from three specified initial states. The initial states considered are: (1) complete equilibrium, (2) nonequilibrium, equipartition (all rotational energy states are assigned the mean energy level obtained at equilibrium with a Boltzmann distribution at the translational temperature), and (3) nonequipartition (the mean rotational energy is different from the equilibrium mean value with respect to the translational energy states). In all cases investigated the present model satisfactorily simulated the principal features of the relaxation effects in nonequilibrium flow of diatomic molecules.

Statistical Equilibrium of Copper in the Solar Atmosphere

NASA Astrophysics Data System (ADS)

Shi, J. R.; Gehren, T.; Zeng, J. L.; Mashonkina, L.; Zhao, G.

2014-02-01

Non-local thermodynamic equilibrium (NLTE) line formation for neutral copper in the one-dimensional solar atmospheres is presented for the atomic model, including 96 terms of Cu I and the ground state of Cu II. The accurate oscillator strengths for all the line transitions in model atom and photoionization cross sections were calculated using the R-matrix method in the Russell-Saunders coupling scheme. The main NLTE mechanism for Cu I is the ultraviolet overionization. We find that NLTE leads to systematically depleted total absorption in the Cu I lines and, accordingly, positive abundance corrections. Inelastic collisions with neutral hydrogen atoms produce minor effects on the statistical equilibrium of Cu I in the solar atmosphere. For the solar Cu I lines, the departures from LTE are found to be small, the mean NLTE abundance correction of ~0.01 dex. It was found that the six low-excitation lines, with excitation energy of the lower level E exc <= 1.64 eV, give a 0.14 dex lower mean solar abundance compared to that from the six E exc > 3.7 eV lines, when applying experimental gf-values of Kock & Richter. Without the two strong resonance transitions, the solar mean NLTE abundance from 10 lines of Cu I is log ɛ⊙(Cu) = 4.19 ± 0.10, which is consistent within the error bars with the meteoritic value 4.25 ± 0.05 of Lodders et al. The discrepancy between E exc = 1.39-1.64 eV and E exc > 3.7 eV lines can be removed when the calculated gf-values are adopted and a mean solar abundance of log ɛ⊙(Cu) = 4.24 ± 0.08 is derived.

Determining Equilibrium Position For Acoustical Levitation

NASA Technical Reports Server (NTRS)

Barmatz, M. B.; Aveni, G.; Putterman, S.; Rudnick, J.

1989-01-01

Equilibrium position and orientation of acoustically-levitated weightless object determined by calibration technique on Earth. From calibration data, possible to calculate equilibrium position and orientation in presence of Earth gravitation. Sample not levitated acoustically during calibration. Technique relies on Boltzmann-Ehrenfest adiabatic-invariance principle. One converts resonant-frequency-shift data into data on normalized acoustical potential energy. Minimum of energy occurs at equilibrium point. From gradients of acoustical potential energy, one calculates acoustical restoring force or torque on objects as function of deviation from equilibrium position or orientation.

Gas-Phase Lithium Cation Basicity: Revisiting the High Basicity Range by Experiment and Theory

NASA Astrophysics Data System (ADS)

Mayeux, Charly; Burk, Peeter; Gal, Jean-Francois; Kaljurand, Ivari; Koppel, Ilmar; Leito, Ivo; Sikk, Lauri

2014-09-01

According to high level calculations, the upper part of the previously published FT-ICR lithium cation basicity (LiCB at 373 K) scale appeared to be biased by a systematic downward shift. The purpose of this work was to determine the source of this systematic difference. New experimental LiCB values at 373 K have been measured for 31 ligands by proton-transfer equilibrium techniques, ranging from tetrahydrofuran (137.2 kJ mol-1) to 1,2-dimethoxyethane (202.7 kJ mol-1). The relative basicities (ΔLiCB) were included in a single self-consistent ladder anchored to the absolute LiCB value of pyridine (146.7 kJ mol-1). This new LiCB scale exhibits a good agreement with theoretical values obtained at G2(MP2) level. By means of kinetic modeling, it was also shown that equilibrium measurements can be performed in spite of the formation of Li+ bound dimers. The key feature for achieving accurate equilibrium measurements is the ion trapping time. The potential causes of discrepancies between the new data and previous experimental measurements were analyzed. It was concluded that the disagreement essentially finds its origin in the estimation of temperature and the calibration of Cook's kinetic method.

PROCEDURES FOR THE DERIVATION OF EQUILIBRIUM ...

EPA Pesticide Factsheets

This equilibrium partitioning sediment benchmark (ESB) document describes procedures to derive concentrations for 32 nonionic organic chemicals in sediment which are protective of the presence of freshwater and marine benthic organisms. The equilibrium partitioning (EqP) approach was chosen because it accounts for the varying biological availability of chemicals in different sediments and allows for the incorporation of the appropriate biological effects concentration. This provides for the derivation of benchmarks that are causally linked to the specific chemical, applicable across sediments, and appropriately protective of benthic organisms. EqP can be used to calculate ESBs for any toxicity endpoint for which there are water-only toxicity data; it is not limited to any single effect endpoint. For the purposes of this document, ESBs for 32 nonionic organic chemicals, including several low molecular weight aliphatic and aromatic compounds, pesticides, and phthalates, were derived using Final Chronic Values (FCV) from Water Quality Criteria (WQC) or Secondary Chronic Values (SCV) derived from existing toxicological data using the Great Lakes Water Quality Initiative (GLI) or narcosis theory approaches. These values are intended to be the concentration of each chemical in water that is protective of the presence of aquatic life. For nonionic organic chemicals demonstrating a narcotic mode of action, ESBs derived using the GLI approach specifically for fres

Ab initio calculation of the shear viscosity of neon in the liquid and hypercritical state over a wide pressure and temperature range

NASA Astrophysics Data System (ADS)

Eggenberger, Rolf; Gerber, Stefan; Huber, Hanspeter; Searles, Debra; Welker, Marc

1992-08-01

The shear viscosity is calculated ab initio for the liquid and hypercritical state, i.e. a previously published potential for Ne 2, obtained from ab initio calculations including electron correlation, is used in classical equilibrium molecular dynamics simulations to obtain the shear viscosity from a Green-Kubo integral. The quality of the results is quite uniform over a large pressure range up to 1000 MPa and a wide temperature range from 26 to 600 K. In most cases the calculated shear viscosity deviates by less than 10% from the experimental value, in general the error being only a few percent.

Structural electronic and mechanical properties of YM2 (M=Mn, Fe, Co) laves phase compounds: First principle calculations analyzed with datamining approach

NASA Astrophysics Data System (ADS)

Saidi, F.; Sebaa, N.; Mahmoudi, A.; Aourag, H.; Merad, G.; Dergal, M.

2018-06-01

We performed first-principle calculations to investigate structural, phase stability, electronic and mechanical properties for the Laves phases YM2 (M = Mn, Fe, Co) with C15, C14 and C36 structures. We used the density functional theory within the framework of both pseudo-potentials and plane wave basis using VASP (Vienna Ab Initio Software Package). The calculated equilibrium structural parameters are in accordance with available theoretical values. Mechanical properties were calculated, discussed, and analyzed with data mining approach in terms of structure stability. The results reveal that YCo2 is harder than YFe2 and YMn2.

A numerical tool for the calculation of non-equilibrium ionisation states in the solar corona and other astrophysical plasma environments

NASA Astrophysics Data System (ADS)

Bradshaw, S. J.

2009-07-01

Context: The effects of non-equilibrium processes on the ionisation state of strongly emitting elements in the solar corona can be extremely difficult to assess and yet they are critically important. For example, there is much interest in dynamic heating events localised in the solar corona because they are believed to be responsible for its high temperature and yet recent work has shown that the hottest (≥107 K) emission predicted to be associated with these events can be observationally elusive due to the difficulty of creating the highly ionised states from which the expected emission arises. This leads to the possibility of observing instruments missing such heating events entirely. Aims: The equations describing the evolution of the ionisaton state are a very stiff system of coupled, partial differential equations whose solution can be numerically challenging and time-consuming. Without access to specialised codes and significant computational resources it is extremely difficult to avoid the assumption of an equilibrium ionisation state even when it clearly cannot be justified. The aim of the current work is to develop a computational tool to allow straightforward calculation of the time-dependent ionisation state for a wide variety of physical circumstances. Methods: A numerical model comprising the system of time-dependent ionisation equations for a particular element and tabulated values of plasma temperature as a function of time is developed. The tabulated values can be the solutions of an analytical model, the output from a numerical code or a set of observational measurements. An efficient numerical method to solve the ionisation equations is implemented. Results: A suite of tests is designed and run to demonstrate that the code provides reliable and accurate solutions for a number of scenarios including equilibration of the ion population and rapid heating followed by thermal conductive cooling. It is found that the solver can evolve the ionisation state to recover exactly the equilibrium state found by an independent, steady-state solver for all temperatures, resolve the extremely small ionisation/recombination timescales associated with rapid temperature changes at high densities, and provide stable and accurate solutions for both dominant and minor ion population fractions. Rapid heating and cooling of low to moderate density plasma is characterised by significant non-equilibrium ionisation conditions. The effective ionisation temperatures are significantly lower than the electron temperature and the values found are in close agreement with the previous work of others. At the very highest densities included in the present study an assumption of equilibrium ionisation is found to be robust. Conclusions: The computational tool presented here provides a straightforward and reliable way to calculate ionisation states for a wide variety of physical circumstances. The numerical code gives results that are accurate and consistent with previous studies, has relatively undemanding computational requirements and is freely available from the author.

Use of JANAF Tables in Equilibrium Calculations and Partition Function Calculations for an Undergraduate Physical Chemistry Course

ERIC Educational Resources Information Center

Cleary, David A.

2014-01-01

The usefulness of the JANAF tables is demonstrated with specific equilibrium calculations. An emphasis is placed on the nature of standard chemical potential calculations. Also, the use of the JANAF tables for calculating partition functions is examined. In the partition function calculations, the importance of the zero of energy is highlighted.

Operating mechanisms of electrolytes in magnesium ion batteries: chemical equilibrium, magnesium deposition, and electrolyte oxidation.

PubMed

Kim, Dong Young; Lim, Younhee; Roy, Basab; Ryu, Young-Gyoon; Lee, Seok-Soo

2014-12-21

Since the early nineties there have been a number of reports on the experimental development of Mg electrolytes based on organo/amide-magnesium chlorides and their transmetalations. However, there are no theoretical papers describing the underlying operating mechanisms of Mg electrolytes, and there is no clear understanding of these mechanisms. We have therefore attempted to clarify the operating mechanisms of Mg electrolytes by studying the characteristics of Mg complexes, solvation, chemical equilibrium, Mg-deposition processes, electrolyte-oxidation processes, and oxidative degradation mechanism of RMgCl-based electrolytes, using ab initio calculations. The formation and solvation energies of Mg complexes highly depend on the characteristics of R groups. Thus, changes in R groups of RMgCl lead to changes in the equilibrium position and the electrochemical reduction and oxidation pathways and energies. We first provide a methodological scheme for calculating Mg reduction potential values in non-aqueous electrolytes and electrochemical windows. We also describe a strategy for designing Mg electrolytes to maximize the electrochemical windows and oxidative stabilities. These results will be useful not only for designing improved Mg electrolytes, but also for developing new electrolytes in the future.

A one-dimensional peridynamic model of defect propagation and its relation to certain other continuum models

NASA Astrophysics Data System (ADS)

Wang, Linjuan; Abeyaratne, Rohan

2018-07-01

The peridynamic model of a solid does not involve spatial gradients of the displacement field and is therefore well suited for studying defect propagation. Here, bond-based peridynamic theory is used to study the equilibrium and steady propagation of a lattice defect - a kink - in one dimension. The material transforms locally, from one state to another, as the kink passes through. The kink is in equilibrium if the applied force is less than a certain critical value that is calculated, and propagates if it exceeds that value. The kinetic relation giving the propagation speed as a function of the applied force is also derived. In addition, it is shown that the dynamical solutions of certain differential-equation-based models of a continuum are the same as those of the peridynamic model provided the micromodulus function is chosen suitably. A formula for calculating the micromodulus function of the equivalent peridynamic model is derived and illustrated. This ability to replace a differential-equation-based model with a peridynamic one may prove useful when numerically studying more complicated problems such as those involving multiple and interacting defects.

Total individual ion activity coefficients of calcium and carbonate in seawater at 25°C and 35%. salinity, and implications to the agreement between apparent and thermodynamic constants of calcite and aragonite

USGS Publications Warehouse

Plummer, Niel; Sundquist, Eric T.

1982-01-01

We have calculated the total individual ion activity coefficients of carbonate and calcium,  and , in seawater. Using the ratios of stoichiometric and thermodynamic constants of carbonic acid dissociation and total mean activity coefficient data measured in seawater, we have obtained values which differ significantly from those widely accepted in the literature. In seawater at 25°C and 35%. salinity the (molal) values of  and  are 0.038 ± 0.002 and 0.173 ± 0.010, respectively. These values of  and  are independent of liquid junction errors and internally consistent with the value . By defining  and  on a common scale (), the product  is independent of the assigned value of  and may be determined directly from thermodynamic measurements in seawater. Using the value  and new thermodynamic equilibrium constants for calcite and aragonite, we show that the apparent constants of calcite and aragonite are consistent with the thermodynamic equilibrium constants at 25°C and 35%. salinity. The demonstrated consistency between thermodynamic and apparent constants of calcite and aragonite does not support a hypothesis of stable Mg-calcite coatings on calcite or aragonite surfaces in seawater, and suggests that the calcite critical carbonate ion curve of Broecker and Takahashi (1978,Deep-Sea Research25, 65–95) defines the calcite equilibrium boundary in the oceans, within the uncertainty of the data.

Thermodynamics of Pb17Li-bismuth interactions

NASA Astrophysics Data System (ADS)

Hubberstey, Peter; Sample, Tony

1994-09-01

Thermodynamic calculations of the PbBiLi ternary system have been completed to rationalise the formation of solid Li 3Bi on reaction of liquid Pb17Li with bismuth. At 723 K, the bismuth activity in equilibrium with liquid Pi17Li and solid Li 3Bi is calculated to be 9.50 × 10 -4; this can be correlated to a solubility of 2.09 × 10 -1 mol% Bi(2520 wppm). The corresponding bismuth activity in equilibrium with liquid Pb17Li and solid LiBi is 5.04 × 10 -2 (an extrapolated value as LiBi decomposes peritectically at 688 K). The minimum lithium content of PbLi alloys required to react with unit activity bismuth to form Li 3Bi at 723 K is calculated to be ˜ 1.8 mol% Li. The dominance of Li 3Bi in the PbBiLi system is attributed to its extreme stability as evidenced by both its high melting point (1418 K) and free energy of formation [ ΔGf0(Li 3Bi, c 723 K) = 212.8 kJ mol -1].

Effect of a finite ionization rate on the radiative heating of outer planet atmospheric entry probes

NASA Technical Reports Server (NTRS)

Nelson, H. F.

1981-01-01

The influence of finite rate ionization in the inviscid gas just behind the stagnation shock wave on the radiation heating of probes entering the hydrogen helium atmospere of the major planets was investigated. At the present time, there is disagreement as to whether the radiative flux increases or decreases relative to its equilibrium value when finite rate ionization is considered. Leibowitz and Kuo content that the finite rate ionization in the hydrogen gas just behind the shock wave reduces the radiative flux to the probe, whereas Tiwari and Szema predict that it increases the radiative flux. The radiation modeling used in the calculations of both pairs of these investigators was reviewed. It is concluded that finite rate ionization in the inviscid region of the shock layer should reduce the cold wall radiative heating below the values predicted by equilibrium chemistry assumptions.

Theoretical Evaluation of Crosslink Density of Chain Extended Polyurethane Networks Based on Hydroxyl Terminated Polybutadiene and Butanediol and Comparison with Experimental Data

NASA Astrophysics Data System (ADS)

Sekkar, Venkataraman; Alex, Ancy Smitha; Kumar, Vijendra; Bandyopadhyay, G. G.

2018-01-01

Polyurethane networks between hydroxyl terminated polybutadiene (HTPB) and butanediol (BD) were prepared using toluene diisocyanate (TDI) as the curative. HTPB and BD were taken at equivalent ratios viz.: 1:0, 1:1, 1:2, 1:4, and 1:8. Crosslink density (CLD) was theoretically calculated using α-model equations developed by Marsh. CLD for the polyurethane networks was experimentally evaluated from equilibrium swell and stress-strain data. Young's modulus and Mooney-Rivlin approaches were adopted to calculate CLD from stress-strain data. Experimentally obtained CLD values were enormously higher than theoretical values especially at higher BD/HTPB equivalent ratios. The difference in the theoretical and experimental values for CLD was explained in terms of local crystallization due to the formation of hard segments and hydrogen bonded interactions.

Two-phase vesicles: a study on evolutionary and stationary models.

PubMed

Sahebifard, MohammadMahdi; Shahidi, Alireza; Ziaei-Rad, Saeed

2017-05-01

In the current article, the dynamic evolution of two-phase vesicles is presented as an extension to a previous stationary model and based on an equilibrium of local forces. In the simplified model, ignoring the effects of membrane inertia, a dynamic equilibrium between the membrane bending potential and local fluid friction is considered in each phase. The equilibrium equations at the domain borders are completed by extended introduction of membrane section reactions. We show that in some cases, the results of stationary and evolutionary models are in agreement with each other and also with experimental observations, while in others the two models differ markedly. The value of our approach is that we can account for unresponsive points of uncertainty using our equations with the local velocity of the lipid membranes and calculating the intermediate states (shapes) in the consequent evolutionary, or response, path.

Thermodynamics at the nanoscale: phase diagrams of nickel-carbon nanoclusters and equilibrium constants for phase transitions

NASA Astrophysics Data System (ADS)

Engelmann, Yannick; Bogaerts, Annemie; Neyts, Erik C.

2014-09-01

Using reactive molecular dynamics simulations, the melting behavior of nickel-carbon nanoclusters is examined. The phase diagrams of icosahedral and Wulff polyhedron clusters are determined using both the Lindemann index and the potential energy. Formulae are derived for calculating the equilibrium constants and the solid and liquid fractions during a phase transition, allowing more rational determination of the melting temperature with respect to the arbitrary Lindemann value. These results give more insight into the properties of nickel-carbon nanoclusters in general and can specifically be very useful for a better understanding of the synthesis of carbon nanotubes using the catalytic chemical vapor deposition method.

Metastable phases of silver and gold in hexagonal structure

NASA Astrophysics Data System (ADS)

Jona, F.; Marcus, P. M.

2004-07-01

Metastable phases of silver and gold in hexagonal close-packed structures are investigated by means of first-principles total-energy calculations. Two different methods are employed to find the equilibrium states: determination of the minima along the hexagonal epitaxial Bain path, and direct determination of minima of the total energy by a new minimum-path procedure. Both metals have two equilibrium states at different values of the hexagonal axial ratio c/a. For both metals, the elastic constants show that the high-c/a states are stable, hence, since the ground states are face-centred cubic, these states represent hexagonal close-packed metastable phases. The elastic constants of the low-c/a states show that they are unstable.

Analysis of three-phase equilibrium conditions for methane hydrate by isometric-isothermal molecular dynamics simulations.

PubMed

Yuhara, Daisuke; Brumby, Paul E; Wu, David T; Sum, Amadeu K; Yasuoka, Kenji

2018-05-14

To develop prediction methods of three-phase equilibrium (coexistence) conditions of methane hydrate by molecular simulations, we examined the use of NVT (isometric-isothermal) molecular dynamics (MD) simulations. NVT MD simulations of coexisting solid hydrate, liquid water, and vapor methane phases were performed at four different temperatures, namely, 285, 290, 295, and 300 K. NVT simulations do not require complex pressure control schemes in multi-phase systems, and the growth or dissociation of the hydrate phase can lead to significant pressure changes in the approach toward equilibrium conditions. We found that the calculated equilibrium pressures tended to be higher than those reported by previous NPT (isobaric-isothermal) simulation studies using the same water model. The deviations of equilibrium conditions from previous simulation studies are mainly attributable to the employed calculation methods of pressure and Lennard-Jones interactions. We monitored the pressure in the methane phase, far from the interfaces with other phases, and confirmed that it was higher than the total pressure of the system calculated by previous studies. This fact clearly highlights the difficulties associated with the pressure calculation and control for multi-phase systems. The treatment of Lennard-Jones interactions without tail corrections in MD simulations also contributes to the overestimation of equilibrium pressure. Although improvements are still required to obtain accurate equilibrium conditions, NVT MD simulations exhibit potential for the prediction of equilibrium conditions of multi-phase systems.

Analysis of three-phase equilibrium conditions for methane hydrate by isometric-isothermal molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Yuhara, Daisuke; Brumby, Paul E.; Wu, David T.; Sum, Amadeu K.; Yasuoka, Kenji

2018-05-01

To develop prediction methods of three-phase equilibrium (coexistence) conditions of methane hydrate by molecular simulations, we examined the use of NVT (isometric-isothermal) molecular dynamics (MD) simulations. NVT MD simulations of coexisting solid hydrate, liquid water, and vapor methane phases were performed at four different temperatures, namely, 285, 290, 295, and 300 K. NVT simulations do not require complex pressure control schemes in multi-phase systems, and the growth or dissociation of the hydrate phase can lead to significant pressure changes in the approach toward equilibrium conditions. We found that the calculated equilibrium pressures tended to be higher than those reported by previous NPT (isobaric-isothermal) simulation studies using the same water model. The deviations of equilibrium conditions from previous simulation studies are mainly attributable to the employed calculation methods of pressure and Lennard-Jones interactions. We monitored the pressure in the methane phase, far from the interfaces with other phases, and confirmed that it was higher than the total pressure of the system calculated by previous studies. This fact clearly highlights the difficulties associated with the pressure calculation and control for multi-phase systems. The treatment of Lennard-Jones interactions without tail corrections in MD simulations also contributes to the overestimation of equilibrium pressure. Although improvements are still required to obtain accurate equilibrium conditions, NVT MD simulations exhibit potential for the prediction of equilibrium conditions of multi-phase systems.

Classical calculation of the equilibrium constants for true bound dimers using complete potential energy surface.

PubMed

Buryak, Ilya; Vigasin, Andrey A

2015-12-21

The present paper aims at deriving classical expressions which permit calculation of the equilibrium constant for weakly interacting molecular pairs using a complete multidimensional potential energy surface. The latter is often available nowadays as a result of the more and more sophisticated and accurate ab initio calculations. The water dimer formation is considered as an example. It is shown that even in case of a rather strongly bound dimer the suggested expression permits obtaining quite reliable estimate for the equilibrium constant. The reliability of our obtained water dimer equilibrium constant is briefly discussed by comparison with the available data based on experimental observations, quantum calculations, and the use of RRHO approximation, provided the latter is restricted to formation of true bound states only.

Classical calculation of the equilibrium constants for true bound dimers using complete potential energy surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buryak, Ilya; Vigasin, Andrey A., E-mail: vigasin@ifaran.ru

The present paper aims at deriving classical expressions which permit calculation of the equilibrium constant for weakly interacting molecular pairs using a complete multidimensional potential energy surface. The latter is often available nowadays as a result of the more and more sophisticated and accurate ab initio calculations. The water dimer formation is considered as an example. It is shown that even in case of a rather strongly bound dimer the suggested expression permits obtaining quite reliable estimate for the equilibrium constant. The reliability of our obtained water dimer equilibrium constant is briefly discussed by comparison with the available data basedmore » on experimental observations, quantum calculations, and the use of RRHO approximation, provided the latter is restricted to formation of true bound states only.« less

Study of Laminar Flame 2-D Scalar Values at Various Fuel to Air Ratios Using an Imaging Fourier-Transform Spectrometer and 2-D CFD Analysis

DTIC Science & Technology

2013-03-01

NASA- Glenn’s Chemical Equilibrium with Applications (CEA) program. UNICORN CFD predictions were in excellent agreement with CEA calculations at...49 Appendix A – UNICORN CFD Inputs and Instruction .....................................................50 Appendix B – NASA-Glenn...17 Figure 7: Schematic of UNICORN CFD card setup. ........................................................ 18 Figure 8: Averaged flame

Characterization of local thermodynamic equilibrium in a laser-induced aluminum alloy plasma.

PubMed

Zhang, Yong; Zhao, Zhenyang; Xu, Tao; Niu, GuangHui; Liu, Ying; Duan, Yixiang

2016-04-01

The electron temperature was evaluated using the line-to-continuum ratio method, and whether the plasma was close to the local thermodynamic equilibrium (LTE) state was investigated in detail. The results showed that approximately 5 μs after the plasma formed, the changes in the electron and excitation temperatures, which were determined using a Boltzmann plot, overlapped in the 15% error range, which indicated that the LTE state was reached. The recombination of electrons and ions and the free electron expansion process led to the deviation from the LTE state. The plasma's expansion rate slowed over time, and when the expansion time was close to the ionization equilibrium time, the LTE state was almost reached. The McWhirter criterion was adopted to calculate the threshold electron density for different species, and the results showed that experimental electron density was greater than the threshold electron density, which meant that the LTE state may have existed. However, for the nonmetal element N, the threshold electron density was greater than the value experimental value approximately 0.8 μs after the plasma formed, which meant that LTE state did not exist for N.

Ab initio predictions of structural and elastic properties of struvite: contribution to urinary stone research.

PubMed

Piechota, Jacek; Prywer, Jolanta; Torzewska, Agnieszka

2012-01-01

In the present work, we carried out density functional calculations of struvite--the main component of the so-called infectious urinary stones--to study its structural and elastic properties. Using a local density approximation and a generalised gradient approximation, we calculated the equilibrium structural parameters and elastic constants C(ijkl). At present, there is no experimental data for these elastic constants C (ijkl) for comparison. Besides the elastic constants, we also present the calculated macroscopic mechanical parameters, namely the bulk modulus (K), the shear modulus (G) and Young's modulus (E). The values of these moduli are found to be in good agreement with available experimental data. Our results imply that the mechanical stability of struvite is limited by the shear modulus, G. The study also explores the energy-band structure to understand the obtained values of the elastic constants.

Pleural pressure theory revisited: a role for capillary equilibrium.

PubMed

Casha, Aaron R; Caruana-Gauci, Roberto; Manche, Alexander; Gauci, Marilyn; Chetcuti, Stanley; Bertolaccini, Luca; Scarci, Marco

2017-04-01

Theories elucidating pleural pressures should explain all observations including the equal and opposite recoil of the chest wall and lungs, the less than expected pleural hydrostatic gradient and its variation at lobar margins, why pleural pressures are negative and how pleural fluid circulation functions. A theoretical model describing equilibrium between buoyancy, hydrostatic forces, and capillary forces is proposed. The capillary equilibrium model described depends on control of pleural fluid volume and protein content, powered by an active pleural pump. The interaction between buoyancy forces, hydrostatic pressure and capillary pressure was calculated, and values for pleural thickness and pressure were determined using values for surface tension, contact angle, pleural fluid and lung densities found in the literature. Modelling can explain the issue of the differing hydrostatic vertical pleural pressure gradient at the lobar margins for buoyancy forces between the pleural fluid and the lung floating in the pleural fluid according to Archimedes' hydrostatic paradox. The capillary equilibrium model satisfies all salient requirements for a pleural pressure model, with negative pressures maximal at the apex, equal and opposite forces in the lung and chest wall, and circulatory pump action. This model predicts that pleural effusions cannot occur in emphysema unless concomitant heart failure increases lung density. This model also explains how the non-confluence of the lung with the chest wall (e.g., lobar margins) makes the pleural pressure more negative, and why pleural pressures would be higher after an upper lobectomy compared to a lower lobectomy. Pathological changes in pleural fluid composition and lung density alter the equilibrium between capillarity and buoyancy hydrostatic pressure to promote pleural effusion formation.

Study of permeability characteristics of membranes

NASA Technical Reports Server (NTRS)

Spiegler, K. S.; Messalem, R. M.; Moore, R. J.; Leibovitz, J.

1971-01-01

Pressure-permeation experiments were performed with the concentration-clamp cell. Streaming potentials and hydraulic permeabilities were measured for an AMF C-103 cation-exchange membrane bounded by 0.1 N NaCl solutions. The streaming potential calculated from the slope of the recorded potential differences versus the applied pressure, yields a value of 1.895 millivolt/dekabar. When comparison with other membranes of similar characteristics could be made, good agreement was found. The values of the hydraulic permeability varied somewhat with the applied pressure difference and are between 1.3 x 10 to the minus 8th power and 3.9 x 10 to the minus 8th power sq cm/dekabar-sec. The specific hydraulic permeabilities were also calculated and compared with data from the literature. Fair agreement was found. The diffusion coefficient of the chloride ion in the AMF C-103 membrane was calculated, using Fick's first law of diffusion based on ion concentrations calculated from the Donnan equilibrium concentration of Cl(-).

Strength Calculation of Inclined Sections of Reinforced Concrete Elements under Transverse Bending

NASA Astrophysics Data System (ADS)

Filatov, V. B.

2017-11-01

The authors propose a design model to determine the strength of inclined sections of bent reinforced concrete elements without shear reinforcement for the action of transverse force taking into account the aggregate interlock forces in the inclined crack. The calculated dependences to find out the components of forces acting in an inclined section are presented. The calculated dependences are obtained from the consideration of equilibrium conditions of the block over the inclined crack. A comparative analysis of the experimental values of the failure loads of the inclined section and the theoretical values obtained for the proposed dependencies and normative calculation methods is performed. It is shown that the proposed design model makes it possible to take into account the effect the longitudinal reinforcement percentage has on the inclined section strength, the element cross section height without the introduction of empirical coefficients which contributes to an increase in the structural safety of design solutions including the safety of high-strength concrete elements.

KREEP basalt petrogenesis: Insights from 15434,181

NASA Astrophysics Data System (ADS)

Cronberger, Karl; Neal, Clive R.

2017-05-01

Returned lunar KREEP basalts originated through impact processes or endogenous melting of the lunar interior. Various methods have been used to distinguish between these two origins, with varying degrees of success. Apollo 15 KREEP basalts are generally considered to be endogenous melts of the lunar interior. For example, sample 15434,181 is reported to have formed by a two-stage cooling process, with large orthopyroxene (Opx) phenocrysts forming first and eventually cocrystalizing with smaller plagioclase crystals. However, major and trace element analyses of Opx and plagioclase coupled with calculated equilibrium liquids are inconsistent with the large orthopyroxenes being a phenocryst phase. Equilibrium liquid rare earth element (REE) profiles are enriched relative to the whole rock (WR) composition, inconsistent with Opx being an early crystallizing phase, and these are distinct from the plagioclase REE equilibrium liquids. Fractional crystallization modeling using the Opx equilibrium liquids as a parental composition cannot reproduce the WR values even with crystallization of late-stage phosphates and zircon. This work concludes that instead of being a phenocryst phase, the large Opx crystals are actually xenocrysts that were subsequently affected by pyroxene overgrowths that formed intergrowths with cocrystallizing plagioclase.

Non-equilibrium transport in the quantum dot: quench dynamics and non-equilibrium steady state

NASA Astrophysics Data System (ADS)

Culver, Adrian; Andrei, Natan

We present an exact method of calculating the non-equilibrium current driven by a voltage drop across a quantum dot. The system is described by the two lead Anderson model at zero temperature with on-site Coulomb repulsion and non-interacting, linearized leads. We prepare the system in an initial state consisting of a free Fermi sea in each lead with the voltage drop given as the difference between the two Fermi levels. We quench the system by coupling the dot to the leads at t = 0 and following the time evolution of the wavefunction. In the long time limit a new type of Bethe Ansatz wavefunction emerges, which satisfies the Lippmann-Schwinger equation with the two Fermi seas serving as the boundary conditions. This exact, non-perturbative solution describes the non-equilibrium steady state of the system. We describe how to use this solution to compute the infinite time limit of the expectation value of the current operator at a given voltage, which would yield the I-V characteristic of the dot. Research supported by NSF Grant DMR 1410583.

Teaching the Concept of Gibbs Energy Minimization through Its Application to Phase-Equilibrium Calculation

ERIC Educational Resources Information Center

Privat, Romain; Jaubert, Jean-Noe¨l; Berger, Etienne; Coniglio, Lucie; Lemaitre, Ce´cile; Meimaroglou, Dimitrios; Warth, Vale´rie

2016-01-01

Robust and fast methods for chemical or multiphase equilibrium calculation are routinely needed by chemical-process engineers working on sizing or simulation aspects. Yet, while industrial applications essentially require calculation tools capable of discriminating between stable and nonstable states and converging to nontrivial solutions,…

Oxo-amphiboles in mantle xenoliths: evidence for H2O-rich melt interacting with the lithospheric mantle of Harrow Peaks (Northern Victoria Land, Antarctica)

NASA Astrophysics Data System (ADS)

Gentili, S.; Bonadiman, C.; Biagioni, C.; Comodi, P.; Coltorti, M.; Zucchini, A.; Ottolini, L.

2015-12-01

Amphiboles are the most widespread hydrous metasomatic phases in spinel-bearing mantle peridotites from Harrow Peaks (HP), Northern Victoria Land (Antarctica). They occur both in veinlets and disseminated in the peridotite matrix (preferentially associated with clinopyroxene and spinel grains). Four amphibole crystals were investigated by single-crystal X-ray diffraction (SC-XRD), electron microprobe analysis (EMPA), secondary ion mass spectrometry (SIMS) and micro-Mössbauer spectroscopy; these crystal-chemical data allow to constrain upper mantle conditions during growth of these amphiboles and the role of volatile circulation during metasomatic processes in the Antarctic region. The HP amphiboles have low Mg# values (69.3-84.1), high TiO2 (2.74-5.30 wt%) and FeOtot contents (3.40 to 6.90 wt%). The Fe3+/Fetot ratios are significantly high (0.53-0.66). The W-site is mainly occupied by O2- (0.984-1.187 apfu) plus OH (H2O: 0.70-1.01 wt%) and minor F (0.04-0.24 wt%) and Cl (0.03-0.08 wt%). Consequently, HP amphiboles are actually characterized by a significant oxo component. The aH2O values were calculated at 1.5 GPa by dehydration equilibrium equations written as H2O-buffering equilibria among end-member components of amphibole and coexisting peridotite phases. Three out of four HP amphibole-bearing peridotites have values of aH2O ranging from 0.122 to 0.335; whereas one sample has aH2O remarkably higher (0.782) approaching an ideal H2O basalt solubility. The HP fO2 values, determined by the olivine-spinel-orthopyroxene oxygeobarometer (ΔQFM = -1.77 : +0.01), are remarkably different from those calculated on the basis of the amphibole dehydration equilibrium and the application of the dissociation reaction (ΔQFM = -2.60 : +6.8). The high aH2O and the extremely high fO2 values, determined by the oxy-amphibole equilibrium with respect to the redox conditions recorded by the co-existing anhydrous minerals (close to QFM buffer), revealed that: i) the amphibole-forming reaction is a relatively recent process with the new phases far from having reached a potential equilibrium with the peridotite matrix; ii) amphibole seems to be formed by the precipitation of migrating H2O-rich melts with a negligible contribution of the peridotite system.

Thermodynamic equilibrium calculations of dimethyl ether steam reforming and dimethyl ether hydrolysis

NASA Astrophysics Data System (ADS)

Semelsberger, Troy A.; Borup, Rodney L.

The production of a hydrogen-rich fuel-cell feed by dimethyl ether (DME) steam reforming was investigated using calculations of thermodynamic equilibrium as a function of steam-to-carbon ratio (0.00-4.00), temperature (100-600 °C), pressure (1-5 atm), and product species. Species considered were acetone, acetylene, carbon dioxide, carbon monoxide, dimethyl ether, ethane, ethanol, ethylene, formaldehyde, formic acid, hydrogen, isopropanol, methane, methanol, methyl-ethyl ether, n-propanol and water. Thermodynamic equilibrium calculations of DME steam reforming indicate complete conversion of dimethyl ether to hydrogen, carbon monoxide and carbon dioxide at temperatures greater than 200 °C and steam-to-carbon ratios greater than 1.25 at atmospheric pressure ( P = 1 atm). Increasing the operating pressure shifts the equilibrium toward the reactants; increasing the pressure from 1 to 5 atm decreases the conversion of dimethyl ether from 99.5 to 76.2%. The trend of thermodynamically stable products in decreasing mole fraction is methane, ethane, isopropyl alcohol, acetone, n-propanol, ethylene, ethanol, methyl-ethyl ether and methanol-formaldehyde, formic acid, and acetylene were not observed. Based on the equilibrium calculations, the optimal processing conditions for dimethyl ether steam reforming occur at a steam-to-carbon ratio of 1.50, a pressure of 1 atm, and a temperature of 200 °C. These thermodynamic equilibrium calculations show dimethyl ether processed with steam will produce hydrogen-rich fuel-cell feeds—with hydrogen concentrations exceeding 70%. The conversion of dimethyl ether via hydrolysis (considering methanol as the only product) is limited by thermodynamic equilibrium. Equilibrium conversion increases with temperature and steam-to-carbon ratio. A maximum dimethyl ether conversion of 62% is achieved at a steam-to-carbon ratio of 5.00 and a processing temperature of 600 °C.

MHD thrust vectoring of a rocket engine

NASA Astrophysics Data System (ADS)

Labaune, Julien; Packan, Denis; Tholin, Fabien; Chemartin, Laurent; Stillace, Thierry; Masson, Frederic

2016-09-01

In this work, the possibility to use MagnetoHydroDynamics (MHD) to vectorize the thrust of a solid propellant rocket engine exhaust is investigated. Using a magnetic field for vectoring offers a mass gain and a reusability advantage compared to standard gimbaled, elastomer-joint systems. Analytical and numerical models were used to evaluate the flow deviation with a 1 Tesla magnetic field inside the nozzle. The fluid flow in the resistive MHD approximation is calculated using the KRONOS code from ONERA, coupling the hypersonic CFD platform CEDRE and the electrical code SATURNE from EDF. A critical parameter of these simulations is the electrical conductivity, which was evaluated using a set of equilibrium calculations with 25 species. Two models were used: local thermodynamic equilibrium and frozen flow. In both cases, chlorine captures a large fraction of free electrons, limiting the electrical conductivity to a value inadequate for thrust vectoring applications. However, when using chlorine-free propergols with 1% in mass of alkali, an MHD thrust vectoring of several degrees was obtained.

Theoretical study on the ground state of the polar alkali-metal-barium molecules: Potential energy curve and permanent dipole moment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gou, Dezhi; Kuang, Xiaoyu, E-mail: scu-kuang@163.com; Gao, Yufeng

2015-01-21

In this paper, we systematically investigate the electronic structure for the {sup 2}Σ{sup +} ground state of the polar alkali-metal-alkaline-earth-metal molecules BaAlk (Alk = Li, Na, K, Rb, and Cs). Potential energy curves and permanent dipole moments (PDMs) are determined using power quantum chemistry complete active space self-consistent field and multi-reference configuration interaction methods. Basic spectroscopic constants are derived from ro-vibrational bound state calculation. From the calculations, it is shown that BaK, BaRb, and BaCs molecules have moderate values of PDM at the equilibrium bond distance (BaK:1.62 D, BaRb:3.32 D, and BaCs:4.02 D). Besides, the equilibrium bond length (4.93 Åmore » and 5.19 Å) and dissociation energy (0.1825 eV and 0.1817 eV) for the BaRb and BaCs are also obtained.« less

Vibrational and thermodynamic properties of β-HMX: a first-principles investigation.

PubMed

Wu, Zhongqing; Kalia, Rajiv K; Nakano, Aiichiro; Vashishta, Priya

2011-05-28

Thermodynamic properties of β-HMX crystal are investigated using the quasi-harmonic approximation and density functional theory within the local density approximation (LDA), generalized gradient approximation (GGA), and GGA + empirical van der Waals (vdW) correction. It is found that GGA well describes the thermal expansion coefficient and heat capacity but fails to produce correct bulk modulus and equilibrium volume. The vdW correction improves the bulk modulus and volume, but worsens the thermal expansion coefficient and heat capacity. In contrast, LDA describes all thermodynamic properties with reasonable accuracy, and overall is a good exchange-correlation functional for β-HMX molecular crystal. The results also demonstrate significant contributions of phonons to the equation of state. The static calculation of equilibrium volume for β-HMX differs from the room-temperature value incorporating lattice vibrations by over 5%. Therefore, for molecular crystals, it is essential to include phonon contributions when calculated equation of state is compared with experimental data at ambient condition. © 2011 American Institute of Physics

Temporal Fourier analysis applied to equilibrium radionuclide cineangiography. Importance in the study of global and regional left ventricular wall motion.

PubMed

Cardot, J C; Berthout, P; Verdenet, J; Bidet, A; Faivre, R; Bassand, J P; Bidet, R; Maurat, J P

1982-01-01

Regional and global left ventricular wall motion was assessed in 120 patients using radionuclide cineangiography (RCA) and contrast angiography. Functional imaging procedures based on a temporal Fourier analysis of dynamic image sequences were applied to the study of cardiac contractility. Two images were constructed by taking the phase and amplitude values of the first harmonic in the Fourier transform for each pixel. These two images aided in determining the perimeter of the left ventricle to calculate the global ejection fraction. Regional left ventricular wall motion was studied by analyzing the phase value and by examining the distribution histogram of these values. The accuracy of global ejection fraction calculation was improved by the Fourier technique. This technique increased the sensitivity of RCA for determining segmental abnormalities especially in the left anterior oblique view (LAO).

Analysis of the 3d(sup 6)4s((sup 6)D)4f-5g supermultiplet of Fe I in laboratory and solar infrared spectra

NASA Technical Reports Server (NTRS)

Johansson, S.; Nave, G.; Geller, M.; Sauval, A. J.; Grevesse, N.; Schoenfeld, W. G.; Change, E. S.; Farmer, C. B.

1994-01-01

The combined laboratory and solar analysis of the highly excited subconfigurations 3d(sup 6)4s((sup 6)D)4f and 3d(sup 6)4s((sup 6)D)5g of Fe I has allowed us to classify 87 lines of the 4f-5g supermultiplet in the spectral region 2545-2585 per cm. The level structure of these JK-coupled configurations is predicted by semiempirical calculations and the quardrupolic approximation. Semiempirical gf-values have been calculated and are compared to gf-values derived from the solar spectrum. The solar analysis has shown that these lines, which should be much less sensitive than lower excitation lines to departures from Local Thermal Equilibrium (LTE) and to temperature uncertanties, lead to a solar abundance of iron which is consistent with the meteoritic value (A(sub Fe) = 7.51).

Non-Equilibrium Properties from Equilibrium Free Energy Calculations

NASA Technical Reports Server (NTRS)

Pohorille, Andrew; Wilson, Michael A.

2012-01-01

Calculating free energy in computer simulations is of central importance in statistical mechanics of condensed media and its applications to chemistry and biology not only because it is the most comprehensive and informative quantity that characterizes the eqUilibrium state, but also because it often provides an efficient route to access dynamic and kinetic properties of a system. Most of applications of equilibrium free energy calculations to non-equilibrium processes rely on a description in which a molecule or an ion diffuses in the potential of mean force. In general case this description is a simplification, but it might be satisfactorily accurate in many instances of practical interest. This hypothesis has been tested in the example of the electrodiffusion equation . Conductance of model ion channels has been calculated directly through counting the number of ion crossing events observed during long molecular dynamics simulations and has been compared with the conductance obtained from solving the generalized Nernst-Plank equation. It has been shown that under relatively modest conditions the agreement between these two approaches is excellent, thus demonstrating the assumptions underlying the diffusion equation are fulfilled. Under these conditions the electrodiffusion equation provides an efficient approach to calculating the full voltage-current dependence routinely measured in electrophysiological experiments.

Estimation of the thermodynamic parameters of hydrogen bonding in alcohol solutions by the method of infrared spectroscopy

NASA Astrophysics Data System (ADS)

Vedernikova, E. V.; Gafurov, M. M.; Ataev, M. B.

2011-01-01

Hydrogen bonding (H-bonding) is a specific type of intermolecular interaction being formed for favorable mutual orientations of the interacting molecules. One of the authors had developed a model concept relating the H-bonding energy with the change of stretching vibrations Δν = νOH - νOH-NC of the alcohol OH-group in acetonitrile and acetone solutions: Δ H = 89.24Δν/ν0. The calculated H-bond energy was 10.45 kJ/mole for acetonitrile and Δ H = 12.12 kJ/mole for acetone. The results obtained are compared with the data calculated using the equilibrium constant of H-bonding reaction; they can also be used to calculate all other thermodynamic H-bond parameters by measuring the equilibrium constant K c in a certain temperature interval. The equilibrium constant is calculated from the Lambert-Bouguer-Beer law: {K_c} = {{C_{{text{OH}} \\cdots {text{NC}}}}}/{{C_{text{OH}} \\cdot {C_{text{NC}}}}} , ∆ F = - RT ṡ ln K c , ∆ H = RT 2 ṡ d(ln K c )/ dT, and Δ S = {Δ H - Δ F}/T . For the methanol solution in acetonitrile, Δν = 115 cm-1, Δ H = 10.87 kJ/mole, and K c = 42 L/mole. For the ethanol solution in acetonitrile, Δν = 118 cm-1, Δ H = 10.01 kJ/mole, and K c = 34 L/mole. For the propanol solution in acetonitrile, Δν = 110 cm-1, Δ H = 8.36 kJ/mole, and K c = 13 L/mole. All calculations are performed using the developed programs. The spectra are recorded on Perkin-Elmer-180 and Specord-84 IR-spectrometers. The values of the thermodynamic parameters calculated and estimated from K c - f( T) are in good agreement with each other and with the available literature data.

A method of solid-solid phase equilibrium calculation by molecular dynamics

NASA Astrophysics Data System (ADS)

Karavaev, A. V.; Dremov, V. V.

2016-12-01

A method for evaluation of solid-solid phase equilibrium curves in molecular dynamics simulation for a given model of interatomic interaction is proposed. The method allows to calculate entropies of crystal phases and provides an accuracy comparable with that of the thermodynamic integration method by Frenkel and Ladd while it is much simpler in realization and less intense computationally. The accuracy of the proposed method was demonstrated in MD calculations of entropies for EAM potential for iron and for MEAM potential for beryllium. The bcc-hcp equilibrium curves for iron calculated for the EAM potential by the thermodynamic integration method and by the proposed one agree quite well.

ASSESSMENT OF INHALATION DOSE FROM THE INDOOR 222Rn AND 220Rn USING RAD7 AND PINHOLE CUP DOSEMETERS.

PubMed

Mehra, R; Jakhu, R; Bangotra, P; Kaur, K; Mittal, H M

2016-10-01

Radon is the most important source of natural radiation and is responsible for approximately half of the received dose from all sources. Most of this dose is from inhalation of the radon progeny, especially in closed atmospheres. Concentration of radon ( 222 Rn) and thoron ( 220 Rn) in the different villages of Jalandhar and Kapurthala district of Punjab has been calculated by pinhole cup dosemeters and RAD7. On an average, it has been observed from the study that the values of all the parameters calculated are higher in case of active monitoring than the passive monitoring. The calculated equilibrium equivalent 222 Rn concentration (EEC Rn ) and equilibrium equivalent 220 Rn concentration (EEC Th ) fluctuate in the range from 5.58 to 34.29 and from 0.35 to 2.7 Bq m -3 as estimated by active technique, respectively. Similarly, the observed mean value of the potential alpha energy concentration of 222 Rn (PAEC Rn ) and 220 Rn (PAEC Th ) is 4.55 and 4.34 mWL, respectively. The dose rate to the soft tissues and lung from indoor 222 Rn varies from 0.06 to 0.38 and from 0.50 to 3.05 nGy h -1 , respectively. The total annual effective dose for the residents of the study area is less than 10 mSv. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Rural-urban migration including formal and informal workers in the urban sector: an agent-based numerical simulation study

NASA Astrophysics Data System (ADS)

Branco, Nilton; Oliveira, Tharnier; Silveira, Jaylson

2012-02-01

The goal of this work is to study rural-urban migration in the early stages of industrialization. We use an agent-based model and take into account the existence of informal and formal workers on the urban sector and possible migration movements, dependent on the agents' social and private utilities. Our agents are place on vertices of a square lattice, such that each vertex has only one agent. Rural, urban informal and urban formal workers are represented by different states of a three-state Ising model. At every step, a fraction a of the agents may change sectors or migrate. The total utility of a given agent is then calculated and compared to a random utility, in order to check if this agent turns into an actual migrant or changes sector. The dynamics is carried out until an equilibrium state is reached and equilibrium variables are then calculated and compared to available data. We find that a generalized Harris-Todaro condition is satisfied [1] on these equilibrium regimes, i.e, the ratio between expected wages between any pair of sectors reach a constant value. [4pt] [1] J. J. Silveira, A. L. Esp'indola and T. J. Penna, Physica A, 364, 445 (2006).

Phi-value analysis of a linear, sequential reaction mechanism: theory and application to ion channel gating.

PubMed

Zhou, Yu; Pearson, John E; Auerbach, Anthony

2005-12-01

We derive the analytical form of a rate-equilibrium free-energy relationship (with slope Phi) for a bounded, linear chain of coupled reactions having arbitrary connecting rate constants. The results confirm previous simulation studies showing that Phi-values reflect the position of the perturbed reaction within the chain, with reactions occurring earlier in the sequence producing higher Phi-values than those occurring later in the sequence. The derivation includes an expression for the transmission coefficients of the overall reaction based on the rate constants of an arbitrary, discrete, finite Markov chain. The results indicate that experimental Phi-values can be used to calculate the relative heights of the energy barriers between intermediate states of the chain but provide no information about the energies of the wells along the reaction path. Application of the equations to the case of diliganded acetylcholine receptor channel gating suggests that the transition-state ensemble for this reaction is nearly flat. Although this mechanism accounts for many of the basic features of diliganded and unliganded acetylcholine receptor channel gating, the experimental rate-equilibrium free-energy relationships appear to be more linear than those predicted by the theory.

Acid precipitation effects on soil pH and base saturation of exchange sites

Treesearch

W. W. McFee; J. M. Kelly; R. H. Beck

1976-01-01

The typical values and probable ranges of acid-precipitation are evaluated in terms of their theoretical effects on pH and cation exchange equilibrium of soils characteristic of the humid temperature region. The extent of probable change in soil pH and the time required to cause such a change are calculated for a range of common soils. Hydrogen ion input by acid...

SP_Ace: Stellar Parameters And Chemical abundances Estimator

NASA Astrophysics Data System (ADS)

Boeche, C.; Grebel, E. K.

2018-05-01

SP_Ace (Stellar Parameters And Chemical abundances Estimator) estimates the stellar parameters Teff, log g, [M/H], and elemental abundances. It employs 1D stellar atmosphere models in Local Thermodynamic Equilibrium (LTE). The code is highly automated and suitable for analyzing the spectra of large spectroscopic surveys with low or medium spectral resolution (R = 2000-20 000). A web service for calculating these values with the software is also available.

Coefficients for calculating thermodynamic and transport properties of individual species

NASA Technical Reports Server (NTRS)

Mcbride, Bonnie J.; Gordon, Sanford; Reno, Martin A.

1993-01-01

Libraries of thermodynamic data and transport properties are given for individual species in the form of least-squares coefficients. Values of C(sup 0)(sub p)(T), H(sup 0)(T), and S(sup 0)(T) are available for 1130 solid, liquid, and gaseous species. Viscosity and thermal conductivity data are given for 155 gases. The original C(sup 0)(sub p)(T) values were fit to a fourth-order polynomial with integration constants for H(sup 0)(T) and S(sup 0)(T). For each species the integration constant for H(sup 0)(T) includes the heat of formation. Transport properties have a different functional form. The temperature range for most of the data is 300 to 5000 K, although some of the newer thermodynamic data have a range of 200 to 6000 K. Because the species are mainly possible products of reaction, the data are useful for chemical equilibrium and kinetics computer codes. Much of the data has been distributed for several years with the NASA Lewis equilibrium program CET89. The thermodynamic properties of the reference elements were updated along with about 175 species that involve the elements carbon, hydrogen, oxygen, and nitrogen. These sets of data will be distributed with the NASA Lewis personal computer program for calculating chemical equilibria, CETPC.

Computer program to solve two-dimensional shock-wave interference problems with an equilibrium chemically reacting air model

NASA Technical Reports Server (NTRS)

Glass, Christopher E.

1990-01-01

The computer program EASI, an acronym for Equilibrium Air Shock Interference, was developed to calculate the inviscid flowfield, the maximum surface pressure, and the maximum heat flux produced by six shock wave interference patterns on a 2-D, cylindrical configuration. Thermodynamic properties of the inviscid flowfield are determined using either an 11-specie, 7-reaction equilibrium chemically reacting air model or a calorically perfect air model. The inviscid flowfield is solved using the integral form of the conservation equations. Surface heating calculations at the impingement point for the equilibrium chemically reacting air model use variable transport properties and specific heat. However, for the calorically perfect air model, heating rate calculations use a constant Prandtl number. Sample calculations of the six shock wave interference patterns, a listing of the computer program, and flowcharts of the programming logic are included.

Computer program to solve two-dimensional shock-wave interference problems with an equilibrium chemically reacting air model

NASA Astrophysics Data System (ADS)

Glass, Christopher E.

1990-08-01

The computer program EASI, an acronym for Equilibrium Air Shock Interference, was developed to calculate the inviscid flowfield, the maximum surface pressure, and the maximum heat flux produced by six shock wave interference patterns on a 2-D, cylindrical configuration. Thermodynamic properties of the inviscid flowfield are determined using either an 11-specie, 7-reaction equilibrium chemically reacting air model or a calorically perfect air model. The inviscid flowfield is solved using the integral form of the conservation equations. Surface heating calculations at the impingement point for the equilibrium chemically reacting air model use variable transport properties and specific heat. However, for the calorically perfect air model, heating rate calculations use a constant Prandtl number. Sample calculations of the six shock wave interference patterns, a listing of the computer program, and flowcharts of the programming logic are included.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lazerson, Samuel A.; Loizu, Joaquim; Hirshman, Steven

The VMEC nonlinear ideal MHD equilibrium code [S. P. Hirshman and J. C. Whitson, Phys. Fluids 26, 3553 (1983)] is compared against analytic linear ideal MHD theory in a screw-pinch-like configuration. The focus of such analysis is to verify the ideal MHD response at magnetic surfaces which possess magnetic transform (ι) which is resonant with spectral values of the perturbed boundary harmonics. A large aspect ratio circular cross section zero-beta equilibrium is considered. This equilibrium possess a rational surface with safety factor q = 2 at a normalized flux value of 0.5. A small resonant boundary perturbation is introduced, excitingmore » a response at the resonant rational surface. The code is found to capture the plasma response as predicted by a newly developed analytic theory that ensures the existence of nested flux surfaces by allowing for a jump in rotational transform (ι=1/q). The VMEC code satisfactorily reproduces these theoretical results without the necessity of an explicit transform discontinuity (Δι) at the rational surface. It is found that the response across the rational surfaces depends upon both radial grid resolution and local shear (dι/dΦ, where ι is the rotational transform and Φ the enclosed toroidal flux). Calculations of an implicit Δι suggest that it does not arise due to numerical artifacts (attributed to radial finite differences in VMEC) or existence conditions for flux surfaces as predicted by linear theory (minimum values of Δι). Scans of the rotational transform profile indicate that for experimentally relevant levels of transform shear the response becomes increasing localised. Furthermore, careful examination of a large experimental tokamak equilibrium, with applied resonant fields, indicates that this shielding response is present, suggesting the phenomena is not limited to this verification exercise.« less

Verification of the ideal magnetohydrodynamic response at rational surfaces in the VMEC code

DOE PAGES

Lazerson, Samuel A.; Loizu, Joaquim; Hirshman, Steven; ...

2016-01-13

The VMEC nonlinear ideal MHD equilibrium code [S. P. Hirshman and J. C. Whitson, Phys. Fluids 26, 3553 (1983)] is compared against analytic linear ideal MHD theory in a screw-pinch-like configuration. The focus of such analysis is to verify the ideal MHD response at magnetic surfaces which possess magnetic transform (ι) which is resonant with spectral values of the perturbed boundary harmonics. A large aspect ratio circular cross section zero-beta equilibrium is considered. This equilibrium possess a rational surface with safety factor q = 2 at a normalized flux value of 0.5. A small resonant boundary perturbation is introduced, excitingmore » a response at the resonant rational surface. The code is found to capture the plasma response as predicted by a newly developed analytic theory that ensures the existence of nested flux surfaces by allowing for a jump in rotational transform (ι=1/q). The VMEC code satisfactorily reproduces these theoretical results without the necessity of an explicit transform discontinuity (Δι) at the rational surface. It is found that the response across the rational surfaces depends upon both radial grid resolution and local shear (dι/dΦ, where ι is the rotational transform and Φ the enclosed toroidal flux). Calculations of an implicit Δι suggest that it does not arise due to numerical artifacts (attributed to radial finite differences in VMEC) or existence conditions for flux surfaces as predicted by linear theory (minimum values of Δι). Scans of the rotational transform profile indicate that for experimentally relevant levels of transform shear the response becomes increasing localised. Furthermore, careful examination of a large experimental tokamak equilibrium, with applied resonant fields, indicates that this shielding response is present, suggesting the phenomena is not limited to this verification exercise.« less

Isochoric, isobaric, and ultrafast conductivities of aluminum, lithium, and carbon in the warm dense matter regime

NASA Astrophysics Data System (ADS)

Dharma-wardana, M. W. C.; Klug, D. D.; Harbour, L.; Lewis, Laurent J.

2017-11-01

We study the conductivities σ of (i) the equilibrium isochoric state σis, (ii) the equilibrium isobaric state σib, and also the (iii) nonequilibrium ultrafast matter state σuf with the ion temperature Ti less than the electron temperature Te. Aluminum, lithium, and carbon are considered, being increasingly complex warm dense matter systems, with carbon having transient covalent bonds. First-principles calculations, i.e., neutral-pseudoatom (NPA) calculations and density-functional theory (DFT) with molecular-dynamics (MD) simulations, are compared where possible with experimental data to characterize σic, σib, and σuf. The NPA σib is closest to the available experimental data when compared to results from DFT with MD simulations, where simulations of about 64-125 atoms are typically used. The published conductivities for Li are reviewed and the value at a temperature of 4.5 eV is examined using supporting x-ray Thomson-scattering calculations. A physical picture of the variations of σ with temperature and density applicable to these materials is given. The insensitivity of σ to Te below 10 eV for carbon, compared to Al and Li, is clarified.

A Tale of Two Limpets (Patella vulgata and Patella stellaeformis): Evaluating a New Proxy for Late Holocene Climate Change in Coastal Areas

NASA Astrophysics Data System (ADS)

Fenger, T. L.; Surge, D. M.; Schoene, B. R.; Carter, J. G.; Milner, N.

2006-12-01

Shells of the European limpet, Patella vulgata, from Late Holocene archaeological deposits potentially contain critical information about climate change in coastal areas. Before deciphering climate information preserved in these zooarchaeological records, we studied the controls on oxygen isotope ratios (δ18O) in modern specimens. We tested the hypothesis that P. vulgata precipitates its shell in isotopic equilibrium with ambient water by comparing δ18OSHELL with expected values. Expected δ18OSHELL was constructed using the calcite-water fractionation equation, observed sea surface temperature (SST), and assuming δ18OWATER is +0.10‰ (VSMOW). Comparison between expected and measured δ18OSHELL revealed a +1.51±0.21‰ (VPDB) offset from expected values. Consequently, estimated SST calculated from δ18OSHELL was 6.50±2.45°C lower than observed SST. However, because the offset was relatively uniform, an adjustment can be made to account for this predictable vital effect and past SST can be reliably reconstructed. To further investigate the source of offset in this genus, we analyzed a fully marine tropical species (Patella stellaeformis) to minimize seasonal variation in environmental factors that influence δ18OSHELL. P. stellaeformis was evaluated to determine whether it has a similar offset from equilibrium as P. vulgata. We tested the hypotheses that: (1) δ18OSHELL in tropical species also displays vital effects; and (2) the offset from equilibrium (if any) would be constant and predictable. Our results indicated: (1) aragonite comprises most of P. stellaeformis' shell; and (2) δ18OSHELL is statistically indistinguishable from expected values calculated using the aragonite-water fractionation equation (Kolmogorov-Smirnov test statistic=0.61, D0.05[56, 57]=1.36) in contrast with our observations in P. vulgata. Differences in mineralogy or growth rates at different latitudes may play a role in mechanisms that influence vital effects.

Partition functions. I. Improved partition functions and thermodynamic quantities for normal, equilibrium, and ortho and para molecular hydrogen

NASA Astrophysics Data System (ADS)

Popovas, A.; Jørgensen, U. G.

2016-11-01

Context. Hydrogen is the most abundant molecule in the Universe. Its thermodynamic quantities dominate the physical conditions in molecular clouds, protoplanetary disks, etc. It is also of high interest in plasma physics. Therefore thermodynamic data for molecular hydrogen have to be as accurate as possible in a wide temperature range. Aims: We here rigorously show the shortcomings of various simplifications that are used to calculate the total internal partition function. These shortcomings can lead to errors of up to 40 percent or more in the estimated partition function. These errors carry on to calculations of thermodynamic quantities. Therefore a more complicated approach has to be taken. Methods: Seven possible simplifications of various complexity are described, together with advantages and disadvantages of direct summation of experimental values. These were compared to what we consider the most accurate and most complete treatment (case 8). Dunham coefficients were determined from experimental and theoretical energy levels of a number of electronically excited states of H2. Both equilibrium and normal hydrogen was taken into consideration. Results: Various shortcomings in existing calculations are demonstrated, and the reasons for them are explained. New partition functions for equilibrium, normal, and ortho and para hydrogen are calculated and thermodynamic quantities are reported for the temperature range 1-20 000 K. Our results are compared to previous estimates in the literature. The calculations are not limited to the ground electronic state, but include all bound and quasi-bound levels of excited electronic states. Dunham coefficients of these states of H2 are also reported. Conclusions: For most of the relevant astrophysical cases it is strongly advised to avoid using simplifications, such as a harmonic oscillator and rigid rotor or ad hoc summation limits of the eigenstates to estimate accurate partition functions and to be particularly careful when using polynomial fits to the computed values. Reported internal partition functions and thermodynamic quantities in the present work are shown to be more accurate than previously available data. The full datasets in 1 K temperature steps are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/595/A130

Computational methods for reactive transport modeling: A Gibbs energy minimization approach for multiphase equilibrium calculations

NASA Astrophysics Data System (ADS)

Leal, Allan M. M.; Kulik, Dmitrii A.; Kosakowski, Georg

2016-02-01

We present a numerical method for multiphase chemical equilibrium calculations based on a Gibbs energy minimization approach. The method can accurately and efficiently determine the stable phase assemblage at equilibrium independently of the type of phases and species that constitute the chemical system. We have successfully applied our chemical equilibrium algorithm in reactive transport simulations to demonstrate its effective use in computationally intensive applications. We used FEniCS to solve the governing partial differential equations of mass transport in porous media using finite element methods in unstructured meshes. Our equilibrium calculations were benchmarked with GEMS3K, the numerical kernel of the geochemical package GEMS. This allowed us to compare our results with a well-established Gibbs energy minimization algorithm, as well as their performance on every mesh node, at every time step of the transport simulation. The benchmark shows that our novel chemical equilibrium algorithm is accurate, robust, and efficient for reactive transport applications, and it is an improvement over the Gibbs energy minimization algorithm used in GEMS3K. The proposed chemical equilibrium method has been implemented in Reaktoro, a unified framework for modeling chemically reactive systems, which is now used as an alternative numerical kernel of GEMS.

Non-equilibrium ionization by a periodic electron beam. II. Synthetic Si IV and O IV transition region spectra

NASA Astrophysics Data System (ADS)

Dzifčáková, Elena; Dudík, Jaroslav

2018-03-01

Context. Transition region (TR) spectra typically show the Si IV 1402.8 Å line to be enhanced by a factor of 5 or more compared to the neighboring O IV 1401.2 Å, contrary to predictions of ionization equilibrium models and the Maxwellian distribution of particle energies. Non-equilibrium effects in TR spectra are therefore expected. Aims: To investigate the combination of non-equilibrium ionization and high-energy particles, we apply the model of the periodic electron beam, represented by a κ-distribution that recurs at periods of several seconds, to plasma at chromospheric temperatures of 104 K. This simple model can approximate a burst of energy release involving accelerated particles. Methods: Instantaneous time-dependent charge states of silicon and oxygen were calculated and used to synthesize the instantaneous and period-averaged spectra of Si IV and O IV. Results: The electron beam drives the plasma out of equilibrium. At electron densities of Ne = 1010 cm-3, the plasma is out of ionization equilibrium at all times in all cases we considered, while for a higher density of Ne = 1011 cm-3, ionization equilibrium can be reached toward the end of each period, depending on the conditions. In turn, the character of the period-averaged synthetic spectra also depends on the properties of the beam. While the case of κ = 2 results in spectra with strong or even dominant O IV, higher values of κ can approximate a range of observed TR spectra. Spectra similar to typically observed spectra, with the Si IV 1402.8 Å line about a factor 5 higher than O IV 1401.2 Å, are obtained for κ = 3. An even higher value of κ = 5 results in spectra that are exclusively dominated by Si IV, with negligible O IV emission. This is a possible interpretation of the TR spectra of UV (Ellerman) bursts, although an interpretation that requires a density that is 1-3 orders of magnitude lower than for equilibrium estimates. Movies associated to Fig. A.1 are available at http://https://www.aanda.org

Prediction of gas/particle partitioning of polybrominated diphenyl ethers (PBDEs) in global air: A theoretical study

NASA Astrophysics Data System (ADS)

Li, Y.-F.; Ma, W.-L.; Yang, M.

2015-02-01

Gas/particle (G/P) partitioning of semi-volatile organic compounds (SVOCs) is an important process that primarily governs their atmospheric fate, long-range atmospheric transport, and their routes of entering the human body. All previous studies on this issue are hypothetically based on equilibrium conditions, the results of which do not predict results from monitoring studies well in most cases. In this study, a steady-state model instead of an equilibrium-state model for the investigation of the G/P partitioning behavior of polybrominated diphenyl ethers (PBDEs) was established, and an equation for calculating the partition coefficients under steady state (KPS) of PBDEs (log KPS = log KPE + logα) was developed in which an equilibrium term (log KPE = log KOA + logfOM -11.91 where fOM is organic matter content of the particles) and a non-equilibrium term (log α, caused by dry and wet depositions of particles), both being functions of log KOA (octanol-air partition coefficient), are included. It was found that the equilibrium is a special case of steady state when the non-equilibrium term equals zero. A criterion to classify the equilibrium and non-equilibrium status of PBDEs was also established using two threshold values of log KOA, log KOA1, and log KOA2, which divide the range of log KOA into three domains: equilibrium, non-equilibrium, and maximum partition domain. Accordingly, two threshold values of temperature t, tTH1 when log KOA = log KOA1 and tTH2 when log KOA = log KOA2, were identified, which divide the range of temperature also into the same three domains for each PBDE congener. We predicted the existence of the maximum partition domain (the values of log KPS reach a maximum constant of -1.53) that every PBDE congener can reach when log KOA ≥ log KOA2, or t ≤ tTH2. The novel equation developed in this study was applied to predict the G/P partition coefficients of PBDEs for our Chinese persistent organic pollutants (POPs) Soil and Air Monitoring Program, Phase 2 (China-SAMP-II) program and other monitoring programs worldwide, including in Asia, Europe, North America, and the Arctic, and the results matched well with all the monitoring data, except those obtained at e-waste sites due to the unpredictable PBDE emissions at these sites. This study provided evidence that the newly developed steady-state-based equation is superior to the equilibrium-state-based equation that has been used in describing the G/P partitioning behavior over decades. We suggest that the investigation on G/P partitioning behavior for PBDEs should be based onsteady-state, not equilibrium state, and equilibrium is just a special case of steady-state when non-equilibrium factors can be ignored. We also believe that our new equation provides a useful tool for environmental scientists in both monitoring and modeling research on G/P partitioning of PBDEs and can be extended to predict G/P partitioning behavior for other SVOCs as well.

Carbon emissions tax policy of urban road traffic and its application in Panjin, China

PubMed Central

Yang, Longhai; Fang, Lin

2018-01-01

How to effectively solve traffic congestion and transportation pollution in urban development is a main research emphasis for transportation management agencies. A carbon emissions tax can affect travelers’ generalized costs and will lead to changes in passenger demand, mode choice and traffic flow equilibrium in road networks, which are of significance in green travel and low-carbon transportation management. This paper first established a mesoscopic model to calculate the carbon emissions tax and determined the value of this charge in China, which was based on road traffic flow, vehicle speed, and carbon emissions. Referring to existing research results to calibrate the value of time, this paper modified the traveler’s generalized cost function, including the carbon emissions tax, fuel surcharge and travel time cost, which can be used in the travel impedance model with the consideration of the carbon emissions tax. Then, a method for analyzing urban road network traffic flow distribution was put forward, and a joint traffic distribution model was established, which considered the relationship between private cars and taxis. Finally, this paper took the city of Panjin as an example to analyze the road traffic carbon emissions tax’s impact. The results illustrated that the carbon emissions tax has a positive effect on road network flow equilibrium and carbon emission reduction. This paper will have good reference value and practical significance for the calculation and implementation of urban traffic carbon emissions taxes in China. PMID:29738580

Carbon emissions tax policy of urban road traffic and its application in Panjin, China.

PubMed

Yang, Longhai; Hu, Xiaowei; Fang, Lin

2018-01-01

How to effectively solve traffic congestion and transportation pollution in urban development is a main research emphasis for transportation management agencies. A carbon emissions tax can affect travelers' generalized costs and will lead to changes in passenger demand, mode choice and traffic flow equilibrium in road networks, which are of significance in green travel and low-carbon transportation management. This paper first established a mesoscopic model to calculate the carbon emissions tax and determined the value of this charge in China, which was based on road traffic flow, vehicle speed, and carbon emissions. Referring to existing research results to calibrate the value of time, this paper modified the traveler's generalized cost function, including the carbon emissions tax, fuel surcharge and travel time cost, which can be used in the travel impedance model with the consideration of the carbon emissions tax. Then, a method for analyzing urban road network traffic flow distribution was put forward, and a joint traffic distribution model was established, which considered the relationship between private cars and taxis. Finally, this paper took the city of Panjin as an example to analyze the road traffic carbon emissions tax's impact. The results illustrated that the carbon emissions tax has a positive effect on road network flow equilibrium and carbon emission reduction. This paper will have good reference value and practical significance for the calculation and implementation of urban traffic carbon emissions taxes in China.

Formation of nitric acid hydrates - A chemical equilibrium approach

NASA Technical Reports Server (NTRS)

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.

The stability of amino acids at submarine hydrothermal vent temperatures

NASA Technical Reports Server (NTRS)

Bada, Jeffrey L.; Miller, Stanley L.; Zhao, Meixun

1995-01-01

It has been postulated that amino acid stability at hydrothermal vent temperatures is controlled by a metastable thermodynamic equilibrium rather than by kinetics. Experiments reported here demonstrate that the amino acids are irreversibly destroyed by heating at 240 C and that quasi-equilibrium calculations give misleading descriptions of the experimental observations. Equilibrium thermodynamic calculations are not applicable to organic compounds under high-temperature submarine vent conditions.

Improving high-altitude emp modeling capabilities by using a non-equilibrium electron swarm model to monitor conduction electron evolution

NASA Astrophysics Data System (ADS)

Pusateri, Elise Noel

An Electromagnetic Pulse (EMP) can severely disrupt the use of electronic devices in its path causing a significant amount of infrastructural damage. EMP can also cause breakdown of the surrounding atmosphere during lightning discharges. This makes modeling EMP phenomenon an important research effort in many military and atmospheric physics applications. EMP events include high-energy Compton electrons or photoelectrons that ionize air and produce low energy conduction electrons. A sufficient number of conduction electrons will damp or alter the EMP through conduction current. Therefore, it is important to understand how conduction electrons interact with air in order to accurately predict the EMP evolution and propagation in the air. It is common for EMP simulation codes to use an equilibrium ohmic model for computing the conduction current. Equilibrium ohmic models assume the conduction electrons are always in equilibrium with the local instantaneous electric field, i.e. for a specific EMP electric field, the conduction electrons instantaneously reach steady state without a transient process. An equilibrium model will work well if the electrons have time to reach their equilibrium distribution with respect to the rise time or duration of the EMP. If the time to reach equilibrium is comparable or longer than the rise time or duration of the EMP then the equilibrium model would not accurately predict the conduction current necessary for the EMP simulation. This is because transport coefficients used in the conduction current calculation will be found based on equilibrium reactions rates which may differ significantly from their non-equilibrium values. We see this deficiency in Los Alamos National Laboratory's EMP code, CHAP-LA (Compton High Altitude Pulse-Los Alamos), when modeling certain EMP scenarios at high altitudes, such as upward EMP, where the ionization rate by secondary electrons is over predicted by the equilibrium model, causing the EMP to short abruptly. The objective of the PhD research is to mitigate this effect by integrating a conduction electron model into CHAP-LA which can calculate the conduction current based on a non-equilibrium electron distribution. We propose to use an electron swarm model to monitor the time evolution of conduction electrons in the EMP environment which is characterized by electric field and pressure. Swarm theory uses various collision frequencies and reaction rates to study how the electron distribution and the resultant transport coefficients change with time, ultimately reaching an equilibrium distribution. Validation of the swarm model we develop is a necessary step for completion of the thesis work. After validation, the swarm model is integrated in the air chemistry model CHAP-LA employs for conduction electron simulations. We test high altitude EMP simulations with the swarm model option in the air chemistry model to show improvements in the computational capability of CHAP-LA. A swarm model has been developed that is based on a previous swarm model developed by Higgins, Longmire and O'Dell 1973, hereinafter HLO. The code used for the swarm model calculation solves a system of coupled differential equations for electric field, electron temperature, electron number density, and drift velocity. Important swarm parameters, including the momentum transfer collision frequency, energy transfer collision frequency, and ionization rate, are recalculated and compared to the previously reported empirical results given by HLO. These swarm parameters are found using BOLSIG+, a two term Boltzmann solver developed by Hagelaar and Pitchford 2005. BOLSIG+ utilizes updated electron scattering cross sections that are defined over an expanded energy range found in the atomic and molecular cross section database published by Phelps in the Phelps Database 2014 on the LXcat website created by Pancheshnyi et al. 2012. The swarm model is also updated from the original HLO model by including additional physical parameters such as the O2 electron attachment rate, recombination rate, and mutual neutralization rate. This necessitates tracking the positive and negative ion densities in the swarm model. Adding these parameters, especially electron attachment, is important at lower EMP altitudes where atmospheric density is high. We compare swarm model equilibrium temperatures and times using the HLO and BOLSIG+ coefficients for a uniform electric field of 1 StatV/cm for a range of atmospheric heights. This is done in order to test sensitivity to the swarm parameters used in the swarm model. It is shown that the equilibrium temperature and time are sensitive to the modifications in the collision frequency and ionization rate based on the updated electron interaction cross sections. We validate the swarm model by comparing ionization coefficients and equilibrium drift velocities to experimental results over a wide range of reduced electric field values. The final part of the PhD thesis work includes integrating the swarm model into CHAP-LA. We discuss the physics included in the CHAP-LA EMP model and demonstrate EMP damping behavior caused by the ohmic model at high altitudes. We report on numerical techniques for incorporation of the swarm model into CHAP-LA's Maxwell solver. This includes a discussion of integration techniques for Maxwell's equations in CHAP-LA using the swarm model calculated conduction current. We show improvements on EMP parameter calculations when modeling a high altitude, upward EMP scenario. This provides a novel computational capability that will have an important impact on the atmospheric and EMP research community.

Computer program for calculation of complex chemical equilibrium compositions and applications. Part 1: Analysis

NASA Technical Reports Server (NTRS)

Gordon, Sanford; Mcbride, Bonnie J.

1994-01-01

This report presents the latest in a number of versions of chemical equilibrium and applications programs developed at the NASA Lewis Research Center over more than 40 years. These programs have changed over the years to include additional features and improved calculation techniques and to take advantage of constantly improving computer capabilities. The minimization-of-free-energy approach to chemical equilibrium calculations has been used in all versions of the program since 1967. The two principal purposes of this report are presented in two parts. The first purpose, which is accomplished here in part 1, is to present in detail a number of topics of general interest in complex equilibrium calculations. These topics include mathematical analyses and techniques for obtaining chemical equilibrium; formulas for obtaining thermodynamic and transport mixture properties and thermodynamic derivatives; criteria for inclusion of condensed phases; calculations at a triple point; inclusion of ionized species; and various applications, such as constant-pressure or constant-volume combustion, rocket performance based on either a finite- or infinite-chamber-area model, shock wave calculations, and Chapman-Jouguet detonations. The second purpose of this report, to facilitate the use of the computer code, is accomplished in part 2, entitled 'Users Manual and Program Description'. Various aspects of the computer code are discussed, and a number of examples are given to illustrate its versatility.

Modeling the dynamic equilibrium between oligomers of (AlOCH3)n in methylaluminoxane (MAO). A theoretical study based on a combined quantum mechanical and statistical mechanical approach.

PubMed

Zurek, E; Woo, T K; Firman, T K; Ziegler, T

2001-01-15

Density functional theory (DFT) has been used to calculate the energies of 36 different methylaluminoxane (MAO) cage structures with the general formula (MeAlO)n, where n ranges from 4 to 16. A least-squares fit has been used to devise a formula which predicts the total energies of the MAO with different n's giving an rms deviation of 4.70 kcal/mol. These energies in conjunction with frequency calculations based on molecular mechanics have been used to estimate the finite temperature enthalpies, entropies, and free energies for these MAO structures. Furthermore, formulas have been devised which predict finite temperature enthalpies and entropies for MAO structures of any n for a temperature range of 198.15-598.15 K. Using these formulas, the free energies at different temperatures have been predicted for MAO structures where n ranges from 17 to 30. The free energy values were then used to predict the percentage of each n found at a given temperature. Our calculations give an average n value of 18.41, 17.23, 16.89, and 15.72 at 198.15, 298.15, 398.15, and 598.15 K, respectively. Topological arguments have also been used to show that the MAO cage structure contains a limited amount of square faces as compared to octagonal and hexagonal ones. It is also suggested that the limited number of square faces with their strained Al-O bonds explain the high molar Al:catalyst ratio required for activation. Moreover, in this study we outline a general methodology which may be used to calculate the percent abundance of an equilibrium mixture of oligomers with the general formula (X)n.

Teaching an Old Dog an Old Trick: FREE-FIX and Free-Boundary Axisymmetric MHD Equilibrium

NASA Astrophysics Data System (ADS)

Guazzotto, Luca

2015-11-01

A common task in plasma physics research is the calculation of an axisymmetric equilibrium for tokamak modeling. The main unknown of the problem is the magnetic poloidal flux ψ. The easiest approach is to assign the shape of the plasma and only solve the equilibrium problem in the plasma / closed-field-lines region (the ``fixed-boundary approach''). Often, one may also need the vacuum fields, i.e. the equilibrium in the open-field-lines region, requiring either coil currents or ψ on some closed curve outside the plasma to be assigned (the ``free-boundary approach''). Going from one approach to the other is a textbook problem, involving the calculation of Green's functions and surface integrals in the plasma. However, no tools are readily available to perform this task. Here we present a code (FREE-FIX) to compute a boundary condition for a free-boundary equilibrium given only the corresponding fixed-boundary equilibrium. An improvement to the standard solution method, allowing for much faster calculations, is presented. Applications are discussed. PPPL fund 245139 and DOE grant G00009102.

Pleural pressure theory revisited: a role for capillary equilibrium

PubMed Central

Caruana-Gauci, Roberto; Manche, Alexander; Gauci, Marilyn; Chetcuti, Stanley; Bertolaccini, Luca

2017-01-01

Background Theories elucidating pleural pressures should explain all observations including the equal and opposite recoil of the chest wall and lungs, the less than expected pleural hydrostatic gradient and its variation at lobar margins, why pleural pressures are negative and how pleural fluid circulation functions. Methods A theoretical model describing equilibrium between buoyancy, hydrostatic forces, and capillary forces is proposed. The capillary equilibrium model described depends on control of pleural fluid volume and protein content, powered by an active pleural pump. Results The interaction between buoyancy forces, hydrostatic pressure and capillary pressure was calculated, and values for pleural thickness and pressure were determined using values for surface tension, contact angle, pleural fluid and lung densities found in the literature. Modelling can explain the issue of the differing hydrostatic vertical pleural pressure gradient at the lobar margins for buoyancy forces between the pleural fluid and the lung floating in the pleural fluid according to Archimedes’ hydrostatic paradox. The capillary equilibrium model satisfies all salient requirements for a pleural pressure model, with negative pressures maximal at the apex, equal and opposite forces in the lung and chest wall, and circulatory pump action. Conclusions This model predicts that pleural effusions cannot occur in emphysema unless concomitant heart failure increases lung density. This model also explains how the non-confluence of the lung with the chest wall (e.g., lobar margins) makes the pleural pressure more negative, and why pleural pressures would be higher after an upper lobectomy compared to a lower lobectomy. Pathological changes in pleural fluid composition and lung density alter the equilibrium between capillarity and buoyancy hydrostatic pressure to promote pleural effusion formation. PMID:28523153

Equilibrium-phase MR angiography: Comparison of unspecific extracellular and protein-binding gadolinium-based contrast media with respect to image quality.

PubMed

Erb-Eigner, Katharina; Taupitz, Matthias; Asbach, Patrick

2016-01-01

The purpose of this study was to compare contrast and image quality of whole-body equilibrium-phase high-spatial-resolution MR angiography using a non-protein-binding unspecific extracellular gadolinium-based contrast medium with that of two contrast media with different protein-binding properties. 45 patients were examined using either 15 mL of gadobutrol (non-protein-binding, n = 15), 32 mL of gadobenate dimeglumine (weakly protein binding, n = 15) or 11 mL gadofosveset trisodium (protein binding, n = 15) followed by equilibrium-phase high-spatial-resolution MR-angiography of four consecutive anatomic regions. The time elapsed between the contrast injection and the beginning of the equilibrium-phase image acquisition in the respective region was measured and was up to 21 min. Signal intensity was measured in two vessels per region and in muscle tissue. Relative contrast (RC) values were calculated. Vessel contrast, artifacts and image quality were rated by two radiologists in consensus on a five-point scale. Compared with gadobutrol, gadofosveset trisodium revealed significantly higher RC values only when acquired later than 15 min after bolus injection. Otherwise, no significant differences between the three contrast media were found regarding vascular contrast and image quality. Equilibrium-phase high-spatial-resolution MR-angiography using a weakly protein-binding or even non-protein-binding contrast medium is equivalent to using a stronger protein-binding contrast medium when image acquisition is within the first 15 min after contrast injection, and allows depiction of the vasculature with high contrast and image quality. The protein-binding contrast medium was superior for imaging only later than 15 min after contrast medium injection. Copyright © 2015 John Wiley & Sons, Ltd.

FastChem: An ultra-fast equilibrium chemistry

NASA Astrophysics Data System (ADS)

Kitzmann, Daniel; Stock, Joachim

2018-04-01

FastChem is an equilibrium chemistry code that calculates the chemical composition of the gas phase for given temperatures and pressures. Written in C++, it is based on a semi-analytic approach, and is optimized for extremely fast and accurate calculations.

Effects of various assumptions on the calculated liquid fraction in isentropic saturated equilibrium expansions

NASA Technical Reports Server (NTRS)

Bursik, J. W.; Hall, R. M.

1980-01-01

The saturated equilibrium expansion approximation for two phase flow often involves ideal-gas and latent-heat assumptions to simplify the solution procedure. This approach is well documented by Wegener and Mack and works best at low pressures where deviations from ideal-gas behavior are small. A thermodynamic expression for liquid mass fraction that is decoupled from the equations of fluid mechanics is used to compare the effects of the various assumptions on nitrogen-gas saturated equilibrium expansion flow starting at 8.81 atm, 2.99 atm, and 0.45 atm, which are conditions representative of transonic cryogenic wind tunnels. For the highest pressure case, the entire set of ideal-gas and latent-heat assumptions are shown to be in error by 62 percent for the values of heat capacity and latent heat. An approximation of the exact, real-gas expression is also developed using a constant, two phase isentropic expansion coefficient which results in an error of only 2 percent for the high pressure case.

Predicting equilibrium states with Reynolds stress closures in channel flow and homogeneous shear flow

NASA Technical Reports Server (NTRS)

Abid, R.; Speziale, C. G.

1993-01-01

Turbulent channel flow and homogeneous shear flow have served as basic building block flows for the testing and calibration of Reynolds stress models. A direct theoretical connection is made between homogeneous shear flow in equilibrium and the log-layer of fully-developed turbulent channel flow. It is shown that if a second-order closure model is calibrated to yield good equilibrium values for homogeneous shear flow it will also yield good results for the log-layer of channel flow provided that the Rotta coefficient is not too far removed from one. Most of the commonly used second-order closure models introduce an ad hoc wall reflection term in order to mask deficient predictions for the log-layer of channel flow that arise either from an inaccurate calibration of homogeneous shear flow or from the use of a Rotta coefficient that is too large. Illustrative model calculations are presented to demonstrate this point which has important implications for turbulence modeling.

Predicting equilibrium states with Reynolds stress closures in channel flow and homogeneous shear flow

NASA Technical Reports Server (NTRS)

Abid, R.; Speziale, C. G.

1992-01-01

Turbulent channel flow and homogeneous shear flow have served as basic building block flows for the testing and calibration of Reynolds stress models. A direct theoretical connection is made between homogeneous shear flow in equilibrium and the log-layer of fully-developed turbulent channel flow. It is shown that if a second-order closure model is calibrated to yield good equilibrium values for homogeneous shear flow it will also yield good results for the log-layer of channel flow provided that the Rotta coefficient is not too far removed from one. Most of the commonly used second-order closure models introduce an ad hoc wall reflection term in order to mask deficient predictions for the log-layer of channel flow that arise either from an inaccurate calibration of homogeneous shear flow or from the use of a Rotta coefficient that is too large. Illustrative model calculations are presented to demonstrate this point which has important implications for turbulence modeling.

On structural transitions, thermodynamic equilibrium, and the phase diagram of DNA and RNA duplexes under torque and tension.

PubMed

Wereszczynski, Jeff; Andricioaei, Ioan

2006-10-31

A precise understanding of the flexibility of double stranded nucleic acids and the nature of their deformed conformations induced by external forces is important for a wide range of biological processes including transcriptional regulation, supercoil and catenane removal, and site-specific recombination. We present, at atomic resolution, a simulation of the dynamics involved in the transitions from B-DNA and A-RNA to Pauling (P) forms and to denatured states driven by application of external torque and tension. We then calculate the free energy profile along a B- to P-transition coordinate and from it, compute a reversible pathway, i.e., an isotherm of tension and torque pairs required to maintain P-DNA in equilibrium. The reversible isotherm maps correctly onto a phase diagram derived from single molecule experiments, and yields values of elongation, twist, and twist-stretch coupling in agreement with measured values. We also show that configurational entropy compensates significantly for the large electrostatic energy increase due to closer-packed P backbones. A similar set of simulations applied to RNA are used to predict a novel structure, P-RNA, with its associated free energy, equilibrium tension, torque and structural parameters, and to assign the location, on the phase-diagram, of a putative force-torque-dependent RNA "triple point."

Vapor-liquid equilibrium thermodynamics of N2 + CH4 - Model and Titan applications

NASA Technical Reports Server (NTRS)

Thompson, W. R.; Zollweg, John A.; Gabis, David H.

1992-01-01

A thermodynamic model is presented for vapor-liquid equilibrium in the N2 + CH4 system, which is implicated in calculations of the Titan tropospheric clouds' vapor-liquid equilibrium thermodynamics. This model imposes constraints on the consistency of experimental equilibrium data, and embodies temperature effects by encompassing enthalpy data; it readily calculates the saturation criteria, condensate composition, and latent heat for a given pressure-temperature profile of the Titan atmosphere. The N2 content of condensate is about half of that computed from Raoult's law, and about 30 percent greater than that computed from Henry's law.

Auditing: Perspectives from Multiperson Decision Theory.

DTIC Science & Technology

1982-10-01

Transmission" by W.P. Rogerson 378. "Unemployment Equilibrium with Stochastic Rationing of Supplies" by Ho-mo i WU. 379. " Optimal Price and Income... rational with enormous powers of calculation. At first this may seem utterly inappropriate for the study of problems in accounting. Nevertheless, there...that at any price the investor offers he will tend to get acceptance only from an owner with assets having a lesser value. Similarly, if the owner

Calculation of Free-Atom Fractions in Hydrocarbon-Fueled Rocket Engine Plume

NASA Technical Reports Server (NTRS)

Verma, Satyajit

2006-01-01

Free atom fractions (Beta) of nine elements are calculated in the exhaust plume of CH4- oxygen and RP-1-oxygen fueled rocket engines using free energy minimization method. The Chemical Equilibrium and Applications (CEA) computer program developed by the Glenn Research Center, NASA is used for this purpose. Data on variation of Beta in both fuels as a function of temperature (1600 K - 3100 K) and oxygen to fuel ratios (1.75 to 2.25 by weight) is presented in both tabular and graphical forms. Recommendation is made for the Beta value for a tenth element, Palladium. The CEA computer code was also run to compare with experimentally determined Beta values reported in literature for some of these elements. A reasonable agreement, within a factor of three, between the calculated and reported values is observed. Values reported in this work will be used as a first approximation for pilot rocket engine testing studies at the Stennis Space Center for at least six elements Al, Ca, Cr, Cu, Fe and Ni - until experimental values are generated. The current estimates will be improved when more complete thermodynamic data on the remaining four elements Ag, Co, Mn and Pd are added to the database. A critique of the CEA code is also included.

Super heavy element Copernicium: Cohesive and electronic properties revisited

NASA Astrophysics Data System (ADS)

Gyanchandani, Jyoti; Mishra, Vinayak; Dey, G. K.; Sikka, S. K.

2018-01-01

First principles scalar relativistic (SR) calculations with and without including the spin orbit (SO) interactions have been performed for solid Copernicium (Cn) to determine its ground state equilibrium structure, volume, bulk modulus, pressure derivative of the bulk modulus, density of states and band structure. Both SR and SR+SO calculations have been performed with 6p levels treated as part of core electrons and also as part of valence electrons. These calculations have been performed for the rhombohedral, BCT, FCC, HCP, BCC and SC structures. Results have been compared with the results for Hg which is lighter homologue of Cn in the periodic table. We find hcp to be the stable crystal structure at SR level of theory and also at SR+SO level of theory when the 6p electrons are treated as part of core electrons. With 6p as part of valence electrons, SR+SO level of computations, however, yield bcc structure to be the most stable structure. Equilibrium volume (V0) of the most stable crystal structure at SR level of theory viz. hcp structure is 188.66 a.u.3whereas its value for the bcc structure, the equilibrium ground state structure at SR+SO level of theory is 165.71 a.u.3 i.e a large change due to relativistic effects is seen. The density of states at Fermi level is much smaller in Cn than in Hg, making it a poorer metal than mercury. In addition the cohesive energy of Cn is computed to be almost two times that of Hg for SR+SO case.

Boundedness and global robust stability analysis of delayed complex-valued neural networks with interval parameter uncertainties.

PubMed

Song, Qiankun; Yu, Qinqin; Zhao, Zhenjiang; Liu, Yurong; Alsaadi, Fuad E

2018-07-01

In this paper, the boundedness and robust stability for a class of delayed complex-valued neural networks with interval parameter uncertainties are investigated. By using Homomorphic mapping theorem, Lyapunov method and inequality techniques, sufficient condition to guarantee the boundedness of networks and the existence, uniqueness and global robust stability of equilibrium point is derived for the considered uncertain neural networks. The obtained robust stability criterion is expressed in complex-valued LMI, which can be calculated numerically using YALMIP with solver of SDPT3 in MATLAB. An example with simulations is supplied to show the applicability and advantages of the acquired result. Copyright © 2018 Elsevier Ltd. All rights reserved.

Multiscale System for Environmentally-Driven Infectious Disease with Threshold Control Strategy

NASA Astrophysics Data System (ADS)

Sun, Xiaodan; Xiao, Yanni

A multiscale system for environmentally-driven infectious disease is proposed, in which control measures at three different scales are implemented when the number of infected hosts exceeds a certain threshold. Our coupled model successfully describes the feedback mechanisms of between-host dynamics on within-host dynamics by employing one-scale variable guided enhancement of interventions on other scales. The modeling approach provides a novel idea of how to link the large-scale dynamics to small-scale dynamics. The dynamic behaviors of the multiscale system on two time-scales, i.e. fast system and slow system, are investigated. The slow system is further simplified to a two-dimensional Filippov system. For the Filippov system, we study the dynamics of its two subsystems (i.e. free-system and control-system), the sliding mode dynamics, the boundary equilibrium bifurcations, as well as the global behaviors. We prove that both subsystems may undergo backward bifurcations and the sliding domain exists. Meanwhile, it is possible that the pseudo-equilibrium exists and is globally stable, or the pseudo-equilibrium, the disease-free equilibrium and the real equilibrium are tri-stable, or the pseudo-equilibrium and the real equilibrium are bi-stable, or the pseudo-equilibrium and disease-free equilibrium are bi-stable, which depends on the threshold value and other parameter values. The global stability of the pseudo-equilibrium reveals that we may maintain the number of infected hosts at a previously given value. Moreover, the bi-stability and tri-stability indicate that whether the number of infected individuals tends to zero or a previously given value or other positive values depends on the parameter values and the initial states of the system. These results highlight the challenges in the control of environmentally-driven infectious disease.

Tokamak plasma high field side response to an n = 3 magnetic perturbation: a comparison of 3D equilibrium solutions from seven different codes

NASA Astrophysics Data System (ADS)

Reiman, A.; Ferraro, N. M.; Turnbull, A.; Park, J. K.; Cerfon, A.; Evans, T. E.; Lanctot, M. J.; Lazarus, E. A.; Liu, Y.; McFadden, G.; Monticello, D.; Suzuki, Y.

2015-06-01

In comparing equilibrium solutions for a DIII-D shot that is amenable to analysis by both stellarator and tokamak three-dimensional (3D) equilibrium codes, a significant disagreement has been seen between solutions of the VMEC stellarator equilibrium code and solutions of tokamak perturbative 3D equilibrium codes. The source of that disagreement has been investigated, and that investigation has led to new insights into the domain of validity of the different equilibrium calculations, and to a finding that the manner in which localized screening currents at low order rational surfaces are handled can affect global properties of the equilibrium solution. The perturbative treatment has been found to break down at surprisingly small perturbation amplitudes due to overlap of the calculated perturbed flux surfaces, and that treatment is not valid in the pedestal region of the DIII-D shot studied. The perturbative treatment is valid, however, further into the interior of the plasma, and flux surface overlap does not account for the disagreement investigated here. Calculated equilibrium solutions for simple model cases and comparison of the 3D equilibrium solutions with those of other codes indicate that the disagreement arises from a difference in handling of localized currents at low order rational surfaces, with such currents being absent in VMEC and present in the perturbative codes. The significant differences in the global equilibrium solutions associated with the presence or absence of very localized screening currents at rational surfaces suggests that it may be possible to extract information about localized currents from appropriate measurements of global equilibrium plasma properties. That would require improved diagnostic capability on the high field side of the tokamak plasma, a region difficult to access with diagnostics.

A theoretical model of grain boundary self-diffusion in metals with phase transitions (case study into titanium and zirconium)

NASA Astrophysics Data System (ADS)

Semenycheva, Alexandra V.; Chuvil'deev, Vladimir N.; Nokhrin, Aleksey V.

2018-05-01

The paper offers a model describing the process of grain boundary self-diffusion in metals with phase transitions in the solid state. The model is based on ideas and approaches found in the theory of non-equilibrium grain boundaries. The range of application of basic relations contained in this theory is shown to expand, as they can be used to calculate the parameters of grain boundary self-diffusion in high-temperature and low-temperature phases of metals with a phase transition. The model constructed is used to calculate grain boundary self-diffusion activation energy in titanium and zirconium and an explanation is provided as to their abnormally low values in the low-temperature phase. The values of grain boundary self-diffusion activation energy are in good agreement with the experiment.

Minimizing the Free Energy: A Computer Method for Teaching Chemical Equilibrium Concepts.

ERIC Educational Resources Information Center

Heald, Emerson F.

1978-01-01

Presents a computer method for teaching chemical equilibrium concepts using material balance conditions and the minimization of the free energy. Method for the calculation of chemical equilibrium, the computer program used to solve equilibrium problems and applications of the method are also included. (HM)

TEA: A Code Calculating Thermochemical Equilibrium Abundances

NASA Astrophysics Data System (ADS)

Blecic, Jasmina; Harrington, Joseph; Bowman, M. Oliver

2016-07-01

We present an open-source Thermochemical Equilibrium Abundances (TEA) code that calculates the abundances of gaseous molecular species. The code is based on the methodology of White et al. and Eriksson. It applies Gibbs free-energy minimization using an iterative, Lagrangian optimization scheme. Given elemental abundances, TEA calculates molecular abundances for a particular temperature and pressure or a list of temperature-pressure pairs. We tested the code against the method of Burrows & Sharp, the free thermochemical equilibrium code Chemical Equilibrium with Applications (CEA), and the example given by Burrows & Sharp. Using their thermodynamic data, TEA reproduces their final abundances, but with higher precision. We also applied the TEA abundance calculations to models of several hot-Jupiter exoplanets, producing expected results. TEA is written in Python in a modular format. There is a start guide, a user manual, and a code document in addition to this theory paper. TEA is available under a reproducible-research, open-source license via https://github.com/dzesmin/TEA.

TEA: A CODE CALCULATING THERMOCHEMICAL EQUILIBRIUM ABUNDANCES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blecic, Jasmina; Harrington, Joseph; Bowman, M. Oliver, E-mail: jasmina@physics.ucf.edu

2016-07-01

We present an open-source Thermochemical Equilibrium Abundances (TEA) code that calculates the abundances of gaseous molecular species. The code is based on the methodology of White et al. and Eriksson. It applies Gibbs free-energy minimization using an iterative, Lagrangian optimization scheme. Given elemental abundances, TEA calculates molecular abundances for a particular temperature and pressure or a list of temperature–pressure pairs. We tested the code against the method of Burrows and Sharp, the free thermochemical equilibrium code Chemical Equilibrium with Applications (CEA), and the example given by Burrows and Sharp. Using their thermodynamic data, TEA reproduces their final abundances, but withmore » higher precision. We also applied the TEA abundance calculations to models of several hot-Jupiter exoplanets, producing expected results. TEA is written in Python in a modular format. There is a start guide, a user manual, and a code document in addition to this theory paper. TEA is available under a reproducible-research, open-source license via https://github.com/dzesmin/TEA.« less

Thermodynamic aspect in using modified Boltzmann model as an acoustic probe for URu2Si2

NASA Astrophysics Data System (ADS)

Kwang-Hua, Chu Rainer

2018-05-01

The approximate system of equations describing ultrasonic attenuation propagating in many electrons of the heavy-fermion materials URu2Si2 under high magnetic fields were firstly derived and then calculated based on the modified Boltzmann model considering the microscopic contributions due to electronic fluids. A system of nonlinear partial differential coupled with integral equations were linearized firstly and approximately solved considering the perturbed thermodynamic equilibrium states. Our numerical data were compared with previous measurements using non-dimensional or normalized physical values. The rather good fit of our numerical calculations with experimental measurements confirms our present approach.

Spectroscopic notes of Methyl Red (MR) dye.

PubMed

El-Mansy, M A M; Yahia, I S

2014-09-15

In the present work, a combined experimental and theoretical study on molecular structure and vibrational frequencies of MR were reported. The FT-IR spectrum of MR is recorded in the solid phase. The equilibrium geometries, harmonic vibrational frequencies, thermo-chemical parameters, total dipole moment and HOMO-LUMO energies are calculated by DFT/B3LYP utilizing 6-311G(d,p) basis set. Results showed that MR is highly recommended to be a promising structure for many applications in optoelectronic devices due to its high calculated dipole moment value (7.2 Debye) and lower HOMO-LUMO energy gap of 3.5 eV. Copyright © 2014 Elsevier B.V. All rights reserved.

Isobaric vapor-liquid equilibria for binary systems α-phenylethylamine + toluene and α-phenylethylamine + cyclohexane at 100 kPa

NASA Astrophysics Data System (ADS)

Wu, Xiaoru; Gao, Yingyu; Ban, Chunlan; Huang, Qiang

2016-09-01

In this paper the results of the vapor-liquid equilibria study at 100 kPa are presented for two binary systems: α-phenylethylamine(1) + toluene (2) and (α-phenylethylamine(1) + cyclohexane(2)). The binary VLE data of the two systems were correlated by the Wilson, NRTL, and UNIQUAC models. For each binary system the deviations between the results of the correlations and the experimental data have been calculated. For the both binary systems the average relative deviations in temperature for the three models were lower than 0.99%. The average absolute deviations in vapour phase composition (mole fractions) and in temperature T were lower than 0.0271 and 1.93 K, respectively. Thermodynamic consistency has been tested for all vapor-liquid equilibrium data by the Herrington method. The values calculated by Wilson and NRTL equations satisfied the thermodynamics consistency test for the both two systems, while the values calculated by UNIQUAC equation didn't.

The effects of rigid motions on elastic network model force constants

PubMed Central

Lezon, Timothy R.

2012-01-01

Elastic network models provide an efficient way to quickly calculate protein global dynamics from experimentally determined structures. The model’s single parameter, its force constant, determines the physical extent of equilibrium fluctuations. The values of force constants can be calculated by fitting to experimental data, but the results depend on the type of experimental data used. Here we investigate the differences between calculated values of force constants _t to data from NMR and X-ray structures. We find that X-ray B factors carry the signature of rigid-body motions, to the extent that B factors can be almost entirely accounted for by rigid motions alone. When fitting to more refined anisotropic temperature factors, the contributions of rigid motions are significantly reduced, indicating that the large contribution of rigid motions to B factors is a result of over-fitting. No correlation is found between force constants fit to NMR data and those fit to X-ray data, possibly due to the inability of NMR data to accurately capture protein dynamics. PMID:22228562

Ro-vibrational averaging of the isotropic hyperfine coupling constant for the methyl radical

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adam, Ahmad Y.; Jensen, Per, E-mail: jensen@uni-wuppertal.de; Yachmenev, Andrey

2015-12-28

We present the first variational calculation of the isotropic hyperfine coupling constant of the carbon-13 atom in the CH{sub 3} radical for temperatures T = 0, 96, and 300 K. It is based on a newly calculated high level ab initio potential energy surface and hyperfine coupling constant surface of CH{sub 3} in the ground electronic state. The ro-vibrational energy levels, expectation values for the coupling constant, and its temperature dependence were calculated variationally by using the methods implemented in the computer program TROVE. Vibrational energies and vibrational and temperature effects for coupling constant are found to be in verymore » good agreement with the available experimental data. We found, in agreement with previous studies, that the vibrational effects constitute about 44% of the constant’s equilibrium value, originating mainly from the large amplitude out-of-plane bending motion and that the temperature effects play a minor role.« less

Bifurcation and Stability Analysis of the Equilibrium States in Thermodynamic Systems in a Small Vicinity of the Equilibrium Values of Parameters

NASA Astrophysics Data System (ADS)

Barsuk, Alexandr A.; Paladi, Florentin

2018-04-01

The dynamic behavior of thermodynamic system, described by one order parameter and one control parameter, in a small neighborhood of ordinary and bifurcation equilibrium values of the system parameters is studied. Using the general methods of investigating the branching (bifurcations) of solutions for nonlinear equations, we performed an exhaustive analysis of the order parameter dependences on the control parameter in a small vicinity of the equilibrium values of parameters, including the stability analysis of the equilibrium states, and the asymptotic behavior of the order parameter dependences on the control parameter (bifurcation diagrams). The peculiarities of the transition to an unstable state of the system are discussed, and the estimates of the transition time to the unstable state in the neighborhood of ordinary and bifurcation equilibrium values of parameters are given. The influence of an external field on the dynamic behavior of thermodynamic system is analyzed, and the peculiarities of the system dynamic behavior are discussed near the ordinary and bifurcation equilibrium values of parameters in the presence of external field. The dynamic process of magnetization of a ferromagnet is discussed by using the general methods of bifurcation and stability analysis presented in the paper.

Computer Programs for Calculating and Plotting the Stability Characteristics of a Balloon Tethered in a Wind

NASA Technical Reports Server (NTRS)

Bennett, R. M.; Bland, S. R.; Redd, L. T.

1973-01-01

Computer programs for calculating the stability characteristics of a balloon tethered in a steady wind are presented. Equilibrium conditions, characteristic roots, and modal ratios are calculated for a range of discrete values of velocity for a fixed tether-line length. Separate programs are used: (1) to calculate longitudinal stability characteristics, (2) to calculate lateral stability characteristics, (3) to plot the characteristic roots versus velocity, (4) to plot the characteristic roots in root-locus form, (5) to plot the longitudinal modes of motion, and (6) to plot the lateral modes for motion. The basic equations, program listings, and the input and output data for sample cases are presented, with a brief discussion of the overall operation and limitations. The programs are based on a linearized, stability-derivative type of analysis, including balloon aerodynamics, apparent mass, buoyancy effects, and static forces which result from the tether line.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ivanov, A. A., E-mail: aai@a5.kiam.ru; Martynov, A. A., E-mail: martynov@a5.kiam.ru; Medvedev, S. Yu., E-mail: medvedev@a5.kiam.ru

In the MHD tokamak plasma theory, the plasma pressure is usually assumed to be isotropic. However, plasma heating by neutral beam injection and RF heating can lead to a strong anisotropy of plasma parameters and rotation of the plasma. The development of MHD equilibrium theory taking into account the plasma inertia and anisotropic pressure began a long time ago, but until now it has not been consistently applied in computational codes for engineering calculations of the plasma equilibrium and evolution in tokamak. This paper contains a detailed derivation of the axisymmetric plasma equilibrium equation in the most general form (withmore » arbitrary rotation and anisotropic pressure) and description of the specialized version of the SPIDER code. The original method of calculation of the equilibrium with an anisotropic pressure and a prescribed rotational transform profile is proposed. Examples of calculations and discussion of the results are also presented.« less

Spectroscopy peculiarities of thermal plasma of electric arc discharge between electrodes with Zn admixtures

NASA Astrophysics Data System (ADS)

Semenyshyn, R. V.; Veklich, A. N.; Babich, I. L.; Boretskij, V. F.

2014-10-01

Plasma of the free burning electric arc between Ag-SnO2-ZnO composite electrodes as well as brass electrodes were investigated. The plasma temperature distributions were obtained by Boltzmann plot method involving Cu I, Ag I or Zn I spectral line emissions. The electron density distributions were obtained from the width and from absolute intensity of spectral lines. The laser absorption spectroscopy was used for measurement of copper atom concentration in plasma. Plasma equilibrium composition was calculated using two independent groups of experimental values (temperature and copper atom concentration, temperature and electron density). It was found that plasma of the free burning electric arc between brass electrodes is in local thermodynamical equilibrium. The experimental verification of the spectroscopic data of Zn I spectral lines was carried out.

Rheological Predictions of Network Systems Swollen with Entangled Solvent

DTIC Science & Technology

2014-04-01

represent binary entanglements and the crosses represent cross-links. Both of which are fixed in space for Green– Kubo calculations or moved affinely for...Two types of calculations can be performed, equilibrium (or Green– Kubo ) calculations in which the rate of deformation tensor21,22 is set to zero and the...autocorrelation function of stress at equilibrium is followed; or flow calculations in which a specific flow field is applied and the stress as a

Comparison of rate constants for (PO3-) transfer by the Mg(II), Cd(II), and Li(I) forms of phosphoglucomutase.

PubMed

Ray, W J; Post, C B; Puvathingal, J M

1989-01-24

Net rate constants that define the steady-state rate through a sequence of steps and the corresponding effective energy barriers for two (PO3-)-transfer steps in the phosphoglucomutase reaction were compared as a function of metal ion, M, where M = Mg2+ and Cd2+. These steps involve the reaction of either the 1-phosphate or the 6-phosphate of glucose 1,6-bisphosphate (Glc-P2) bound to the dephosphoenzyme (ED) to produce the phosphoenzyme (EP) and the free monophosphates, glucose 1-phosphate (Glc-1-P) or glucose 6-phosphate (Glc-6-P): EP.M + Glc-1-P----ED.M.Glc-P2----EP.M.Glc-6-P6. Before this comparison was made, net rate constants for the Cd2+ enzyme, obtained at high enzyme concentration via 31P NMR saturation-transfer studies [Post, C. B., Ray, W. J., Jr., & Gorenstein, D. G. (1989) Biochemistry (preceding paper in this issue)], were appropriately scaled by using the observed constants to calculate both the expected isotope-transfer rate at equilibrium and the steady-state rate under initial velocity conditions and comparing the calculated values with those measured in dilute solution. For the Mg2+ enzyme, narrow limits on possible values of the corresponding net rate constants were imposed on the basis of initial velocity rate constants for the forward and reverse directions plus values for the equilibrium distribution of central complexes, since direct measurement is not feasible. The effective energy barriers for both the Mg2+ and Cd2+ enzymes, calculated from the respective net rate constants, together with previously values for the equilibrium distribution of complexes in both enzymic systems [Ray, W. J., Jr., & Long, J. W. (1976) Biochemistry 15, 4018-4025], show that the 100-fold decrease in the kappa cat for the Cd2+ relative to the Mg2+ enzyme is caused by two factors: the increased stability of the intermediate bisphosphate complex and the decreased ability to cope with the phosphate ester involving the 1-hydroxyl group of the glucose ring. In fact, it is unlikely that the efficiency of (PO3-) transfer to the 6-hydroxyl group of bound Glc-1-P (thermodynamically favorable direction) is reduced by more than an order of magnitude in the Cd2+ enzyme. By contrast, the efficiency of the Li+ enzyme in the same (PO3-)-transfer step is less than 4 x 10(-8) that of the Mg2+ enzyme.(ABSTRACT TRUNCATED AT 400 WORDS)

Photochemical ozone budget during the BIBLE A and B campaigns

NASA Astrophysics Data System (ADS)

Ko, Malcolm; Hu, Wenjie; Rodríguez, José M.; Kondo, Yutaka; Koike, Makoto; Kita, Kazuyuki; Kawakami, Shuji; Blake, Donald; Liu, Shaw; Ogawa, Toshihiro

2003-02-01

Using the measured concentrations of NO, O3, H2O, CO, CH4, and NMHCs along the flight tracks, a photochemical box model is used to calculate the concentrations of the Ox radicals, the HOx radicals, and the nitrogen species at the sampling points. The calculations make use of the measurements from radiometers to scale clear sky photolysis rates to account for cloud cover and ground albedo at the sampling time/point. The concentrations of the nitrogen species in each of the sampled air parcels are computed assuming they are in instantaneous equilibrium with the measured NO and O3. The diurnally varying species concentrations are next calculated using the box model and used to estimate the diurnally averaged production and removal rates of ozone for the sampled air parcels. Clear sky photolysis rates are used in the diurnal calculations. The campaign also provided measured concentration of NOy. The observed NO/NOy ratio is usually larger than the model calculated equilibrium value. There are several possible explanations. It could be a result of recent injection of NO into the air parcel, recent removal of HNO3 from the parcel, recent rapid transport of an air parcel from another location, or a combination of all processes. Our analyses suggest that the local production rate of O3 can be used as another indicator of recent NO injection. However, more direct studies using air trajectory analyses and other collaborative evidences are needed to ascertain the roles played by individual process.

Photochemical ozone budget during the BIBLE A and B campaigns

NASA Astrophysics Data System (ADS)

Ko, Malcolm; Hu, Wenjie; RodríGuez, José M.; Kondo, Yutaka; Koike, Makoto; Kita, Kazuyuki; Kawakami, Shuji; Blake, Donald; Liu, Shaw; Ogawa, Toshihiro

2002-02-01

Using the measured concentrations of NO, O3, H2O, CO, CH4, and NMHCs along the flight tracks, a photochemical box model is used to calculate the concentrations of the Ox radicals, the HOx radicals, and the nitrogen species at the sampling points. The calculations make use of the measurements from radiometers to scale clear sky photolysis rates to account for cloud cover and ground albedo at the sampling time/point. The concentrations of the nitrogen species in each of the sampled air parcels are computed assuming they are in instantaneous equilibrium with the measured NO and O3. The diurnally varying species concentrations are next calculated using the box model and used to estimate the diurnally averaged production and removal rates of ozone for the sampled air parcels. Clear sky photolysis rates are used in the diurnal calculations. The campaign also provided measured concentration of NOy. The observed NO/NOy ratio is usually larger than the model calculated equilibrium value. There are several possible explanations. It could be a result of recent injection of NO into the air parcel, recent removal of HNO3 from the parcel, recent rapid transport of an air parcel from another location, or a combination of all processes. Our analyses suggest that the local production rate of O3 can be used as another indicator of recent NO injection. However, more direct studies using air trajectory analyses and other collaborative evidences are needed to ascertain the roles played by individual process.

Shock melting and vaporization of lunar rocks and minerals.

NASA Technical Reports Server (NTRS)

Ahrens, T. J.; O'Keefe, J. D.

1972-01-01

The entropy associated with the thermodynamic states produced by hypervelocity meteoroid impacts at various velocities are calculated for a series of lunar rocks and minerals and compared with the entropy values required for melting and vaporization. Taking into account shock-induced phase changes in the silicates, we calculate that iron meteorites impacting at speeds varying from 4 to 6 km/sec will produce shock melting in quartz, plagioclase, olivine, and pyroxene. Although calculated with less certainty, impact speeds required for incipient vaporization vary from 7 to 11 km/sec for the range of minerals going from quartz to periclase for aluminum (silicate-like) projectiles. The impact velocities, which are required to induce melting in a soil, are calculated to be in the range of 3 to 4 km/sec, provided thermal equilibrium is achieved in the shock state.

Out-of-equilibrium relaxation of the thermal Casimir effect in a model polarizable material

NASA Astrophysics Data System (ADS)

Dean, David S.; Démery, Vincent; Parsegian, V. Adrian; Podgornik, Rudolf

2012-03-01

Relaxation of the thermal Casimir or van der Waals force (the high temperature limit of the Casimir force) for a model dielectric medium is investigated. We start with a model of interacting polarization fields with a dynamics that leads to a frequency dependent dielectric constant of the Debye form. In the static limit, the usual zero frequency Matsubara mode component of the Casimir force is recovered. We then consider the out-of-equilibrium relaxation of the van der Waals force to its equilibrium value when two initially uncorrelated dielectric bodies are brought into sudden proximity. For the interaction between dielectric slabs, it is found that the spatial dependence of the out-of-equilibrium force is the same as the equilibrium one, but it has a time dependent amplitude, or Hamaker coefficient, which increases in time to its equilibrium value. The final relaxation of the force to its equilibrium value is exponential in systems with a single or finite number of polarization field relaxation times. However, in systems, such as those described by the Havriliak-Negami dielectric constant with a broad distribution of relaxation times, we observe a much slower power law decay to the equilibrium value.

Particle orbits in two-dimensional equilibrium models for the magnetotail

NASA Technical Reports Server (NTRS)

Karimabadi, H.; Pritchett, P. L.; Coroniti, F. V.

1990-01-01

Assuming that there exist an equilibrium state for the magnetotail, particle orbits are investigated in two-dimensional kinetic equilibrium models for the magnetotail. Particle orbits in the equilibrium field are compared with those calculated earlier with one-dimensional models, where the main component of the magnetic field (Bx) was approximated as either a hyperbolic tangent or a linear function of z with the normal field (Bz) assumed to be a constant. It was found that the particle orbits calculated with the two types of models are significantly different, mainly due to the neglect of the variation of Bx with x in the one-dimensional fields.

[The accuracy of rapid equilibrium assumption in steady-state enzyme kinetics is the function of equilibrium segment structure and properties].

PubMed

Vrzheshch, P V

2015-01-01

Quantitative evaluation of the accuracy of the rapid equilibrium assumption in the steady-state enzyme kinetics was obtained for an arbitrary mechanism of an enzyme-catalyzed reaction. This evaluation depends only on the structure and properties of the equilibrium segment, but doesn't depend on the structure and properties of the rest (stationary part) of the kinetic scheme. The smaller the values of the edges leaving equilibrium segment in relation to values of the edges within the equilibrium segment, the higher the accuracy of determination of intermediate concentrations and reaction velocity in a case of the rapid equilibrium assumption.

Simultaneous separation and purification of chlorogenic acid, epicatechin, hyperoside and phlorizin from thinned young Qinguan apples by successive use of polyethylene and polyamide resins.

PubMed

Sun, Lijun; Liu, Dongjie; Sun, Jiaojiao; Yang, Xingbin; Fu, Minghai; Guo, Yurong

2017-09-01

The method for separating and purifying chlorogenic acid (CA), epicatechin (EC), hyperoside (HY) and phlorizin (PH) simutaneously from young Qinguan apples by successive use of X-5 and polyamide resins has been developed in this study. The order of adsorption capacities of X-5 for the four phenolics was PH>HY>EC>CA, and the adsorption equilibriums of the four phenolics onto X-5 resin conformed to Langmuir isotherms preferentially. The adsorption kinetics of EC and CA onto X-5 conformed to the pseudo-first-order model, while that of HY and PH accorded with the pseudo-second-order model. Interestingly, the values of equilibrium adsorption capacities (Q e ) calculated in the preferential kinetics models were closer to that of theoretical maximum adsorption capacities (Q 0 ) calculated by Langmuir isotherms. Through dynamic adsorption and desorption using X-5 and polyamide resins with ethanol solution as strippant, CA, EC, HY and PH were obtained with purities of 96.21%, 95.34%, 95.36% and 97.36%, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

Strain-induced topological quantum phase transition in phosphorene oxide

NASA Astrophysics Data System (ADS)

Kang, Seoung-Hun; Park, Jejune; Woo, Sungjong; Kwon, Young-Kyun

Using ab initio density functional theory, we investigate the structural stability and electronic properties of phosphorene oxides (POx) with different oxygen compositions x. A variety of configurations are modeled and optimized geometrically to search for the equilibrium structure for each x value. Our electronic structure calculations on the equilibrium configuration obtained for each x reveal that the band gap tends to increase with the oxygen composition of x < 0.5, and then to decrease with x > 0.5. We further explore the strain effect on the electronic structure of the fully oxidized phosphorene, PO, with x = 1. At a particular strain without spin-orbit coupling (SOC) is observed a band gap closure near the Γ point in the k space. We further find the strain in tandem with SOC induces an interesting band inversion with a reopened very small band gap (5 meV), and thus gives rise to a topological quantum phase transition from a normal insulator to a topological insulator. Such a topological phase transition is confirmed by the wave function analysis and the band topology identified by the Z2 invariant calculation.

Adsorption of Zinc(II) on diatomite and manganese-oxide-modified diatomite: a kinetic and equilibrium study.

PubMed

Caliskan, Necla; Kul, Ali Riza; Alkan, Salih; Sogut, Eda Gokirmak; Alacabey, Ihsan

2011-10-15

The removal of Zn(II) ions from aqueous solution was studied using natural and MnO(2) modified diatomite samples at different temperatures. The linear Langmuir, Freundlich and Dubinin-Radushkevich (D-R) adsorption equations were applied to describe the equilibrium isotherms. From the D-R model, the mean adsorption energy was calculated as >8 kJ mol(-1), indicating that the adsorption of Zn(II) onto diatomite and Mn-diatomite was physically carried out. In addition, the pseudo-first-order, pseudo-second-order and intraparticle diffusion models were used to determine the kinetic data. The experimental data were well fitted by the pseudo-second-order kinetic model. Thermodynamic parameters such as the enthalpy (ΔH(0)), Gibbs' free energy (ΔG(0)) and entropy (ΔS(0)) were calculated for natural and MnO(2) modified diatomite. These values showed that the adsorption of Zn(II) ions onto diatomite samples was controlled by a physical mechanism and occurred spontaneously. Copyright © 2011 Elsevier B.V. All rights reserved.

Effect of accelerated aging on the cross-link density of medical grade silicones.

PubMed

Mahomed, Aziza; Pormehr, Negin Bagheri

2016-11-25

Four specimens of Nagor silicone of different hardness (soft, medium and hard) were swollen, until they reached equilibrium (i.e. constant mass) in five liquids at 25°C, before and after accelerated aging. For the specimens swollen before accelerated aging, the greatest swelling was obtained in methyl cyclohexane, while for the specimens swollen after accelerated aging, the greatest swelling was obtained in cyclohexane. The cross-link density, υ, was also calculated from the swelling measurements for all the specimens, before and after accelerated aging, using the Flory-Rehner equation. The softer silicones, which swelled the most, had lower υ values than harder silicones. The amount of swelling (measured in terms of ϕ) and υ varied significantly (p<0.05) in some cases, between the different silicone hardness and between different liquids. Furthermore, the cross-link density, υ, significantly (p<0.05) increased after accelerated aging in most liquids.Note: ϕ is defined as the volume fraction of polymer in its equilibrium swollen state. A probability value of statistical significance of 0.05 or 5% was selected, hence if a p value of less than 0.05 was obtained, the null hypothesis was rejected (i.e. significant if p<0.05).

Determination of Oxygen Fugacity using Olivine-Melt Equilibrium: Implications for the Redox States of Mid-Ocean Ridge Basalt, Ocean Island Basalt, and Island Arc Basalt Mantle Source Regions

NASA Astrophysics Data System (ADS)

Peterman, K. J.; Bryson, S.; Rilling-Hall, S.; Barton, M.

2017-12-01

In order to connect volcanic rocks to their mantle sources, it is essential to consider redox equilibria and their dependence on temperature, pressure, chemical composition, and oxygen fugacity. Oxygen fugacity (fO2) is an intensive variable that strongly affects the behavior of those elements in magmas that are sensitive to changes in redox state, such as Fe, and therefore Mg-Fe silicates, such as olivine. Since fO2 plays an important role in fractional crystallization, in principle it is possible to estimate fO2 from analyses of olivine in equilibrium with the melt. This research describes a new method based on this principle called the Olivine-Melt Equilibrium Method. The Fe3+ and Fe2+ contents of melt in equilibrium with olivine are calculated from the relationship of Gee and Sack (1988) that describes the partitioning of Mg and Fe2+ between olivine and melt. The Fe3+ and Fe2+ contents of the melt are then used to calculate the fO2 at which olivine and melt are in equilibrium using the model of Kress and Carmichael (1991) for the relationship between Fe3+/Fe2+ , fO2, T, P, and melt composition. We have calculated oxygen fugacities from published analyses of coexisting glass and olivine pairs in 1020 samples from three different tectonic settings. The results (expressed as ΔFMQ) for Mid-Ocean Ridge Basalts from the Mid-Atlantic Ridge (-1.55 ± 0.75), the East Pacific Rise (-0.65 ± 0.51), the Juan de Fuca Ridge (-0.77 ± 0.42), and the Galápagos Spreading Center (+0.08 ± 0.48) agree with results obtained using other methods and average -1.09 ± 0.89. Ocean Island Basalts from Iceland and the Galápagos Islands (ΔFMQ = -0.43 ± 0.71 and -0.33 ± 0.35 respectively) also yield values consistent with those obtained by other methods and fall in the same range as MORB. However, lavas from the Canary Islands are more oxidized than typical MORB and OIB, with values (average = +0.68 ± 0.52) approaching those for island arc magmas. We obtain ΔFMQ = +1.03 ± 0.52 for olivine-melt pairs from Sunda arc basalts. The results for MORB and OIB potentially provide evidence for redox heterogeneity in the mantle, possibly as the result of crustal recycling. However it is necessary to evaluate the possibility that fO2 changes during magma ascent before concluding that the oxygen fugacities of erupted magmas directly reflect those of the mantle source regions.

FORTRAN 4 computer program for calculation of thermodynamic and transport properties of complex chemical systems

NASA Technical Reports Server (NTRS)

Svehla, R. A.; Mcbride, B. J.

1973-01-01

A FORTRAN IV computer program for the calculation of the thermodynamic and transport properties of complex mixtures is described. The program has the capability of performing calculations such as:(1) chemical equilibrium for assigned thermodynamic states, (2) theoretical rocket performance for both equilibrium and frozen compositions during expansion, (3) incident and reflected shock properties, and (4) Chapman-Jouguet detonation properties. Condensed species, as well as gaseous species, are considered in the thermodynamic calculation; but only the gaseous species are considered in the transport calculations.

Proton bombarded reactions of Calcium target nuclei

NASA Astrophysics Data System (ADS)

Tel, Eyyup; Sahan, Muhittin; Sarpün, Ismail Hakki; Kavun, Yusuf; Gök, Ali Armagan; Depedelen, Mesut

2017-09-01

In this study, proton bombarded nuclear reactions calculations of Calcium target nuclei have been investigated in the incident proton energy range of 1-50 MeV. The excitation functions for 40Ca target nuclei reactions have been calculated by using PCROSS nuclear reaction calculation code. Weisskopf-Ewing and the full exciton models were used for equilibrium and for pre-equilibrium calculations, respectively. The excitation functions for 40Ca target nuclei reactions (p,α), (p,n), (p,p) have been calculated using the semi-empirical formula Tel et al. [5].

Metastability in the Spin-1 Blume-Emery-Griffiths Model within Constant Coupling Approximation

NASA Astrophysics Data System (ADS)

Ekiz, C.

2017-02-01

In this paper, the equilibrium properties of spin-1 Blume-Emery-Griffiths model are studied by using constant-coupling approximation. The dipolar and quadrupolar order parameters, the stable, metastable and unstable states and free energy of the model are investigated. The states are defined in terms of local minima of the free energy of system. The numerical calculations are presented for several values of exchange interactions on the simple cubic lattice with q = 6.

Kinetic Theory of Reactive Molecular Gases

DTIC Science & Technology

2009-09-01

vibrational non-equilibrium, i.e. 1 V V VD VD D V E E E E k k E kT               , (35) where VDE represents the...162 The term VDE , is calculated at first order, like Dk . We can note that realistic values for VDE lie in the range 0.3-0.5 DE [13]. In

Computing Properties Of Chemical Mixtures At Equilibrium

NASA Technical Reports Server (NTRS)

Mcbride, B. J.; Gordon, S.

1995-01-01

Scientists and engineers need data on chemical equilibrium compositions to calculate theoretical 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 is general program that calculates chemical equilibrium compositions and properties of mixtures for any chemical system for which thermodynamic data are available. Includes thermodynamic data for more than 1,300 gaseous and condensed species and thermal-transport data for 151 gases. Written in FORTRAN 77.

Electrophoretic Study of the SnO2/Aqueous Solution Interface up to 260 degrees C.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rodriguez-Santiago, V; Fedkin, Mark V.; Wesolowski, David J

2009-01-01

An electrophoresis cell developed in our laboratory was utilized to determine the zeta potential at the SnO{sub 2} (cassiterite)/aqueous solution (10{sup -3} mol kg{sup -1} NaCl) interface over the temperature range from 25 to 260 C. Experimental techniques and methods for the calculation of zeta potential at elevated temperature are described. From the obtained zeta potential data as a function of pH, the isoelectric points (IEPs) of SnO{sub 2} were obtained for the first time. From these IEP values, the standard thermodynamic functions were calculated for the protonation-deprotonation equilibrium at the SnO{sub 2} surface, using the 1-pK surface complexation model.more » It was found that the IEP values for SnO{sub 2} decrease with increasing temperature, and this behavior is compared to the predicted values by the multisite complexation (MUSIC) model and other semitheoretical treatments, and were found to be in excellent agreement.« less

Computer program determines chemical composition of physical system at equilibrium

NASA Technical Reports Server (NTRS)

Kwong, S. S.

1966-01-01

FORTRAN 4 digital computer program calculates equilibrium composition of complex, multiphase chemical systems. This is a free energy minimization method with solution of the problem reduced to mathematical operations, without concern for the chemistry involved. Also certain thermodynamic properties are determined as byproducts of the main calculations.

Calculating Shocks In Flows At Chemical Equilibrium

NASA Technical Reports Server (NTRS)

Eberhardt, Scott; Palmer, Grant

1988-01-01

Boundary conditions prove critical. Conference paper describes algorithm for calculation of shocks in hypersonic flows of gases at chemical equilibrium. Although algorithm represents intermediate stage in development of reliable, accurate computer code for two-dimensional flow, research leading up to it contributes to understanding of what is needed to complete task.

Structure and binding energy of the H2S dimer at the CCSD(T) complete basis set limit.

PubMed

Lemke, Kono H

2017-06-21

This study presents results for the binding energy and geometry of the H 2 S dimer which have been computed using Møller-Plesset perturbation theory (MP2, MP4) and coupled cluster (CCSD, CCSD(T)) calculations with basis sets up to aug-cc-pV5Z. Estimates of D e , E ZPE , D o , and dimer geometry have been obtained at each level of theory by taking advantage of the systematic convergence behavior toward the complete basis set (CBS) limit. The CBS limit binding energy values of D e are 1.91 (MP2), 1.75 (MP4), 1.41 (CCSD), and 1.69 kcal/mol (CCSD[T]). The most accurate values for the equilibrium S-S distance r SS (without counterpoise correction) are 4.080 (MP2/aug-cc-pV5Z), 4.131 (MP4/aug-cc-pVQZ), 4.225 (CCSD/aug-cc-pVQZ), and 4.146 Å (CCSD(T)/aug-cc-pVQZ). This study also evaluates the effect of counterpoise correction on the H 2 S dimer geometry and binding energy. As regards the structure of (H 2 S) 2 , MPn, CCSD, and CCSD(T) level values of r SS , obtained by performing geometry optimizations on the counterpoise-corrected potential energy surface, converge systematically to CBS limit values of 4.099 (MP2), 4.146 (MP4), 4.233 (CCSD), and 4.167 Å (CCSD(T)). The corresponding CBS limit values of the equilibrium binding energy D e are 1.88 (MP2), 1.76 (MP4), 1.41 (CCSD), and 1.69 kcal/mol (CCSD(T)), the latter in excellent agreement with the measured binding energy value of 1.68 ± 0.02 kcal/mol reported by Ciaffoni et al. [Appl. Phys. B 92, 627 (2008)]. Combining CBS electronic binding energies D e with E ZPE predicted by CCSD(T) vibrational second-order perturbation theory calculations yields D o = 1.08 kcal/mol, which is around 0.6 kcal/mol smaller than the measured value of 1.7 ± 0.3 kcal/mol. Overall, the results presented here demonstrate that the application of high level calculations, in particular CCSD(T), in combination with augmented correlation consistent basis sets provides valuable insight into the structure and energetics of the hydrogen sulfide dimer.

Structure and binding energy of the H2S dimer at the CCSD(T) complete basis set limit

NASA Astrophysics Data System (ADS)

Lemke, Kono H.

2017-06-01

This study presents results for the binding energy and geometry of the H2S dimer which have been computed using Møller-Plesset perturbation theory (MP2, MP4) and coupled cluster (CCSD, CCSD(T)) calculations with basis sets up to aug-cc-pV5Z. Estimates of De, EZPE, Do, and dimer geometry have been obtained at each level of theory by taking advantage of the systematic convergence behavior toward the complete basis set (CBS) limit. The CBS limit binding energy values of De are 1.91 (MP2), 1.75 (MP4), 1.41 (CCSD), and 1.69 kcal/mol (CCSD[T]). The most accurate values for the equilibrium S-S distance rSS (without counterpoise correction) are 4.080 (MP2/aug-cc-pV5Z), 4.131 (MP4/aug-cc-pVQZ), 4.225 (CCSD/aug-cc-pVQZ), and 4.146 Å (CCSD(T)/aug-cc-pVQZ). This study also evaluates the effect of counterpoise correction on the H2S dimer geometry and binding energy. As regards the structure of (H2S)2, MPn, CCSD, and CCSD(T) level values of rSS, obtained by performing geometry optimizations on the counterpoise-corrected potential energy surface, converge systematically to CBS limit values of 4.099 (MP2), 4.146 (MP4), 4.233 (CCSD), and 4.167 Å (CCSD(T)). The corresponding CBS limit values of the equilibrium binding energy De are 1.88 (MP2), 1.76 (MP4), 1.41 (CCSD), and 1.69 kcal/mol (CCSD(T)), the latter in excellent agreement with the measured binding energy value of 1.68 ± 0.02 kcal/mol reported by Ciaffoni et al. [Appl. Phys. B 92, 627 (2008)]. Combining CBS electronic binding energies De with EZPE predicted by CCSD(T) vibrational second-order perturbation theory calculations yields Do = 1.08 kcal/mol, which is around 0.6 kcal/mol smaller than the measured value of 1.7 ± 0.3 kcal/mol. Overall, the results presented here demonstrate that the application of high level calculations, in particular CCSD(T), in combination with augmented correlation consistent basis sets provides valuable insight into the structure and energetics of the hydrogen sulfide dimer.

DFT and AIM study of the protonation of nitrous acid and the pKa of nitrous acidium ion.

PubMed

Crugeiras, Juan; Ríos, Ana; Maskill, Howard

2011-11-10

The gas phase and aqueous thermochemistry, NMR chemical shifts, and the topology of chemical bonding of nitrous acid (HONO) and nitrous acidium ion (H(2)ONO(+)) have been investigated by ab initio methods using density functional theory. By the same methods, the dissociation of H(2)ONO(+) to give the nitrosonium ion (NO(+)) and water has also been investigated. We have used Becke's hybrid functional (B3LYP), and geometry optimizations were performed with the 6-311++G(d,p) basis set. In addition, highly accurate ab initio composite methods (G3 and CBS-Q) were used. Solvation energies were calculated using the conductor-like polarizable continuum model, CPCM, at the B3LYP/6-311++G(d,p) level of theory, with the UAKS cavity model. The pK(a) value of H(2)ONO(+) was calculated using two different schemes: the direct method and the proton exchange method. The calculated pK(a) values at different levels of theory range from -9.4 to -15.6, showing that H(2)ONO(+) is a strong acid (i.e., HONO is only a weak base). The equilibrium constant, K(R), for protonation of nitrous acid followed by dissociation to give NO(+) and H(2)O has also been calculated using the same methodologies. The pK(R) value calculated by the G3 and CBS-QB3 methods is in best (and satisfactory) agreement with experimental results, which allows us to narrow down the likely value of the pK(a) of H(2)ONO(+) to about -10, a value appreciably more acidic than literature values.

Thermodynamics of enzyme-catalyzed esterifications: II. Levulinic acid esterification with short-chain alcohols.

PubMed

Altuntepe, Emrah; Emel'yanenko, Vladimir N; Forster-Rotgers, Maximilian; Sadowski, Gabriele; Verevkin, Sergey P; Held, Christoph

2017-10-01

Levulinic acid was esterified with methanol, ethanol, and 1-butanol with the final goal to predict the maximum yield of these equilibrium-limited reactions as function of medium composition. In a first step, standard reaction data (standard Gibbs energy of reaction Δ R g 0 ) were determined from experimental formation properties. Unexpectedly, these Δ R g 0 values strongly deviated from data obtained with classical group contribution methods that are typically used if experimental standard data is not available. In a second step, reaction equilibrium concentrations obtained from esterification catalyzed by Novozym 435 at 323.15 K were measured, and the corresponding activity coefficients of the reacting agents were predicted with perturbed-chain statistical associating fluid theory (PC-SAFT). The so-obtained thermodynamic activities were used to determine Δ R g 0 at 323.15 K. These results could be used to cross-validate Δ R g 0 from experimental formation data. In a third step, reaction-equilibrium experiments showed that equilibrium position of the reactions under consideration depends strongly on the concentration of water and on the ratio of levulinic acid: alcohol in the initial reaction mixtures. The maximum yield of the esters was calculated using Δ R g 0 data from this work and activity coefficients of the reacting agents predicted with PC-SAFT for varying feed composition of the reaction mixtures. The use of the new Δ R g 0 data combined with PC-SAFT allowed good agreement to the measured yields, while predictions based on Δ R g 0 values obtained with group contribution methods showed high deviations to experimental yields.

A "User-Friendly" Program for Vapor-Liquid Equilibrium.

ERIC Educational Resources Information Center

Da Silva, Francisco A.; And Others

1991-01-01

Described is a computer software package suitable for teaching and research in the area of multicomponent vapor-liquid equilibrium. This program, which has a complete database, can accomplish phase-equilibrium calculations using various models and graph the results. (KR)

Determination of CEC value (Cation Exchange Capacity) of Bentonites from North Aceh and Bener Meriah, Aceh Province, Indonesia using three methods

NASA Astrophysics Data System (ADS)

Rihayat, T.; Salim, S.; Arlina, A.; Fona, Z.; Jalal, R.; Alam, P. N.; Zaimahwati; Sami, M.; Syarif, J.; Juhan, N.

2018-03-01

Research on determination of value CEC (Cation Exchange Capacity) Bentonite North Aceh and Bener Meriah with three methods has been studied. The purpose of this study was to determine the value of CEC bentonite North Aceh and Bener Meriah. The methods used in this research were pH equilibrium, BaCl2/MgSO4 and the adsorption of methylene blue. These three methods used to determine, compare, and calculation of the CEC value and determine the effect of particle size of bentonite on the value of the CEC. Bentonite North Aceh and Bener Meriah sieved with particle sizes of 80, 100, 150, 200, 250 mesh. The results showed that determination of the value of CEC bentonite North Aceh using BaCl2/MgSO4 with a particle size of 250 mesh is the value of the highest, reaching 79.09 meq/100 g.

Ranking nano-enabled hybrid media for simultaneous removal of contaminants with different chemistries: Pseudo-equilibrium sorption tests versus column tests.

PubMed

Custodio, Tomas; Garcia, Jose; Markovski, Jasmina; McKay Gifford, James; Hristovski, Kiril D; Olson, Larry W

2017-12-15

The underlying hypothesis of this study was that pseudo-equilibrium and column testing conditions would provide the same sorbent ranking trends although the values of sorbents' performance descriptors (e.g. sorption capacity) may vary because of different kinetics and competition effects induced by the two testing approaches. To address this hypothesis, nano-enabled hybrid media were fabricated and its removal performances were assessed for two model contaminants under multi-point batch pseudo-equilibrium and continuous-flow conditions. Calculation of simultaneous removal capacity indices (SRC) demonstrated that the more resource demanding continuous-flow tests are able to generate the same performance rankings as the ones obtained by conducing the simpler pseudo-equilibrium tests. Furthermore, continuous overlap between the 98% confidence boundaries for each SRC index trend, not only validated the hypothesis that both testing conditions provide the same ranking trends, but also pointed that SRC indices are statistically the same for each media, regardless of employed method. In scenarios where rapid screening of new media is required to obtain the best performing synthesis formulation, use of pseudo-equilibrium tests proved to be reliable. Considering that kinetics induced effects on sorption capacity must not be neglected, more resource demanding column test could be conducted only with the top performing media that exhibit the highest sorption capacity. Copyright © 2017 Elsevier B.V. All rights reserved.

Underlying thermodynamics of pH-dependent allostery.

PubMed

Di Russo, Natali V; Martí, Marcelo A; Roitberg, Adrian E

2014-11-13

Understanding the effects of coupling protein protonation and conformational states is critical to the development of drugs targeting pH sensors and to the rational engineering of pH switches. In this work, we address this issue by performing a comprehensive study of the pH-regulated switch from the closed to the open conformation in nitrophorin 4 (NP4) that determines its pH-dependent activity. Our calculations show that D30 is the only amino acid that has two significantly different pKas in the open and closed conformations, confirming its critical role in regulating pH-dependent behavior. In addition, we describe the free-energy landscape of the conformational change as a function of pH, obtaining accurate estimations of free-energy barriers and equilibrium constants using different methods. The underlying thermodynamic model of the switch workings suggests the possibility of tuning the observed pKa only through the conformational equilibria, keeping the same conformation-specific pKas, as evidenced by the proposed K125L mutant. Moreover, coupling between the protonation and conformational equilibria results in efficient regulation and pH-sensing around physiological pH values only for some combinations of protonation and conformational equilibrium constants, placing constraints on their possible values and leaving a narrow space for protein molecular evolution. The calculations and analysis presented here are of general applicability and provide a guide as to how more complex systems can be studied, offering insight into how pH-regulated allostery works of great value for designing drugs that target pH sensors and for rational engineering of pH switches beyond the common histidine trigger.

Polydimethylsiloxane-air partition ratios for semi-volatile organic compounds by GC-based measurement and COSMO-RS estimation: Rapid measurements and accurate modelling.

PubMed

Okeme, Joseph O; Parnis, J Mark; Poole, Justen; Diamond, Miriam L; Jantunen, Liisa M

2016-08-01

Polydimethylsiloxane (PDMS) shows promise for use as a passive air sampler (PAS) for semi-volatile organic compounds (SVOCs). To use PDMS as a PAS, knowledge of its chemical-specific partitioning behaviour and time to equilibrium is needed. Here we report on the effectiveness of two approaches for estimating the partitioning properties of polydimethylsiloxane (PDMS), values of PDMS-to-air partition ratios or coefficients (KPDMS-Air), and time to equilibrium of a range of SVOCs. Measured values of KPDMS-Air, Exp' at 25 °C obtained using the gas chromatography retention method (GC-RT) were compared with estimates from a poly-parameter free energy relationship (pp-FLER) and a COSMO-RS oligomer-based model. Target SVOCs included novel flame retardants (NFRs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), organophosphate flame retardants (OPFRs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). Significant positive relationships were found between log KPDMS-Air, Exp' and estimates made using the pp-FLER model (log KPDMS-Air, pp-LFER) and the COSMOtherm program (log KPDMS-Air, COSMOtherm). The discrepancy and bias between measured and predicted values were much higher for COSMO-RS than the pp-LFER model, indicating the anticipated better performance of the pp-LFER model than COSMO-RS. Calculations made using measured KPDMS-Air, Exp' values show that a PDMS PAS of 0.1 cm thickness will reach 25% of its equilibrium capacity in ∼1 day for alpha-hexachlorocyclohexane (α-HCH) to ∼ 500 years for tris (4-tert-butylphenyl) phosphate (TTBPP), which brackets the volatility range of all compounds tested. The results presented show the utility of GC-RT method for rapid and precise measurements of KPDMS-Air. Copyright © 2016. Published by Elsevier Ltd.

Monte Carlo simulation of photon buildup factors for shielding materials in diagnostic x-ray facilities.

PubMed

Kharrati, Hedi; Agrebi, Amel; Karoui, Mohamed Karim

2012-10-01

A simulation of buildup factors for ordinary concrete, steel, lead, plate glass, lead glass, and gypsum wallboard in broad beam geometry for photons energies from 10 keV to 150 keV at 5 keV intervals is presented. Monte Carlo N-particle radiation transport computer code has been used to determine the buildup factors for the studied shielding materials. An example concretizing the use of the obtained buildup factors data in computing the broad beam transmission for tube potentials at 70, 100, 120, and 140 kVp is given. The half value layer, the tenth value layer, and the equilibrium tenth value layer are calculated from the broad beam transmission for these tube potentials. The obtained values compared with those calculated from the published data show the ability of these data to predict shielding transmission curves. Therefore, the buildup factors data can be combined with primary, scatter, and leakage x-ray spectra to provide a computationally based solution to broad beam transmission for barriers in shielding x-ray facilities.

Monte Carlo simulation of photon buildup factors for shielding materials in diagnostic x-ray facilities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kharrati, Hedi; Agrebi, Amel; Karoui, Mohamed Karim

2012-10-15

Purpose: A simulation of buildup factors for ordinary concrete, steel, lead, plate glass, lead glass, and gypsum wallboard in broad beam geometry for photons energies from 10 keV to 150 keV at 5 keV intervals is presented. Methods: Monte Carlo N-particle radiation transport computer code has been used to determine the buildup factors for the studied shielding materials. Results: An example concretizing the use of the obtained buildup factors data in computing the broad beam transmission for tube potentials at 70, 100, 120, and 140 kVp is given. The half value layer, the tenth value layer, and the equilibrium tenthmore » value layer are calculated from the broad beam transmission for these tube potentials. Conclusions: The obtained values compared with those calculated from the published data show the ability of these data to predict shielding transmission curves. Therefore, the buildup factors data can be combined with primary, scatter, and leakage x-ray spectra to provide a computationally based solution to broad beam transmission for barriers in shielding x-ray facilities.« less

Computational chemical analysis of unconjugated bilirubin anions and insights into pKa values clarification

NASA Astrophysics Data System (ADS)

Vega-Hissi, Esteban G.; Estrada, Mario R.; Lavecchia, Martín J.; Pis Diez, Reinaldo

2013-01-01

The pKa, the negative logarithm of the acid dissociation equilibrium constant, of the carboxylic acid groups of unconjugated bilirubin in water is a discussed issue because there are quite different experimental values reported. Using quantum mechanical calculations we have studied the conformational behavior of unconjugated bilirubin species (in gas phase and in solution modeled implicitly and explicitly) to provide evidence that may clarify pKa values because of its pathophysiological relevance. Our results show that rotation of carboxylate group, which is not restricted, settles it in a suitable place to establish stronger interactions that stabilizes the monoanion and the dianion to be properly solvated, demonstrating that the rationalization used to justify the high pKa values of unconjugated bilirubin is inappropriate. Furthermore, low unconjugated bilirubin (UCB) pKa values were estimated from a linear regression analysis.

Arginine: Its pKa value revisited

PubMed Central

Fitch, Carolyn A; Platzer, Gerald; Okon, Mark; Garcia-Moreno E, Bertrand; McIntosh, Lawrence P

2015-01-01

Using complementary approaches of potentiometry and NMR spectroscopy, we have determined that the equilibrium acid dissociation constant (pKa value) of the arginine guanidinium group is 13.8 ± 0.1. This is substantially higher than that of ∼12 often used in structure-based electrostatics calculations and cited in biochemistry textbooks. The revised intrinsic pKa value helps explains why arginine side chains in proteins are always predominantly charged, even at pH values as great as 10. The high pKa value also reinforces the observation that arginine side chains are invariably protonated under physiological conditions of near neutral pH. This occurs even when the guanidinium moiety is buried in a hydrophobic micro-environment, such as that inside a protein or a lipid membrane, thought to be incompatible with the presence of a charged group. PMID:25808204

Theoretical modeling of the urinary supersaturation of calcium salts in healthy individuals and kidney stone patients: Precursors, speciation and therapeutic protocols for decreasing its value

NASA Astrophysics Data System (ADS)

Rodgers, Allen L.; Allie-Hamdulay, Shameez; Jackson, Graham E.; Durbach, Ian

2013-11-01

BackgroundSupersaturation (SS) of urinary salts has been extensively invoked for assessing the risk of renal stone formation, but precursors have often been ignored. Our objectives were to establish by computer modeling, which urinary components are essential for calculating reliable SS values, to investigate whether unique equilibrium processes occur in the urine of stone formers (SF) which might account for their higher SS levels relative to healthy controls (N), to determine the relative efficacies of three different, widely-used protocols for lowering urinary SS of calcium salts and to examine the influence of precursors.

Alloying effects on structural and thermal behavior of Ti{sub 1-x}Zr{sub x}C: A first principles study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chauhan, Mamta, E-mail: mamta-physics@yahoo.co.in; Gupta, Dinesh C., E-mail: sosfizix@gmail.com

2016-05-06

The formation energy, equilibrium lattice parameter, bulk modulus, Debye temperature and heat capacity at constant volume have been calculated for TiC, ZrC, and their intermediate alloys (Ti{sub 1-x}Zr{sub x}C, x = 0,0.25.0.5,0.75,1) using first principles approach. The calculated values of lattice parameter and bulk modulus agree well with the available experimental and earlier theoretical reports. The variation of lattice parameter and bulk modulus with the change in concentration of Zr atom in Ti{sub 1-x}Zr{sub x}C has also been reported. The heat capacities of TiC, ZrC, and their intermediate alloys have been calculated by considering both vibrational and electronic contributions.

Estimates of nonequilibrium radiation for Venus entry. [generated by chemical reactions in shock layers

NASA Technical Reports Server (NTRS)

Grose, W. L.; Nealy, J. E.

1975-01-01

The present investigation is an analysis of the radiation from the chemical nonequilibrium region in the shock layer about a vehicle during Venus entry. The radiation and the flow were assumed to be uncoupled. An inviscid, nonequilibrium flowfield was calculated and an effective electronic temperature was determined for the predominant radiating species. Species concentrations and electronic temperature were then input into a radiation transport code to calculate heating rates. The present results confirm earlier investigations which indicate that the radiation should be calculated using electronic temperatures for the radiating species. These temperatures are not related in a simple way to the local translational temperature. For the described mission, the nonequilibrium radiative heating rate is approximately twice the corresponding equilibrium value at peak heating.

Effect of non-equilibrium flow chemistry and surface catalysis on surface heating to AFE

NASA Technical Reports Server (NTRS)

Stewart, David A.; Henline, William D.; Chen, Yih-Kanq

1991-01-01

The effect of nonequilibrium flow chemistry on the surface temperature distribution over the forebody heat shield on the Aeroassisted Flight Experiment (AFE) vehicle was investigated using a reacting boundary-layer code. Computations were performed by using boundary-layer-edge properties determined from global iterations between the boundary-layer code and flow field solutions from a viscous shock layer (VSL) and a full Navier-Stokes solution. Surface temperature distribution over the AFE heat shield was calculated for two flight conditions during a nominal AFE trajectory. This study indicates that the surface temperature distribution is sensitive to the nonequilibrium chemistry in the shock layer. Heating distributions over the AFE forebody calculated using nonequilibrium edge properties were similar to values calculated using the VSL program.

A General Method for Automatic Computation of Equilibrium Compositions and Theoretical Rocket Performance of Propellants

NASA Technical Reports Server (NTRS)

Gordon, Sanford; Zeleznik, Frank J.; Huff, Vearl N.

1959-01-01

A general computer program for chemical equilibrium and rocket performance calculations was written for the IBM 650 computer with 2000 words of drum storage, 60 words of high-speed core storage, indexing registers, and floating point attachments. The program is capable of carrying out combustion and isentropic expansion calculations on a chemical system that may include as many as 10 different chemical elements, 30 reaction products, and 25 pressure ratios. In addition to the equilibrium composition, temperature, and pressure, the program calculates specific impulse, specific impulse in vacuum, characteristic velocity, thrust coefficient, area ratio, molecular weight, Mach number, specific heat, isentropic exponent, enthalpy, entropy, and several thermodynamic first derivatives.

Calculating and Visualizing Thermodynamic Equilibrium: A Tutorial on the Isolated System with an Internal Adiabatic Piston

ERIC Educational Resources Information Center

Ferreira, Joao Paulo M.

2007-01-01

The problem of the equilibrium state of an isolated composite system with a movable internal adiabatic wall is a recurrent one in the literature. Classical equilibrium thermodynamics is unable to predict the equilibrium state, unless supplemented with information about the process taking place. This conclusion is clearly demonstrated in this…

Infrared spectra of molecules and materials of astrophysical interest

NASA Technical Reports Server (NTRS)

Durig, J. R.

1978-01-01

The Raman spectra of gaseous, liquid and solid, and infrared spectra of gaseous and solid isopropylamine-d sub 0 and -d sub 2 was investigated between 4000 and 50 cm superscript -1. Differences between the spectrum of the solid phase and that of the fluid phases were interpreted in terms of an equilibrium between low energy s-trans and high energy gauche conformers, and a complete vibrational assignment was proposed for the s-trans conformer. The far infrared spectra of the gaseous compounds contained bands due to the asymmetric amino and coupled methyl torsions; the assignment of these bands was aided by observation of a number of two quantum transitions for each vibrational mode. The asymmetric potential functions were calculated, which resulted in values for the enthalpy differences between conformers in the gaseous phase of 446 and 523 callmole for the sub 0 -d and -d sub 2 compounds, respectively. The methyl torsional potential function of isopropylamine-d sub 0 was calculated which led to a value for the barrier height to internal rotation of the methyl rotors of 4.23 + or - 0.06 kcal/mole. Values for the ideal gas thermodynamic functions were calculated over a range of temperatures.

Electron-phonon interaction in the binary superconductor lutetium carbide LuC2 via first-principles calculations

NASA Astrophysics Data System (ADS)

Dilmi, S.; Saib, S.; Bouarissa, N.

2018-06-01

Structural, electronic, electron-phonon coupling and superconducting properties of the intermetallic compound LuC2 are investigated by means of ab initio pseudopotential plane wave method within the generalized gradient approximation. The calculated equilibrium lattice parameters yielded a very good accord with experiment. There is no imaginary phonon frequency in the whole Brillouin zone supporting thus the dynamical stability in the material of interest. The average electron-phonon coupling parameter is found to be 0.59 indicating thus a weak-coupling BCS superconductor. Using a reasonable value of μ* = 0.12 for the effective Coulomb repulsion parameter, the superconducting critical temperature Tc is found to be 3.324 which is in excellent agreement with the experimental value of 3.33 K. The effect of the spin-orbit coupling on the superconducting properties of the material of interest has been examined and found to be weak.

Systematic Approach to Calculate the Concentration of Chemical Species in Multi-Equilibrium Problems

ERIC Educational Resources Information Center

Baeza-Baeza, Juan Jose; Garcia-Alvarez-Coque, Maria Celia

2011-01-01

A general systematic approach is proposed for the numerical calculation of multi-equilibrium problems. The approach involves several steps: (i) the establishment of balances involving the chemical species in solution (e.g., mass balances, charge balance, and stoichiometric balance for the reaction products), (ii) the selection of the unknowns (the…

Quantum-chemical calculations and electron diffraction study of the equilibrium molecular structure of vitamin K3

NASA Astrophysics Data System (ADS)

Khaikin, L. S.; Tikhonov, D. S.; Grikina, O. E.; Rykov, A. N.; Stepanov, N. F.

2014-05-01

The equilibrium molecular structure of 2-methyl-1,4-naphthoquinone (vitamin K3) having C s symmetry is experimentally characterized for the first time by means of gas-phase electron diffraction using quantum-chemical calculations and data on the vibrational spectra of related compounds.

Co-solvent effects on reaction rate and reaction equilibrium of an enzymatic peptide hydrolysis.

PubMed

Wangler, A; Canales, R; Held, C; Luong, T Q; Winter, R; Zaitsau, D H; Verevkin, S P; Sadowski, G

2018-04-25

This work presents an approach that expresses the Michaelis constant KaM and the equilibrium constant Kth of an enzymatic peptide hydrolysis based on thermodynamic activities instead of concentrations. This provides KaM and Kth values that are independent of any co-solvent. To this end, the hydrolysis reaction of N-succinyl-l-phenylalanine-p-nitroanilide catalysed by the enzyme α-chymotrypsin was studied in pure buffer and in the presence of the co-solvents dimethyl sulfoxide, trimethylamine-N-oxide, urea, and two salts. A strong influence of the co-solvents on the measured Michaelis constant (KM) and equilibrium constant (Kx) was observed, which was found to be caused by molecular interactions expressed as activity coefficients. Substrate and product activity coefficients were used to calculate the activity-based values KaM and Kth for the co-solvent free reaction. Based on these constants, the co-solvent effect on KM and Kx was predicted in almost quantitative agreement with the experimental data. The approach presented here does not only reveal the importance of understanding the thermodynamic non-ideality of reactions taking place in biological solutions and in many technological applications, it also provides a framework for interpreting and quantifying the multifaceted co-solvent effects on enzyme-catalysed reactions that are known and have been observed experimentally for a long time.

A superlinear iteration method for calculation of finite length journal bearing's static equilibrium position.

PubMed

Zhou, Wenjie; Wei, Xuesong; Wang, Leqin; Wu, Guangkuan

2017-05-01

Solving the static equilibrium position is one of the most important parts of dynamic coefficients calculation and further coupled calculation of rotor system. The main contribution of this study is testing the superlinear iteration convergence method-twofold secant method, for the determination of the static equilibrium position of journal bearing with finite length. Essentially, the Reynolds equation for stable motion is solved by the finite difference method and the inner pressure is obtained by the successive over-relaxation iterative method reinforced by the compound Simpson quadrature formula. The accuracy and efficiency of the twofold secant method are higher in comparison with the secant method and dichotomy. The total number of iterative steps required for the twofold secant method are about one-third of the secant method and less than one-eighth of dichotomy for the same equilibrium position. The calculations for equilibrium position and pressure distribution for different bearing length, clearance and rotating speed were done. In the results, the eccentricity presents linear inverse proportional relationship to the attitude angle. The influence of the bearing length, clearance and bearing radius on the load-carrying capacity was also investigated. The results illustrate that larger bearing length, larger radius and smaller clearance are good for the load-carrying capacity of journal bearing. The application of the twofold secant method can greatly reduce the computational time for calculation of the dynamic coefficients and dynamic characteristics of rotor-bearing system with a journal bearing of finite length.

A superlinear iteration method for calculation of finite length journal bearing's static equilibrium position

PubMed Central

Zhou, Wenjie; Wei, Xuesong; Wang, Leqin

2017-01-01

Solving the static equilibrium position is one of the most important parts of dynamic coefficients calculation and further coupled calculation of rotor system. The main contribution of this study is testing the superlinear iteration convergence method—twofold secant method, for the determination of the static equilibrium position of journal bearing with finite length. Essentially, the Reynolds equation for stable motion is solved by the finite difference method and the inner pressure is obtained by the successive over-relaxation iterative method reinforced by the compound Simpson quadrature formula. The accuracy and efficiency of the twofold secant method are higher in comparison with the secant method and dichotomy. The total number of iterative steps required for the twofold secant method are about one-third of the secant method and less than one-eighth of dichotomy for the same equilibrium position. The calculations for equilibrium position and pressure distribution for different bearing length, clearance and rotating speed were done. In the results, the eccentricity presents linear inverse proportional relationship to the attitude angle. The influence of the bearing length, clearance and bearing radius on the load-carrying capacity was also investigated. The results illustrate that larger bearing length, larger radius and smaller clearance are good for the load-carrying capacity of journal bearing. The application of the twofold secant method can greatly reduce the computational time for calculation of the dynamic coefficients and dynamic characteristics of rotor-bearing system with a journal bearing of finite length. PMID:28572997

CET89 - CHEMICAL EQUILIBRIUM WITH TRANSPORT PROPERTIES, 1989

NASA Technical Reports Server (NTRS)

Mcbride, B.

1994-01-01

Scientists and engineers need chemical equilibrium composition data to calculate the theoretical thermodynamic properties of a chemical system. This information is essential in the design and analysis of equipment such as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical processing equipment. The substantial amount of numerical computation required to obtain equilibrium compositions and transport properties for complex chemical systems led scientists at NASA's Lewis Research Center to develop CET89, a program designed to calculate the thermodynamic and transport properties of these systems. CET89 is a general program which will calculate chemical equilibrium compositions and mixture properties for any chemical system with available thermodynamic data. Generally, mixtures may include condensed and gaseous products. CET89 performs the following operations: it 1) obtains chemical equilibrium compositions for assigned thermodynamic states, 2) calculates dilute-gas transport properties of complex chemical mixtures, 3) obtains Chapman-Jouguet detonation properties for gaseous species, 4) calculates incident and reflected shock properties in terms of assigned velocities, and 5) calculates theoretical rocket performance for both equilibrium and frozen compositions during expansion. The rocket performance function allows the option of assuming either a finite area or an infinite area combustor. CET89 accommodates problems involving up to 24 reactants, 20 elements, and 600 products (400 of which may be condensed). The program includes a library of thermodynamic and transport properties in the form of least squares coefficients for possible reaction products. It includes thermodynamic data for over 1300 gaseous and condensed species and transport data for 151 gases. The subroutines UTHERM and UTRAN convert thermodynamic and transport data to unformatted form for faster processing. The program conforms to the FORTRAN 77 standard, except for some input in NAMELIST format. It requires about 423 KB memory, and is designed to be used on mainframe, workstation, and mini computers. Due to its memory requirements, this program does not readily lend itself to implementation on MS-DOS based machines.

Franck-Condon factor formulae for astrophysical and other molecules

NASA Technical Reports Server (NTRS)

Nicholls, R. W.

1981-01-01

Simple closed-form, approximate, analytic expressions for Franck-Condon factors are given. They provide reliable estimates for Franck-Condon factor arrays for molecular band systems for which only vibrational-frequency, equilibrium internuclear separation and reduced mass values are known, as is often the case for astrophysically interesting molecules such as CeO, CoH, CrH, CrO, CuH, GeH, LaO, NiH, SnH, and ZnH for band systems of which Franck-Condon arrays have been calculated.

Influence of tungsten fiber’s slow drift on the measurement of G with angular acceleration method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Jie; Wu, Wei-Huang; Zhan, Wen-Ze

In the measurement of the gravitational constant G with angular acceleration method, the equilibrium position of torsion pendulum with tungsten fiber undergoes a linear slow drift, which results in a quadratic slow drift on the angular velocity of the torsion balance turntable under feedback control unit. The accurate amplitude determination of the useful angular acceleration signal with known frequency is biased by the linear slow drift and the coupling effect of the drifting equilibrium position and the room fixed gravitational background signal. We calculate the influences of the linear slow drift and the complex coupling effect on the value ofmore » G, respectively. The result shows that the bias of the linear slow drift on G is 7 ppm, and the influence of the coupling effect is less than 1 ppm.« less

A study of reacting free and ducted hydrogen/air jets

NASA Technical Reports Server (NTRS)

Beach, H. L., Jr.

1975-01-01

The mixing and reaction of a supersonic jet of hydrogen in coaxial free and ducted high temperature test gases were investigated. The importance of chemical kinetics on computed results, and the utilization of free-jet theoretical approaches to compute enclosed flow fields were studied. Measured pitot pressure profiles were correlated by use of a parabolic mixing analysis employing an eddy viscosity model. All computations, including free, ducted, reacting, and nonreacting cases, use the same value of the empirical constant in the viscosity model. Equilibrium and finite rate chemistry models were utilized. The finite rate assumption allowed prediction of observed ignition delay, but the equilibrium model gave the best correlations downstream from the ignition location. Ducted calculations were made with finite rate chemistry; correlations were, in general, as good as the free-jet results until problems with the boundary conditions were encountered.

Interaction between methyl glyoxal and ascorbic acid: experimental and theoretical aspects

NASA Astrophysics Data System (ADS)

Banerjee, D.; Koll, A.; Filarowski, A.; Bhattacharyya, S. P.; Mukherjee, S.

2004-06-01

The absorption spectral change of methyl glyoxal (MG) due to the interaction with ascorbic acid (AA or Vitamin C) has been investigated using steady-state spectroscopic technique. A plausible explanation for the spectral change has been discussed on the basis of hydrogen bonding interaction between the two interacting species. The equilibrium constant for the complex formation due to hydrogen bonding interaction between MG and AA has been obtained from absorption spectral changes. Ab inito calculations with DFT B3LYP/6/31G (d,p) basis sets have been used to find out the molecular structure of the hydrogen bonded complex. The O⋯H distance found in the OH⋯O hydrogen bond turns out to be quite short (1.974 Å) which is in conformity with the large value of the equilibrium constant determined experimentally.

Influence of tungsten fiber's slow drift on the measurement of G with angular acceleration method.

PubMed

Luo, Jie; Wu, Wei-Huang; Xue, Chao; Shao, Cheng-Gang; Zhan, Wen-Ze; Wu, Jun-Fei; Milyukov, Vadim

2016-08-01

In the measurement of the gravitational constant G with angular acceleration method, the equilibrium position of torsion pendulum with tungsten fiber undergoes a linear slow drift, which results in a quadratic slow drift on the angular velocity of the torsion balance turntable under feedback control unit. The accurate amplitude determination of the useful angular acceleration signal with known frequency is biased by the linear slow drift and the coupling effect of the drifting equilibrium position and the room fixed gravitational background signal. We calculate the influences of the linear slow drift and the complex coupling effect on the value of G, respectively. The result shows that the bias of the linear slow drift on G is 7 ppm, and the influence of the coupling effect is less than 1 ppm.

Influence of tungsten fiber's slow drift on the measurement of G with angular acceleration method

NASA Astrophysics Data System (ADS)

Luo, Jie; Wu, Wei-Huang; Xue, Chao; Shao, Cheng-Gang; Zhan, Wen-Ze; Wu, Jun-Fei; Milyukov, Vadim

2016-08-01

In the measurement of the gravitational constant G with angular acceleration method, the equilibrium position of torsion pendulum with tungsten fiber undergoes a linear slow drift, which results in a quadratic slow drift on the angular velocity of the torsion balance turntable under feedback control unit. The accurate amplitude determination of the useful angular acceleration signal with known frequency is biased by the linear slow drift and the coupling effect of the drifting equilibrium position and the room fixed gravitational background signal. We calculate the influences of the linear slow drift and the complex coupling effect on the value of G, respectively. The result shows that the bias of the linear slow drift on G is 7 ppm, and the influence of the coupling effect is less than 1 ppm.

Kinetic and mechanism of the oxidation of chromium(III) complex with anthranil- N, N-diacetic acid by periodate ion in acidic aqueous solutions

NASA Astrophysics Data System (ADS)

Ali, Ismat H.

2015-06-01

The kinetics of oxidation of [CrIII(atda)(H2O)2] (atda = anthranil- N, N-diacetato) complex by IO{4/-} was studied spectrophotometrically in aqueous solutions with pH range 2.20-3.34, 0.30 M ionic strength and in 20.0-40.0°C temperature range. The rate law of the reaction exhibited saturation kinetics. Values of the rate constant for the electron transfer process, the equilibrium constant for dissociation of [CrIII (atda)(H2O)2] to [CrIII (atda) (H2O)OH]+ + H+ and the pre-equilibrium formation constant were calculated. The thermodynamic activation parameters are reported. It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of the IVII to chromium(III).

Influence of point defects on the thermal conductivity in FeSi

NASA Astrophysics Data System (ADS)

Stern, Robin; Wang, Tao; Carrete, Jesús; Mingo, Natalio; Madsen, Georg K. H.

2018-05-01

The unique transport properties of B20 FeSi have been investigated for decades. The progress in theoretical calculations allows the explanation and prediction of more and more of such properties. In this paper we investigate the lattice thermal conductivity of FeSi. Calculation for pristine FeSi severely overestimates the lattice thermal conductivity compared to experiment. We point out that the defect concentration can be considerably larger than indicated by the Hall coefficient. The defect formation energies are calculated and it is found that a substantial amount of iron vacancies can form at thermal equilibrium. These will lead to an increased phonon scattering. To explain the thermal conductivity of FeSi, we consider phonon-phonon, isotope, and phonon-defect scattering to assess possible scattering mechanisms. The calculated thermal conductivities indicate that phonon-defect scattering is important in order to explain the reported experimental values.

An implicit flux-split algorithm to calculate hypersonic flowfields in chemical equilibrium

NASA Technical Reports Server (NTRS)

Palmer, Grant

1987-01-01

An implicit, finite-difference, shock-capturing algorithm that calculates inviscid, hypersonic flows in chemical equilibrium is presented. The flux vectors and flux Jacobians are differenced using a first-order, flux-split technique. The equilibrium composition of the gas is determined by minimizing the Gibbs free energy at every node point. The code is validated by comparing results over an axisymmetric hemisphere against previously published results. The algorithm is also applied to more practical configurations. The accuracy, stability, and versatility of the algorithm have been promising.

Aggregation of 2-aminobenzimidazole--a combined experimental and theoretical investigation.

PubMed

Angelova, Silvia E; Spassova, Milena I; Deneva, Vera V; Rogojerov, Marin I; Antonov, Liudmil M

2011-06-20

An investigation of 2-aminobenzimidazole was carried out by calculations at HF, MP2, and DFT levels of theory and also by UV and IR spectroscopy. The quantum chemical calculations predict a full shift of the equilibrium towards the amino form, but the absorption spectra in different solvents distinctly show a two-component equilibrium system. Examination of possible equilibria in solution shows that an equilibrium between two dimeric forms of the amino tautomer of 2-aminobenzimidazole explains the spectral observations. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-Organisation and Intermittent Coherent Oscillations in the EXTRAP T2 Reversed Field Pinch

NASA Astrophysics Data System (ADS)

Cecconello, M.; Malmberg, J.-A.; Sallander, E.; Drake, J. R.

Many reversed-field pinch (RFP) experiments exhibit a coherent oscillatory behaviour that is characteristic of discrete dynamo events and is associated with intermittent current profile self-organisation phenomena. However, in the vast majority of the discharges in the resistive shell RFP experiment EXTRAP T2, the dynamo activity does not show global, coherent oscillatory behaviour. The internally resonant tearing modes are phase-aligned and wall-locked resulting in a large localised magnetic perturbation. Equilibrium and plasma parameters have a level of high frequency fluctuations but the average values are quasi-steady. For some discharges, however, the equilibrium parameters exhibit the oscillatory behaviour characteristic of the discrete dynamo events. For these discharges, the trend observed in the tearing mode spectra, associated with the onset of the discrete relaxation event behaviour, is a relative higher amplitude of m = 0 mode activity and relative lower amplitude of the m = 1 mode activity compared with their average values. Global plasma parameters and model profile calculations for sample discharges representing the two types of relaxation dynamics are presented.

A Mathematical Model of Anthrax Transmission in Animal Populations.

PubMed

Saad-Roy, C M; van den Driessche, P; Yakubu, Abdul-Aziz

2017-02-01

A general mathematical model of anthrax (caused by Bacillus anthracis) transmission is formulated that includes live animals, infected carcasses and spores in the environment. The basic reproduction number [Formula: see text] is calculated, and existence of a unique endemic equilibrium is established for [Formula: see text] above the threshold value 1. Using data from the literature, elasticity indices for [Formula: see text] and type reproduction numbers are computed to quantify anthrax control measures. Including only herbivorous animals, anthrax is eradicated if [Formula: see text]. For these animals, oscillatory solutions arising from Hopf bifurcations are numerically shown to exist for certain parameter values with [Formula: see text] and to have periodicity as observed from anthrax data. Including carnivores and assuming no disease-related death, anthrax again goes extinct below the threshold. Local stability of the endemic equilibrium is established above the threshold; thus, periodic solutions are not possible for these populations. It is shown numerically that oscillations in spore growth may drive oscillations in animal populations; however, the total number of infected animals remains about the same as with constant spore growth.

Exponential 6 parameterization for the JCZ3-EOS

DOE Office of Scientific and Technical Information (OSTI.GOV)

McGee, B.C.; Hobbs, M.L.; Baer, M.R.

1998-07-01

A database has been created for use with the Jacobs-Cowperthwaite-Zwisler-3 equation-of-state (JCZ3-EOS) to determine thermochemical equilibrium for detonation and expansion states of energetic materials. The JCZ3-EOS uses the exponential 6 intermolecular potential function to describe interactions between molecules. All product species are characterized by r*, the radius of the minimum pair potential energy, and {var_epsilon}/k, the well depth energy normalized by Boltzmann`s constant. These parameters constitute the JCZS (S for Sandia) EOS database describing 750 gases (including all the gases in the JANNAF tables), and have been obtained by using Lennard-Jones potential parameters, a corresponding states theory, pure liquid shockmore » Hugoniot data, and fit values using an empirical EOS. This database can be used with the CHEETAH 1.40 or CHEETAH 2.0 interface to the TIGER computer program that predicts the equilibrium state of gas- and condensed-phase product species. The large JCZS-EOS database permits intermolecular potential based equilibrium calculations of energetic materials with complex elemental composition.« less

LSENS, The NASA Lewis Kinetics and Sensitivity Analysis Code

NASA Technical Reports Server (NTRS)

Radhakrishnan, K.

2000-01-01

A general chemical kinetics and sensitivity analysis code for complex, homogeneous, gas-phase reactions is described. The main features of the code, LSENS (the NASA Lewis kinetics and sensitivity analysis code), are its flexibility, efficiency and convenience in treating many different chemical reaction models. The models include: static system; steady, one-dimensional, inviscid flow; incident-shock initiated reaction in a shock tube; and a perfectly stirred reactor. In addition, equilibrium computations can be performed for several assigned states. An implicit numerical integration method (LSODE, the Livermore Solver for Ordinary Differential Equations), which works efficiently for the extremes of very fast and very slow reactions, is used to solve the "stiff" ordinary differential equation systems that arise in chemical kinetics. For static reactions, the code uses the decoupled direct method to calculate sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of dependent variables and/or the rate coefficient parameters. Solution methods for the equilibrium and post-shock conditions and for perfectly stirred reactor problems are either adapted from or based on the procedures built into the NASA code CEA (Chemical Equilibrium and Applications).

NaSi⇌CaAl exchange equilibrium between plagioclase and amphibole

NASA Astrophysics Data System (ADS)

Spear, Frank S.

1980-03-01

The exchange equilibrium between plagioclase and amphibole, 2 albite+tschermakite=2 anorthite+glaucophane, has been calibrated empirically using data from natural amphibolites. The partition coefficient, K D, for the exchange reaction is ( X an/ X ab)plag ·(Na, M4/Ca, M4)amph.. Partitioning is systematic between plagioclase and amphibole in suites collected from single exposures, but the solid solutions are highly non-ideal: values of In K D range from -3.0 at X an=0.30 to -1.0 at X an=0.90 in samples from a single roadcut. Changes in both K D and the topology of the ternary reciprocal exchange diagram occur with increasing metamorphic grade. Temperature dependence of In K D is moderate with Δ ¯H≃35 to 47 kcal at X an=0.25; pressure dependence is small with Δ ¯V≃ -0.24 cal/bar. Usefulness of this exchange equilibrium as a geothermometer is restricted by uncertainties in the calculation of the amphibole formula from a microprobe analysis, especially with regard to Na, M4 in amphibole, to approximately ±50 ° C.

Adsorption-desorption behavior of atrazine on agricultural soils in China.

PubMed

Yue, Lin; Ge, ChengJun; Feng, Dan; Yu, Huamei; Deng, Hui; Fu, Bomin

2017-07-01

Adsorption and desorption are important processes that affect atrazine transport, transformation, and bioavailability in soils. In this study, the adsorption-desorption characteristics of atrazine in three soils (laterite, paddy soil and alluvial soil) were evaluated using the batch equilibrium method. The results showed that the kinetics of atrazine in soils was completed in two steps: a "fast" adsorption and a "slow" adsorption and could be well described by pseudo-second-order model. In addition, the adsorption equilibrium isotherms were nonlinear and were well fitted by Freundlich and Langmuir models. It was found that the adsorption data on laterite, and paddy soil were better fitted by the Freundlich model; as for alluvial soil, the Langmuir model described it better. The maximum atrazine sorption capacities ranked as follows: paddy soil>alluvial soil>laterite. Results of thermodynamic calculations indicated that atrazine adsorption on three tested soils was spontaneous and endothermic. The desorption data showed that negative hysteresis occurred. Furthermore, lower solution pH value was conducive to the adsorption of atrazine in soils. The atrazine adsorption in these three tested soils was controlled by physical adsorption, including partition and surface adsorption. At lower equilibrium concentration, the atrazine adsorption process in soils was dominated by surface adsorption; while with the increase of equilibrium concentration, partition was predominant. Copyright © 2016. Published by Elsevier B.V.

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

ERIC Educational Resources Information Center

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…

Prediction of gas/particle partitioning of polybrominated diphenyl ethers (PBDEs) in global air: a theoretical study

NASA Astrophysics Data System (ADS)

Li, Y.-F.; Ma, W.-L.; Yang, M.

2014-09-01

Gas/particle (G / P) partitioning for most semivolatile organic compounds (SVOCs) is an important process that primarily governs their atmospheric fate, long-range atmospheric transport potential, and their routs to enter human body. All previous studies on this issue have been hypothetically derived from equilibrium conditions, the results of which do not predict results from monitoring studies well in most cases. In this study, a steady-state model instead of an equilibrium-state model for the investigation of the G / P partitioning behavior for polybrominated diphenyl ethers (PBDEs) was established, and an equation for calculating the partition coefficients under steady state (KPS) for PBDE congeners (log KPS = log KPE + logα) was developed, in which an equilibrium term (log KPE = log KOA + logfOM -11.91, where fOM is organic matter content of the particles) and a nonequilibrium term (logα, mainly caused by dry and wet depositions of particles), both being functions of log KOA (octanol-air partition coefficient), are included, and the equilibrium is a special case of steady state when the nonequilibrium term equals to zero. A criterion to classify the equilibrium and nonequilibrium status for PBDEs was also established using two threshold values of log KOA, log KOA1 and log KOA2, which divide the range of log KOA into 3 domains: equilibrium, nonequilibrium, and maximum partition domains; and accordingly, two threshold values of temperature t, tTH1 when log KOA = log KOA1 and tTH2 when log KOA = log KOA2, were identified, which divide the range of temperature also into the same 3 domains for each BDE congener. We predicted the existence of the maximum partition domain (the values of log KPS reach a maximum constant of -1.53) that every PBDE congener can reach when log KOA ≥ log KOA2, or t ≤ tTH2. The novel equation developed in this study was applied to predict the G / P partition coefficients of PBDEs for the published monitoring data worldwide, including Asia, Europe, North America, and the Arctic, and the results matched well with all the monitoring data, except those obtained at e-waste sites due to the unpredictable PBDE emissions at these sites. This study provided evidence that, the new developed steady-state-based equation is superior to the equilibrium-state-based equation that has been used in describing the G / P partitioning behavior in decades. We suggest that, the investigation on G / P partitioning behavior for PBDEs should be based on steady state, not equilibrium state, and equilibrium is just a special case of steady state when nonequilibrium factors can be ignored. We also believe that our new equation provides a useful tool for environmental scientists in both monitoring and modeling research on G / P partitioning for PBDEs and can be extended to predict G / P partitioning behavior for other SVOCs as well.

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

NASA Astrophysics Data System (ADS)

Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

2015-10-01

;Clumped-isotope; thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope ;clumps;). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals. We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect. Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3- and CO32-. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many natural systems. The two types of experiments yielded statistically indistinguishable results, and these measurements yield a calibration that overlaps with our theoretical predictions for calcite at equilibrium. The slow-growing Devils Hole calcite exhibits Δ47 and δ18O values consistent with lattice equilibrium. Factors influencing DIC speciation (pH, salinity) and the timescale for DIC equilibration, as well as reactions at the mineral-solution interface, have the potential to influence clumped-isotope signatures and the δ18O of carbonate minerals. In fast-growing carbonate minerals, solution chemistry may be an important factor, particularly over extremes of pH and salinity. If a crystal grows too rapidly to reach an internal equilibrium (i.e., achieve the value for the temperature-dependent mineral lattice equilibrium), it may record the clumped-isotope signature of a DIC species (e.g., the temperature-dependent equilibrium of HCO3-) or a mixture of DIC species, and hence record a disequilibrium mineral composition. For extremely slow-growing crystals, and for rapidly-grown samples grown at a pH where HCO3- dominates the DIC pool at equilibrium, effects of solution chemistry are likely to be relatively small or negligible. In summary, growth environment, solution chemistry, surface equilibria, and precipitation rate may all play a role in dictating whether a crystal achieves equilibrium or disequilibrium clumped-isotope signatures.

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

USGS Publications Warehouse

Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

2015-01-01

“Clumped-isotope” thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope “clumps”). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals.We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect.Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3− and CO32−. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many natural systems. The two types of experiments yielded statistically indistinguishable results, and these measurements yield a calibration that overlaps with our theoretical predictions for calcite at equilibrium. The slow-growing Devils Hole calcite exhibits Δ47 and δ18O values consistent with lattice equilibrium.Factors influencing DIC speciation (pH, salinity) and the timescale for DIC equilibration, as well as reactions at the mineral–solution interface, have the potential to influence clumped-isotope signatures and the δ18O of carbonate minerals. In fast-growing carbonate minerals, solution chemistry may be an important factor, particularly over extremes of pH and salinity. If a crystal grows too rapidly to reach an internal equilibrium (i.e., achieve the value for the temperature-dependent mineral lattice equilibrium), it may record the clumped-isotope signature of a DIC species (e.g., the temperature-dependent equilibrium of HCO3−) or a mixture of DIC species, and hence record a disequilibrium mineral composition. For extremely slow-growing crystals, and for rapidly-grown samples grown at a pH where HCO3- dominates the DIC pool at equilibrium, effects of solution chemistry are likely to be relatively small or negligible. In summary, growth environment, solution chemistry, surface equilibria, and precipitation rate may all play a role in dictating whether a crystal achieves equilibrium or disequilibrium clumped-isotope signatures.

Improved Simulation of the Pre-equilibrium Triton Emission in Nuclear Reactions Induced by Nucleons

NASA Astrophysics Data System (ADS)

Konobeyev, A. Yu.; Fischer, U.; Pereslavtsev, P. E.; Blann, M.

2014-04-01

A new approach is proposed for the calculation of non-equilibrium triton energy distributions in nuclear reactions induced by nucleons of intermediate energies. It combines models describing the nucleon pick-up, the coalescence and the triton knock-out processes. Emission and absorption rates for excited particles are represented by the pre-equilibrium hybrid model. The model of Sato, Iwamoto, Harada is used to describe the nucleon pick-up and the coalescence of nucleons from exciton configurations starting from (2p,1h) states. The contribution of the direct nucleon pick-up is described phenomenologically. Multiple pre-equilibrium emission of tritons is accounted for. The calculated triton energy distributions are compared with available experimental data.

Delineating Spatial Patterns in the Yellowstone Hydrothermal System using Geothermometry

NASA Astrophysics Data System (ADS)

King, J.; Hurwitz, S.; Lowenstern, J. B.

2015-12-01

Yellowstone National Park is unmatched with regard to its quantity of active hydrothermal features. Origins of thermal waters in its geyser basins have been traced to mixing of a deep parent water with meteoric waters in shallow local reservoirs (Fournier, 1989). A mineral-solution equilibrium model was developed to calculate water-rock chemical re-equilibration temperatures in these shallow reservoirs. We use the GeoT program, which uses water composition data as input to calculate saturation indices of selected minerals; the "best-clustering" minerals are then statistically determined to infer reservoir temperatures (Spycher et al., 2013). We develop the method using water composition data from Heart Lake Geyser Basin (HLGB), for which both chemical and isotopic geothermometers predict a reservoir water temperature of 205°C ± 10°C (Lowenstern et al., 2012), and minerals found in drill cores in Yellowstone's geyser basins. We test the model for sensitivity to major element composition, pH, Total Inorganic Carbon (TIC) and selected minerals to optimize model parameters. Calculated temperatures are most accurate at pH values below 9.0, and closely match the equilibrium saturation indices of quartz, stilbite, microcline, and albite. The model is optimized with a TIC concentration that is consistent with the mass of diffuse CO2 flux in HLGB (Lowenstern et al., 2012). We then use water compositions from other thermal basins in Yellowstone in search of spatial variations in reservoir temperatures. We then compare the calculated temperatures with various SiO2 and cation geothermometers.

Ab initio study of the positronation of the CaO and SrO molecules including calculation of annihilation rates.

PubMed

Buenker, Robert J; Liebermann, Heinz-Peter

2012-07-15

Ab initio multireference single- and double-excitation configuration interaction calculations have been performed to compute potential curves for ground and excited states of the CaO and SrO molecules and their positronic complexes, e(+)CaO, and e(+)SrO. The adiabatic dissociation limit for the (2)Σ(+) lowest states of the latter systems consists of the positive metal ion ground state (M(+)) and the OPs complex (e(+)O(-)), although the lowest energy limit is thought to be e(+)M + O. Good agreement is found between the calculated and experimental spectroscopic constants for the neutral diatomics wherever available. The positron affinity of the closed-shell X (1)Σ(+) ground states of both systems is found to lie in the 0.16-0.19 eV range, less than half the corresponding values for the lighter members of the alkaline earth monoxide series, BeO and MgO. Annihilation rates (ARs) have been calculated for all four positronated systems for the first time. The variation with bond distance is generally similar to what has been found earlier for the alkali monoxide series of positronic complexes, falling off gradually from the OPs AR value at their respective dissociation limits. The e(+)SrO system shows some exceptional behavior, however, with its AR value reaching a minimum at a relatively large bond distance and then rising to more than twice the OPs value close to its equilibrium distance. Copyright © 2012 Wiley Periodicals, Inc.

Austenite grain growth simulation considering the solute-drag effect and pinning effect.

PubMed

Fujiyama, Naoto; Nishibata, Toshinobu; Seki, Akira; Hirata, Hiroyuki; Kojima, Kazuhiro; Ogawa, Kazuhiro

2017-01-01

The pinning effect is useful for restraining austenite grain growth in low alloy steel and improving heat affected zone toughness in welded joints. We propose a new calculation model for predicting austenite grain growth behavior. The model is mainly comprised of two theories: the solute-drag effect and the pinning effect of TiN precipitates. The calculation of the solute-drag effect is based on the hypothesis that the width of each austenite grain boundary is constant and that the element content maintains equilibrium segregation at the austenite grain boundaries. We used Hillert's law under the assumption that the austenite grain boundary phase is a liquid so that we could estimate the equilibrium solute concentration at the austenite grain boundaries. The equilibrium solute concentration was calculated using the Thermo-Calc software. Pinning effect was estimated by Nishizawa's equation. The calculated austenite grain growth at 1473-1673 K showed excellent correspondence with the experimental results.

Computation of thermodynamic equilibrium in systems under stress

NASA Astrophysics Data System (ADS)

Vrijmoed, Johannes C.; Podladchikov, Yuri Y.

2016-04-01

Metamorphic reactions may be partly controlled by the local stress distribution as suggested by observations of phase assemblages around garnet inclusions related to an amphibolite shear zone in granulite of the Bergen Arcs in Norway. A particular example presented in fig. 14 of Mukai et al. [1] is discussed here. A garnet crystal embedded in a plagioclase matrix is replaced on the left side by a high pressure intergrowth of kyanite and quartz and on the right side by chlorite-amphibole. This texture apparently represents disequilibrium. In this case, the minerals adapt to the low pressure ambient conditions only where fluids were present. Alternatively, here we compute that this particular low pressure and high pressure assemblage around a stressed rigid inclusion such as garnet can coexist in equilibrium. To do the computations we developed the Thermolab software package. The core of the software package consists of Matlab functions that generate Gibbs energy of minerals and melts from the Holland and Powell database [2] and aqueous species from the SUPCRT92 database [3]. Most up to date solid solutions are included in a general formulation. The user provides a Matlab script to do the desired calculations using the core functions. Gibbs energy of all minerals, solutions and species are benchmarked versus THERMOCALC, PerpleX [4] and SUPCRT92 and are reproduced within round off computer error. Multi-component phase diagrams have been calculated using Gibbs minimization to benchmark with THERMOCALC and Perple_X. The Matlab script to compute equilibrium in a stressed system needs only two modifications of the standard phase diagram script. Firstly, Gibbs energy of phases considered in the calculation is generated for multiple values of thermodynamic pressure. Secondly, for the Gibbs minimization the proportion of the system at each particular thermodynamic pressure needs to be constrained. The user decides which part of the stress tensor is input as thermodynamic pressure. To compute a case of high and low pressure around a stressed inclusion we first did a Finite Element Method calculation of a rigid inclusion in a viscous matrix under simple shear. From the computed stress distribution we took the local pressure (mean stress) in each grid point of the FEM calculation. This was used as input thermodynamic pressure in the Gibbs minimization and the result showed it is possible to have an equilibrium situation in which chlorite-amphibole is stable in the low pressure domain and kyanite in the high pressure domain of the stress field around the inclusion. Interestingly, the calculation predicts the redistribution of fluid from an average content of fluid in the system. The fluid in equilibrium tends to accumulate in the low pressure areas whereas it leaves the high pressure areas dry. Transport of fluid components occurs not necessarily by fluid flow, but may happen for example by diffusion. We conclude that an apparent disequilibrium texture may be explained by equilibrium under pressure variations, and apparent fluid addition by redistribution of fluid controlled by the local stress distribution. [1] Mukai et al. (2014), Journal of Petrology, 55 (8), p. 1457-1477. [2] Holland and Powell (1998), Journal of Metamorphic Geology, 16, p. 309-343 [3] Johnson et al. (1992), Computers & Geosciences, 18 (7), p. 899-947 [4] Connolly (2005), Earth and Planetary Science Letters, 236, p. 524-541

The effects of rigid motions on elastic network model force constants.

PubMed

Lezon, Timothy R

2012-04-01

Elastic network models provide an efficient way to quickly calculate protein global dynamics from experimentally determined structures. The model's single parameter, its force constant, determines the physical extent of equilibrium fluctuations. The values of force constants can be calculated by fitting to experimental data, but the results depend on the type of experimental data used. Here, we investigate the differences between calculated values of force constants and data from NMR and X-ray structures. We find that X-ray B factors carry the signature of rigid-body motions, to the extent that B factors can be almost entirely accounted for by rigid motions alone. When fitting to more refined anisotropic temperature factors, the contributions of rigid motions are significantly reduced, indicating that the large contribution of rigid motions to B factors is a result of over-fitting. No correlation is found between force constants fit to NMR data and those fit to X-ray data, possibly due to the inability of NMR data to accurately capture protein dynamics. Copyright © 2011 Wiley Periodicals, Inc.

A novel method for measuring polymer-water partition coefficients.

PubMed

Zhu, Tengyi; Jafvert, Chad T; Fu, Dafang; Hu, Yue

2015-11-01

Low density polyethylene (LDPE) often is used as the sorbent material in passive sampling devices to estimate the average temporal chemical concentration in water bodies or sediment pore water. To calculate water phase chemical concentrations from LDPE concentrations accurately, it is necessary to know the LDPE-water partition coefficients (KPE-w) of the chemicals of interest. However, even moderately hydrophobic chemicals have large KPE-w values, making direct measurement experimentally difficult. In this study we evaluated a simple three phase system from which KPE-w can be determined easily and accurately. In the method, chemical equilibrium distribution between LDPE and a surfactant micelle pseudo-phase is measured, with the ratio of these concentrations equal to the LDPE-micelle partition coefficient (KPE-mic). By employing sufficient mass of polymer and surfactant (Brij 30), the mass of chemical in the water phase remains negligible, albeit in equilibrium. In parallel, the micelle-water partition coefficient (Kmic-w) is determined experimentally. KPE-w is the product of KPE-mic and Kmic-w. The method was applied to measure values of KPE-w for 17 polycyclic aromatic hydrocarbons, 37 polychlorinated biphenyls, and 9 polybrominated diphenylethers. These values were compared to literature values. Mass fraction-based chemical activity coefficients (γ) were determined in each phase and showed that for each chemical, the micelles and LDPE had nearly identical affinity. Copyright © 2014 Elsevier Ltd. All rights reserved.

Engel-Vosko GGA calculations of the structural, electronic and optical properties of LiYO2

NASA Astrophysics Data System (ADS)

Muhammad, Nisar; Khan, Afzal; Haidar Khan, Shah; Sajjaj Siraj, Muhammad; Shah, Syed Sarmad Ali; Murtaza, Ghulam

2017-09-01

Structural, electronic and optical properties of lithium yttrium oxide (LiYO2) are investigated using density functional theory (DFT). These calculations are based on full potential linearized augmented plane wave (FP-LAPW) method implemented by WIEN2k. The generalized gradient approximation (GGA) is used as an exchange correlation potential with Perdew-Burk-Ernzerhof (PBE) and Engel-Vosko (EV) as exchange correlation functional. The structural properties are calculated with PBE-GGA as it gives the equilibrium lattice constants very close to the experimental values. While, the band structure and optical properties are calculated with EV-GGA obtain much closer results to their experimental values. Our calculations confirm LiYO2 as large indirect band gap semiconductor having band gap of 5.23 eV exhibiting the characteristics of ultrawide band gap materials showing the properties like higher critical breakdown field, higher temperature operation and higher radiation tolerance. In this article, we report the density of states (DOS) in terms of contribution from s, p, and d-states of the constituent atoms, the band structure, the electronic structure, and the frequency-dependent optical properties of LiYO2. The optical properties presented in this article reveal LiYO2 a suitable candidate for the field of optoelectronic and optical devices.

Non-equilibrium ionization by a periodic electron beam. I. Synthetic coronal spectra and implications for interpretation of observations

NASA Astrophysics Data System (ADS)

Dzifčáková, E.; Dudík, J.; Mackovjak, Š.

2016-05-01

Context. Coronal heating is currently thought to proceed via the mechanism of nanoflares, small-scale and possibly recurring heating events that release magnetic energy. Aims: We investigate the effects of a periodic high-energy electron beam on the synthetic spectra of coronal Fe ions. Methods: Initially, the coronal plasma is assumed to be Maxwellian with a temperature of 1 MK. The high-energy beam, described by a κ-distribution, is then switched on every period P for the duration of P/ 2. The periods are on the order of several tens of seconds, similar to exposure times or cadences of space-borne spectrometers. Ionization, recombination, and excitation rates for the respective distributions are used to calculate the resulting non-equilibrium ionization state of Fe and the instantaneous and period-averaged synthetic spectra. Results: Under the presence of the periodic electron beam, the plasma is out of ionization equilibrium at all times. The resulting spectra averaged over one period are almost always multithermal if interpreted in terms of ionization equilibrium for either a Maxwellian or a κ-distribution. Exceptions occur, however; the EM-loci curves appear to have a nearly isothermal crossing-point for some values of κs. The instantaneous spectra show fast changes in intensities of some lines, especially those formed outside of the peak of the respective EM(T) distributions if the ionization equilibrium is assumed. Movies 1-5 are available in electronic form at http://www.aanda.org

Sodium sulfate: Vaporization thermodynamics and role in corrosive flames

NASA Technical Reports Server (NTRS)

Kohl, F. J.

1975-01-01

Gaseous species over liquid Na2SO4 were identified by the technique of molecular beam mass spectrometry. The heat and entropy of vaporization of the Na2SO4 molecule were measured directly. Comparisons of the experimental entropy with values calculated using various molecular parameters were used to estimate the molecular structure and vibrational frequencies. The thermodynamic properties of gaseous and condensed phase Na2SO4, along with additional pertinent species, were used in a computer program to calculate equilibrium flame compositions and temperatures for representative turbine engine and burner rig flames. Compositions were calculated at various fuel-to-oxidant ratios with additions of sulfur to the fuel and the components of sea salt to the intake air. Temperatures for condensation of Na2SO4 were obtained as a function of sulfur and sea salt concentrations.

The equation of state of n-pentane in the atomistic model TraPPE-EH

NASA Astrophysics Data System (ADS)

Valeev, B. U.; Pisarev, V. V.

2018-01-01

In this work, we study the vapor-liquid equilibrium in n-pentane. We use the TraPPE-EH (transferable potentials for phase equilibria-explicit hydrogen) forcefield, where each hydrogen and carbon atom is considered as independent center of force. The fluid behavior was investigated with different values of density and temperature by molecular dynamics method. The n-pentane evaporation curve was calculated in the temperature range of 290 to 390 K. The densities of the coexisting phases are also calculated. The compression curve at 370 K was calculated and isothermal bulk modulus was found. The simulated properties of n-pentane are in good agreement with data from a database of the National Institute of Standards and Technology, so the TraPPE-EH model can be recommended for simulations of hydrocarbons.

Oxygen self-diffusion mechanisms in monoclinic Zr O2 revealed and quantified by density functional theory, random walk analysis, and kinetic Monte Carlo calculations

NASA Astrophysics Data System (ADS)

Yang, Jing; Youssef, Mostafa; Yildiz, Bilge

2018-01-01

In this work, we quantify oxygen self-diffusion in monoclinic-phase zirconium oxide as a function of temperature and oxygen partial pressure. A migration barrier of each type of oxygen defect was obtained by first-principles calculations. Random walk theory was used to quantify the diffusivities of oxygen interstitials by using the calculated migration barriers. Kinetic Monte Carlo simulations were used to calculate diffusivities of oxygen vacancies by distinguishing the threefold- and fourfold-coordinated lattice oxygen. By combining the equilibrium defect concentrations obtained in our previous work together with the herein calculated diffusivity of each defect species, we present the resulting oxygen self-diffusion coefficients and the corresponding atomistically resolved transport mechanisms. The predicted effective migration barriers and diffusion prefactors are in reasonable agreement with the experimentally reported values. This work provides insights into oxygen diffusion engineering in Zr O2 -related devices and parametrization for continuum transport modeling.

Computer Program for Calculation of Complex Chemical Equilibrium Compositions, Rocket Performance, Incident and Reflected Shocks, and Chapman-Jouguet Detonations. Interim Revision, March 1976

NASA Technical Reports Server (NTRS)

Gordon, S.; Mcbride, B. J.

1976-01-01

A detailed description of the equations and computer program for computations involving chemical equilibria in complex systems is given. A free-energy minimization technique is used. The program permits calculations such as (1) chemical equilibrium for assigned thermodynamic states (T,P), (H,P), (S,P), (T,V), (U,V), or (S,V), (2) theoretical rocket performance for both equilibrium and frozen compositions during expansion, (3) incident and reflected shock properties, and (4) Chapman-Jouguet detonation properties. The program considers condensed species as well as gaseous species.

Isotherm, kinetic, and thermodynamic study of ciprofloxacin sorption on sediments.

PubMed

Mutavdžić Pavlović, Dragana; Ćurković, Lidija; Grčić, Ivana; Šimić, Iva; Župan, Josip

2017-04-01

In this study, equilibrium isotherms, kinetics and thermodynamics of ciprofloxacin on seven sediments in a batch sorption process were examined. The effects of contact time, initial ciprofloxacin concentration, temperature and ionic strength on the sorption process were studied. The K d parameter from linear sorption model was determined by linear regression analysis, while the Freundlich and Dubinin-Radushkevich (D-R) sorption models were applied to describe the equilibrium isotherms by linear and nonlinear methods. The estimated K d values varied from 171 to 37,347 mL/g. The obtained values of E (free energy estimated from D-R isotherm model) were between 3.51 and 8.64 kJ/mol, which indicated a physical nature of ciprofloxacin sorption on studied sediments. According to obtained n values as measure of intensity of sorption estimate from Freundlich isotherm model (from 0.69 to 1.442), ciprofloxacin sorption on sediments can be categorized from poor to moderately difficult sorption characteristics. Kinetics data were best fitted by the pseudo-second-order model (R 2  > 0.999). Thermodynamic parameters including the Gibbs free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) were calculated to estimate the nature of ciprofloxacin sorption. Results suggested that sorption on sediments was a spontaneous exothermic process.

Study of silicon crystal surface formation based on molecular dynamics simulation results

NASA Astrophysics Data System (ADS)

Barinovs, G.; Sabanskis, A.; Muiznieks, A.

2014-04-01

The equilibrium shape of <110>-oriented single crystal silicon nanowire, 8 nm in cross-section, was found from molecular dynamics simulations using LAMMPS molecular dynamics package. The calculated shape agrees well to the shape predicted from experimental observations of nanocavities in silicon crystals. By parametrization of the shape and scaling to a known value of {111} surface energy, Wulff form for solid-vapor interface was obtained. The Wulff form for solid-liquid interface was constructed using the same model of the shape as for the solid-vapor interface. The parameters describing solid-liquid interface shape were found using values of surface energies in low-index directions known from published molecular dynamics simulations. Using an experimental value of the liquid-vapor interface energy for silicon and graphical solution of Herring's equation, we constructed angular diagram showing relative equilibrium orientation of solid-liquid, liquid-vapor and solid-vapor interfaces at the triple phase line. The diagram gives quantitative predictions about growth angles for different growth directions and formation of facets on the solid-liquid and solid-vapor interfaces. The diagram can be used to describe growth ridges appearing on the crystal surface grown from a melt. Qualitative comparison to the ridges of a Float zone silicon crystal cone is given.

A high-fidelity Monte Carlo evaluation of CANDU-6 safety parameters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Y.; Hartanto, D.

2012-07-01

Important safety parameters such as the fuel temperature coefficient (FTC) and the power coefficient of reactivity (PCR) of the CANDU-6 (CANada Deuterium Uranium) reactor have been evaluated by using a modified MCNPX code. For accurate analysis of the parameters, the DBRC (Doppler Broadening Rejection Correction) scheme was implemented in MCNPX in order to account for the thermal motion of the heavy uranium nucleus in the neutron-U scattering reactions. In this work, a standard fuel lattice has been modeled and the fuel is depleted by using the MCNPX and the FTC value is evaluated for several burnup points including the mid-burnupmore » representing a near-equilibrium core. The Doppler effect has been evaluated by using several cross section libraries such as ENDF/B-VI, ENDF/B-VII, JEFF, JENDLE. The PCR value is also evaluated at mid-burnup conditions to characterize safety features of equilibrium CANDU-6 reactor. To improve the reliability of the Monte Carlo calculations, huge number of neutron histories are considered in this work and the standard deviation of the k-inf values is only 0.5{approx}1 pcm. It has been found that the FTC is significantly enhanced by accounting for the Doppler broadening of scattering resonance and the PCR are clearly improved. (authors)« less

Analysis of a model of gambiense sleeping sickness in humans and cattle.

PubMed

Ndondo, A M; Munganga, J M W; Mwambakana, J N; Saad-Roy, C M; van den Driessche, P; Walo, R O

2016-01-01

Human African Trypanosomiasis (HAT) and Nagana in cattle, commonly called sleeping sickness, is caused by trypanosome protozoa transmitted by bites of infected tsetse flies. We present a deterministic model for the transmission of HAT caused by Trypanosoma brucei gambiense between human hosts, cattle hosts and tsetse flies. The model takes into account the growth of the tsetse fly, from its larval stage to the adult stage. Disease in the tsetse fly population is modeled by three compartments, and both the human and cattle populations are modeled by four compartments incorporating the two stages of HAT. We provide a rigorous derivation of the basic reproduction number R0. For R0 < 1, the disease free equilibrium is globally asymptotically stable, thus HAT dies out; whereas (assuming no return to susceptibility) for R0 >1, HAT persists. Elasticity indices for R0 with respect to different parameters are calculated with baseline parameter values appropriate for HAT in West Africa; indicating parameters that are important for control strategies to bring R0 below 1. Numerical simulations with R0 > 1 show values for the infected populations at the endemic equilibrium, and indicate that with certain parameter values, HAT could not persist in the human population in the absence of cattle.

Adsorptive Removal of Cadmium (II) from Aqueous Solution by Multi-Carboxylic-Functionalized Silica Gel: Equilibrium, Kinetics and Thermodynamics

NASA Astrophysics Data System (ADS)

Li, Min; Meng, Xiaojing; Yuan, Jinhai; Deng, Wenwen; Liang, Xiuke

2018-01-01

In the present study, the adsorption behavior of cadmium (II) ion from aqueous solution onto multi-carboxylic-functionalized silica gel (SG-MCF) has been investigated in detail by means of batch and column experiments. Batch experiments were performed to evaluate the effects of various experimental parameters such as pH value, contact time and initial concentration on adsorption capacity of cadmium (II) ion. The kinetic data were analyzed on the basis of the pseudo-first-order kinetic and the pseudo-second-order kinetic models and consequently, the pseudo-second-order kinetic can better describe the adsorption process than the pseudo-first-order kinetic model. Equilibrium isotherms for the adsorption of cadmium (II) ion were analyzed by Freundlich and Langmuir isotherm models, the results indicate that Langmuir isotherm model was found to be credible to express the data for cadmium (II) ion from aqueous solution onto the SG-MCF. Various thermodynamics parameters of the adsorption process, including free energy of adsorption (ΔG0 ), the enthalpy of adsorption (ΔH0 ) and standard entropy changes (ΔS0 ), were calculated to predict the nature of adsorption. The positive value of the enthalpy change and the negative value of free energy change indicate that the process is endothermic and spontaneous process.

A review of reaction rates in high temperature air

NASA Technical Reports Server (NTRS)

Park, Chul

1989-01-01

The existing experimental data on the rate coefficients for the chemical reactions in nonequilibrium high temperature air are reviewed and collated, and a selected set of such values is recommended for use in hypersonic flow calculations. For the reactions of neutral species, the recommended values are chosen from the experimental data that existed mostly prior to 1970, and are slightly different from those used previously. For the reactions involving ions, the recommended rate coefficients are newly chosen from the experimental data obtained more recently. The reacting environment is assumed to lack thermal equilibrium, and the rate coefficients are expressed as a function of the controlling temperature, incorporating the recent multitemperature reaction concept.

Kicks of magnetized strange quark stars induced by anisotropic emission of neutrinos

NASA Astrophysics Data System (ADS)

Ayala, Alejandro; Manreza Paret, D.; Pérez Martínez, A.; Piccinelli, Gabriella; Sánchez, Angel; Ruíz Montaño, Jorge S.

2018-05-01

We study the anisotropic neutrino emission from the core of neutron stars induced by the star's magnetic field. We model the core as made out of a magnetized ideal gas of strange quark matter and implement the conditions for stellar equilibrium in this environment. The calculation is performed without resorting to analytical simplifications and for temperature, density, and magnetic field values corresponding to typical conditions for a neutron star's evolution. The anisotropic neutrino emission produces a rocket effect that contributes to the star's kick velocity. We find that the computed values for the kick velocity lie within the range of the observed values, reaching velocities of the order of ˜1000 km s-1 for magnetic fields between 1015-1018 G and radii of 20 to 5 km, respectively.

Rare earth element variations resulting from inversion of pigeonite and subsolidus reequilibration in lunar ferroan anorthosites

USGS Publications Warehouse

James, O.B.; Floss, C.; McGee, J.J.

2002-01-01

We present results of a secondary ion mass spectrometry study of the rare earth elements (REEs) in the minerals of two samples of lunar ferroan anorthosite, and the results are applicable to studies of REEs in all igneous rocks, no matter what their planet of origin. Our pyroxene analyses are used to determine solid-solid REE distribution coefficients (D = CREE in low-Ca pyroxene/CREE in augite) in orthopyroxene-augite pairs derived by inversion of pigeonite. Our data and predictions from crystal-chemical considerations indicate that as primary pigeonite inverts to orthopyroxene plus augite and subsolidus reequilibration proceeds, the solid-solid Ds for orthopyroxene-augite pairs progressively decrease for all REEs; the decrease is greatest for the LREEs. The REE pattern of solid-solid Ds for inversion-derived pyroxene pairs is close to a straight line for Sm-Lu and turns upward for REEs lighter than Sm; the shape of this pattern is predicted by the shapes of the REE patterns for the individual minerals. Equilibrium liquids calculated for one sample from the compositions of primary phases, using measured or experimentally determined solid-liquid Ds, have chondrite-normalized REE patterns that are very slightly enriched in LREEs. The plagioclase equilibrium liquid is overall less rich in REEs than pyroxene equilibrium liquids, and the discrepancy probably arises because the calculated plagioclase equilibrium liquid represents a liquid earlier in the fractionation sequence than the pyroxene equilibrium liquids. "Equilibrium" liquids calculated from the compositions of inversion-derived pyroxenes or orthopyroxene derived by reaction of olivine are LREE depleted (in some cases substantially) in comparison with equilibrium liquids calculated from the compositions of primary phases. These discrepancies arise because the inversion-derived and reaction-derived pyroxenes did not crystallize directly from liquid, and the use of solid-liquid Ds is inappropriate. The LREE depletion of the calculated liquids is a relic of formation of these phases from primary LREE-depleted minerals. Thus, if one attempts to calculate the compositions of equilibrium liquids from pyroxene compositions, it is important to establish that the pyroxenes are primary. In addition, our data suggest that experimental studies have underestimated solid-liquid Ds for REEs in pigeonite and that REE contents of liquids calculated using these Ds are overestimates. Our results have implications for Sm-Nd age studies. Our work shows that if pigeonite inversion and/or subsolidus reequilibration between augite and orthopyroxene occured significantly after crystallization, and if pyroxene separates isolated for Sm-Nd studies do not have the bulk composition of the primary pyroxenes, then the Sm-Nd isochron age and ??Nd will be in error. Copyright ?? 2002 Elsevier Science Ltd.

Thermal conductivity of silicon using reverse non-equilibrium molecular dynamics

NASA Astrophysics Data System (ADS)

El-Genk, Mohamed S.; Talaat, Khaled; Cowen, Benjamin J.

2018-05-01

Simulations are performed using the reverse non-equilibrium molecular dynamics (rNEMD) method and the Stillinger-Weber (SW) potential to determine the input parameters for achieving ±1% convergence of the calculated thermal conductivity of silicon. These parameters are then used to investigate the effects of the interatomic potentials of SW, Tersoff II, Environment Dependent Interatomic Potential (EDIP), Second Nearest Neighbor, Modified Embedded-Atom Method (MEAM), and Highly Optimized Empirical Potential MEAM on determining the bulk thermal conductivity as a function of temperature (400-1000 K). At temperatures > 400 K, data collection and swap periods of 15 ns and 150 fs, system size ≥6 × 6 UC2 and system lengths ≥192 UC are adequate for ±1% convergence with all potentials, regardless of the time step size (0.1-0.5 fs). This is also true at 400 K, except for the SW potential, which requires a data collection period ≥30 ns. The calculated bulk thermal conductivities using the rNEMD method and the EDIP potential are close to, but lower than experimental values. The 10% difference at 400 K increases gradually to 20% at 1000 K.

Charge equilibrium and radiation of low-energy cosmic rays passing through interstellar medium

NASA Technical Reports Server (NTRS)

Rule, D. W.; Omidvar, K.

1979-01-01

The charge equilibrium and radiation of an oxygen and an iron beam in the MeV per nucleon energy range, representing a typical beam of low-energy cosmic rays passing through the interstellar medium, are considered. Electron loss of the beam has been taken into account by means of the first Born approximation, allowing for the target atom to remain unexcited or to be excited to all possible states. Electron-capture cross sections have been calculated by means of the scaled Oppenheimer-Brinkman-Kramers approximation, taking into account all atomic shells of the target atoms and capture into all excited states of the projectile. The capture and loss cross sections are found to be within 20%-30% of the existing experimental values for most of the cases considered. Radiation of the beam due to electron capture into the excited states of the ion, collisional excitation, and collisional inner-shell ionization, taking into account the fluorescence yield of the ions, has been considered. Effective X-ray production cross sections and multiplicities for the most energetic X-ray lines emitted by the Fe and O beams have been calculated, and error estimates made for the results.

The Lewis Chemical Equilibrium Program with parametric study capability

NASA Technical Reports Server (NTRS)

Sevigny, R.

1981-01-01

The program was developed to determine chemical equilibrium in complex systems. Using a free energy minimization technique, the program permits calculations such as: chemical equilibrium for assigned thermodynamic states; theoretical rocket performance for both equilibrium and frozen compositions during expansion; incident and reflected shock properties; and Chapman-Jouget detonation properties. It is shown that the same program can handle solid coal in an entrained flow coal gasification problem.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siol, Sebastian; Holder, Aaron; Ortiz, Brenden R.

Here, the controlled decomposition of metastable alloys is an attractive route to form nanostructured thermoelectric materials with reduced thermal conductivity. The ternary SnTe–MnTe and SnTe–SnSe heterostructural alloys have been demonstrated as promising materials for thermoelectric applications. In this work, the quaternary Sn 1–yMnyTe 1–xSe x phase space serves as a relevant model system to explore how a combination of computational and combinatorial-growth methods can be used to study equilibrium and non-equilibrium solubility limits. Results from first principle calculations indicate low equilibrium solubility for x,y < 0.05 that are in good agreement with results obtained from bulk equilibrium synthesis experiments andmore » predict significantly higher spinodal limits. An experimental screening using sputtered combinatorial thin film sample libraries showed a remarkable increase in non-equilibrium solubility for x,y > 0.2. These theoretical and experimental results were used to guide the bulk synthesis of metastable alloys. The ability to reproduce the non-equilibrium solubility levels in bulk materials indicates that such theoretical calculations and combinatorial growth can inform bulk synthetic routes. Further, the large difference between equilibrium and non-equilibrium solubility limits in Sn 1–yMn yTe 1–xSe x indicates these metastable alloys are attractive in terms of nano-precipitate formation for potential thermoelectric applications.« less

Atomic kinetic energy, momentum distribution, and structure of solid neon at zero temperature

NASA Astrophysics Data System (ADS)

Cazorla, C.; Boronat, J.

2008-01-01

We report on the calculation of the ground-state atomic kinetic energy Ek and momentum distribution of solid Ne by means of the diffusion Monte Carlo method and Aziz HFD-B pair potential. This approach is shown to perform notably for this crystal since we obtain very good agreement with respect to experimental thermodynamic data. Additionally, we study the structural properties of solid Ne at densities near the equilibrium by estimating the radial pair-distribution function, Lindemann’s ratio, and atomic density profile around the positions of the perfect crystalline lattice. Our value for Ek at the equilibrium density is 41.51(6)K , which agrees perfectly with the recent prediction made by Timms , 41(2)K , based on their deep-inelastic neutron scattering experiments carried out over the temperature range 4-20K , and also with previous path integral Monte Carlo results obtained with the Lennard-Jones and Aziz HFD-C2 atomic pairwise interactions. The one-body density function of solid Ne is calculated accurately and found to fit perfectly, within statistical uncertainty, to a Gaussian curve. Furthermore, we analyze the degree of anharmonicity of solid Ne by calculating some of its microscopic ground-state properties within traditional harmonic approaches. We provide insightful comparison to solid He4 in terms of the Debye model in order to assess the relevance of anharmonic effects in Ne.

Assessing bioavailability levels of metals in effluent-affected rivers: effect of Fe(III) and chelating agents on the distribution of metal speciation.

PubMed

Han, Shuping; Naito, Wataru; Masunaga, Shigeki

To assess the effects of Fe(III) and anthropogenic ligands on the bioavailability of Ni, Cu, Zn, and Pb, concentrations of bioavailable metals were measured by the DGT (diffusive gradients in thin films) method in some urban rivers, and were compared with concentrations calculated by a chemical equilibrium model (WHAM 7.0). Assuming that dissolved Fe(III) (<0.45 μm membrane filtered) was in equilibrium with colloidal iron oxide, the WHAM 7.0 model estimated that bioavailable concentrations of Ni, Cu, and Zn were slightly higher than the corresponding values estimated assuming that dissolved Fe(III) was absent. In contrast, lower levels of free Pb were predicted by the WHAM 7.0 model when dissolved Fe(III) was included. Estimates showed that most of the dissolved Pb was present as colloidal iron-Pb complex. Ethylene-diamine-tetra-acetic acid (EDTA) concentrations at sampling sites were predicted from the relationship between EDTA and the calculated bioavailable concentration of Zn. When both colloidal iron and predicted EDTA concentrations were included in the WHAM 7.0 calculations, dissolved metals showed a strong tendency to form EDTA complexes, in the order Ni > Cu > Zn > Pb. With the inclusion of EDTA, bioavailable concentrations of Ni, Cu, and Zn predicted by WHAM 7.0 were different from those predicted considering only humic substances and colloidal iron.

Dynamical configurations of celestial systems comprised of multiple irregular bodies

NASA Astrophysics Data System (ADS)

Jiang, Yu; Zhang, Yun; Baoyin, Hexi; Li, Junfeng

2016-09-01

This manuscript considers the main features of the nonlinear dynamics of multiple irregular celestial body systems. The gravitational potential, static electric potential, and magnetic potential are considered. Based on the three established potentials, we show that three conservative values exist for this system, including a Jacobi integral. The equilibrium conditions for the system are derived and their stability analyzed. The equilibrium conditions of a celestial system comprised of n irregular bodies are reduced to 12n - 9 equations. The dynamical results are applied to simulate the motion of multiple-asteroid systems. The simulation is useful for the study of the stability of multiple irregular celestial body systems and for the design of spacecraft orbits to triple-asteroid systems discovered in the solar system. The dynamical configurations of the five triple-asteroid systems 45 Eugenia, 87 Sylvia, 93 Minerva, 216 Kleopatra, and 136617 1994CC, and the six-body system 134340 Pluto are calculated and analyzed.

Nonlinear Reynolds stress model for turbulent shear flows

NASA Technical Reports Server (NTRS)

Barton, J. Michael; Rubinstein, R.; Kirtley, K. R.

1991-01-01

A nonlinear algebraic Reynolds stress model, derived using the renormalization group, is applied to equilibrium homogeneous shear flow and fully developed flow in a square duct. The model, which is quadratically nonlinear in the velocity gradients, successfully captures the large-scale inhomogeneity and anisotropy of the flows studied. The ratios of normal stresses, as well as the actual magnitudes of the stresses are correctly predicted for equilibrium homogeneous shear flow. Reynolds normal stress anisotropy and attendant turbulence driven secondary flow are predicted for a square duct. Profiles of mean velocity and normal stresses are in good agreement with measurements. Very close to walls, agreement with measurements diminishes. The model has the benefit of containing no arbitrary constants; all values are determined directly from the theory. It seems that near wall behavior is influenced by more than the large scale anisotropy accommodated in the current model. More accurate near wall calculations may well require a model for anisotropic dissipation.

The effect of photochemical models on calculated equilibria and cooling rates in the stratosphere

NASA Technical Reports Server (NTRS)

Blake, D.; Lindzen, R. S.

1973-01-01

Simplified models were developed for radiative heating and cooling and for ozone photochemistry in the region 22-60 km. The latter permit the inclusion of nitrogen and hydrogen reactions in addition to simple oxygen reactions. The simplicity of the scheme facilitates the use of a wide variety of cooling and reaction rates. It is shown that joint radiative-photochemical equilibrium is appropriate to the mean state of the atmosphere between 35 and 60 km. The relaxation of perturbations from joint radiative-photochemical equilibrium was also investigated. In all cases the coupling between temperature dependent ozone photochemistry and radiation lead to a reduction of the thermal relaxation time from its purely radiative value. The latter, which amounts to about 10 days, is reduced to 2-4 days at heights of 31-35 km. This greatly enhances the dissipation of waves traveling through the stratosphere.

Influence of pH for the determination of serum albumin by a dye-binding method in the presence of a detergent.

PubMed

Suzuki, Yuji

2008-08-01

In the dye-binding method, the absorbance increase caused by a protein error of a pH indicator is observed only in a restricted pH range. However, this pH range in the presence of a detergent has not yet been examined. Thus, the author investigated the pH (pH(UL)) where the absorbance increase becomes zero by a calculation based on the chemical equilibrium of a protein error of a pH indicator, and by experiments using four sulfonephthalein dyes. The pH(UL) value changed only with the detergent concentration, but did not change at all due to the dye, buffer solution or protein concentrations. Although the pH(UL) value was different according to the kind of dye used, it correlated well with the pK(D) values (dissociation constant) of BPB, BCG, BCP and BTB. The characteristics of pH(UL) in the reactions of the four dyes indicated good agreement with that obtained by a calculation.

When Density Functional Approximations Meet Iron Oxides.

PubMed

Meng, Yu; Liu, Xing-Wu; Huo, Chun-Fang; Guo, Wen-Ping; Cao, Dong-Bo; Peng, Qing; Dearden, Albert; Gonze, Xavier; Yang, Yong; Wang, Jianguo; Jiao, Haijun; Li, Yongwang; Wen, Xiao-Dong

2016-10-11

Three density functional approximations (DFAs), PBE, PBE+U, and Heyd-Scuseria-Ernzerhof screened hybrid functional (HSE), were employed to investigate the geometric, electronic, magnetic, and thermodynamic properties of four iron oxides, namely, α-FeOOH, α-Fe 2 O 3 , Fe 3 O 4 , and FeO. Comparing our calculated results with available experimental data, we found that HSE (a = 0.15) (containing 15% "screened" Hartree-Fock exchange) can provide reliable values of lattice constants, Fe magnetic moments, band gaps, and formation energies of all four iron oxides, while standard HSE (a = 0.25) seriously overestimates the band gaps and formation energies. For PBE+U, a suitable U value can give quite good results for the electronic properties of each iron oxide, but it is challenging to accurately get other properties of the four iron oxides using the same U value. Subsequently, we calculated the Gibbs free energies of transformation reactions among iron oxides using the HSE (a = 0.15) functional and plotted the equilibrium phase diagrams of the iron oxide system under various conditions, which provide reliable theoretical insight into the phase transformations of iron oxides.

Temperature elevation in the fetus from electromagnetic exposure during magnetic resonance imaging

NASA Astrophysics Data System (ADS)

Kikuchi, Satoru; Saito, Kazuyuki; Takahashi, Masaharu; Ito, Koichi

2010-04-01

This study computationally assessed the temperature elevations due to electromagnetic wave energy deposition during magnetic resonance imaging in non-pregnant and pregnant woman models. We used a thermal model with thermoregulatory response of the human body for our calculations. We also considered the effect of blood temperature variation on body core temperature. In a thermal equilibrium state, the temperature elevations in the intrinsic tissues of the woman and fetal tissues were 0.85 and 0.61 °C, respectively, at a whole-body averaged specific absorption rate of 2.0 W kg-1, which is the restriction value of the International Electrotechnical Commission for the normal operating mode. As predicted, these values are below the temperature elevation of 1.5 °C that is expected to be teratogenic. However, these values exceeded the recommended temperature elevation limit of 0.5 °C by the International Commission on Non-Ionizing Radiation Protection. We also assessed the irradiation time required for a temperature elevation of 0.5 °C at the aforementioned specific absorption rate. As a result, the calculated irradiation time was 40 min.

Numerical Experiments Based on the Catastrophe Model of Solar Eruptions

NASA Astrophysics Data System (ADS)

Xie, X. Y.; Ziegler, U.; Mei, Z. X.; Wu, N.; Lin, J.

2017-11-01

On the basis of the catastrophe model developed by Isenberg et al., we use the NIRVANA code to perform the magnetohydrodynamics (MHD) numerical experiments to look into various behaviors of the coronal magnetic configuration that includes a current-carrying flux rope used to model the prominence levitating in the corona. These behaviors include the evolution in equilibrium heights of the flux rope versus the change in the background magnetic field, the corresponding internal equilibrium of the flux rope, dynamic properties of the flux rope after the system loses equilibrium, as well as the impact of the referential radius on the equilibrium heights of the flux rope. In our calculations, an empirical model of the coronal density distribution given by Sittler & Guhathakurta is used, and the physical diffusion is included. Our experiments show that the deviation of simulations in the equilibrium heights from the theoretical results exists, but is not apparent, and the evolutionary features of the two results are similar. If the flux rope is initially locate at the stable branch of the theoretical equilibrium curve, the flux rope will quickly reach the equilibrium position in the simulation after several rounds of oscillations as a result of the self-adjustment of the system; and the flux rope lose the equilibrium if the initial location of the flux rope is set at the critical point on the theoretical equilibrium curve. Correspondingly, the internal equilibrium of the flux rope can be reached as well, and the deviation from the theoretical results is somewhat apparent since the approximation of the small radius of the flux rope is lifted in our experiments, but such deviation does not affect the global equilibrium in the system. The impact of the referential radius on the equilibrium heights of the flux rope is consistent with the prediction of the theory. Our calculations indicate that the motion of the flux rope after the loss of equilibrium is consistent with which is predicted by the Lin-Forbes model and observations. Formation of the fast mode shock ahead of the flux rope is observed in our experiments. Outward motions of the flux rope are smooth, and magnetic energy is continuously converted into the other types of energy because both the diffusions are considered in calculations, and magnetic reconnection is allowed to occur successively in the current sheet behind the flux rope.

Tearing Mode Stability of Evolving Toroidal Equilibria

NASA Astrophysics Data System (ADS)

Pletzer, A.; McCune, D.; Manickam, J.; Jardin, S. C.

2000-10-01

There are a number of toroidal equilibrium (such as JSOLVER, ESC, EFIT, and VMEC) and transport codes (such as TRANSP, BALDUR, and TSC) in our community that utilize differing equilibrium representations. There are also many heating and current drive (LSC and TORRAY), and stability (PEST1-3, GATO, NOVA, MARS, DCON, M3D) codes that require this equilibrium information. In an effort to provide seamless compatibility between the codes that produce and need these equilibria, we have developed two Fortran 90 modules, MEQ and XPLASMA, that serve as common interfaces between these two classes of codes. XPLASMA provides a common equilibrium representation for the heating and current drive applications while MEQ provides common equilibrium and associated metric information needed by MHD stability codes. We illustrate the utility of this approach by presenting results of PEST-3 tearing stability calculations of an NSTX discharge performed on profiles provided by the TRANSP code. Using the MEQ module, the TRANSP equilibrium data are stored in a Fortran 90 derived type and passed to PEST3 as a subroutine argument. All calculations are performed on the fly, as the profiles evolve.

The calculation of the viscosity from the autocorrelation function using molecular and atomic stress tensors

NASA Astrophysics Data System (ADS)

Cui, S. T.

The stress-stress correlation function and the viscosity of a united-atom model of liquid decane are studied by equilibrium molecular dynamics simulation using two different formalisms for the stress tensor: the atomic and the molecular formalisms. The atomic and molecular correlation functions show dramatic difference in short-time behaviour. The integrals of the two correlation functions, however, become identical after a short transient period whichis significantly shorter than the rotational relaxation time of the molecule. Both reach the same plateau value in a time period corresponding to this relaxation time. These results provide a convenient guide for the choice of the upper integral time limit in calculating the viscosity by the Green-Kubo formula.

First principle study of AlX (X=3d, 4d, 5d elements and Lu) dimer.

PubMed

Ouyang, Yifang; Wang, Jianchuan; Hou, Yuhua; Zhong, Xiaping; Du, Yong; Feng, Yuanping

2008-02-21

The ground state equilibrium bond length, harmonic vibrational frequency, and dissociation energy of AlX (X=3d,4d,5d elements and Lu) dimers are investigated by density functional method B3LYP. The present results are in good agreement with the available experimental and other theoretical values except the dissociation energy of AlCr. The present calculations show that the late transition metal can combine strongly with aluminum compared with the former transition metal. The present calculation also indicates that it is more reasonable to replace La with Lu in the Periodic Table and that the bonding strengths of zinc, cadmium, and mercury with aluminum are very weak.

Wang-Landau density of states based study of the folding-unfolding transition in the mini-protein Trp-cage (TC5b)

NASA Astrophysics Data System (ADS)

Singh, Priya; Sarkar, Subir K.; Bandyopadhyay, Pradipta

2014-07-01

We present the results of a high-statistics equilibrium study of the folding/unfolding transition for the 20-residue mini-protein Trp-cage (TC5b) in water. The ECEPP/3 force field is used and the interaction with water is treated by a solvent-accessible surface area method. A Wang-Landau type simulation is used to calculate the density of states and the conditional probabilities for the various values of the radius of gyration and the number of native contacts at fixed values of energy—along with a systematic check on their convergence. All thermodynamic quantities of interest are calculated from this information. The folding-unfolding transition corresponds to a peak in the temperature dependence of the computed specific heat. This is corroborated further by the structural signatures of folding in the distributions for radius of gyration and the number of native contacts as a function of temperature. The potentials of mean force are also calculated for these variables, both separately and jointly. A local free energy minimum, in addition to the global minimum, is found in a temperature range substantially below the folding temperature. The free energy at this second minimum is approximately 5 kBT higher than the value at the global minimum.

Equilibrium time correlation functions and the dynamics of fluctuations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luban, Marshall; Luscombe, James H.

1999-12-01

Equilibrium time correlation functions are of great importance because they probe the equilibrium dynamical response to external perturbations. We discuss the properties of time correlation functions for several systems that are simple enough to illustrate the calculational steps involved. The discussion underscores the need for avoiding language which misleadingly suggests that thermal equilibrium is associated with a quiescent or moribund state of the system. (c) 1999 American Association of Physics Teachers.

Non-equilibrium dynamics from RPMD and CMD.

PubMed

Welsch, Ralph; Song, Kai; Shi, Qiang; Althorpe, Stuart C; Miller, Thomas F

2016-11-28

We investigate the calculation of approximate non-equilibrium quantum time correlation functions (TCFs) using two popular path-integral-based molecular dynamics methods, ring-polymer molecular dynamics (RPMD) and centroid molecular dynamics (CMD). It is shown that for the cases of a sudden vertical excitation and an initial momentum impulse, both RPMD and CMD yield non-equilibrium TCFs for linear operators that are exact for high temperatures, in the t = 0 limit, and for harmonic potentials; the subset of these conditions that are preserved for non-equilibrium TCFs of non-linear operators is also discussed. Furthermore, it is shown that for these non-equilibrium initial conditions, both methods retain the connection to Matsubara dynamics that has previously been established for equilibrium initial conditions. Comparison of non-equilibrium TCFs from RPMD and CMD to Matsubara dynamics at short times reveals the orders in time to which the methods agree. Specifically, for the position-autocorrelation function associated with sudden vertical excitation, RPMD and CMD agree with Matsubara dynamics up to O(t 4 ) and O(t 1 ), respectively; for the position-autocorrelation function associated with an initial momentum impulse, RPMD and CMD agree with Matsubara dynamics up to O(t 5 ) and O(t 2 ), respectively. Numerical tests using model potentials for a wide range of non-equilibrium initial conditions show that RPMD and CMD yield non-equilibrium TCFs with an accuracy that is comparable to that for equilibrium TCFs. RPMD is also used to investigate excited-state proton transfer in a system-bath model, and it is compared to numerically exact calculations performed using a recently developed version of the Liouville space hierarchical equation of motion approach; again, similar accuracy is observed for non-equilibrium and equilibrium initial conditions.

Permanent electric dipole moments of PtX (X = H, F, Cl, Br, and I) by the composite approach

NASA Astrophysics Data System (ADS)

Deng, Dan; Lian, Yongqin; Zou, Wenli

2017-11-01

Using the FPD composite approach of Peterson et. al. we calculate the permanent electric dipole moments of PtX (X = H, F, Cl, Br, and I) at the equilibrium geometries of their ground states. The dipole moment of PtF is estimated to be 3.421 Debye, being very close to the experimental value of 3.42(6) Debye. This research also suggests the ordering of dipole moments of PtX being proportional to the electronegativity of X.

Hybrid functional study of α-uranium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaur, Gurpreet, E-mail: gurpreet@igcar.gov.in; Chinnappan, Ravi; Panigrahi, B. K.

2016-05-23

We have used the hybrid density functionals to study the structural and electronic properties of alpha-U. The fraction of exact Hartree Folk exchange used is varied from 0.0 to 0.6. The equilibrium volume is found to be underestimated and bulk modulus overestimated with HSE as compared to both calculated by PBE and the experimental values. Electronic bands below the Fermi level are found to shift to lower energy with respect to PBE electronic bands which itself gives the bands shifted to lower energies as compared to UPS experiments.

Standard Gibbs energy of metabolic reactions: II. Glucose-6-phosphatase reaction and ATP hydrolysis.

PubMed

Meurer, Florian; Do, Hoang Tam; Sadowski, Gabriele; Held, Christoph

2017-04-01

ATP (adenosine triphosphate) is a key reaction for metabolism. Tools from systems biology require standard reaction data in order to predict metabolic pathways accurately. However, literature values for standard Gibbs energy of ATP hydrolysis are highly uncertain and differ strongly from each other. Further, such data usually neglect the activity coefficients of reacting agents, and published data like this is apparent (condition-dependent) data instead of activity-based standard data. In this work a consistent value for the standard Gibbs energy of ATP hydrolysis was determined. The activity coefficients of reacting agents were modeled with electrolyte Perturbed-Chain Statistical Associating Fluid Theory (ePC-SAFT). The Gibbs energy of ATP hydrolysis was calculated by combining the standard Gibbs energies of hexokinase reaction and of glucose-6-phosphate hydrolysis. While the standard Gibbs energy of hexokinase reaction was taken from previous work, standard Gibbs energy of glucose-6-phosphate hydrolysis reaction was determined in this work. For this purpose, reaction equilibrium molalities of reacting agents were measured at pH7 and pH8 at 298.15K at varying initial reacting agent molalities. The corresponding activity coefficients at experimental equilibrium molalities were predicted with ePC-SAFT yielding the Gibbs energy of glucose-6-phosphate hydrolysis of -13.72±0.75kJ·mol -1 . Combined with the value for hexokinase, the standard Gibbs energy of ATP hydrolysis was finally found to be -31.55±1.27kJ·mol -1 . For both, ATP hydrolysis and glucose-6-phosphate hydrolysis, a good agreement with own and literature values were obtained when influences of pH, temperature, and activity coefficients were explicitly taken into account in order to calculate standard Gibbs energy at pH7, 298.15K and standard state. Copyright © 2017 Elsevier B.V. All rights reserved.

Aqueous solubility calculation for petroleum mixtures in soil using comprehensive two-dimensional gas chromatography analysis data.

PubMed

Mao, Debin; Lookman, Richard; Van De Weghe, Hendrik; Vanermen, Guido; De Brucker, Nicole; Diels, Ludo

2009-04-03

An assessment of aqueous solubility (leaching potential) of soil contaminations with petroleum hydrocarbons (TPH) is important in the context of the evaluation of (migration) risks and soil/groundwater remediation. Field measurements using monitoring wells often overestimate real TPH concentrations in case of presence of pure oil in the screened interval of the well. This paper presents a method to calculate TPH equilibrium concentrations in groundwater using soil analysis by high-performance liquid chromatography followed by comprehensive two-dimensional gas chromatography (HPLC-GCXGC). The oil in the soil sample is divided into 79 defined hydrocarbon fractions on two GCXGC color plots. To each of these fractions a representative water solubility is assigned. Overall equilibrium water solubility of the non-aqueous phase liquid (NAPL) present in the sample and the water phase's chemical composition (in terms of the 79 fractions defined) are then calculated using Raoult's law. The calculation method was validated using soil spiked with 13 different TPH mixtures and 1 field-contaminated soil. Measured water solubilities using a column recirculation equilibration experiment agreed well to calculated equilibrium concentrations and water phase TPH composition.

Dust formation in LBV envelopes

NASA Astrophysics Data System (ADS)

Gail, H.-P.; Duschl, W. J.; Ferrarotti, A. S.; Weis, K.

2005-09-01

The condensation process for the peculiar element mixture of CNO cycle processed material in the pre-SN ejecta of massive stars is investigated. From thermodynamic equilibrium calculations it is shown that the most likely solids to be formed in CNO process equilibrated materials are solid FeSi, metallic Fe, and small quantities of forsterite (Mg2SiO4). Nucleation may be triggered by TiC. Some SiC may be formed by non-equilibrium condensation. As a case study for these substances the non-equilibrium dust condensation in the outflow is calculated for a simple stationary wind model which shows, that these dust species indeed can be formed in the ejecta.

Molecular simulations of Crussard curves of detonation product mixtures at chemical equilibrium: Microscopic calculation of the Chapman-Jouguet state

NASA Astrophysics Data System (ADS)

Bourasseau, Emeric; Dubois, Vincent; Desbiens, Nicolas; Maillet, Jean-Bernard

2007-06-01

The simultaneous use of the Reaction Ensemble Monte Carlo (ReMC) method and the Adaptative Erpenbeck EOS (AE-EOS) method allows us to calculate direclty the thermodynamical and chemical equilibrium of a mixture on the hugoniot curve. The ReMC method allow to reach chemical equilibrium of detonation products and the AE-EOS method constraints ths system to satisfy the Hugoniot relation. Once the Crussard curve of detonation products has been established, CJ state properties may be calculated. An additional NPT simulation is performed at CJ conditions in order to compute derivative thermodynamic quantities like Cp, Cv, Gruneisen gama, sound velocity, and compressibility factor. Several explosives has been studied, of which PETN, nitromethane, tetranitromethane, and hexanitroethane. In these first simulations, solid carbon is eventually treated using an EOS.

A mass balance approach for calculation of recovery and binding enables the use of ultrafiltration as a rapid method for measurement of plasma protein binding for even highly lipophilic compounds.

PubMed

Wang, Changguang; Williams, Noelle S

2013-03-05

The aim of this study is to further validate the use of ultrafiltration (UF) as a method for determining plasma protein binding (PPB) by demonstrating that non-specific binding (NSB) is not a limitation, even for highly lipophilic compounds, because NSB sites on the apparatus are passivated in the presence of plasma. Mass balance theory was used to calculate recovery of 20 commercial and seven investigational compounds during ultrafiltration in the presence and absence of plasma. PPB was also measured using this mass balance approach for comparison to PPB determined by rapid equilibrium dialysis (RED) and as found in the literature. Compound recovery during UF was dramatically different in the presence and absence of plasma for compounds with high NSB in PBS only. A comparison of PPB calculated by ultrafiltration with literature values or calculated by RED gave concordant results. Discrepancies could be explained by changes in pH, insufficient time to equilibrium, or compound instability during RED, problems which were circumvented by ultrafiltration. Therefore, NSB, as measured by the traditional incubation of compound in PBS, need not be an issue when choosing UF as a PPB assay method. It is more appropriate to calculate compound recovery from the device in plasma as measured by mass balance to determine the suitability of the method for an individual compound. The speed with which UF can be conducted additionally avoids changes in pH or compound loss that can occur with other methods. The mass balance approach to UF is thus a preferred method for rapid determination of PPB. Copyright © 2012 Elsevier B.V. All rights reserved.

Evolutions and equilibrium parameters of foam films from individual solutions of Bovine serum albumin, n-dodecyl-β-D-maltoside and from their mixed solutions

NASA Astrophysics Data System (ADS)

Gerasimova, Anelia Tsvetanova; Angarska, Jana Krumova; Tachev, Krasimir Dimov

2017-03-01

The evolutions of thinning of films from individual solutions of BSA, C12G2 and from their mixed solutions with molar ratios 1:1, 1:7.5, 1:50 and 1:100 with pH = 4.9 were recorded by modified (with video camera) interferometric method. Based on them the stages through which the film goes from its formation to the equilibrium state were distinguished. It was shown that: (i) the difference between the kinetic of drainage of films stabilized by high and low molecular surfactants is drastic; (ii) only the change of the pH solution under or above isoelectric point strongly retards the film drainage; (iii) the transition of the kinetic of thinning of films from mixed solutions from a kinetic typical for high molecular substances towards a kinetic for low substances depends on the molar ratio between the components in the solution. From the picture of film corresponding to its equilibrium state the type of film was determined. From the analysis of this picture the equilibrium thickness and contact angle were calculated. It was found that the criterion for Newtonium black films (based on the values of film thickness and contact angle) is not directly applicable for films from protein solutions or mixed solutions with the participation of proteins.

Understanding of surface pit formation mechanism of GaN grown in MOCVD based on local thermodynamic equilibrium assumption

NASA Astrophysics Data System (ADS)

Zhi-Yuan, Gao; Xiao-Wei, Xue; Jiang-Jiang, Li; Xun, Wang; Yan-Hui, Xing; Bi-Feng, Cui; De-Shu, Zou

2016-06-01

Frank’s theory describes that a screw dislocation will produce a pit on the surface, and has been evidenced in many material systems including GaN. However, the size of the pit calculated from the theory deviates significantly from experimental result. Through a careful observation of the variations of surface pits and local surface morphology with growing temperature and V/III ratio for c-plane GaN, we believe that Frank’s model is valid only in a small local surface area where thermodynamic equilibrium state can be assumed to stay the same. If the kinetic process is too vigorous or too slow to reach a balance, the local equilibrium range will be too small for the center and edge of the screw dislocation spiral to be kept in the same equilibrium state. When the curvature at the center of the dislocation core reaches the critical value 1/r 0, at the edge of the spiral, the accelerating rate of the curvature may not fall to zero, so the pit cannot reach a stationary shape and will keep enlarging under the control of minimization of surface energy to result in a large-sized surface pit. Project supported by the National Natural Science Foundation of China (Grant Nos. 11204009 and 61204011) and the Beijing Municipal Natural Science Foundation, China (Grant No. 4142005).

Austenite grain growth simulation considering the solute-drag effect and pinning effect

PubMed Central

Fujiyama, Naoto; Nishibata, Toshinobu; Seki, Akira; Hirata, Hiroyuki; Kojima, Kazuhiro; Ogawa, Kazuhiro

2017-01-01

Abstract The pinning effect is useful for restraining austenite grain growth in low alloy steel and improving heat affected zone toughness in welded joints. We propose a new calculation model for predicting austenite grain growth behavior. The model is mainly comprised of two theories: the solute-drag effect and the pinning effect of TiN precipitates. The calculation of the solute-drag effect is based on the hypothesis that the width of each austenite grain boundary is constant and that the element content maintains equilibrium segregation at the austenite grain boundaries. We used Hillert’s law under the assumption that the austenite grain boundary phase is a liquid so that we could estimate the equilibrium solute concentration at the austenite grain boundaries. The equilibrium solute concentration was calculated using the Thermo-Calc software. Pinning effect was estimated by Nishizawa’s equation. The calculated austenite grain growth at 1473–1673 K showed excellent correspondence with the experimental results. PMID:28179962

Modelling Equilibrium and Fractional Crystallization in the System MgO-FeO-CaO-Al2O3-SiO2

NASA Technical Reports Server (NTRS)

Herbert, F.

1985-01-01

A mathematical modelling technique for use in petrogenesis calculations in the system MgO-FeO-CaO-Al2O3-SiO2 is reported. Semiempirical phase boundary and elemental distribution information was combined with mass balance to compute approximate equilibrium crystallization paths for arbitrary system compositions. The calculation is applicable to a range of system compositions and fractionation calculations are possible. The goal of the calculation is the computation of the composition and quantity of each phase present as a function of the degree of solidification. The degree of solidification is parameterized by the heat released by the solidifying phases. The mathematical requirement for the solution of this problem is: (1) An equation constraining the composition of the magma for each solid phase in equilibrium with the liquidus phase, and (2) an equation for each solid phase and each component giving the distribution of that element between that phase and the magma.

Many-Body Spectral Functions from Steady State Density Functional Theory.

PubMed

Jacob, David; Kurth, Stefan

2018-03-14

We propose a scheme to extract the many-body spectral function of an interacting many-electron system from an equilibrium density functional theory (DFT) calculation. To this end we devise an ideal scanning tunneling microscope (STM) setup and employ the recently proposed steady-state DFT formalism (i-DFT) which allows one to calculate the steady current through a nanoscopic region coupled to two biased electrodes. In our setup, one of the electrodes serves as a probe ("STM tip"), which is weakly coupled to the system we want to measure. In the ideal STM limit of vanishing coupling to the tip, the system is restored to quasi-equilibrium and the normalized differential conductance yields the exact equilibrium many-body spectral function. Calculating this quantity from i-DFT, we derive an exact relation expressing the interacting spectral function in terms of the Kohn-Sham one. As illustrative examples, we apply our scheme to calculate the spectral functions of two nontrivial model systems, namely the single Anderson impurity model and the Constant Interaction Model.

Reconstruction of equilibrium trajectories during whole-body movements.

PubMed

Domen, K; Latash, M L; Zatsiorsky, V M

1999-03-01

The framework of the equilibrium-point hypothesis was used to reconstruct equilibrium trajectories (ETs) of the ankle, hip and body center of mass during quick voluntary hip flexions ('Japanese courtesy bow') by standing subjects. Different spring loads applied to the subject's back were used to introduce smooth perturbations that are necessary to reconstruct ETs based on a series of trials at the same task. Time patterns of muscle torques were calculated using inverse dynamics techniques. A second-order linear model was employed to calculate the instantaneous position of the spring-like joint or center of mass characteristic at different times during the movement. ETs of the joints and of the center of mass had significantly different shapes from the actual trajectories. Integral measures of electromyographic bursts of activity in postural muscles demonstrated a relation to muscle length corresponding to the equilibrium-point hypothesis.

Kinetics and Thermochemistry of the Br((sup 2)P3/2) + NO2 Association Reaction

NASA Technical Reports Server (NTRS)

Kreutter, K. D.; Nicovich, J. M.; Wine, P. H.

1997-01-01

A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the Br((sup 2)P3/2) + NO2 association reaction as a function of temperature (259-432 K) pressure (12.5 - 700 Torr), and buffer gas identity (He, Ar, H2, N2, CO2, CF4, SF6). The reaction is found to be in the falloff regime between third and second order over the entire range of conditions investigated. At temperatures below 350 K, the association reaction is found to be irreversible on the time scale of the experiment (approximately 30 ms). At higher temperatures reversible addition is observed, allowing equilibrium constants for BrNO2 formation and dissociation to be determined. Second- and third-law analyses of the equilibrium data are in only fair agreement and lead to the following thermochemical parameters for the association reaction: Delta-H(298) = 19.6 +/- 1.7 kcal/mol, Delta-H(0) = -18.6 +/- 2.0 kcal/mol, Delta-S(298) = 29.3 +/- 4.2 cal/mol/K, Delta-H(sub f)(sub 298)(BrNO2) = 17.0 +/-1.8 kcal/mol(uncertainties are 2 sigma estimates of absolute accuracy). The value for Delta-H(0) determined in this study has been employed to calculate k(sub 0)(sup SC), the low-pressure third-order rate coefficient in the strong collision limit, by using the method of Troe; calculated values of k(sub 0)(sup SC) are inconsistent with experimental results unless Delta-H(0) is assigned a value near the lower limit derived from analysis of the high-temperature approach to equilibrium data, i.e. delta-H(0) approximately equals -16.6 kcal/mol. A potential source of systematic error in the calculation of both k(sub 0)(sup SC) and the absolute entropy of BrNO2 results from the complete lack of knowledge of the energies and degeneracies of the electronic states of BrNO3. The procedure developed by Troe and co-workers has been employed to extrapolate experimental falloff curves to the low- and high-pressure limits. Derived values for k(sub 0)(M,298K) in units of 10(exp -31) cm(exp 6)/sq molecule/s range from 2.75 for M = He to 6.54 for M = CO2; 2 sigma uncertainties are estimated to be +/- 20%. Values for k(sub 0)(N2,T) in units of 10(exp -31) cm(exp 6)/sq molecule/s are 5.73 at 259 K, 4.61 at 298 K, and 3.21 at 346 K; the observed temperature dependence for k(sub 0)(N2,T) is consistent with the theoretical temperature dependence for Beta(sub c)k(sub 0)(sup SC). Values for k(sub infinity)(T) in units of 10(exp -11) cu cm/molecule/s are 2.86 at 259 K, 3.22 at 298 K, and 3.73 at 346 K; 2 sigma uncertainties are estimated to be a factor of 2. Approximate falloff parameters in a convenient format for atmospheric modeling are also derived.

Atomic structure data based on average-atom model for opacity calculations in astrophysical plasmas

NASA Astrophysics Data System (ADS)

Trzhaskovskaya, M. B.; Nikulin, V. K.

2018-03-01

Influence of the plasmas parameters on the electron structure of ions in astrophysical plasmas is studied on the basis of the average-atom model in the local thermodynamic equilibrium approximation. The relativistic Dirac-Slater method is used for the electron density estimation. The emphasis is on the investigation of an impact of the plasmas temperature and density on the ionization stages required for calculations of the plasmas opacities. The level population distributions and level energy spectra are calculated and analyzed for all ions with 6 ≤ Z ≤ 32 occurring in astrophysical plasmas. The plasma temperature range 2 - 200 eV and the density range 2 - 100 mg/cm3 are considered. The validity of the method used is supported by good agreement between our values of ionization stages for a number of ions, from oxygen up to uranium, and results obtained earlier by various methods among which are more complicated procedures.

Electric field control of spin transfer torque in multiferroic tunnel junctions

NASA Astrophysics Data System (ADS)

Useinov, Artur; Kalitsov, Alan; Velev, Julian; Kioussis, Nicholas

2014-03-01

Based on model calculations we predict that the spin transfer torque (STT) in magnetic tunnel junctions with ferroelectric barriers can be strongly influenced by the saturated polarization of the barrier. The STT in such multiferroic tunnel junctions is calculated within the non-equilibrium Keldysh formalism generalized for non-collinear transport and implemented in the framework of a single-band tight-binding (TB) model. We calculate the bias dependence of both the in-plane (T∥) and out-of-plane (T⊥) components of STT as a function of the ferroelectric polarization (P) in the barrier. We find that the components of STT strongly depend on both the magnitude and the direction of the polarization. In particular switching of the polarization direction can dramatically alter the value of the STT and can even lead to a change of sign of T∥ and the voltage-induced part of T⊥. The effect is proportional to the magnitude of the polarization.

Gaseous Sulfate Solubility in Glass: Experimental Method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bliss, Mary

2013-11-30

Sulfate solubility in glass is a key parameter in many commercial glasses and nuclear waste glasses. This report summarizes key publications specific to sulfate solubility experimental methods and the underlying physical chemistry calculations. The published methods and experimental data are used to verify the calculations in this report and are expanded to a range of current technical interest. The calculations and experimental methods described in this report will guide several experiments on sulfate solubility and saturation for the Hanford Waste Treatment Plant Enhanced Waste Glass Models effort. There are several tables of sulfate gas equilibrium values at high temperature tomore » guide experimental gas mixing and to achieve desired SO3 levels. This report also describes the necessary equipment and best practices to perform sulfate saturation experiments for molten glasses. Results and findings will be published when experimental work is finished and this report is validated from the data obtained.« less

Ab-initio calculations of electronic, transport, and structural properties of boron phosphide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ejembi, J. I.; Nwigboji, I. H.; Franklin, L.

2014-09-14

We present results from ab-initio, self-consistent density functional theory calculations of electronic and related properties of zinc blende boron phosphide (zb-BP). We employed a local density approximation potential and implemented the linear combination of atomic orbitals formalism. This technique follows the Bagayoko, Zhao, and Williams method, as enhanced by the work of Ekuma and Franklin. The results include electronic energy bands, densities of states, and effective masses. The calculated band gap of 2.02 eV, for the room temperature lattice constant of a=4.5383 Å, is in excellent agreement with the experimental value of 2.02±0.05 eV. Our result for the bulk modulus,more » 155.7 GPa, agrees with experiment (152–155 GPa). Our predictions for the equilibrium lattice constant and the corresponding band gap, for very low temperatures, are 4.5269 Å and 2.01 eV, respectively.« less

Ab-initio calculations on melting of thorium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mukherjee, D., E-mail: debojyoti@barc.gov.in; Sahoo, B. D.; Joshi, K. D.

2016-05-23

Ab-initio molecular dynamics study has been performed on face centered cubic structured thorium to determine its melting temperature at room pressure. The ion-electron interaction potential energy calculated as a function of temperature for three volumes (a{sub 0}){sup 3} and (1.02a{sub 0}){sup 3} and (1.04a{sub 0}){sup 3} increases gradually with temperature and undergoes a sharp jump at ~2200 K, ~2100 K and ~1800 K, respectively. Here, a{sub 0} = 5.043 Å is the equilibrium lattice parameter at 0 K obtained from ab-initio calculations. These jumps in interaction energy are treated as due to the onset of melting and corresponding temperatures asmore » melting point. The melting point of 2100 K is close to the experimental value of 2023 K. Further, the same has been verified by plotting the atomic arrangement evolved at various temperatures and corresponding pair correlation functions.« less

First principles study of pressure induced polymorphic phase transition in trimethylamine

NASA Astrophysics Data System (ADS)

Abraham, B. Moses; Vaitheeswaran, G.

2018-04-01

The pressure induced variations on the crystal structure of various polymorphs of Trimethyamine (TMA-I, TMA-II, TMAIII) has been studied theoretically using first principles calculations up to 5 GPa. The obtained equilibrium lattice parameters using standard PBE-GGA functional for the ambient and high pressure phases are found to be in good agreement with the experimental values. We calculated the enthalpies of each phase to assess their relative stability. Our results also supports the existence of additional phase transitions of TMA into two new polymorphs under external pressure. The TMA-I to TMA-II transition is found to occur at 1.41 GPa and the TMA-II to TMA-III transition at 3.33 GPa. The electronic band structure calculations using Tran Blaha-modified Becke Johnson (TB-mBJ) potential show that these polymorphs of TMA are indirect band gap insulators.

Structural and vibrational analyses of new potential anticancer drug 2-(phenylmethyl)-2-azaspiro[5.11]heptadecane-1,3,7-trione

NASA Astrophysics Data System (ADS)

Vitnik, Željko J.; Popović-Đorđević, Jelena B.; Vitnik, Vesna D.

2017-06-01

The establishment of the most stable structures of 2-(phenylmethyl)-2-azaspiro[5.11]heptadecane-1,3,7-trione, potential anticancer and antimicrobial drug has been investigated in this work. A detailed interpretation of experimental and calculated IR, UV and NMR spectra were reported. The equilibrium geometry, harmonic vibrational frequencies and electronic properties have been investigated with Density Functional Theory using B3LYP/6-311++G(d,p) method. The scaled theoretical wavenumber showed very good agreement with the experimental values. The charge transfer in the molecule was confirmed with NBO analysis. Ultraviolet-visible spectrum was calculated using TD-DFT method and compared with experimental spectrum. The calculated energy and oscillator strength well reproduce the experimental data. The molecular electrostatic potential surface map portrays potential binding sites of the title molecule.

U-Th-Pb, Rb-Sr, and Sm-Nd isotopic systematics of lunar troctolitic cumulate 76535 - Implications on the age and origin of this early lunar, deep-seated cumulate

NASA Technical Reports Server (NTRS)

Premo, Wayne R.; Tatsumoto, M.

1992-01-01

The U-Th-Pb, Rb-Sr, and Sm-Nd isotopic systematics of four lightly leached residues of pristine, high-Mg, troctolitic cumulate 76535 were analyzed in order to determine their ages and magma sources. The data indicate that the cumulate was in isotopic equilibrium with a fluid or magma characterized by a high U-238/Pb-204 (mu) value of 600 at 4.236 Ga. Two and three stage Pb evolution calculations define even greater source mu values of about 1000, assuming low lunar initial mu values between 5 and 40 prior to about 4.43 Ga. These results are similar to mu values for KREEP sources and are also consistent with values from 78235, suggesting that at least some high-Mg suite rocks were derived from magma sources with high-mu values similar to KREEP, and support that idea that these rocks postdate primary lunar differentiation and formation of ferroan anorthosites.

A note on AB INITIO semiconductor band structures

NASA Astrophysics Data System (ADS)

Fiorentini, Vincenzo

1992-09-01

We point out that only the internal features of the DFT ab initio theoretical picture of a crystal should be used in a consistent ab initio calculation of the band structure. As a consequence, we show that ground-state band structure calculations should be performed for the system in equilibrium at zero pressure, i.e. at the computed equilibrium cell volume ω th. Examples of consequences of this attitude are considered.

Solute rotational dynamics at the water liquid/vapor interface.

PubMed

Benjamin, Ilan

2007-11-28

The rotational dynamics of a number of diatomic molecules adsorbed at different locations at the interface between water and its own vapors are studied using classical molecular dynamics computer simulations. Both equilibrium orientational and energy correlations and nonequilibrium orientational and energy relaxation correlations are calculated. By varying the dipole moment of the molecule and its location, and by comparing the results with those in bulk water, the effects of dielectric and mechanical frictions on reorientation dynamics and on rotational energy relaxation can be studied. It is shown that for nonpolar and weekly polar solutes, the equilibrium orientational relaxation is much slower in the bulk than at the interface. As the solute becomes more polar, the rotation slows down and the surface and bulk dynamics become similar. The energy relaxation (both equilibrium and nonequilibrium) has the opposite trend with the solute dipole (larger dipoles relax faster), but here again the bulk and surface results converge as the solute dipole is increased. It is shown that these behaviors correlate with the peak value of the solvent-solute radial distribution function, which demonstrates the importance of the first hydration shell structure in determining the rotational dynamics and dependence of these dynamics on the solute dipole and location.

Ergodic Theory, Interpretations of Probability and the Foundations of Statistical Mechanics

NASA Astrophysics Data System (ADS)

van Lith, Janneke

The traditional use of ergodic theory in the foundations of equilibrium statistical mechanics is that it provides a link between thermodynamic observables and microcanonical probabilities. First of all, the ergodic theorem demonstrates the equality of microcanonical phase averages and infinite time averages (albeit for a special class of systems, and up to a measure zero set of exceptions). Secondly, one argues that actual measurements of thermodynamic quantities yield time averaged quantities, since measurements take a long time. The combination of these two points is held to be an explanation why calculating microcanonical phase averages is a successful algorithm for predicting the values of thermodynamic observables. It is also well known that this account is problematic. This survey intends to show that ergodic theory nevertheless may have important roles to play, and it explores three other uses of ergodic theory. Particular attention is paid, firstly, to the relevance of specific interpretations of probability, and secondly, to the way in which the concern with systems in thermal equilibrium is translated into probabilistic language. With respect to the latter point, it is argued that equilibrium should not be represented as a stationary probability distribution as is standardly done; instead, a weaker definition is presented.

Use of the augmented Young-Laplace equation to model equilibrium and evaporating extended menisci

DOE Office of Scientific and Technical Information (OSTI.GOV)

DasGupta, S.; Schonberg, J.A.; Kim, I.Y.

1993-05-01

The generic importance of fluid flow and change-of-phase heat transfer in the contact line region of an extended meniscus has led to theoretical and experimental research on the details of these transport processes. Numerical solutions of equilibrium and nonequilibrium models based on the augmented Young-Laplace equation were successfully used to evaluate experimental data for an extended meniscus. The data for the equilibrium and nonequilibrium meniscus profiles were obtained optically using ellipsometry and image processing interferometry. A Taylor series expansion of the fourth-order nonlinear transport model was used to obtain the extremely sensitive initial conditions at the interline. The solid-liquid-vapor Hamakermore » constants for the systems were obtained from the experimental data. The consistency of the data was demonstrated by using the combining rules to calculate the unknown value of the Hamaker constant for the experimental substrate. The sensitivity of the meniscus profile to small changes in the environment was demonstrated. Both temperature and intermolecular forces need to be included in modeling transport processes in the contact line region because the chemical potential is a function of both temperature and pressure.« less

Tidal Love Numbers of Neutron Stars

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hinderer, Tanja

For a variety of fully relativistic polytropic neutron star models we calculate the star's tidal Love number k{sub 2}. Most realistic equations of state for neutron stars can be approximated as a polytrope with an effective index n {approx} 0.5-1.0. The equilibrium stellar model is obtained by numerical integration of the Tolman-Oppenheimer-Volkhov equations. We calculate the linear l = 2 static perturbations to the Schwarzschild spacetime following the method of Thorne and Campolattaro. Combining the perturbed Einstein equations into a single second-order differential equation for the perturbation to the metric coefficient g{sub tt} and matching the exterior solution to themore » asymptotic expansion of the metric in the star's local asymptotic rest frame gives the Love number. Our results agree well with the Newtonian results in the weak field limit. The fully relativistic values differ from the Newtonian values by up to {approx}24%. The Love number is potentially measurable in gravitational wave signals from inspiralling binary neutron stars.« less

Equilibrium, thermodynamic and kinetic investigations for biosorption of uranium with green algae (Cladophora hutchinsiae).

PubMed

Bağda, Esra; Tuzen, Mustafa; Sarı, Ahmet

2017-09-01

Removal of toxic chemicals from environmental samples with low-cost methods and materials are very useful approach for especially large-scale applications. Green algae are highly abundant biomaterials which are employed as useful biosorbents in many studies. In the present study, an interesting type of green algae, Cladophora hutchinsiae (C. hutchinsiae) was used for removal of highly toxic chemical such as uranium. The pH, biosorbent concentration, contact time and temperature were optimized as 5.0, 12 g/L, 60 min and 20 °C, respectively. For the equilibrium calculations, three well known isotherm models (Langmuir, Freundlich and Dubinin-Radushkevich) were employed. The maximum biosorption capacity of the biosorbent was calculated as about 152 mg/g under the optimum batch conditions. The mean energy of biosorption was calculated as 8.39 kJ/mol from the D-R biosorption isotherm. The thermodynamic and kinetic characteristics of biosorption were also investigated to explain the nature of the process. The kinetic data best fits the pseudo-second-order kinetic model with a regression coefficient of >0.99 for all studied temperatures. The calculated ΔH° and ΔG° values showed that the biosorption process is exothermic and spontaneous for temperatures between 293 and 333 K. Furthermore, after seven cycling process, the sorption and desorption efficiencies of the biosorbent were found to be 70, and 58%, respectively meaning that the biosorbent had sufficiently high reusability performance as a clean-up tool. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ionization balance of impurities in turbulent scrape-off layer plasmas I: local ionization-recombination equilibrium

NASA Astrophysics Data System (ADS)

Guzman, F.; Marandet, Y.; Tamain, P.; Bufferand, H.; Ciraolo, G.; Ghendrih, Ph; Guirlet, R.; Rosato, J.; Valentinuzzi, M.

2015-12-01

In magnetized fusion devices, cross field impurity transport is often dominated by turbulence, in particular in the scrape-off layer. In these outer regions of the plasma, fluctuations of plasma parameters can be comparable to mean values, and the way ionization and recombination sources are treated in transport codes becomes questionnable. In fact, sources are calculated using the mean density and temperature values, with no account of fluctuations. In this work we investigate the modeling uncertainties introduced by this approximation, both qualitatively and quantitatively for the local ionization equilibrium. As a first step transport effects are neglected, and their role will be discussed in a companion paper. We show that temperature fluctuations shift the ionization balance towards lower temperatures, essentially because of the very steep temperature dependence of the ionization rate coefficients near the threshold. To reach this conclusion, a thorough analysis of the time scales involved is carried out, in order to devise a proper way of averaging over fluctuations. The effects are found to be substantial only for fairly large relative fluctuation levels for temperature, that is of the order of a few tens of percents.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shi, Chang-Sheng; Zhang, Shuang-Nan; Li, Xiang-Dong, E-mail: zhangsn@ihep.ac.cn

We re-estimate the surface magnetic fields of neutron stars (NSs) in Be X-ray binaries (BeXBs) with different models of torque, improved beyond Klus et al. In particular, a new torque model is applied to three models of magnetosphere radius. Unlike the previous models, the new torque model does not lead to divergent results for any fastness parameter. The inferred surface magnetic fields of these NSs for the two compressed magnetosphere models are much higher than that for the uncompressed magnetosphere model. The new torque model using the compressed magnetosphere radius leads to unique solutions near spin equilibrium in all cases, unlike other modelsmore » that usually give two branches of solutions. Although our conclusions are still affected by the simplistic assumptions about the magnetosphere radius calculations, we show several groups of possible surface magnetic field values with our new models when the interaction between the magnetosphere and the infalling accretion plasma is considered. The estimated surface magnetic fields for NSs BeXBs in the Large Magellanic Cloud, the Small Magellanic Cloud and the Milk Way are between the quantum critical field and the maximum “virial” value by the spin equilibrium condition.« less

Equilibrium properties of blackbody radiation with an ultraviolet energy cut-off

NASA Astrophysics Data System (ADS)

Mishra, Dheeraj Kumar; Chandra, Nitin; Vaibhav, Vinay

2017-10-01

We study various equilibrium thermodynamic properties of blackbody radiation (i.e. a photon gas) with an ultraviolet energy cut-off. We find that the energy density, specific heat etc. follow usual acoustic phonon dynamics as have been well studied by Debye. Other thermodynamic quantities like pressure, entropy etc. have also been calculated. The usual Stefan-Boltzmann law gets modified. We observe that the values of the thermodynamic quantities with the energy cut-off is lower than the corresponding values in the theory without any such scale. The phase-space measure is also expected to get modified for an exotic spacetime appearing at Planck scale, which in turn leads to the modification of Planck energy density distribution and the Wien's displacement law. We found that the non-perturbative nature of the thermodynamic quantities in the SR limit (for both unmodified and modified cases), due to nonanalyticity of the leading term, is a general feature of the theory accompanied with an ultraviolet energy cut-off. We have also discussed the possible modification in the case of Big Bang and the Stellar objects and have suggested a table top experiment for verification in effective low energy case.

Determination of flash point in air and pure oxygen using an equilibrium closed bomb apparatus.

PubMed

Kong, Dehong; am Ende, David J; Brenek, Steven J; Weston, Neil P

2003-08-29

The standard closed testers for flash point measurements may not be feasible for measuring flash point in special atmospheres like oxygen because the test atmosphere cannot be maintained due to leakage and the laboratory safety can be compromised. To address these limitations we developed a new "equilibrium closed bomb" (ECB). The ECB generally gives lower flash point values than standard closed cup testers as shown by the results of six flammable liquids. The present results are generally in good agreement with the values calculated from the reported lower flammability limits and the vapor pressures. Our measurements show that increased oxygen concentration had little effect on the flash points of the tested flammable liquids. While generally regarded as non-flammable because of the lack of observed flash point in standard closed cup flash point testers, dichloromethane is known to form flammable mixtures. The flash point of dichloromethane in oxygen measured in the ECB is -7.1 degrees C. The flash point of dichloromethane in air is dependent on the type and energy of the ignition source. Further research is being carried out to establish the relationship between the flash point of dichloromethane and the energy of the ignition source.

All human Na(+)-K(+)-ATPase alpha-subunit isoforms have a similar affinity for cardiac glycosides.

PubMed

Wang, J; Velotta, J B; McDonough, A A; Farley, R A

2001-10-01

Three alpha-subunit isoforms of the sodium pump, which is the receptor for cardiac glycosides, are expressed in human heart. The aim of this study was to determine whether these isoforms have distinct affinities for the cardiac glycoside ouabain. Equilibrium ouabain binding to membranes from a panel of different human tissues and cell lines derived from human tissues was compared by an F statistic to determine whether a single population of binding sites or two populations of sites with different affinities would better fit the data. For all tissues, the single-site model fit the data as well as the two-site model. The mean equilibrium dissociation constant (K(d)) for all samples calculated using the single-site model was 18 +/- 6 nM (mean +/- SD). No difference in K(d) was found between nonfailing and failing human heart samples, although the maximum number of binding sites in failing heart was only approximately 50% of the number of sites in nonfailing heart. Measurement of association rate constants and dissociation rate constants confirmed that the binding affinities of the different human alpha-isoforms are similar to each other, although calculated K(d) values were lower than those determined by equilibrium binding. These results indicate both that the affinity of all human alpha-subunit isoforms for ouabain is similar and that the increased sensitivity of failing human heart to cardiac glycosides is probably due to a reduction in the number of pumps in the heart rather than to a selective inhibition of a subset of pumps with different affinities for the drugs.

Kinetic sorption of contaminants of emerging concern by a palygorskite-montmorillonite filter medium.

PubMed

Berhane, Tedros M; Levy, Jonathan; Krekeler, Mark P S; Danielson, Neil D

2017-06-01

Kinetic sorption of bisphenol A (BPA), carbamazepine (CMZ) and ciprofloxacin (CIP) by three palygorskite-montmorillonite (Pal-Mt) granule sizes was studied. For BPA, CMZ and CIP, apparent sorption equilibrium was reached within about 3, 5 and 16 h, respectively. The highest and the lowest sorption capacities were by the small and the large granule sizes, respectively. Experimental results were compared to various sorption kinetics models to gain insights regarding the sorption processes and achieve a predictive capacity. The pseudo-second order (PSO) and the Elovich models performed the best while the pseudo-first order (PFO) model was only adequate for CMZ. The intraparticle-diffusion (IPD) model showed a two-step linear plot of BPA, CMZ and CIP sorption versus square root of time that was indicative of surface-sorption followed by IPD as a rate-limiting process before equilibrium was reached. Using the pseudo-first order (PFO) and the pseudo-second order (PSO) rate constants combined with previously-established Langmuir equilibrium sorption models, the kinetic sorption (k a ) and desorption (k d ) Langmuir kinetic rate constants were theoretically calculated for BPA and CIP. Kinetic sorption was then simulated using these theoretically calculated k a and k d values, and the simulations were compared to the observed behavior. The simulations fit the observed sorbed concentrations better during the early part of the experiments; the observed sorption during later times occurred more slowly than expected, supporting the hypothesis that IPD becomes a rate-limiting process during the course of the experiment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Infinitely dilute partial molar properties of proteins from computer simulation.

PubMed

Ploetz, Elizabeth A; Smith, Paul E

2014-11-13

A detailed understanding of temperature and pressure effects on an infinitely dilute protein's conformational equilibrium requires knowledge of the corresponding infinitely dilute partial molar properties. Established molecular dynamics methodologies generally have not provided a way to calculate these properties without either a loss of thermodynamic rigor, the introduction of nonunique parameters, or a loss of information about which solute conformations specifically contributed to the output values. Here we implement a simple method that is thermodynamically rigorous and possesses none of the above disadvantages, and we report on the method's feasibility and computational demands. We calculate infinitely dilute partial molar properties for two proteins and attempt to distinguish the thermodynamic differences between a native and a denatured conformation of a designed miniprotein. We conclude that simple ensemble average properties can be calculated with very reasonable amounts of computational power. In contrast, properties corresponding to fluctuating quantities are computationally demanding to calculate precisely, although they can be obtained more easily by following the temperature and/or pressure dependence of the corresponding ensemble averages.

A Study of Interdiffusion in the Fe-C/Ti System Under Equilibrium and Nonequilibrium Conditions

NASA Astrophysics Data System (ADS)

Prasanthi, T. N.; Sudha, C.; Saroja, S.

2017-04-01

In the present study, diffusion behavior under equilibrium and nonequilibrium conditions in a Fe-C/Ti system is studied in the temperature range of 773 K to 1073 K (500 °C to 800 °C). A defect-free weld joint between mild steel (MS) (Fe-0.14 pct C) and Ti Grade 2 obtained by friction welding is diffusion annealed for various durations to study the interdiffusion behavior under equilibrium conditions, while an explosive clad joint is used to study interdiffusion under nonequilibrium conditions. From the elemental concentration profiles obtained across the MS-Ti interface using electron-probe microanalysis and imaging of the interface, the formation of distinct diffusion zones as a function of temperature and time is established. Concentration and temperature dependence of the interdiffusion coefficients ( D( c)) and activation energies are determined. Under equilibrium conditions, the change in molar volume with concentration shows a close match with the ideal Vegard's law, whereas a negative deviation is observed for nonequilibrium conditions. This deviation can be attributed to the formation of secondary phases, which, in turn, alters the D( c) values of diffusing species. Calculations showed that the D 0 and activation energy for interdiffusion under equilibrium is on the order of 10-11 m2/s and 147 kJ/mol, whereas it is far lower in the nonequilibrium case (10-10 m2/s and 117 kJ/mol) in the compositional range of 40 to 50 wt pct Fe, which also manifests as accelerated growth kinetics of the different diffusion zones.

Technical note: Evaluation of the simultaneous measurements of mesospheric OH, HO2, and O3 under a photochemical equilibrium assumption - a statistical approach

NASA Astrophysics Data System (ADS)

Kulikov, Mikhail Y.; Nechaev, Anton A.; Belikovich, Mikhail V.; Ermakova, Tatiana S.; Feigin, Alexander M.

2018-05-01

This Technical Note presents a statistical approach to evaluating simultaneous measurements of several atmospheric components under the assumption of photochemical equilibrium. We consider simultaneous measurements of OH, HO2, and O3 at the altitudes of the mesosphere as a specific example and their daytime photochemical equilibrium as an evaluating relationship. A simplified algebraic equation relating local concentrations of these components in the 50-100 km altitude range has been derived. The parameters of the equation are temperature, neutral density, local zenith angle, and the rates of eight reactions. We have performed a one-year simulation of the mesosphere and lower thermosphere using a 3-D chemical-transport model. The simulation shows that the discrepancy between the calculated evolution of the components and the equilibrium value given by the equation does not exceed 3-4 % in the full range of altitudes independent of season or latitude. We have developed a statistical Bayesian evaluation technique for simultaneous measurements of OH, HO2, and O3 based on the equilibrium equation taking into account the measurement error. The first results of the application of the technique to MLS/Aura data (Microwave Limb Sounder) are presented in this Technical Note. It has been found that the satellite data of the HO2 distribution regularly demonstrate lower altitudes of this component's mesospheric maximum. This has also been confirmed by model HO2 distributions and comparison with offline retrieval of HO2 from the daily zonal means MLS radiance.

Calculations of Excitation Functions of Some Structural Fusion Materials for ( n, t) Reactions up to 50 MeV Energy

NASA Astrophysics Data System (ADS)

Tel, E.; Durgu, C.; Aktı, N. N.; Okuducu, Ş.

2010-06-01

Fusion serves an inexhaustible energy for humankind. Although there have been significant research and development studies on the inertial and magnetic fusion reactor technology, there is still a long way to go to penetrate commercial fusion reactors to the energy market. Tritium self-sufficiency must be maintained for a commercial power plant. For self-sustaining (D-T) fusion driver tritium breeding ratio should be greater than 1.05. So, the working out the systematics of ( n, t) reaction cross sections is of great importance for the definition of the excitation function character for the given reaction taking place on various nuclei at different energies. In this study, ( n, t) reactions for some structural fusion materials such as 27Al, 51V, 52Cr, 55Mn, and 56Fe have been investigated. The new calculations on the excitation functions of 27Al( n, t)25Mg, 51V( n, t)49Ti, 52Cr( n, t)50V, 55Mn( n, t)53Cr and 56Fe( n, t)54Mn reactions have been carried out up to 50 MeV incident neutron energy. In these calculations, the pre-equilibrium and equilibrium effects have been investigated. The pre-equilibrium calculations involve the new evaluated the geometry dependent hybrid model, hybrid model and the cascade exciton model. Equilibrium effects are calculated according to the Weisskopf-Ewing model. Also in the present work, we have calculated ( n, t) reaction cross-sections by using new evaluated semi-empirical formulas developed by Tel et al. at 14-15 MeV energy. The calculated results are discussed and compared with the experimental data taken from the literature.

Uniform electron gases. III. Low-density gases on three-dimensional spheres.

PubMed

Agboola, Davids; Knol, Anneke L; Gill, Peter M W; Loos, Pierre-François

2015-08-28

By combining variational Monte Carlo (VMC) and complete-basis-set limit Hartree-Fock (HF) calculations, we have obtained near-exact correlation energies for low-density same-spin electrons on a three-dimensional sphere (3-sphere), i.e., the surface of a four-dimensional ball. In the VMC calculations, we compare the efficacies of two types of one-electron basis functions for these strongly correlated systems and analyze the energy convergence with respect to the quality of the Jastrow factor. The HF calculations employ spherical Gaussian functions (SGFs) which are the curved-space analogs of Cartesian Gaussian functions. At low densities, the electrons become relatively localized into Wigner crystals, and the natural SGF centers are found by solving the Thomson problem (i.e., the minimum-energy arrangement of n point charges) on the 3-sphere for various values of n. We have found 11 special values of n whose Thomson sites are equivalent. Three of these are the vertices of four-dimensional Platonic solids - the hyper-tetrahedron (n = 5), the hyper-octahedron (n = 8), and the 24-cell (n = 24) - and a fourth is a highly symmetric structure (n = 13) which has not previously been reported. By calculating the harmonic frequencies of the electrons around their equilibrium positions, we also find the first-order vibrational corrections to the Thomson energy.

Radionuclide calorimeter system

DOEpatents

Donohoue, Thomas P.; Oertel, Christopher P.; Tyree, William H.; Valdez, Joe L.

1991-11-26

A circuit for measuring temperature differentials in a calorimeter is disclosed. The temperature differential between the reference element and sample element containing a radioactive material is measured via a wheatstone bridge arrangement of thermistors. The bridge is driven with an alternating current on a pulsed basis to maintain the thermal floor of the calorimeter at a low reference value. A lock-in amplifier connected to the bridge phase locks a signal from the bridge to the input pulsed AC signal to provide a DC voltage. The DC voltage is sampled over time and provided to a digital computer. The digital computer, using curve fitting algorithms, will derive a function for the sample data. From the function, an equilibrium value for the temperature may be calculated.

Radionuclide calorimeter system

DOEpatents

Donohoue, T.P.; Oertel, C.P.; Tyree, W.H.; Valdez, J.L.

1991-11-26

A circuit for measuring temperature differentials in a calorimeter is disclosed. The temperature differential between the reference element and sample element containing a radioactive material is measured via a Wheatstone bridge arrangement of thermistors. The bridge is driven with an alternating current on a pulsed basis to maintain the thermal floor of the calorimeter at a low reference value. A lock-in amplifier connected to the bridge phase locks a signal from the bridge to the input pulsed AC signal to provide a DC voltage. The DC voltage is sampled over time and provided to a digital computer. The digital computer, using curve fitting algorithms, will derive a function for the sample data. From the function, an equilibrium value for the temperature may be calculated. 7 figures.

A transformation theory of stochastic evolution in Red Moon methodology to time evolution of chemical reaction process in the full atomistic system.

PubMed

Suzuki, Yuichi; Nagaoka, Masataka

2017-05-28

Atomistic information of a whole chemical reaction system, e.g., instantaneous microscopic molecular structures and orientations, offers important and deeper insight into clearly understanding unknown chemical phenomena. In accordance with the progress of a number of simultaneous chemical reactions, the Red Moon method (a hybrid Monte Carlo/molecular dynamics reaction method) is capable of simulating atomistically the chemical reaction process from an initial state to the final one of complex chemical reaction systems. In the present study, we have proposed a transformation theory to interpret the chemical reaction process of the Red Moon methodology as the time evolution process in harmony with the chemical kinetics. For the demonstration of the theory, we have chosen the gas reaction system in which the reversible second-order reaction H 2 + I 2  ⇌ 2HI occurs. First, the chemical reaction process was simulated from the initial configurational arrangement containing a number of H 2 and I 2 molecules, each at 300 K, 500 K, and 700 K. To reproduce the chemical equilibrium for the system, the collision frequencies for the reactions were taken into consideration in the theoretical treatment. As a result, the calculated equilibrium concentrations [H 2 ] eq and equilibrium constants K eq at all the temperatures were in good agreement with their corresponding experimental values. Further, we applied the theoretical treatment for the time transformation to the system and have shown that the calculated half-life τ's of [H 2 ] reproduce very well the analytical ones at all the temperatures. It is, therefore, concluded that the application of the present theoretical treatment with the Red Moon method makes it possible to analyze reasonably the time evolution of complex chemical reaction systems to chemical equilibrium at the atomistic level.

[Application of classical isothermal adsorption models in heavy metal ions/ diatomite system and related problems].

PubMed

Zhu, Jian; Wu, Qing-Ding; Wang, Ping; Li, Ke-Lin; Lei, Ming-Jing; Zhang, Wei-Li

2013-11-01

In order to fully understand adsorption nature of Cu2+, Zn2+, Pb2+, Cd2+, Mn2+, Fe3+ onto natural diatomite, and to find problems of classical isothermal adsorption models' application in liquid/solid system, a series of isothermal adsorption tests were conducted. As results indicate, the most suitable isotherm models for describing adsorption of Pb2+, Cd2+, Cu2+, Zn2+, Mn2+, Fe3+ onto natural diatomite are Tenkin, Tenkin, Langmuir, Tenkin, Freundlich and Freundlich, respectively, the adsorption of each ion onto natural diatomite is mainly a physical process, and the adsorption reaction is favorable. It also can be found that, when using classical isothermal adsorption models to fit the experimental data in liquid/solid system, the equilibrium adsorption amount q(e) is not a single function of ion equilibrium concentration c(e), while is a function of two variables, namely c(e) and the adsorbent concentration W0, q(e) only depends on c(e)/W(0). Results also show that the classical isothermal adsorption models have a significant adsorbent effect, and their parameter values are unstable, the simulation values of parameter differ greatly from the measured values, which is unhelpful for practical use. The tests prove that four-adsorption-components model can be used for describing adsorption behavior of single ion in nature diatomite-liquid system, its parameters k and q(m) have constant values, which is favorable for practical quantitative calculation in a given system.

Temperature-Dependent Estimation of Gibbs Energies Using an Updated Group-Contribution Method.

PubMed

Du, Bin; Zhang, Zhen; Grubner, Sharon; Yurkovich, James T; Palsson, Bernhard O; Zielinski, Daniel C

2018-06-05

Reaction-equilibrium constants determine the metabolite concentrations necessary to drive flux through metabolic pathways. Group-contribution methods offer a way to estimate reaction-equilibrium constants at wide coverage across the metabolic network. Here, we present an updated group-contribution method with 1) additional curated thermodynamic data used in fitting and 2) capabilities to calculate equilibrium constants as a function of temperature. We first collected and curated aqueous thermodynamic data, including reaction-equilibrium constants, enthalpies of reaction, Gibbs free energies of formation, enthalpies of formation, entropy changes of formation of compounds, and proton- and metal-ion-binding constants. Next, we formulated the calculation of equilibrium constants as a function of temperature and calculated the standard entropy change of formation (Δ f S ∘ ) using a model based on molecular properties. The median absolute error in estimating Δ f S ∘ was 0.013 kJ/K/mol. We also estimated magnesium binding constants for 618 compounds using a linear regression model validated against measured data. We demonstrate the improved performance of the current method (8.17 kJ/mol in median absolute residual) over the current state-of-the-art method (11.47 kJ/mol) in estimating the 185 new reactions added in this work. The efforts here fill in gaps for thermodynamic calculations under various conditions, specifically different temperatures and metal-ion concentrations. These, to our knowledge, new capabilities empower the study of thermodynamic driving forces underlying the metabolic function of organisms living under diverse conditions. Copyright © 2018 Biophysical Society. Published by Elsevier Inc. All rights reserved.

On the use of the double floating probe method to infer the difference between the electron and the heavy particles temperatures in an atmospheric pressure, vortex-stabilized nitrogen plasma jet

NASA Astrophysics Data System (ADS)

Prevosto, L.; Kelly, H.; Mancinelli, B. R.

2014-05-01

Sweeping double probe measurements in an atmospheric pressure direct current vortex-stabilized plasma jet are reported (plasma conditions: 100 A discharge current, N2 gas flow rate of 25 Nl/min, thoriated tungsten rod-type cathode, copper anode with 5 mm inner diameter). The interpretation of the double probe characteristic was based on a generalization of the standard double floating probe formulae for non-uniform plasmas coupled to a non-equilibrium plasma composition model. Perturbations caused by the current to the probe together with collisional and thermal processes inside the probe perturbed region were taken into account. Radial values of the average electron and heavy particle temperatures as well as the electron density were obtained. The calculation of the temperature values did not require any specific assumption about a temperature relationship between different particle species. An electron temperature of 10 900 ± 900 K, a heavy particle temperature of 9300 ± 900 K, and an electron density of about 3.5 × 1022 m-3 were found at the jet centre at 3.5 mm downstream from the torch exit. Large deviations from kinetic equilibrium were found toward the outer border of the plasma jet. These results showed good agreement with those previously reported by the authors by using a single probe technique. The calculations have shown that this method is particularly useful for studying spraying-type plasma torches operated at power levels of about 15 kW.

Reliable Viscosity Calculation from Equilibrium Molecular Dynamics Simulations: A Time Decomposition Method.

PubMed

Zhang, Yong; Otani, Akihito; Maginn, Edward J

2015-08-11

Equilibrium molecular dynamics is often used in conjunction with a Green-Kubo integral of the pressure tensor autocorrelation function to compute the shear viscosity of fluids. This approach is computationally expensive and is subject to a large amount of variability because the plateau region of the Green-Kubo integral is difficult to identify unambiguously. Here, we propose a time decomposition approach for computing the shear viscosity using the Green-Kubo formalism. Instead of one long trajectory, multiple independent trajectories are run and the Green-Kubo relation is applied to each trajectory. The averaged running integral as a function of time is fit to a double-exponential function with a weighting function derived from the standard deviation of the running integrals. Such a weighting function minimizes the uncertainty of the estimated shear viscosity and provides an objective means of estimating the viscosity. While the formal Green-Kubo integral requires an integration to infinite time, we suggest an integration cutoff time tcut, which can be determined by the relative values of the running integral and the corresponding standard deviation. This approach for computing the shear viscosity can be easily automated and used in computational screening studies where human judgment and intervention in the data analysis are impractical. The method has been applied to the calculation of the shear viscosity of a relatively low-viscosity liquid, ethanol, and relatively high-viscosity ionic liquid, 1-n-butyl-3-methylimidazolium bis(trifluoromethane-sulfonyl)imide ([BMIM][Tf2N]), over a range of temperatures. These test cases show that the method is robust and yields reproducible and reliable shear viscosity values.

Progress towards a more predictive model for hohlraum radiation drive and symmetry

NASA Astrophysics Data System (ADS)

Jones, O. S.; Suter, L. J.; Scott, H. A.; Barrios, M. A.; Farmer, W. A.; Hansen, S. B.; Liedahl, D. A.; Mauche, C. W.; Moore, A. S.; Rosen, M. D.; Salmonson, J. D.; Strozzi, D. J.; Thomas, C. A.; Turnbull, D. P.

2017-05-01

For several years, we have been calculating the radiation drive in laser-heated gold hohlraums using flux-limited heat transport with a limiter of 0.15, tabulated values of local thermodynamic equilibrium gold opacity, and an approximate model for not in a local thermodynamic equilibrium (NLTE) gold emissivity (DCA_2010). This model has been successful in predicting the radiation drive in vacuum hohlraums, but for gas-filled hohlraums used to drive capsule implosions, the model consistently predicts too much drive and capsule bang times earlier than measured. In this work, we introduce a new model that brings the calculated bang time into better agreement with the measured bang time. The new model employs (1) a numerical grid that is fully converged in space, energy, and time, (2) a modified approximate NLTE model that includes more physics and is in better agreement with more detailed offline emissivity models, and (3) a reduced flux limiter value of 0.03. We applied this model to gas-filled hohlraum experiments using high density carbon and plastic ablator capsules that had hohlraum He fill gas densities ranging from 0.06 to 1.6 mg/cc and hohlraum diameters of 5.75 or 6.72 mm. The new model predicts bang times to within ±100 ps for most experiments with low to intermediate fill densities (up to 0.85 mg/cc). This model predicts higher temperatures in the plasma than the old model and also predicts that at higher gas fill densities, a significant amount of inner beam laser energy escapes the hohlraum through the opposite laser entrance hole.

On the use of the double floating probe method to infer the difference between the electron and the heavy particles temperatures in an atmospheric pressure, vortex-stabilized nitrogen plasma jet.

PubMed

Prevosto, L; Kelly, H; Mancinelli, B R

2014-05-01

Sweeping double probe measurements in an atmospheric pressure direct current vortex-stabilized plasma jet are reported (plasma conditions: 100 A discharge current, N2 gas flow rate of 25 Nl/min, thoriated tungsten rod-type cathode, copper anode with 5 mm inner diameter). The interpretation of the double probe characteristic was based on a generalization of the standard double floating probe formulae for non-uniform plasmas coupled to a non-equilibrium plasma composition model. Perturbations caused by the current to the probe together with collisional and thermal processes inside the probe perturbed region were taken into account. Radial values of the average electron and heavy particle temperatures as well as the electron density were obtained. The calculation of the temperature values did not require any specific assumption about a temperature relationship between different particle species. An electron temperature of 10,900 ± 900 K, a heavy particle temperature of 9300 ± 900 K, and an electron density of about 3.5 × 10(22) m(-3) were found at the jet centre at 3.5 mm downstream from the torch exit. Large deviations from kinetic equilibrium were found toward the outer border of the plasma jet. These results showed good agreement with those previously reported by the authors by using a single probe technique. The calculations have shown that this method is particularly useful for studying spraying-type plasma torches operated at power levels of about 15 kW.

On the calculation of solubilities via direct coexistence simulations: Investigation of NaCl aqueous solutions and Lennard-Jones binary mixtures.

PubMed

Espinosa, J R; Young, J M; Jiang, H; Gupta, D; Vega, C; Sanz, E; Debenedetti, P G; Panagiotopoulos, A Z

2016-10-21

Direct coexistence molecular dynamics simulations of NaCl solutions and Lennard-Jones binary mixtures were performed to explore the origin of reported discrepancies between solubilities obtained by direct interfacial simulations and values obtained from the chemical potentials of the crystal and solution phases. We find that the key cause of these discrepancies is the use of crystal slabs of insufficient width to eliminate finite-size effects. We observe that for NaCl crystal slabs thicker than 4 nm (in the direction perpendicular to the interface), the same solubility values are obtained from the direct coexistence and chemical potential routes, namely, 3.7 ± 0.2 molal at T = 298.15 K and p = 1 bar for the JC-SPC/E model. Such finite-size effects are absent in the Lennard-Jones system and are likely caused by surface dipoles present in the salt crystals. We confirmed that μs-long molecular dynamics runs are required to obtain reliable solubility values from direct coexistence calculations, provided that the initial solution conditions are near the equilibrium solubility values; even longer runs are needed for equilibration of significantly different concentrations. We do not observe any effects of the exposed crystal face on the solubility values or equilibration times. For both the NaCl and Lennard-Jones systems, the use of a spherical crystallite embedded in the solution leads to significantly higher apparent solubility values relative to the flat-interface direct coexistence calculations and the chemical potential values. Our results have broad implications for the determination of solubilities of molecular models of ionic systems.

Finite-Difference Solution for Laminar or Turbulent Boundary Layer Flow over Axisymmetric Bodies with Ideal Gas, CF4, or Equilibrium Air Chemistry

NASA Technical Reports Server (NTRS)

Hamilton, H. Harris, II; Millman, Daniel R.; Greendyke, Robert B.

1992-01-01

A computer code was developed that uses an implicit finite-difference technique to solve nonsimilar, axisymmetric boundary layer equations for both laminar and turbulent flow. The code can treat ideal gases, air in chemical equilibrium, and carbon tetrafluoride (CF4), which is a useful gas for hypersonic blunt-body simulations. This is the only known boundary layer code that can treat CF4. Comparisons with experimental data have demonstrated that accurate solutions are obtained. The method should prove useful as an analysis tool for comparing calculations with wind tunnel experiments and for making calculations about flight vehicles where equilibrium air chemistry assumptions are valid.

Finite-difference solution for laminar or turbulent boundary layer flow over axisymmetric bodies with ideal gas, CF4, or equilibrium air chemistry

NASA Astrophysics Data System (ADS)

Hamilton, H. Harris, II; Millman, Daniel R.; Greendyke, Robert B.

1992-12-01

A computer code was developed that uses an implicit finite-difference technique to solve nonsimilar, axisymmetric boundary layer equations for both laminar and turbulent flow. The code can treat ideal gases, air in chemical equilibrium, and carbon tetrafluoride (CF4), which is a useful gas for hypersonic blunt-body simulations. This is the only known boundary layer code that can treat CF4. Comparisons with experimental data have demonstrated that accurate solutions are obtained. The method should prove useful as an analysis tool for comparing calculations with wind tunnel experiments and for making calculations about flight vehicles where equilibrium air chemistry assumptions are valid.

Equilibrium Spline Interface (ESI) for magnetic confinement codes

NASA Astrophysics Data System (ADS)

Li, Xujing; Zakharov, Leonid E.

2017-12-01

A compact and comprehensive interface between magneto-hydrodynamic (MHD) equilibrium codes and gyro-kinetic, particle orbit, MHD stability, and transport codes is presented. Its irreducible set of equilibrium data consists of three (in the 2-D case with occasionally one extra in the 3-D case) functions of coordinates and four 1-D radial profiles together with their first and mixed derivatives. The C reconstruction routines, accessible also from FORTRAN, allow the calculation of basis functions and their first derivatives at any position inside the plasma and in its vicinity. After this all vector fields and geometric coefficients, required for the above mentioned types of codes, can be calculated using only algebraic operations with no further interpolation or differentiation.

First-principles atomistic Wulff constructions for an equilibrium rutile TiO2 shape modeling

NASA Astrophysics Data System (ADS)

Jiang, Fengzhou; Yang, Lei; Zhou, Dali; He, Gang; Zhou, Jiabei; Wang, Fanhou; Chen, Zhi-Gang

2018-04-01

Identifying the exposed surfaces of rutile TiO2 crystal is crucial for its industry application and surface engineering. In this study, the shape of the rutile TiO2 was constructed by applying equilibrium thermodynamics of TiO2 crystals via first-principles density functional theory (DFT) and Wulff principles. From the DFT calculations, the surface energies of six low-index stoichiometric facets of TiO2 are determined after the calibrations of crystal structure. And then, combined surface energy calculations and Wulff principles, a geometric model of equilibrium rutile TiO2 is built up, which is coherent with the typical morphology of fully-developed equilibrium TiO2 crystal. This study provides fundamental theoretical guidance for the surface analysis and surface modification of the rutile TiO2-based materials from experimental research to industry manufacturing.

Grain formation in astronomical systems: A critical review of condensation processes

NASA Technical Reports Server (NTRS)

Donn, B.

1978-01-01

An analysis is presented of the assumption and the applicability of the three theoretical methods for calculating condensations in cosmic clouds where no pre-existing nuclei exist. The three procedures are: thermodynamic equilibrium calculations, nucleation theory, and a kinetic treatment which would take into account the characteristics of each individual collision. Thermodynamics provide detailed results on the composition temperature and composition of the condensate provided the system attains equilibrium. Because of the cosmic abundance mixture of elements, large supersaturations in some cases and low pressures, equilibrium is not expected in astronomical clouds. Nucleation theory, a combination of thermodynamics and kinetics, has the limitations of each scheme. Kinetics, not requiring equilibrium, avoids nearly all the thermodynamics difficulties but requires detailed knowledge of many reactions which thermodynamics avoids. It appears to be the only valid way to treat grain formation in space. A review of experimental studies is given.

Development of an R-based wrapper code for the computation of hydrochemical predominance diagrams based on PHREEQC modeling outputs

NASA Astrophysics Data System (ADS)

Mork, M. W.; Kracht, O.

2012-04-01

When investigating stability relations in aquatic solutions or rock-water interactions, the number of dissolved species and mineral phases involved can be overwhelming. To facilitate an overview about equilibrium relationships and how chemical elements are distributed between different aqueous ions, complexes, and solids, predominance diagrams are a widely used tool in aquatic chemistry. In the simplest approach, the predominance field boundaries can be calculated based on a set of mass action equations and log K values for the reactions between different species. Example given, for the popular redox diagram (pe-pH diagram), half cell reactions according to Nernst's equation can be used (Garrels & Christ 1965). In such case, boundaries between different species are "equal-activity" lines. However, for boundaries between solids and dissolved species a specific concentration needs to be stipulated, and the same applies if other components than those displayed in the diagram are involved in the possible reactions. In such case, the predominance field boundaries depend on the actual concentration values chosen. An alternative approach can be the computation of predominance diagrams using the full speciation obtained from a geochemical speciation program, which then needs to be coupled with an external wrapper code for appropriate control and data pre- and post-processing. In this way, the distribution of different species can be based on the consideration of complete chemical analysis obtained from laboratory investigations. We present the results of a student semester-project that aimed to develop and test an external wrapper program for the computation of pe-pH diagrams based on modeling outputs obtained with PHREEQC (Parkhurst & Appelo 1999). We have chosen PHREEQC for this core task as a geochemical calculation module, because of its capabilities to simulate a wide range of equilibrium reactions between water and minerals. Due to the intended final users, a free and extensible simulation platform was considered important. The wrapper program was created in the R environment which is freely available under the GNU General Public License (R Development Core Team 2011). The wrapper reads in analytical data in the standard PHREEQC input file format and then iterates over a systematic selection of pe and pH values. These data are transferred to PHREEQC for the calculation of a corresponding set of hydrochemical speciations based on thermodynamic equilibrium. The results of the PHREEQC simulations are subsequently analyzed by a postprocessor function in order to derive a two-dimensional representation of the dominant aquatic species in the pe-pH plane. In this step, the most abundant species at each grid point is identified as the predominant one. To investigate the utility of the program, differences in the speciation of iron were calculated from chemical compositions of water samples from one of our current field sites (Gardermoen / Øvre Romerike aquifer in S-Norway).

The reversibility of virus attachment to mineral surfaces

USGS Publications Warehouse

Loveland, J.P.; Ryan, J.N.; Amy, G.L.; Harvey, R.W.

1996-01-01

Virus transport through groundwater is limited by attachment to mineral surfaces and inactivation. Current virus transport models do not consider the implications of the reversibility of virus attachment to minerals. To explore the reversibility of virus attachment to mineral surfaces, we attached PRD1, a bacteriophage considered to be a good model of enteric viruses, to quartz and ferric oxyhydroxide-coated quartz surfaces over a range of pH values in equilibrium 'static columns'. Following attachment, we detached the viruses by replacing the pore solution with solutions of equal and higher pH. The extent of virus attachment followed an attachment 'edge' that occurred at a pH value about 2.5-3.5 pH units above the pH(IEP) of the mineral surfaces. Viruses attached below this edge were irreversibly attached until the pH of the detachment solution exceeded the pH value of the attachment edge. Viruses attached above this edge were reversibly attached. Derjaguin-Landau-Verwey-Overbeek (DEVO) potential energy calculations showed that the attachment edge occurred at the pH at which the potential energy of the primary minimum was near zero, implying that the position of the primary minimum (attractive or repulsive) controlled the equilibrium distribution of the viruses. The results suggest that the reversibility of virus attachment must be considered in virus transport models for accurate predictions of virus travel time.

Stable isotope geochemical study of Pamukkale travertines: New evidences of low-temperature non-equilibrium calcite-water fractionation

NASA Astrophysics Data System (ADS)

Kele, Sándor; Özkul, Mehmet; Fórizs, István; Gökgöz, Ali; Baykara, Mehmet Oruç; Alçiçek, Mehmet Cihat; Németh, Tibor

2011-06-01

In this paper we present the first detailed geochemical study of the world-famous actively forming Pamukkale and Karahayit travertines (Denizli Basin, SW-Turkey) and associated thermal waters. Sampling was performed along downstream sections through different depositional environments (vent, artificial channel and lake, terrace-pools and cascades of proximal slope, marshy environment of distal slope). δ 13C travertine values show significant increase (from + 6.1‰ to + 11.7‰ PDB) with increasing distance from the spring orifice, whereas the δ 18O travertine values show only slight increase downstream (from - 10.7‰ to - 9.1‰ PDB). Mainly the CO 2 outgassing caused the positive downstream shift (~ 6‰) in the δ 13C travertine values. The high δ 13C values of Pamukkale travertines located closest to the spring orifice (not affected by secondary processes) suggest the contribution of CO 2 liberated by thermometamorphic decarbonation besides magmatic sources. Based on the gradual downstream increase of the concentration of the conservative Na +, K +, Cl -, evaporation was estimated to be 2-5%, which coincides with the moderate effect of evaporation on the water isotope composition. Stable isotopic compositions of the Pamukkale thermal water springs show of meteoric origin, and indicate a Local Meteoric Water Line of Denizli Basin to be between the Global Meteoric Water Line (Craig, 1961) and Western Anatolian Meteoric Water Line (Şimşek, 2003). Detailed evaluation of several major and trace element contents measured in the water and in the precipitated travertine along the Pamukkale MM section revealed which elements are precipitated in the carbonate or concentrated in the detrital minerals. Former studies on the Hungarian Egerszalók travertine (Kele et al., 2008a, b, 2009) had shown that the isotopic equilibrium is rarely maintained under natural conditions during calcite precipitation in the temperature range between 41 and 67 °C. In this paper, besides the detailed geochemical analyses along downstream sections, we present new evidences of non-equilibrium calcite-water fractionation in lower temperature range (13.3 to 51.3 °C). Our measurements and calculations on natural hot water travertine precipitations at Pamukkale and Egerszalók revealed that the δ 18O travertine is equal with the δ 18O HCO3 at the orifice of the thermal springs, which means that practically there is no oxygen isotope fractionation between these two phases. High rate of CO 2 degassing with rapid precipitation of carbonate could be responsible for this as it was theoretically supposed by O'Neil et al. (1969). Thus, for the determination of the deposition temperature of a fossil travertine deposit we propose to use the water-bicarbonate oxygen isotope equilibrium fractionation instead of the water-travertine fractionation, which can result 8-9 °C difference in the calculated values. Our study is the first detailed empirical proof of O'Neil's hypothesis on a natural carbonate depositing system. The presented observations can be used to identify more precisely the deposition temperature of fossil travertines during paleoclimate studies.

Nucleon matter equation of state, particle number fluctuations, and shear viscosity within UrQMD box calculations

NASA Astrophysics Data System (ADS)

Motornenko, A.; Bravina, L.; Gorenstein, M. I.; Magner, A. G.; Zabrodin, E.

2018-03-01

Properties of equilibrated nucleon system are studied within the ultra-relativistic quantum molecular dynamics (UrQMD) transport model. The UrQMD calculations are done within a finite box with periodic boundary conditions. The system achieves thermal equilibrium due to nucleon-nucleon elastic scattering. For the UrQMD-equilibrium state, nucleon energy spectra, equation of state, particle number fluctuations, and shear viscosity η are calculated. The UrQMD results are compared with both, statistical mechanics and Chapman-Enskog kinetic theory, for a classical system of nucleons with hard-core repulsion.

Quantum statistical mechanics of dense partially ionized hydrogen

NASA Technical Reports Server (NTRS)

Dewitt, H. E.; Rogers, F. J.

1972-01-01

The theory of dense hydrogen plasmas beginning with the two component quantum grand partition function is reviewed. It is shown that ionization equilibrium and molecular dissociation equilibrium can be treated in the same manner with proper consideration of all two-body states. A quantum perturbation expansion is used to give an accurate calculation of the equation of state of the gas for any degree of dissociation and ionization. The statistical mechanical calculation of the plasma equation of state is intended for stellar interiors. The general approach is extended to the calculation of the equation of state of the outer layers of large planets.

Study on magnetic circuit of moving magnet linear compressor

NASA Astrophysics Data System (ADS)

Xia, Ming; Chen, Xiaoping; Chen, Jun

2015-05-01

The moving magnet linear compressors are very popular in the tactical miniature stirling cryocoolers. The magnetic circuit of LFC3600 moving magnet linear compressor, manufactured by Kunming institute of Physics, was studied in this study. Three methods of the analysis theory, numerical calculation and experiment study were applied in the analysis process. The calculated formula of magnetic reluctance and magnetomotive force were given in theoretical analysis model. The magnetic flux density and magnetic flux line were analyzed in numerical analysis model. A testing method was designed to test the magnetic flux density of the linear compressor. When the piston of the motor was in the equilibrium position, the value of the magnetic flux density was at the maximum of 0.27T. The results were almost equal to the ones from numerical analysis.

Ab initio NMR parameters of BrCH3 and ICH3 with relativistic and vibrational corrections

NASA Astrophysics Data System (ADS)

Uhlíková, Tereza; Urban, Štěpán

2018-05-01

This study is focused on two effects identified when NMR parameters are calculated based on first principles. These effects are 1. vibrational correction of properties when using ab initio optimized equilibrium geometry; 2. relativistic effects and limits of using the Flygare equation. These effects have been investigated and determined for nuclear spin-rotation constants and nuclear magnetic shieldings for the CH3Br and CH3I molecules. The most significant result is the difference between chemical shieldings determined based on the ab initio relativistic four-component Dirac-Coulomb Hamiltonian and chemical shieldings calculated using experimental values and the Flygare equation. This difference is approximately 320 ppm and 1290 ppm for 79Br and 127I in the CH3X molecule, respectively.

Coexistence pressure for a martensitic transformation from theory and experiment: Revisiting the bcc-hcp transition of iron under pressure

DOE PAGES

Zarkevich, N. A.; Johnson, D. D.

2015-05-12

We revisit results from decades of pressure experiments on the bcc ↔ hcp transformations in iron, which are sensitive to non-hydrostatic conditions and sample size. We emphasize the role of martensitic stress in the observed pressure hysteresis and address the large spread in values for onset pressures of the nucleating phase. From electronic-structure calculations, we find a bcc ↔ hcp equilibrium coexistence pressure of 8.4 GPa. Accounting for non-hydrostatic martensitic stress and a stress-dependent transition barrier, we suggest a pressure inequality for better comparison to experiment and observed hysteresis. We construct the equation of state for bcc and hcp phasesmore » under hydrostatic pressure, and compare to experiments and previous calculations.« less

Para hydrogen equilibration in the atmospheres of the outer planets

NASA Technical Reports Server (NTRS)

Conrath, Barney J.

1986-01-01

The thermodynamic behavior of the atmospheres of the Jovian planets is strongly dependent on the extent to which local thermal equilibration of the ortho and para states of molecular hydrogen is achieved. Voyager IRIS data from Jupiter imply substantial departures of the para hydrogen fraction from equilibrium in the upper troposphere at low latitudes, but with values approaching equilibrium at higher latitudes. Data from Saturn are less sensitive to the orth-para ratio, but suggest para hydrogen fractions near the equilibrium value. Above approximately the 200 K temperature level, para hydrogen conversion can enhance the efficiency of convection, resulting in a substantial increase in overturning times on all of the outer planets. Currently available data cannot definitively establish the ortho-para ratios in the atmospheres of Uranus and Neptune, but suggest values closer to local equilibrium than to the 3.1 normal ratio. Modeling of sub-millimeter wavelength measurements of these planets suggest thermal structures with frozen equilibrium lapse rates in their convective regions.

Thermodynamic properties of α-uranium

NASA Astrophysics Data System (ADS)

Ren, Zhiyong; Wu, Jun; Ma, Rong; Hu, Guichao; Luo, Chao

2016-11-01

The lattice constants and equilibrium atomic volume of α-uranium were calculated by Density Functional Theory (DFT). The first principles calculation results of the lattice for α-uranium are in agreement with the experimental results well. The thermodynamic properties of α-uranium from 0 to 900 K and 0-100 GPa were calculated with the quasi-harmonic Debye model. Volume, bulk modulus, entropy, Debye temperature, thermal expansion coefficient and the heat capacity of α-uranium were calculated. The calculated results show that the bulk modulus and Debye temperature increase with the increasing pressure at a given temperature while decreasing with the increasing temperature at a given pressure. Volume, entropy, thermal expansion coefficient and the heat capacity decrease with the increasing pressure while increasing with the increasing temperature. The theoretical results of entropy, Debye temperature, thermal expansion coefficient and the heat capacity show good agreement with the general trends of the experimental values. The constant-volume heat capacity shows typical Debye T3 power-law behavior at low temperature limit and approaches to the classical asymptotic Dulong-Petit limit at high temperature limit.

Group Contribution Methods for Phase Equilibrium Calculations.

PubMed

Gmehling, Jürgen; Constantinescu, Dana; Schmid, Bastian

2015-01-01

The development and design of chemical processes are carried out by solving the balance equations of a mathematical model for sections of or the whole chemical plant with the help of process simulators. For process simulation, besides kinetic data for the chemical reaction, various pure component and mixture properties are required. Because of the great importance of separation processes for a chemical plant in particular, a reliable knowledge of the phase equilibrium behavior is required. The phase equilibrium behavior can be calculated with the help of modern equations of state or g(E)-models using only binary parameters. But unfortunately, only a very small part of the experimental data for fitting the required binary model parameters is available, so very often these models cannot be applied directly. To solve this problem, powerful predictive thermodynamic models have been developed. Group contribution methods allow the prediction of the required phase equilibrium data using only a limited number of group interaction parameters. A prerequisite for fitting the required group interaction parameters is a comprehensive database. That is why for the development of powerful group contribution methods almost all published pure component properties, phase equilibrium data, excess properties, etc., were stored in computerized form in the Dortmund Data Bank. In this review, the present status, weaknesses, advantages and disadvantages, possible applications, and typical results of the different group contribution methods for the calculation of phase equilibria are presented.

On the concept of critical surface excess of micellization.

PubMed

Talens-Alesson, Federico I

2010-11-16

The critical surface excess of micellization (CSEM) should be regarded as the critical condition for micellization of ionic surfactants instead of the critical micelle concentration (CMC). There is a correspondence between the surface excesses Γ of anionic, cationic, and zwitterionic surfactants at their CMCs, which would be the CSEM values, and the critical association distance for ionic pair association calculated using Bjerrum's correlation. Further support to this concept is given by an accurate method for the prediction of the relative binding of alkali cations onto dodecylsulfate (NaDS) micelles. This method uses a relative binding strength parameter calculated from the values of surface excess Γ at the CMC of the alkali dodecylsulfates. This links both the binding of a given cation onto micelles and the onset for micellization of its surfactant salt. The CSEM concept implies that micelles form at the air-water interface unless another surface with greater affinity for micelles exists. The process would start when surfactant monomers are close enough to each other for ionic pairing with counterions and the subsequent assembly of these pairs becomes unavoidable. This would explain why the surface excess Γ values of different surfactants are more similar than their CMCs: the latter are just the bulk phase concentrations in equilibrium with chemicals with different hydrophobicity. An intriguing implication is that CSEM values may be used to calculate the actual critical distances of ionic pair formation for different cations, replacing Bjerrum's estimates, which only discriminate by the magnitude of the charge.

Some comments on thermodynamic consistency for equilibrium mixture equations of state

DOE PAGES

Grove, John W.

2018-03-28

We investigate sufficient conditions for thermodynamic consistency for equilibrium mixtures. Such models assume that the mass fraction average of the material component equations of state, when closed by a suitable equilibrium condition, provide a composite equation of state for the mixture. Here, we show that the two common equilibrium models of component pressure/temperature equilibrium and volume/temperature equilibrium (Dalton, 1808) define thermodynamically consistent mixture equations of state and that other equilibrium conditions can be thermodynamically consistent provided appropriate values are used for the mixture specific entropy and pressure.

Partition functions and equilibrium constants for diatomic molecules and atoms of astrophysical interest

NASA Astrophysics Data System (ADS)

Barklem, P. S.; Collet, R.

2016-04-01

Partition functions and dissociation equilibrium constants are presented for 291 diatomic molecules for temperatures in the range from near absolute zero to 10 000 K, thus providing data for many diatomic molecules of astrophysical interest at low temperature. The calculations are based on molecular spectroscopic data from the book of Huber & Herzberg (1979, Constants of Diatomic Molecules) with significant improvements from the literature, especially updated data for ground states of many of the most important molecules by Irikura (2007, J. Phys. Chem. Ref. Data, 36, 389). Dissociation energies are collated from compilations of experimental and theoretical values. Partition functions for 284 species of atoms for all elements from H to U are also presented based on data collected at NIST. The calculated data are expected to be useful for modelling a range of low density astrophysical environments, especially star-forming regions, protoplanetary disks, the interstellar medium, and planetary and cool stellar atmospheres. The input data, which will be made available electronically, also provides a possible foundation for future improvement by the community. Full Tables 1-8 are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/588/A96

Determination of kinetic and equilibrium parameters of the batch adsorption of Mn(II), Co(II), Ni(II) and Cu(II) from aqueous solution by black carrot (Daucus carota L.) residues.

PubMed

Güzel, Fuat; Yakut, Hakan; Topal, Giray

2008-05-30

In this study, the effect of temperature on the adsorption of Mn(II), Ni(II), Co(II) and Cu(II) from aqueous solution by modified carrot residues (MCR) was investigated. The equilibrium contact times of adsorption process for each heavy metals-MCR systems were determined. Kinetic data obtained for each heavy metal by MCR at different temperatures were applied to the Lagergren equation, and adsorption rate constants (kads) at these temperatures were determined. These rate constants related to the adsorption of heavy metal by MCR were applied to the Arrhenius equation, and activation energies (Ea) were determined. In addition, the isotherms for adsorption of each heavy metal by MCR at different temperatures were also determined. These isothermal data were applied to linear forms of isotherm equations that they fit the Langmuir adsorption isotherm, and the Langmuir constants (qm and b) were calculated. b constants determined at different temperatures were applied to thermodynamic equations, and thermodynamic parameters such as enthalpy (Delta H), free energy (Delta G), and entropy (Delta S) were calculated and these values show that adsorption of heavy metal on MCR was an endothermic process and process of adsorption was favoured at high temperatures.

Solubility limits in quaternary SnTe-based alloys [Metastability and solubility limits in quaternary SnTe-based alloys guided by combinatorial sputtering

DOE PAGES

Siol, Sebastian; Holder, Aaron; Ortiz, Brenden R.; ...

2017-05-09

Here, the controlled decomposition of metastable alloys is an attractive route to form nanostructured thermoelectric materials with reduced thermal conductivity. The ternary SnTe–MnTe and SnTe–SnSe heterostructural alloys have been demonstrated as promising materials for thermoelectric applications. In this work, the quaternary Sn 1–yMnyTe 1–xSe x phase space serves as a relevant model system to explore how a combination of computational and combinatorial-growth methods can be used to study equilibrium and non-equilibrium solubility limits. Results from first principle calculations indicate low equilibrium solubility for x,y < 0.05 that are in good agreement with results obtained from bulk equilibrium synthesis experiments andmore » predict significantly higher spinodal limits. An experimental screening using sputtered combinatorial thin film sample libraries showed a remarkable increase in non-equilibrium solubility for x,y > 0.2. These theoretical and experimental results were used to guide the bulk synthesis of metastable alloys. The ability to reproduce the non-equilibrium solubility levels in bulk materials indicates that such theoretical calculations and combinatorial growth can inform bulk synthetic routes. Further, the large difference between equilibrium and non-equilibrium solubility limits in Sn 1–yMn yTe 1–xSe x indicates these metastable alloys are attractive in terms of nano-precipitate formation for potential thermoelectric applications.« less

Calculation of a double reactive azeotrope using stochastic optimization approaches

NASA Astrophysics Data System (ADS)

Mendes Platt, Gustavo; Pinheiro Domingos, Roberto; Oliveira de Andrade, Matheus

2013-02-01

An homogeneous reactive azeotrope is a thermodynamic coexistence condition of two phases under chemical and phase equilibrium, where compositions of both phases (in the Ung-Doherty sense) are equal. This kind of nonlinear phenomenon arises from real world situations and has applications in chemical and petrochemical industries. The modeling of reactive azeotrope calculation is represented by a nonlinear algebraic system with phase equilibrium, chemical equilibrium and azeotropy equations. This nonlinear system can exhibit more than one solution, corresponding to a double reactive azeotrope. The robust calculation of reactive azeotropes can be conducted by several approaches, such as interval-Newton/generalized bisection algorithms and hybrid stochastic-deterministic frameworks. In this paper, we investigate the numerical aspects of the calculation of reactive azeotropes using two metaheuristics: the Luus-Jaakola adaptive random search and the Firefly algorithm. Moreover, we present results for a system (with industrial interest) with more than one azeotrope, the system isobutene/methanol/methyl-tert-butyl-ether (MTBE). We present convergence patterns for both algorithms, illustrating - in a bidimensional subdomain - the identification of reactive azeotropes. A strategy for calculation of multiple roots in nonlinear systems is also applied. The results indicate that both algorithms are suitable and robust when applied to reactive azeotrope calculations for this "challenging" nonlinear system.

Thermodynamic and transport properties of gaseous tetrafluoromethane in chemical equilibrium

NASA Technical Reports Server (NTRS)

Hunt, J. L.; Boney, L. R.

1973-01-01

Equations and in computer code are presented for the thermodynamic and transport properties of gaseous, undissociated tetrafluoromethane (CF4) in chemical equilibrium. The computer code calculates the thermodynamic and transport properties of CF4 when given any two of five thermodynamic variables (entropy, temperature, volume, pressure, and enthalpy). Equilibrium thermodynamic and transport property data are tabulated and pressure-enthalpy diagrams are presented.

Freshwater Mussel Shell δ13C Values as a Proxy for δ13CDIC in a Polluted, Temperate River

NASA Astrophysics Data System (ADS)

Graniero, L. E.; Gillikin, D. P.; Surge, D. M.

2017-12-01

Freshwater mussel shell δ13C values have been examined as an indicator of ambient δ13C composition of dissolved inorganic carbon (DIC) in temperate rivers. However, shell δ13C values may be obscured by the assimilation of respired, metabolic carbon (CM) derived from the organism's diet. Water δ18O and δ13CDIC values were collected fortnightly from August 2015 through July 2017 from three sites (one agricultural, one downstream of a wastewater treatment plant, one urban) in the Neuse River, NC to test the reliability of Elliptio complanata shell δ13C values as a proxy for δ13CDIC values. Muscle, mantle, gill, and stomach δ13C values were analyzed to approximate the %CM incorporated into the shell. All tissue δ13C values were within 2‰ of each other, which equates to a ±1% difference in calculated %CM. As such, muscle tissue δ13C values will be used for calculating the %CM, because they have the slowest turnover rate of the tissues sampled. Water temperature and δ18O values were used to calculate predicted aragonite shell δ18O­ values (δ18O­ar) based on the aragonite-water fractionation relationship. To assign dates to each shell microsample, predicted δ18O­ar values were compared to high-resolution serially sampled shell values. Consistent with previous studies, E. complanata cease growth in winter when temperatures are below about 12ºC. Preliminary results indicate that during the growing season, shell δ13C values are lower than expected equilibrium values, reflecting the assimilation of 15% CM, on average. Shell δ13C values are not significantly different than δ13CDIC values, but do not capture the full range of δ13CDIC values during each growing season. Thus, δ13C values of E. complanata shells can be used to reliably reconstruct past δ13CDIC values within 2‰ of coeval values. Further research will investigate how differing land-use affects the relationship between shell δ13C, CM, and δ13CDIC values.

Equilibrium Phase Behavior of the Square-Well Linear Microphase-Forming Model.

PubMed

Zhuang, Yuan; Charbonneau, Patrick

2016-07-07

We have recently developed a simulation approach to calculate the equilibrium phase diagram of particle-based microphase formers. Here, this approach is used to calculate the phase behavior of the square-well linear model for different strengths and ranges of the linear long-range repulsive component. The results are compared with various theoretical predictions for microphase formation. The analysis further allows us to better understand the mechanism for microphase formation in colloidal suspensions.

User's guide for vectorized code EQUIL for calculating equilibrium chemistry on Control Data STAR-100 computer

NASA Technical Reports Server (NTRS)

Kumar, A.; Graves, R. A., Jr.; Weilmuenster, K. J.

1980-01-01

A vectorized code, EQUIL, was developed for calculating the equilibrium chemistry of a reacting gas mixture on the Control Data STAR-100 computer. The code provides species mole fractions, mass fractions, and thermodynamic and transport properties of the mixture for given temperature, pressure, and elemental mass fractions. The code is set up for the electrons H, He, C, O, N system of elements. In all, 24 chemical species are included.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grove, John W.

We investigate sufficient conditions for thermodynamic consistency for equilibrium mixtures. Such models assume that the mass fraction average of the material component equations of state, when closed by a suitable equilibrium condition, provide a composite equation of state for the mixture. Here, we show that the two common equilibrium models of component pressure/temperature equilibrium and volume/temperature equilibrium (Dalton, 1808) define thermodynamically consistent mixture equations of state and that other equilibrium conditions can be thermodynamically consistent provided appropriate values are used for the mixture specific entropy and pressure.

A Numerical Characterization of the Gravito-Electrostatic Sheath Equilibrium Structure in Solar Plasma

NASA Astrophysics Data System (ADS)

Karmakar, Pralay Kumar

This article describes the equilibrium structure of the solar interior plasma (SIP) and solar wind plasma (SWP) in detail under the framework of the gravito-electrostatic sheath (GES) model. This model gives a precise definition of the solar surface boundary (SSB), surface origin mechanism of the subsonic SWP, and its supersonic acceleration. Equilibrium parameters like plasma potential, self-gravity, population density, flow, their gradients, and all the relevant inhomogeneity scale lengths are numerically calculated and analyzed as an initial value problem. Physical significance of the structure condition for the SSB is discussed. The plasma oscillation and Jeans time scales are also plotted and compared. In addition, different coupling parameters, and electric current profiles are also numerically studied. The current profiles exhibit an important behavior of directional reversibility, i.e., an electrodynamical transition from negative to positive value. It occurs beyond a few Jeans lengths away from the SSB. The virtual spherical surface lying at the current reversal point, where the net current becomes zero, has the property of a floating surface behavior of the real physical wall. Our investigation indicates that the SWP behaves as an ion current-carrying plasma system. The basic mechanism behind the GES formation and its distinctions from conventional plasma sheath are discussed. The electromagnetic properties of the Sun derived from our model with the most accurate available inputs are compared with those of others. These results are useful as an input element to study the properties of the linear and nonlinear dynamics of various solar plasma waves, oscillations and instabilities.

"Non-equilibrium" block copolymer micelles with glassy cores: a predictive approach based on theory of equilibrium micelles.

PubMed

Nagarajan, Ramanathan

2015-07-01

Micelles generated in water from most amphiphilic block copolymers are widely recognized to be non-equilibrium structures. Typically, the micelles are prepared by a kinetic process, first allowing molecular scale dissolution of the block copolymer in a common solvent that likes both the blocks and then gradually replacing the common solvent by water to promote the hydrophobic blocks to aggregate and create the micelles. The non-equilibrium nature of the micelle originates from the fact that dynamic exchange between the block copolymer molecules in the micelle and the singly dispersed block copolymer molecules in water is suppressed, because of the glassy nature of the core forming polymer block and/or its very large hydrophobicity. Although most amphiphilic block copolymers generate such non-equilibrium micelles, no theoretical approach to a priori predict the micelle characteristics currently exists. In this work, we propose a predictive approach for non-equilibrium micelles with glassy cores by applying the equilibrium theory of micelles in two steps. In the first, we calculate the properties of micelles formed in the mixed solvent while true equilibrium prevails, until the micelle core becomes glassy. In the second step, we freeze the micelle aggregation number at this glassy state and calculate the corona dimension from the equilibrium theory of micelles. The condition when the micelle core becomes glassy is independently determined from a statistical thermodynamic treatment of diluent effect on polymer glass transition temperature. The predictions based on this "non-equilibrium" model compare reasonably well with experimental data for polystyrene-polyethylene oxide diblock copolymer, which is the most extensively studied system in the literature. In contrast, the application of the equilibrium model to describe such a system significantly overpredicts the micelle core and corona dimensions and the aggregation number. The non-equilibrium model suggests ways to obtain different micelle sizes for the same block copolymer, by the choices we can make of the common solvent and the mode of solvent substitution. Published by Elsevier Inc.

Oxygen isotope trajectories of crystallizing melts: Insights from modeling and the plutonic record

NASA Astrophysics Data System (ADS)

Bucholz, Claire E.; Jagoutz, Oliver; VanTongeren, Jill A.; Setera, Jacob; Wang, Zhengrong

2017-06-01

Elevated oxygen isotope values in igneous rocks are often used to fingerprint supracrustal alteration or assimilation of material that once resided near the surface of the earth. The δ18O value of a melt, however, can also increase through closed-system fractional crystallization. In order to quantify the change in melt δ18O due to crystallization, we develop a detailed closed-system fractional crystallization mass balance model and apply it to six experimentally- and naturally-determined liquid lines of descent (LLDs), which cover nearly complete crystallization intervals (melt fractions of 1 to <0.1). The studied LLDs vary from anhydrous tholeiitic basalts to hydrous high-K and calc-alkaline basalts and are characterized by distinct melt temperature-SiO2 trajectories, as well as, crystallizing phase relationships. Our model results demonstrate that melt fraction-temperature-SiO2 relationships of crystallizing melts, which are strongly a function of magmatic water content, will control the specific δ18O path of a crystallizing melt. Hydrous melts, typical of subduction zones, undergo larger increases in δ18O during early stages of crystallization due to their lower magmatic temperatures, greater initial increases in SiO2 content, and high temperature stability of low δ18O phases, such as oxides, amphibole, and anorthitic plagioclase (versus albite). Conversely, relatively dry, tholeiitic melts only experience significant increases in δ18O at degrees of crystallization greater than 80%. Total calculated increases in melt δ18O of 1.0-1.5‰ can be attributed to crystallization from ∼50 to 70 wt.% SiO2 for modeled closed-system crystallizing melt compositions. As an example application, we compare our closed system model results to oxygen isotope mineral data from two natural plutonic sequences, a relatively dry, tholeiitic sequence from the Upper and Upper Main Zones (UUMZ) of the Bushveld Complex (South Africa) and a high-K, hydrous sequence from the arc-related Dariv Igneous Complex (Mongolia). These two sequences were chosen as their major and trace element compositions appear to have been predominantly controlled by closed-system fractional crystallization and their LLDs have been modeled in detail. We calculated equilibrium melt δ18O values using the measured mineral δ18O values and calculated mineral-melt fractionation factors. Increases of 2-3‰ and 1-1.5‰ in the equilibrium melts are observed for the Dariv Igneous Complex and the UUMZ of the Bushveld Complex, respectively. Closed-system fractional crystallization model results reproduce the 1‰ increase observed in the equilibrium melt δ18O for the Bushveld UUMZ, whereas for the Dariv Igneous Complex assimilation of high δ18O material is necessary to account for the increase in melt δ18O values. Assimilation of evolved supracrustal material is also confirmed with Sr and Nd isotope analyses of clinopyroxene from the sequence. Beginning with a range of mantle-derived basalt δ18O values of 5.7‰ ("pristine" mantle) to ∼7.0‰ (heavily subduction-influenced mantle), our model results demonstrated that high-silica melts (i.e. granites) with δ18O of up to 8.5‰ can be produced through fractional crystallization alone. Lastly, we model the zircon-melt δ18O fractionations of different LLDs, emphasizing their dependence on the specific SiO2-T relationships of a given crystallizing melt. Wet, relatively cool granitic melts will have larger zircon-melt fractionations, potentially by ∼1.5‰, compared to hot, dry granites. Therefore, it is critical to constrain zircon-melt fractionations specific to a system of interest when using zircon δ18O values to calculate melt δ18O.

On the time needed to reach an equilibrium structure of the radiation belts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ripoll, J. -F.; Loran, V.; Cunningham, Gregory Scott

In this paper, we complement the notion of equilibrium states of the radiation belts with a discussion on the dynamics and time needed to reach equilibrium. We solve for the equilibrium states obtained using 1D radial diffusion with recently developed hiss and chorus lifetimes at constant values of Kp = 1, 3 and 6. We find that the equilibrium states at moderately low Kp, when plotted vs L-shell (L) and energy (E), display the same interesting S-shape for the inner edge of the outer belt as recently observed by the Van Allen Probes. The S-shape is also produced as themore » radiation belts dynamically evolve toward the equilibrium state when initialized to simulate the buildup after a massive dropout or to simulate loss due to outward diffusion from a saturated state. Physically, this shape, intimately linked with the slot structure, is due to the dependence of electron loss rate (originating from wave-particle interactions) on both energy and L-shell. Equilibrium electron flux profiles are governed by the Biot number (τ Diffusion/τ loss), with large Biot number corresponding to low fluxes and low Biot number to large fluxes. The time it takes for the flux at a specific (L, E) to reach the value associated with the equilibrium state, starting from these different initial states, is governed by the initial state of the belts, the property of the dynamics (diffusion coefficients), and the size of the domain of computation. Its structure shows a rather complex scissor form in the (L, E) plane. The equilibrium value (phase space density or flux) is practically reachable only for selected regions in (L, E) and geomagnetic activity. Convergence to equilibrium requires hundreds of days in the inner belt for E > 300 keV and moderate Kp (≤3). It takes less time to reach equilibrium during disturbed geomagnetic conditions (Kp ≥ 3), when the system evolves faster. Restricting our interest to the slot region, below L = 4, we find that only small regions in (L, E) space can reach the equilibrium value: E ~ [200, 300] keV for L = [3.7, 4] at Kp = 1, E ~ [0.6, 1] MeV for L = [3, 4] at Kp = 3, and E ~ 300 keV for L = [3.5, 4] at Kp = 6 assuming no new incoming electrons.« less

On the time needed to reach an equilibrium structure of the radiation belts

DOE PAGES

Ripoll, J. -F.; Loran, V.; Cunningham, Gregory Scott; ...

2016-08-01

In this paper, we complement the notion of equilibrium states of the radiation belts with a discussion on the dynamics and time needed to reach equilibrium. We solve for the equilibrium states obtained using 1D radial diffusion with recently developed hiss and chorus lifetimes at constant values of Kp = 1, 3 and 6. We find that the equilibrium states at moderately low Kp, when plotted vs L-shell (L) and energy (E), display the same interesting S-shape for the inner edge of the outer belt as recently observed by the Van Allen Probes. The S-shape is also produced as themore » radiation belts dynamically evolve toward the equilibrium state when initialized to simulate the buildup after a massive dropout or to simulate loss due to outward diffusion from a saturated state. Physically, this shape, intimately linked with the slot structure, is due to the dependence of electron loss rate (originating from wave-particle interactions) on both energy and L-shell. Equilibrium electron flux profiles are governed by the Biot number (τ Diffusion/τ loss), with large Biot number corresponding to low fluxes and low Biot number to large fluxes. The time it takes for the flux at a specific (L, E) to reach the value associated with the equilibrium state, starting from these different initial states, is governed by the initial state of the belts, the property of the dynamics (diffusion coefficients), and the size of the domain of computation. Its structure shows a rather complex scissor form in the (L, E) plane. The equilibrium value (phase space density or flux) is practically reachable only for selected regions in (L, E) and geomagnetic activity. Convergence to equilibrium requires hundreds of days in the inner belt for E > 300 keV and moderate Kp (≤3). It takes less time to reach equilibrium during disturbed geomagnetic conditions (Kp ≥ 3), when the system evolves faster. Restricting our interest to the slot region, below L = 4, we find that only small regions in (L, E) space can reach the equilibrium value: E ~ [200, 300] keV for L = [3.7, 4] at Kp = 1, E ~ [0.6, 1] MeV for L = [3, 4] at Kp = 3, and E ~ 300 keV for L = [3.5, 4] at Kp = 6 assuming no new incoming electrons.« less

The NATA code: Theory and analysis, volume 1. [user manuals (computer programming) - gas dynamics, wind tunnels

NASA Technical Reports Server (NTRS)

Bade, W. L.; Yos, J. M.

1975-01-01

A computer program for calculating quasi-one-dimensional gas flow in axisymmetric and two-dimensional nozzles and rectangular channels is presented. Flow is assumed to start from a state of thermochemical equilibrium at a high temperature in an upstream reservoir. The program provides solutions based on frozen chemistry, chemical equilibrium, and nonequilibrium flow with finite reaction rates. Electronic nonequilibrium effects can be included using a two-temperature model. An approximate laminar boundary layer calculation is given for the shear and heat flux on the nozzle wall. Boundary layer displacement effects on the inviscid flow are considered also. Chemical equilibrium and transport property calculations are provided by subroutines. The code contains precoded thermochemical, chemical kinetic, and transport cross section data for high-temperature air, CO2-N2-Ar mixtures, helium, and argon. It provides calculations of the stagnation conditions on axisymmetric or two-dimensional models, and of the conditions on the flat surface of a blunt wedge. The primary purpose of the code is to describe the flow conditions and test conditions in electric arc heated wind tunnels.

Combining MOSCED with molecular simulation free energy calculations or electronic structure calculations to develop an efficient tool for solvent formulation and selection

NASA Astrophysics Data System (ADS)

Cox, Courtney E.; Phifer, Jeremy R.; Ferreira da Silva, Larissa; Gonçalves Nogueira, Gabriel; Ley, Ryan T.; O'Loughlin, Elizabeth J.; Pereira Barbosa, Ana Karolyne; Rygelski, Brett T.; Paluch, Andrew S.

2017-02-01

Solubility parameter based methods have long been a valuable tool for solvent formulation and selection. Of these methods, the MOdified Separation of Cohesive Energy Density (MOSCED) has recently been shown to correlate well the equilibrium solubility of multifunctional non-electrolyte solids. However, before it can be applied to a novel solute, a limited amount of reference solubility data is required to regress the necessary MOSCED parameters. Here we demonstrate for the solutes methylparaben, ethylparaben, propylparaben, butylparaben, lidocaine and ephedrine how conventional molecular simulation free energy calculations or electronic structure calculations in a continuum solvent, here the SMD or SM8 solvation model, can instead be used to generate the necessary reference data, resulting in a predictive flavor of MOSCED. Adopting the melting point temperature and enthalpy of fusion of these compounds from experiment, we are able to predict equilibrium solubilities. We find the method is able to well correlate the (mole fraction) equilibrium solubility in non-aqueous solvents over four orders of magnitude with good quantitative agreement.

Combining MOSCED with molecular simulation free energy calculations or electronic structure calculations to develop an efficient tool for solvent formulation and selection.

PubMed

Cox, Courtney E; Phifer, Jeremy R; Ferreira da Silva, Larissa; Gonçalves Nogueira, Gabriel; Ley, Ryan T; O'Loughlin, Elizabeth J; Pereira Barbosa, Ana Karolyne; Rygelski, Brett T; Paluch, Andrew S

2017-02-01

Solubility parameter based methods have long been a valuable tool for solvent formulation and selection. Of these methods, the MOdified Separation of Cohesive Energy Density (MOSCED) has recently been shown to correlate well the equilibrium solubility of multifunctional non-electrolyte solids. However, before it can be applied to a novel solute, a limited amount of reference solubility data is required to regress the necessary MOSCED parameters. Here we demonstrate for the solutes methylparaben, ethylparaben, propylparaben, butylparaben, lidocaine and ephedrine how conventional molecular simulation free energy calculations or electronic structure calculations in a continuum solvent, here the SMD or SM8 solvation model, can instead be used to generate the necessary reference data, resulting in a predictive flavor of MOSCED. Adopting the melting point temperature and enthalpy of fusion of these compounds from experiment, we are able to predict equilibrium solubilities. We find the method is able to well correlate the (mole fraction) equilibrium solubility in non-aqueous solvents over four orders of magnitude with good quantitative agreement.

Effects of surface stability on the morphological transformation of metals and metal oxides as investigated by first-principles calculations.

PubMed

Andrés, Juan; Gracia, Lourdes; Gouveia, Amanda Fernandes; Ferrer, Mateus Meneghetti; Longo, Elson

2015-10-09

Morphology is a key property of materials. Owing to their precise structure and morphology, crystals and nanocrystals provide excellent model systems for joint experimental and theoretical investigations into surface-related properties. Faceted polyhedral crystals and nanocrystals expose well-defined crystallographic planes depending on the synthesis method, which allow for thoughtful investigations into structure-reactivity relationships under practical conditions. This feature article introduces recent work, based on the combined use of experimental findings and first-principles calculations, to provide deeper knowledge of the electronic, structural, and energetic properties controlling the morphology and the transformation mechanisms of different metals and metal oxides: Ag, anatase TiO2, BaZrO3, and α-Ag2WO4. According to the Wulff theorem, the equilibrium shapes of these systems are obtained from the values of their respective surface energies. These investigations are useful to gain further understanding of how to achieve morphological control of complex three-dimensional crystals by tuning the ratio of the surface energy values of the different facets. This strategy allows the prediction of possible morphologies for a crystal and/or nanocrystal by controlling the relative values of surface energies.

Liquid-vapor phase equilibria and the thermodynamic properties of 2-methylpropanol- n-alkyl propanoate solutions

NASA Astrophysics Data System (ADS)

Suntsov, Yu. K.; Goryunov, V. A.; Chuikov, A. M.; Meshcheryakov, A. V.

2016-08-01

The boiling points of solutions of five binary systems are measured via ebulliometry in the pressure range of 2.05-103.3 kPa. Equilibrium vapor phase compositions, the values of the excess Gibbs energies, enthalpies, and entropies of solution of these systems are calculated. Patterns in the changes of phase equilibria and thermodynamic properties of solutions are established, depending on the compositions and temperatures of the systems. Liquid-vapor equilibria in the systems are described using the equations of Wilson and the NRTL (Non-Random Two-Liquid Model).

Sound velocity in five-component air mixtures of various densities

NASA Astrophysics Data System (ADS)

Bogdanova, N. V.; Rydalevskaya, M. A.

2018-05-01

The local equilibrium flows of five-component air mixtures are considered. Gas dynamic equations are derived from the kinetic equations for aggregate values of collision invariants. It is shown that the traditional formula for sound velocity is true in air mixtures considered with the chemical reactions and the internal degrees of freedom. This formula connects the square of sound velocity with pressure and density. However, the adiabatic coefficient is not constant under existing conditions. The analytical expression for this coefficient is obtained. The examples of its calculation in air mixtures of various densities are presented.

Open Heisenberg chain under boundary fields: A magnonic logic gate

NASA Astrophysics Data System (ADS)

Landi, Gabriel T.; Karevski, Dragi

2015-05-01

We study the spin transport in the quantum Heisenberg spin chain subject to boundary magnetic fields and driven out of equilibrium by Lindblad dissipators. An exact solution is given in terms of matrix product states, which allows us to calculate exactly the spin current for any chain size. It is found that the system undergoes a discontinuous spin-valve-like quantum phase transition from ballistic to subdiffusive spin current, depending on the value of the boundary fields. Thus, the chain behaves as an extremely sensitive magnonic logic gate operating with the boundary fields as the base element.

Melt-Vapor Phase Diagram of the Te-S System

NASA Astrophysics Data System (ADS)

Volodin, V. N.; Trebukhov, S. A.; Kenzhaliyev, B. K.; Nitsenko, A. V.; Burabaeva, N. M.

2018-03-01

The values of partial pressure of saturated vapor of the constituents of the Te-S system are determined from boiling points. The boundaries of the melt-vapor phase transition at atmospheric pressure and in vacuum of 2000 and 100 Pa are calculated on the basis of partial pressures. A phase diagram that includes vapor-liquid equilibrium fields whose boundaries allow us to assess the behavior of elements upon distillation fractioning is plotted. It is established that the separation of elements is possible at the first evaporation-condensation cycle. Complications can be caused by crystallization of a sulfur solid solution in tellurium.

Computer program determines chemical equilibria in complex systems

NASA Technical Reports Server (NTRS)

Gordon, S.; Zeleznik, F. J.

1966-01-01

Computer program numerically solves nonlinear algebraic equations for chemical equilibrium based on iteration equations independent of choice of components. This program calculates theoretical performance for frozen and equilibrium composition during expansion and Chapman-Jouguet flame properties, studies combustion, and designs hardware.

Simulation of electron-proton coupling with a Monte Carlo method: application to cytochrome c3 using continuum electrostatics.

PubMed Central

Baptista, A M; Martel, P J; Soares, C M

1999-01-01

A new method is presented for simulating the simultaneous binding equilibrium of electrons and protons on protein molecules, which makes it possible to study the full equilibrium thermodynamics of redox and protonation processes, including electron-proton coupling. The simulations using this method reflect directly the pH and electrostatic potential of the environment, thus providing a much closer and realistic connection with experimental parameters than do usual methods. By ignoring the full binding equilibrium, calculations usually overlook the twofold effect that binding fluctuations have on the behavior of redox proteins: first, they affect the energy of the system by creating partially occupied sites; second, they affect its entropy by introducing an additional empty/occupied site disorder (here named occupational entropy). The proposed method is applied to cytochrome c3 of Desulfovibrio vulgaris Hildenborough to study its redox properties and electron-proton coupling (redox-Bohr effect), using a continuum electrostatic method based on the linear Poisson-Boltzmann equation. Unlike previous studies using other methods, the full reduction order of the four hemes at physiological pH is successfully predicted. The sites more strongly involved in the redox-Bohr effect are identified by analysis of their titration curves/surfaces and the shifts of their midpoint redox potentials and pKa values. Site-site couplings are analyzed using statistical correlations, a method much more realistic than the usual analysis based on direct interactions. The site found to be more strongly involved in the redox-Bohr effect is propionate D of heme I, in agreement with previous studies; other likely candidates are His67, the N-terminus, and propionate D of heme IV. Even though the present study is limited to equilibrium conditions, the possible role of binding fluctuations in the concerted transfer of protons and electrons under nonequilibrium conditions is also discussed. The occupational entropy contributions to midpoint redox potentials and pKa values are computed and shown to be significant. PMID:10354425

An improved lattice Boltzmann scheme for multiphase fluid with multi-range interactions

NASA Astrophysics Data System (ADS)

Maquignon, Nicolas; Duchateau, Julien; Roussel, Gilles; Rousselle, François; Renaud, Christophe

2014-10-01

Modeling of fluids with liquid to gas phase transition has become important for understanding many environmental or industrial processes. Such simulations need new techniques, because traditional solvers are often limited. The Lattice Boltzmann Model (LBM) allows simulate complex fluids, because its mesoscopic nature gives possibility to incorporate additional physics in comparison to usual methods. In this work, an improved lattice Boltzmann model for phase transition flow will be introduced. First, the state of art for Shan & Chen [1] [2] (SC) type of LBM will be reminded. Then, link to real thermodynamics will be established with Maxwell equal areas construction. Convergence to isothermal liquid vapor equilibrium will be shown and discussed. Inclusion of an equation of state for real fluid and better incorporation of force term is presented [4] [5]. Multi-range interactions have been used for SC model [8], but it hasn't been yet applied to real fluid with non-ideal equation of state. In this work, we evaluate this model when it is applied to real liquid-vapor equilibrium. We show that important differences are found for evaluation of gas density. In order to recover thermodynamic consistency, we use a new scheme for calculation of force term, which is a combination of multi range model and numerical weighting used by Gong & Cheng [6] [7]. We show the superiority of our new model by studying convergence to equilibrium values over a large temperature range. We prove that spurious velocities remaining at equilibrium are decreased.

An improved lattice Boltzmann scheme for multiphase fluid with multi-range interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maquignon, Nicolas; Duchateau, Julien; Roussel, Gilles

2014-10-06

Modeling of fluids with liquid to gas phase transition has become important for understanding many environmental or industrial processes. Such simulations need new techniques, because traditional solvers are often limited. The Lattice Boltzmann Model (LBM) allows simulate complex fluids, because its mesoscopic nature gives possibility to incorporate additional physics in comparison to usual methods. In this work, an improved lattice Boltzmann model for phase transition flow will be introduced. First, the state of art for Shan and Chen (SC) type of LBM will be reminded. Then, link to real thermodynamics will be established with Maxwell equal areas construction. Convergence tomore » isothermal liquid vapor equilibrium will be shown and discussed. Inclusion of an equation of state for real fluid and better incorporation of force term is presented. Multi-range interactions have been used for SC model, but it hasn't been yet applied to real fluid with non-ideal equation of state. In this work, we evaluate this model when it is applied to real liquid-vapor equilibrium. We show that important differences are found for evaluation of gas density. In order to recover thermodynamic consistency, we use a new scheme for calculation of force term, which is a combination of multi range model and numerical weighting used by Gong and Cheng. We show the superiority of our new model by studying convergence to equilibrium values over a large temperature range. We prove that spurious velocities remaining at equilibrium are decreased.« less

Mineral-solution equilibria—III. The system Na 2OAl 2O 3SiO 2H 2OHCl

NASA Astrophysics Data System (ADS)

Popp, Robert K.; Frantz, John D.

1980-07-01

Chemical equilibrium between sodium-aluminum silicate minerals and chloride bearing fluid has been experimentally determined in the range 500-700°C at 1 kbar, using rapid-quench hydrothermal methods and two modifications of the Ag + AgCl acid buffer technique. The temperature dependence of the thermodynamic equilibrium constant ( K) for the reaction NaAlSi 3O 8 + HCl o = NaCl o + 1/2Al 2SiO 5, + 5/2SiO 2 + 1/2H 2O Albite Andalusite Qtz. K = (a NaCl o) /(a H 2O ) 1/2/(a HCl o) can be described by the following equation: log k = -4.437 + 5205.6/ T( K) The data from this study are consistent with experimental results reported by MONTOYA and HEMLEY (1975) for lower temperature equilibria defined by the assemblages albite + paragonite + quartz + fluid and paragonite + andalusite + quartz + fluid. Values of the equilibrium constants for the above reactions were used to estimate the difference in Gibbs free energy of formation between NaCl o and HCl o in the range 400-700°C and 1-2 kbar. Similar calculations using data from phase equilibrium studies reported in the literature were made to determine the difference in Gibbs free energy of formation between KCl o and HCl o. These data permit modelling of the chemical interaction between muscovite + kspar + paragonite + albite + quartz assemblages and chloride-bearing hydrothermal fluids.

Potential energy function for CH3+CH3 ⇆ C2H6: Attributes of the minimum energy path

NASA Astrophysics Data System (ADS)

Robertson, S. H.; Wardlaw, D. M.; Hirst, D. M.

1993-11-01

The region of the potential energy surface for the title reaction in the vicinity of its minimum energy path has been predicted from the analysis of ab initio electronic energy calculations. The ab initio procedure employs a 6-31G** basis set and a configuration interaction calculation which uses the orbitals obtained in a generalized valence bond calculation. Calculated equilibrium properties of ethane and of isolated methyl radical are compared to existing theoretical and experimental results. The reaction coordinate is represented by the carbon-carbon interatomic distance. The following attributes are reported as a function of this distance and fit to functional forms which smoothly interpolate between reactant and product values of each attribute: the minimum energy path potential, the minimum energy path geometry, normal mode frequencies for vibrational motion orthogonal to the reaction coordinate, a torsional potential, and a fundamental anharmonic frequency for local mode, out-of-plane CH3 bending (umbrella motion). The best representation is provided by a three-parameter modified Morse function for the minimum energy path potential and a two-parameter hyperbolic tangent switching function for all other attributes. A poorer but simpler representation, which may be satisfactory for selected applications, is provided by a standard Morse function and a one-parameter exponential switching function. Previous applications of the exponential switching function to estimate the reaction coordinate dependence of the frequencies and geometry of this system have assumed the same value of the range parameter α for each property and have taken α to be less than or equal to the ``standard'' value of 1.0 Å-1. Based on the present analysis this is incorrect: The α values depend on the property and range from ˜1.2 to ˜1.8 Å-1.

Fugacity and concentration gradients in a gravity field

NASA Technical Reports Server (NTRS)

May, C. E.

1986-01-01

Equations are reviewed which show that at equilibrium fugacity and concentration gradients can exist in gravitational fields. At equilibrium, the logarithm of the ratio of the fugacities of a species at two different locations in a gravitational field is proportional to the difference in the heights of the two locations and the molecular weight of the species. An analogous relation holds for the concentration ratios in a multicomponent system. The ratio is calculated for a variety of examples. The kinetics for the general process are derived, and the time required to approach equilibrium is calculated for several systems. The following special topics are discussed: ionic solutions, polymers, multiphase systems, hydrostatic pressure, osmotic pressure, and solubility gradients in a gravity field.

Determination of Adsorption Equations for Chloro Derivatives of Aniline on Halloysite Adsorbents Using Inverse Liquid Chromatography.

PubMed

Słomkiewicz, Piotr M; Szczepanik, Beata; Garnuszek, Magdalena; Rogala, Paweł; Witkiewicz, Zygfryd

2017-11-01

Chloro derivatives of aniline are commonly used in the production of dyes, pharmaceuticals, and agricultural agents. They are toxic compounds with a large accumulation ability and low natural biodegradability. Halloysite is known as an efficient adsorbent of toxic compounds, such as phenols or herbicides, from wastewater. Inverse LC was applied to measure the adsorption of aniline and 2-chloroaniline (2-CA), 3-chloroaniline (3-CA), and 4-chloroaniline (4-CA) on halloysite adsorbents. A peak division (PD) method was used to determine a Langmuir equation in accordance with the adsorption measurement results. The values of adsorption equilibrium constants and enthalpy were determined and compared by breakthrough curve and PD methods. The physical sense of the calculated adsorption enthalpy values was checked by applying Boudart's entropy criteria. Of note, adsorption enthalpy values for halloysite adsorbents decreased in the following order: aniline > 4-CA > 2-CA > 3-CA.

Recommendations for terminology and databases for biochemical thermodynamics.

PubMed

Alberty, Robert A; Cornish-Bowden, Athel; Goldberg, Robert N; Hammes, Gordon G; Tipton, Keith; Westerhoff, Hans V

2011-05-01

Chemical equations are normally written in terms of specific ionic and elemental species and balance atoms of elements and electric charge. However, in a biochemical context it is usually better to write them with ionic reactants expressed as totals of species in equilibrium with each other. This implies that atoms of elements assumed to be at fixed concentrations, such as hydrogen at a specified pH, should not be balanced in a biochemical equation used for thermodynamic analysis. However, both kinds of equations are needed in biochemistry. The apparent equilibrium constant K' for a biochemical reaction is written in terms of such sums of species and can be used to calculate standard transformed Gibbs energies of reaction Δ(r)G'°. This property for a biochemical reaction can be calculated from the standard transformed Gibbs energies of formation Δ(f)G(i)'° of reactants, which can be calculated from the standard Gibbs energies of formation of species Δ(f)G(j)° and measured apparent equilibrium constants of enzyme-catalyzed reactions. Tables of Δ(r)G'° of reactions and Δ(f)G(i)'° of reactants as functions of pH and temperature are available on the web, as are functions for calculating these properties. Biochemical thermodynamics is also important in enzyme kinetics because apparent equilibrium constant K' can be calculated from experimentally determined kinetic parameters when initial velocities have been determined for both forward and reverse reactions. Specific recommendations are made for reporting experimental results in the literature. Copyright © 2011 Elsevier B.V. All rights reserved.

Hysteresis of the Contact Angle of a Meniscus Inside a Capillary with Smooth, Homogeneous Solid Walls.

PubMed

Kuchin, Igor V; Starov, Victor M

2016-05-31

A theory of contact angle hysteresis of a meniscus inside thin capillaries with smooth, homogeneous solid walls is developed in terms of surface forces (disjoining/conjoining pressure isotherm) using a quasi-equilibrium approach. The disjoining/conjoining pressure isotherm includes electrostatic, intermolecular, and structural components. The values of the static receding θr, advancing θa, and equilibrium θe contact angles in thin capillaries were calculated on the basis of the shape of the disjoining/conjoining pressure isotherm. It was shown that both advancing and receding contact angles depend on the capillary radius. The suggested mechanism of the contact angle hysteresis has a direct experimental confirmation: the process of receding is accompanied by the formation of thick β-films on the capillary walls. The effect of the transition from partial to complete wetting in thin capillaries is predicted and analyzed. This effect takes place in very thin capillaries, when the receding contact angle decreases to zero.

A highly accurate ab initio potential energy surface for methane.

PubMed

Owens, Alec; Yurchenko, Sergei N; Yachmenev, Andrey; Tennyson, Jonathan; Thiel, Walter

2016-09-14

A new nine-dimensional potential energy surface (PES) for methane has been generated using state-of-the-art ab initio theory. The PES is based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set limit and incorporates a range of higher-level additive energy corrections. These include core-valence electron correlation, higher-order coupled cluster terms beyond perturbative triples, scalar relativistic effects, and the diagonal Born-Oppenheimer correction. Sub-wavenumber accuracy is achieved for the majority of experimentally known vibrational energy levels with the four fundamentals of (12)CH4 reproduced with a root-mean-square error of 0.70 cm(-1). The computed ab initio equilibrium C-H bond length is in excellent agreement with previous values despite pure rotational energies displaying minor systematic errors as J (rotational excitation) increases. It is shown that these errors can be significantly reduced by adjusting the equilibrium geometry. The PES represents the most accurate ab initio surface to date and will serve as a good starting point for empirical refinement.

Dual-echo EPI for non-equilibrium fMRI - implications of different echo combinations and masking procedures.

PubMed

Beissner, Florian; Baudrexel, Simon; Volz, Steffen; Deichmann, Ralf

2010-08-15

Dual-echo EPI is based on the acquisition of two images with different echo times per excitation, thus allowing for the calculation of purely T2(*) weighted data. The technique can be used for the measurement of functional activation whenever the prerequisite of constant equilibrium magnetization cannot be fulfilled due to variable inter-volume delays. The latter is the case when image acquisition is triggered by physiological parameters (e.g. cardiac gating) or by the subject's response. Despite its frequent application, there is currently no standardized way of combining the information obtained from the two acquired echoes. The goal of this study was to quantify the implication of different echo combination methods (quotients of echoes and quantification of T(2)(*)) and calculation modalities, either pre-smoothing data before combination or subjecting unsmoothed combined data to masking (no masking, volume-wise masking, joint masking), on the theoretically predicted signal-to-noise ratio (SNR) of the BOLD response and on activation results of two fMRI experiments using finger tapping and visual stimulation in one group (n=5) and different motor paradigms to activate motor areas in the cortex and the brainstem in another group (n=21). A significant impact of echo combination and masking procedure was found for both SNR and activation results. The recommended choice is a direct calculation of T(2)(*) values, either using joint masking on unsmoothed data, or pre-smoothing images prior to T(2)(*) calculation. This method was most beneficial in areas close to the surface of the brain or adjacent to the ventricles and may be especially relevant to brainstem fMRI. Copyright (c) 2010 Elsevier Inc. All rights reserved.

Modeling the adiabatic connection in H2.

PubMed

Peach, Michael J G; Teale, Andrew M; Tozer, David J

2007-06-28

Full configuration interaction (FCI) data are used to quantify the accuracy of approximate adiabatic connection (AC) forms in describing the ground state potential energy curve of H2, within spin-restricted density functional theory (DFT). For each internuclear separation R, accurate properties of the AC are determined from large basis set FCI calculations. The parameters in the approximate AC form are then determined so as to reproduce these FCI values exactly, yielding an exchange-correlation energy expressed entirely in terms of FCI-derived quantities. This is combined with other FCI-derived energy components to give the total electronic energy; comparison with the FCI energy quantifies the accuracy of the AC form. Initial calculations focus on a [1/1]-Padé-based form. The potential energy curve determined using the procedure is a notable improvement over those from existing DFT functionals. The accuracy near equilibrium is quantified by calculating the bond length and vibrational wave numbers; errors in the latter are below 0.5%. The molecule dissociates correctly, which can be traced to the use of virtual orbital eigenvalues in the slope in the noninteracting limit, capturing static correlation. At intermediate R, the potential energy curve exhibits an unphysical barrier, similar to that noted previously using the random phase approximation. Alternative forms of the AC are also considered, paying attention to size extensivity and the behavior in the strong-interaction limit; none provide an accurate potential energy curve for all R, although good accuracy can be achieved near equilibrium. The study demonstrates how data from correlated ab initio calculations can provide valuable information about AC forms and highlight areas where further theoretical progress is required.

Calculating the mean time to capture for tethered ligands and its effect on the chemical equilibrium of bound ligand pairs.

PubMed

Shen, Lu; Decker, Caitlin G; Maynard, Heather D; Levine, Alex J

2016-09-01

We present here the calculation of the mean time to capture of a tethered ligand to the receptor. This calculation is then used to determine the shift in the partitioning between (1) free, (2) singly bound, and (3) doubly bound ligands in chemical equilibrium as a function of the length of the tether. These calculations are used in the research article Fibroblast Growth Factor 2 Dimer with Superagonist in vitro Activity Improves Granulation Tissue Formation During Wound Healing (Decker et al., in press [1]) to explain quantitatively how changes in polymeric linker length in the ligand dimers modifies the efficacy of these molecules relative to that of free ligands.

Dynamics of a gravity-gradient stabilized flexible spacecraft

NASA Technical Reports Server (NTRS)

Meirovitch, L.; Juang, J. N.

1974-01-01

The dynamics of gravity-gradient stabilized flexible satellite in the neighborhood of a deformed equilibrium configuration are discussed. First the equilibrium configuration was determined by solving a set of nonlinear differential equations. Then stability of motion about the deformed equilibrium was tested by means of the Liapunov direct method. The natural frequencies of oscillation of the complete structure were calculated. The analysis is applicable to the RAE/B satellite.

Computing Equilibrium Chemical Compositions

NASA Technical Reports Server (NTRS)

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.

Calculation of the equilibrium distribution for a deleterious gene by the finite Fourier transform.

PubMed

Lange, K

1982-03-01

In a population of constant size every deleterious gene eventually attains a stochastic equilibrium between mutation and selection. The individual probabilities of this equilibrium distribution can be computed by an application of the finite Fourier transform to an appropriate branching process formula. Specific numerical examples are discussed for the autosomal dominants, Huntington's chorea and chondrodystrophy, and for the X-linked recessive, Becker's muscular dystrophy.

Chemical bonding and the equilibrium composition of Grignard reagents in ethereal solutions.

PubMed

Henriques, André M; Barbosa, André G H

2011-11-10

A thorough analysis of the electronic structure and thermodynamic aspects of Grignard reagents and its associated equilibrium composition in ethereal solutions is performed. Considering methylmagnesium halides containing fluorine, chlorine, and bromine, we studied the neutral, charged, and radical species associated with their chemical equilibrium in solution. The ethereal solvents considered, tetrahydrofuran (THF) and ethyl ether (Et(2)O), were modeled using the polarizable continuum model (PCM) and also by explicit coordination to the Mg atoms in a cluster. The chemical bonding of the species that constitute the Grignard reagent is analyzed in detail with generalized valence bond (GVB) wave functions. Equilibrium constants were calculated with the DFT/M06 functional and GVB wave functions, yielding similar results. According to our calculations and existing kinetic and electrochemical evidence, the species R(•), R(-), (•)MgX, and RMgX(2)(-) must be present in low concentration in the equilibrium. We conclude that depending on the halogen, a different route must be followed to produce the relevant equilibrium species in each case. Chloride and bromide must preferably follow a "radical-based" pathway, and fluoride must follow a "carbanionic-based" pathway. These different mechanisms are contrasted against the available experimental results and are proven to be consistent with the existing thermodynamic data on the Grignard reagent equilibria.

The procedure and results of calculations of the equilibrium isotopic composition of a demonstration subcritical molten salt reactor

NASA Astrophysics Data System (ADS)

Nevinitsa, V. A.; Dudnikov, A. A.; Blandinskiy, V. Yu.; Balanin, A. L.; Alekseev, P. N.; Titarenko, Yu. E.; Batyaev, V. F.; Pavlov, K. V.; Titarenko, A. Yu.

2015-12-01

A subcritical molten salt reactor with an external neutron source is studied computationally as a facility for incineration and transmutation of minor actinides from spent nuclear fuel of reactors of VVER-1000 type and for producing 233U from 232Th. The reactor configuration is chosen, the requirements to be imposed on the external neutron source are formulated, and the equilibrium isotopic composition of heavy nuclides and the key parameters of the fuel cycle are calculated.

TMAP: Tübingen NLTE Model-Atmosphere Package

NASA Astrophysics Data System (ADS)

Werner, Klaus; Dreizler, Stefan; Rauch, Thomas

2012-12-01

The Tübingen NLTE Model-Atmosphere Package (TMAP) is a tool to calculate stellar atmospheres in spherical or plane-parallel geometry in hydrostatic and radiative equilibrium allowing departures from local thermodynamic equilibrium (LTE) for the population of atomic levels. It is based on the Accelerated Lambda Iteration (ALI) method and is able to account for line blanketing by metals. All elements from hydrogen to nickel may be included in the calculation with model atoms which are tailored for the aims of the user.

Surface structure and stability of partially hydroxylated silica surfaces

DOE PAGES

Rimsza, J. M.; Jones, R. E.; Criscenti, L. J.

2017-04-04

Surface energies of silicates influence crack propagation during brittle fracture and decrease with surface relaxation caused by annealing and hydroxylation. Molecular-level simulations are particularly suited for the investigation of surface processes. In this work, classical MD simulations of silica surfaces are performed with two force fields (ClayFF and ReaxFF) to investigate the effect of force field reactivity on surface structure and energy as a function of surface hydroxylation. An unhydroxylated fracture surface energy of 5.1 J/m 2 is calculated with the ClayFF force field, and 2.0 J/m 2 is calculated for the ReaxFF force field. The ClayFF surface energies aremore » consistent with the experimental results from double cantilever beam fracture tests (4.5 J/m 2), whereas ReaxFF underestimated these surface energies. Surface relaxation via annealing and hydroxylation was performed by creating a low-energy equilibrium surface. Annealing condensed neighboring siloxane bonds increased the surface connectivity, and decreased the surface energies by 0.2 J/m 2 for ClayFF and 0.8 J/m 2 for ReaxFF. Posthydroxylation surface energies decreased further to 4.6 J/m 2 with the ClayFF force field and to 0.2 J/m 2 with the ReaxFF force field. Experimental equilibrium surface energies are ~0.35 J/m 2, consistent with the ReaxFF force field. Although neither force field was capable of replicating both the fracture and equilibrium surface energies reported from experiment, each was consistent with one of these conditions. Furthermore, future computational investigations that rely on accurate surface energy values should consider the surface state of the system and select the appropriate force field.« less

In silico prediction of medium effects on esterification equilibrium using the COSMO-RS method.

PubMed

Fermeglia, Maurizio; Braiuca, Paolo; Gardossi, Lucia; Pricl, Sabrina; Halling, Peter J

2006-01-01

This paper presents a new approach for predicting solvent effects on esterification reactions of industrial importance in the field of biocatalysis. The COSMO-RS method has been used to calculate the activity coefficients of the chemical species involved in various reactions, carried out in different solvents. For comparison we also used the traditional UNIFAC method. Three lipase-catalyzed esterifications were considered: (1) 1-dodecanoic acid with menthol in n-hexane, n-heptane, cyclohexane, 2,2,4-trimethylpentane, toluene, acetonitrile, and 2-methyl-2-butanol; (2) 1-dodecanoic acid and 1-dodecanol in n-hexane, n-heptane, cyclohexane, 2,2,4-trimethylpentane, and toluene; and (3) glycerol and n-octanoic acid in acetonitrile, benzene, and toluene and in the neat reaction mixture (without any solvent). Predicted activities were used to calculate the thermodynamic equilibrium ratio. This should be independent of medium, and the variation in COSMO-RS values is at most 9-fold (corresponding to a DeltaG degrees of about 5.5 kJ/mol, which would still be a very useful prediction) and often only 2-fold (corresponding to less than 2 kJ/mol or 0.5 kcal/mol, therefore comparable with experimental error). UNIFAC is weaker, especially when important roles are played by conformational freedom, intramolecular interactions, strong polar effects, and charge distribution of molecules in the mixture. The relative percent deviations from the mean of equilibrium constants in different solvents range between 17 and 49 for COSMO-RS versus 32 to 65 for UNIFAC. The COSMO-RS method opens up new perspectives for the development of theoretical models for solvent selection with general applicability.

Donnan membrane speciation of Al, Fe, trace metals and REEs in coastal lowland acid sulfate soil-impacted drainage waters.

PubMed

Jones, Adele M; Xue, Youjia; Kinsela, Andrew S; Wilcken, Klaus M; Collins, Richard N

2016-03-15

Donnan dialysis has been applied to forty filtered drainage waters collected from five coastal lowland acid sulfate soil (CLASS) catchments across north-eastern NSW, Australia. Despite having average pH values<3.9, 78 and 58% of Al and total Fe, respectively, were present as neutral or negatively-charged species. Complementary isotope dilution experiments with (55)Fe and (26)Al demonstrated that only soluble (i.e. no colloidal) species were present. Trivalent rare earth elements (REEs) were also mainly present (>70%) as negatively-charged complexes. In contrast, the speciation of the divalent trace metals Co, Mn, Ni and Zn was dominated by positively-charged complexes and was strongly correlated with the alkaline earth metals Ca and Mg. Thermodynamic equilibrium speciation calculations indicated that natural organic matter (NOM) complexes dominated Fe(III) speciation in agreement with that obtained by Donnan dialysis. In the case of Fe(II), however, the free cation was predicted to dominate under thermodynamic equilibrium, whilst our results indicated that Fe(II) was mainly present as neutral or negatively-charged complexes (most likely with sulfate). For all other divalent metals thermodynamic equilibrium speciation calculations agreed well with the Donnan dialysis results. The proportion of Al and REEs predicted to be negatively-charged was also grossly underestimated, relative to the experimental results, highlighting possible inaccuracies in the stability constants developed for these trivalent Me(SO4)2(-) and/or Me-NOM complexes and difficulties in modeling complex environmental samples. These results will help improve metal mobility and toxicity models developed for CLASS-affected environments, and also demonstrate that Australian CLASS environments can discharge REEs at concentrations an order of magnitude greater than previously reported. Copyright © 2015 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rimsza, J. M.; Jones, R. E.; Criscenti, L. J.

Surface energies of silicates influence crack propagation during brittle fracture and decrease with surface relaxation caused by annealing and hydroxylation. Molecular-level simulations are particularly suited for the investigation of surface processes. In this work, classical MD simulations of silica surfaces are performed with two force fields (ClayFF and ReaxFF) to investigate the effect of force field reactivity on surface structure and energy as a function of surface hydroxylation. An unhydroxylated fracture surface energy of 5.1 J/m 2 is calculated with the ClayFF force field, and 2.0 J/m 2 is calculated for the ReaxFF force field. The ClayFF surface energies aremore » consistent with the experimental results from double cantilever beam fracture tests (4.5 J/m 2), whereas ReaxFF underestimated these surface energies. Surface relaxation via annealing and hydroxylation was performed by creating a low-energy equilibrium surface. Annealing condensed neighboring siloxane bonds increased the surface connectivity, and decreased the surface energies by 0.2 J/m 2 for ClayFF and 0.8 J/m 2 for ReaxFF. Posthydroxylation surface energies decreased further to 4.6 J/m 2 with the ClayFF force field and to 0.2 J/m 2 with the ReaxFF force field. Experimental equilibrium surface energies are ~0.35 J/m 2, consistent with the ReaxFF force field. Although neither force field was capable of replicating both the fracture and equilibrium surface energies reported from experiment, each was consistent with one of these conditions. Furthermore, future computational investigations that rely on accurate surface energy values should consider the surface state of the system and select the appropriate force field.« less

46 CFR 28.515 - Submergence test as an alternative to stability calculations.

Code of Federal Regulations, 2011 CFR

2011-10-01

... float in calm water after being submerged for 18 hours so that— (1) The vessel has an equilibrium heel... in paragraph (c) of this section, except that the equilibrium heel angle must not exceed 30° and the...

Steps toward identifying a biogeochemical signal in non-equilibrium methane clumped isotope measurements

NASA Astrophysics Data System (ADS)

Douglas, P. M.; Eiler, J. M.; Sessions, A. L.; Dawson, K.; Walter Anthony, K. M.; Smith, D. A.; Lloyd, M. K.; Yanay, E.

2016-12-01

Microbially produced methane is a globally important greenhouse gas, energy source, and biological substrate. Methane clumped isotope measurements have recently been developed as a new analytical tool for understanding the source of methane in different environments. When methane forms in isotopic equilibrium clumped isotope values are determined by formation temperature, but in many cases microbial methane clumped isotope values deviate strongly from expected equilibrium values. Indeed, we observe a very wide range of clumped isotope values in microbial methane, which are likely strongly influenced by kinetic isotope effects, but thus far the biological and environmental parameters controlling this variability are not understood. We will present data from both culture experiments and natural environments to explore patterns of variability in non-equilibrium clumped isotope values on temporal and spatial scales. In methanogen batch cultures sampled at different time points along a growth curve we observe significant variability in clumped isotope values, with values decreasing from early to late exponential growth. Clumped isotope values then increase during stationary growth. This result is consistent with previous work suggesting that differences in the reversibility of methanogenesis related to metabolic rates control non-equilibrium clumped isotope values. Within single lakes in Alaska and Sweden we observe substantial variability in clumped isotope values on the order of 5‰. Lower clumped isotope values are associated with larger 2H isotopic fractionation between water and methane, which is also consistent with a kinetic isotope effect determined by the reversibility of methanogenesis. Finally, we analyzed a time-series clumped isotope compositions of methane emitted from two seeps in an Alaskan lake over several months. Temporal variability in these seeps is on the order of 2‰, which is much less than the observed spatial variability within the lake. Comparing carbon isotope fractionation between CO2 and CH4 with clumped isotope data suggests the temporal variability may result from changes in methane oxidation.

Collisional Ionization Equilibrium for Optically Thin Plasmas

NASA Technical Reports Server (NTRS)

Bryans, P.; Mitthumsiri, W.; Savin, D. W.; Badnell, N. R.; Gorczyca, T. W.; Laming, J. M.

2006-01-01

Reliably interpreting spectra from electron-ionized cosmic plasmas requires accurate ionization balance calculations for the plasma in question. However, much of the atomic data needed for these calculations have not been generated using modern theoretical methods and their reliability are often highly suspect. We have utilized state-of-the-art calculations of dielectronic recombination (DR) rate coefficients for the hydrogenic through Na-like ions of all elements from He to Zn. We have also utilized state-of-the-art radiative recombination (RR) rate coefficient calculations for the bare through Na-like ions of all elements from H to Zn. Using our data and the recommended electron impact ionization data of Mazzotta et al. (1998), we have calculated improved collisional ionization equilibrium calculations. We compare our calculated fractional ionic abundances using these data with those presented by Mazzotta et al. (1998) for all elements from H to Ni, and with the fractional abundances derived from the modern DR and RR calculations of Gu (2003a,b, 2004) for Mg, Si, S, Ar, Ca, Fe, and Ni.

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

ERIC Educational Resources Information Center

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…

Paths to equilibrium in non-conformal collisions

NASA Astrophysics Data System (ADS)

Attems, Maximilian; Bea, Yago; Casalderrey-Solana, Jorge; Mateos, David; Santos-Oliván, Daniel; Sopuerta, Carlos F.; Triana, Miquel; Zilhão, Miguel

2018-03-01

Ever since fast hydrodynamization has been observed in heavy ion collisions the understanding of the hot early out-of-equilibrium stage of such collisions has been a topic of intense research. We use the gauge/gravity duality to model the creation of a strongly coupled Quark-Gluon plasma in a non-conformal gauge theory. This numerical relativity study is the first non-conformal holographic simulation of a heavy ion collision and reveals the existence of new relaxation channels due to the presence of non-vanishing bulk viscosity. We study shock wave collisions at different energies in gauge theories with different degrees of non-conformality and compare three relaxation times which can occur in different orderings: the hydrodynamization time (when hydrodynamics becomes applicable), the EoSization time (when the average pressure approaches its equilibrium value) and the condensate relaxation time (when the expectation value of a scalar operator approaches its equilibrium value). We find that these processes can occur in several different orderings. In particular, the condensate can remain far from equilibrium even long after the plasma has hydrodynamized and EoSized.

On the equilibrium charge density at tilt grain boundaries

NASA Astrophysics Data System (ADS)

Srikant, V.; Clarke, D. R.

1998-05-01

The equilibrium charge density and free energy of tilt grain boundaries as a function of their misorientation is computed using a Monte Carlo simulation that takes into account both the electrostatic and configurational energies associated with charges at the grain boundary. The computed equilibrium charge density increases with the grain-boundary angle and approaches a saturation value. The equilibrium charge density at large-angle grain boundaries compares well with experimental values for large-angle tilt boundaries in GaAs. The computed grain-boundary electrostatic energy is in agreement with the analytical solution to a one-dimensional Poisson equation at high donor densities but indicates that the analytical solution overestimates the electrostatic energy at lower donor densities.

Climate system properties determining the social cost of carbon

NASA Astrophysics Data System (ADS)

Otto, Alexander; Todd, Benjamin J.; Bowerman, Niel; Frame, David J.; Allen, Myles R.

2013-06-01

The choice of an appropriate scientific target to guide global mitigation efforts is complicated by uncertainties in the temperature response to greenhouse gas emissions. Much climate policy discourse has been based on the equilibrium global mean temperature increase following a concentration stabilization scenario. This is determined by the equilibrium climate sensitivity (ECS) which, in many studies, shows persistent, fat-tailed uncertainty. However, for many purposes, the equilibrium response is less relevant than the transient response. Here, we show that one prominent policy variable, the social cost of carbon (SCC), is generally better constrained by the transient climate response (TCR) than by the ECS. Simple analytic expressions show the SCC to be directly proportional to the TCR under idealized assumptions when the rate at which we discount future damage equals 2.8%. Using ensemble simulations of a simple climate model we find that knowing the true value of the TCR can reduce the relative uncertainty in the SCC substantially more, up to a factor of 3, than knowing the ECS under typical discounting assumptions. We conclude that the TCR, which is better constrained by observations, less subject to fat-tailed uncertainty and more directly related to the SCC, is generally preferable to the ECS as a single proxy for the climate response in SCC calculations.

Facile chemical synthesis and equilibrium unfolding properties of CopG

PubMed Central

Wales, Thomas E.; Richardson, Jane S.; Fitzgerald, Michael C.

2004-01-01

The 45-amino acid polypeptide chain of the homodimeric transcriptional repressor, CopG, was chemically synthesized by stepwise solid phase peptide synthesis (SPPS) using a protocol based on Boc-chemistry. The product obtained from the synthesis was readily purified by reversed-phase HPLC to give a good overall yield (21% by weight). Moreover, the synthetic CopG constructs prepared in this work folded into three-dimensional structures similar to the wild-type protein prepared using conventional recombinant methods as judged by far UV-CD spectroscopy. A fluorescent CopG analog, (Y39W)CopG, was also designed and chemically synthesized to facilitate biophysical studies of CopG’s protein folding and assembly reaction. The guanidinium chloride-induced equilibrium unfolding properties of the wild-type CopG and (Y39W)CopG constructs in this work were characterized and used to develop a model for CopG’s equilibrium unfolding reaction. Our results indicate that CopG’s folding and assembly reaction is well modeled by a two-state process involving folded dimer and unfolded monomer. Using this model, ΔGf and m-values of −13.42 ± 0.04 kcal/mole dimer and 1.92 ± 0.01 kcal/(mole M) were calculated for CopG. PMID:15169951

Ternary liquid-liquid equilibrium for eugenol + tert-butanol + water system at 303.15 and 323.15K and atmospheric pressure

NASA Astrophysics Data System (ADS)

Sucipto, Retno Kumala Hesti; Kuswandi, Wibawa, Gede

2017-05-01

The objective of this study was to determine ternary liquid-liquid equilibrium for eugenol + tert-butanol + water system at 303.15 and 323.15K and atmospheric pressure. Using 25 mL equilibrium cell equipped jacketted water connected to water bath to maintain equilibrium temperature constant. The procedure of this experiment was conducted by inserting mixture of eugenol + tert-butanol + water system at certain composition into equilibrium cell. The solution was stirred for 4 hours and then was allowed for 20 hours in order to separate aqueous and organic phases completely. The temperature equilibrium cell of and the atmosphere pressure were recorded as equilibrium temperature and pressure for each measurenment. The equilibrium compositions of each phase were analyzed using Gas Chromatography. The experimental data obtained in this work were correlated with NRTL and UNIQUAC models with root mean square deviation between esperimental and calculated equilibrium compositions of 0.03% and 0.04% respectively.

Another dimension to metamorphic phase equilibria: the power of interactive movies for understanding complex phase diagram sections

NASA Astrophysics Data System (ADS)

Moulas, E.; Caddick, M. J.; Tisato, N.; Burg, J.-P.

2012-04-01

The investigation of metamorphic phase equilibria, using software packages that perform thermodynamic calculations, involves a series of important assumptions whose validity can often be questioned but are difficult to test. For example, potential influences of deformation on phase relations, and modification of effective reactant composition (X) at successive stages of equilibrium may both introduce significant uncertainty into phase diagram calculations. This is generally difficult to model with currently available techniques, and is typically not well quantified. We present here a method to investigate such phenomena along pre-defined Pressure-Temperature (P-T) paths, calculating local equilibrium via Gibbs energy minimization. An automated strategy to investigate complex changes in the effective equilibration composition has been developed. This demonstrates the consequences of specified X modification and, more importantly, permits automated calculation of X changes that are likely along the requested path if considering several specified processes. Here we describe calculations considering two such processes and show an additional example of a metamorphic texture that is difficult to model with current techniques. Firstly, we explore the assumption that although water saturation and bulk-rock equilibrium are generally considered to be valid assumptions in the calculation of phase equilibria, the saturation of thermodynamic components ignores mechanical effects that the fluid/melt phase can impose on the rock, which in turn can modify the effective equilibrium composition. Secondly, we examine how mass fractionation caused by porphyroblast growth at low temperatures or progressive melt extraction at high temperatures successively modifies X out of the plane of the initial diagram, complicating the process of determining best-fit P-T paths for natural samples. In particular, retrograde processes are poorly modeled without careful consideration of prograde fractionation processes. Finally we show how, although the effective composition of symplectite growth is not easy to determine and quantify, it is possible to successfully model by constructing a series of phase equilibria calculations.

Solar heating of common lunar minerals for the production of oxygen

NASA Technical Reports Server (NTRS)

Senior, C. L.

1991-01-01

The purpose of this work was to demonstrate the feasibility of vapor-phase reduction (pyrolysis) of lunar materials to produce oxygen. Solar furnace experiments were conducted on two common lunar minerals, ilmenite and anorthite. Thermodynamic equilibrium calculations predicted that ilmenite should show a larger pressure increase than anorthite under conditions of the experiments and this was confirmed by the experiments. The measured mass loss of the ilmenite sample was consistent with loss of oxygen by reduction of iron in the liquid phase; this result was also predicted from equilibrium calculations. Based on preliminary experiments and equilibrium calculations, the temperatures needed for pyrolysis are expected to be in the range of 2000 to 2500 K, giving total gas pressures of 0.01 to 1 torr. Bulk regolith can be used as a feedstock without extensive beneficiation. Further, selective condensation of metal-containing species from the gas phase may yield metallic iron and silicon as byproducts from the process.

Pollutant threshold concentration determination in marine ecosystems using an ecological interaction endpoint.

PubMed

Wang, Changyou; Liang, Shengkang; Guo, Wenting; Yu, Hua; Xing, Wenhui

2015-09-01

The threshold concentrations of pollutants are determined by extrapolating single-species effect data to community-level effects. This assumes the most sensitive endpoint of the life cycle of individuals and the species sensitivity distribution from single-species toxic effect tests, thus, ignoring the ecological interactions. The uncertainties due to this extrapolation can be partially overcome using the equilibrium point of a customized ecosystem. This method incorporates ecological interactions and integrates the effects on growth, survival, and ingestion into a single effect measure, the equilibrium point excursion in the customized ecosystem, in order to describe the toxic effects on plankton. A case study showed that the threshold concentration of copper calculated with the endpoint of the equilibrium point was 10 μg L(-1), which is significantly different from the threshold calculated with a single-species endpoint. The endpoint calculated using this method provides a more relevant measure of the ecological impact than any single individual-level endpoint. Copyright © 2015 Elsevier Ltd. All rights reserved.

Predicting the equilibrium solubility of solid polycyclic aromatic hydrocarbons and dibenzothiophene using a combination of MOSCED plus molecular simulation or electronic structure calculations

NASA Astrophysics Data System (ADS)

Phifer, Jeremy R.; Cox, Courtney E.; da Silva, Larissa Ferreira; Nogueira, Gabriel Gonçalves; Barbosa, Ana Karolyne Pereira; Ley, Ryan T.; Bozada, Samantha M.; O'Loughlin, Elizabeth J.; Paluch, Andrew S.

2017-06-01

Methods to predict the equilibrium solubility of non-electrolyte solids are important for the design of novel separation processes. Here we demonstrate how conventional molecular simulation free energy calculations or electronic structure calculations in a continuum solvent, here SMD or SM8, can be used to predict parameters for the MOdified Separation of Cohesive Energy Density (MOSCED) method. The method is applied to the solutes naphthalene, anthracene, phenanthrene, pyrene and dibenzothiophene, compounds of interested to the petroleum industry and for environmental remediation. Adopting the melting point temperature and enthalpy of fusion of these compounds from experiment, we are able to predict equilibrium solubilities. Comparing to a total of 422 non-aqueous and 193 aqueous experimental solubilities, we find the proposed method is able to well correlate the data. The use of MOSCED is additionally advantageous as it is a solubility parameter-based method useful for intuitive solvent selection and formulation.

Adsorption studies on the removal of COD and BOD from treated sewage using activated carbon prepared from date palm waste.

PubMed

Nayl, Abd ElAziz A; Elkhashab, Reda A; El Malah, Tamer; Yakout, Sobhy M; El-Khateeb, Mohamed A; Ali, Mahmoud M S; Ali, Hazim M

2017-10-01

In this work, the adsorption of chemical oxygen demand (COD) and biological oxygen demand (BOD) from treated sewage with low-cost activated carbon prepared from date palm shell waste by chemical activation method was studied. Different parameters affecting the adsorption process such as carbon dose, pH, contact time, agitation rate, and temperature were studied. Adsorption equilibrium was attained after 150 min at pH 6.0 with agitation rate of 400 rpm at 25 °C. The results showed that COD removal percentage of 95.4 and 92.8% for BOD was obtained with carbon dosage of 0.1 g/100 ml of solution. The experimental batch equilibrium results follow linear, Langmuir, and Freundlich isotherm models. The experimental data was fitted to a pseudo-second-order kinetics model controlled by pore diffusion. Thermodynamic parameter values of ΔH 0 , ΔG 0 , and ΔS 0 were calculated. The obtained data indicated that the adsorption was spontaneous, endothermic nature and reflects an increased randomness and degree of disorderliness at the activated carbon/sewage interface during the adsorption process investigated in this study. Concentrations of different impurities were reduced to very small value by investigated adsorption process.

Predicting Stability Constants for Uranyl Complexes Using Density Functional Theory

DOE PAGES

Vukovic, Sinisa; Hay, Benjamin P.; Bryantsev, Vyacheslav S.

2015-04-02

The ability to predict the equilibrium constants for the formation of 1:1 uranyl:ligand complexes (log K 1 values) provides the essential foundation for the rational design of ligands with enhanced uranyl affinity and selectivity. We also use density functional theory (B3LYP) and the IEFPCM continuum solvation model to compute aqueous stability constants for UO 2 2+ complexes with 18 donor ligands. Theoretical calculations permit reasonably good estimates of relative binding strengths, while the absolute log K 1 values are significantly overestimated. Accurate predictions of the absolute log K 1 values (root mean square deviation from experiment < 1.0 for logmore » K 1 values ranging from 0 to 16.8) can be obtained by fitting the experimental data for two groups of mono and divalent negative oxygen donor ligands. The utility of correlations is demonstrated for amidoxime and imide dioxime ligands, providing a useful means of screening for new ligands with strong chelate capability to uranyl.« less

Particle Sorting and Motility Out of Equilibrium

NASA Astrophysics Data System (ADS)

Sandford, Cato

The theory of equilibrium statistical physics, formulated over a century ago, provides an excellent description of physical systems which have reached a static, relaxed state. Such systems can be loosely thought of as maximally disordered, in keeping with the Second Law of Thermodynamics which states that a thermal system in equilibrium has reached a state of highest entropy. However, many entities in the world around us maintain themselves in an remarkably ordered and dynamic state, and must pay for this by producing entropy in their surroundings. Organisms, for example, convert chemical energy (food) into heat, which is then dumped into the environment, raising its entropy. Systems which produce entropy through any mechanism must be described by theories of non-equilibrium statistical physics, for which there currently exists no unified framework or ontology. Here we examine two specific cases of non-equilibrium phenomena from a theoretical perspective. First, we explore the behaviour of microscopic particles which continually dissipate energy to propel themselves through their environment. Second, we consider how devices which distinguish between different types of particles can exploit non-equilibrium processes to enhance their performance. For the case of self-propelled particles, we consider a theoretical model where the particle's propulsion force has "memory"--it is a random process whose instantaneous value depends on its past evolution. This introduces a persistence in the particle's motion, and requires the dissipation of energy into its surroundings. These particles are found to exhibit a variety of behaviours forbidden in equilibrium systems: for instance they may cluster around barriers, exert unbalanced forces, and sustain steady flows through space. We develop the understanding of these particles' dynamics through a combination of explicit calculations, approximations and numerical simulation which characterise and quantify their non-equilibrium behaviour. The second situation investigated concerns the physics of particle-sorting, which is fundamental to biological systems. We introduce a number of model devices designed to distinguish between and segregate two species of particles, and analyse how the quality and speed of their operation may be influenced by providing them with an energy source which pushes them out of equilibrium. We identify different physical regimes, where our devices may consume energy to deliver better results or deliver them faster or both; and we furthermore connect the broader theory of particle sorting to the fundamental theoretical framework of statistical physics.

The Equilibrium and Pre-equilibrium Triton Emission Spectra of Some Target Nuclei for ( n, xt) Reactions up to 45 MeV Energy

NASA Astrophysics Data System (ADS)

Tel, E.; Kaplan, A.; Aydın, A.; Özkorucuklu, S.; Büyükuslu, H.; Yıldırım, G.

2010-08-01

Although there have been significant research and development studies on the inertial and magnetic fusion reactor technology, there is still a long way to go to penetrate commercial fusion reactors to the energy market. Tritium self-sufficiency must be maintained for a commercial power plant. For self-sustaining (D-T) fusion driver tritium breeding ratio should be greater than 1.05. So, working out the systematics of ( n,t) reaction cross sections and triton emission differential data are important for the given reaction taking place on various nuclei at different energies. In this study, ( n,xt) reactions for some target nuclei as 16O, 27Al, 59Co and 209Bi have been investigated up to 45 MeV incident neutron energy. In the calculations of the triton emission spectra, the pre-equilibrium and equilibrium effects have been used. The calculated results have been compared with the experimental data taken from the literature.

Intermolecular symmetry-adapted perturbation theory study of large organic complexes.

PubMed

Heßelmann, Andreas; Korona, Tatiana

2014-09-07

Binding energies for the complexes of the S12L database by Grimme [Chem. Eur. J. 18, 9955 (2012)] were calculated using intermolecular symmetry-adapted perturbation theory combined with a density-functional theory description of the interacting molecules. The individual interaction energy decompositions revealed no particular change in the stabilisation pattern as compared to smaller dimer systems at equilibrium structures. This demonstrates that, to some extent, the qualitative description of the interaction of small dimer systems may be extrapolated to larger systems, a method that is widely used in force-fields in which the total interaction energy is decomposed into atom-atom contributions. A comparison of the binding energies with accurate experimental reference values from Grimme, the latter including thermodynamic corrections from semiempirical calculations, has shown a fairly good agreement to within the error range of the reference binding energies.

Dissociation Energies of the Alkaline Earth Monofluorides

DOE Office of Scientific and Technical Information (OSTI.GOV)

BLUE, GARY D.; GREEN, JOHN W.; EHLERT, THOMAS C.

1963-08-24

New results and theoretical calculations are presented that indicate consistently high dissocintion energies for all the alkaline earth monofluorides. Experimental results were obtained by utilizing a mass spectrometer to analyze the vapors from a heated Ta Knudsen cell containing an alkaline earth fluoride salt with Al present as a reducing agent. Ionization efficiency curves were obtained and temperature dependence investigations were made to determine the molecular precursor of the ions observed. Values of the equilibrium constants at different temperatures were used together with the free-energy functions to calculate the third law heats of reaction at 298 deg K. Data aremore » tabulated for the heats of various reactions for Al--MF2 systems with M = Mg, Ca, Sr, and Ba, and dissociation energies of MF molecules by various methods for Be, Mg, Ca, Sr, and Ba. (C.H.)« less

Electrostatic and hydrodynamics effects in a sedimented magnetorheological suspension.

PubMed

Domínguez-García, P; Pastor, J M; Melle, Sonia; Rubio, Miguel A

2009-08-01

We present experimental results on the equilibrium microstructure of a sedimented magnetorheological suspension, namely, an aqueous suspension of micron-sized superparamagnetic particles. We develop a study of the electrical interactions on the suspension by processing video-microscopy images of the sedimented particles. We calculate the pair distribution function, g(r), which yields the electrostatic pair potential u(r), showing an anomalous attractive interaction for distances on the order of twice the particle diameter, with characteristic parameters whose values show a dependence with the two-dimensional concentration of particles. The repulsive body of the potential is adjusted to a DLVO expression in order to calculate the Debye screening length and the effective surface charge density. Influence of confinement and variations on the Boltzmann sedimentation profile because of the electrostatic interactions appear to be essential for the interpretation of experimental results.

Concentration effect on inter-mineral equilibrium isotope fractionation: insights from Mg and Ca isotopic systems

NASA Astrophysics Data System (ADS)

Huang, F.; Wang, W.; Zhou, C.; Kang, J.; Wu, Z.

2017-12-01

Many naturally occurring minerals, such as carbonate, garnet, pyroxene, and feldspar, are solid solutions with large variations in chemical compositions. Such variations may affect mineral structures and modify the chemical bonding environment around atoms, which further impacts the equilibrium isotope fractionation factors among minerals. Here we investigated the effects of Mg content on equilibrium Mg and Ca isotope fractionation among carbonates and Ca content on equilibrium Ca isotope fractionation between orthopyroxene (opx) and clinopyroxene (cpx) using first-principles calculations. Our results show that the average Mg-O bond length increases with decreasing Mg/(Mg+Ca) in calcite when it is greater than 1/48[1] and the average Ca-O bond length significantly decreases with decreasing Ca/(Ca+Mg+Fe) in opx when it ranges from 2/16 to 1/48[2]. Equilibrium isotope fractionation is mainly controlled by bond strengths, which could be measured by bond lengths. Thus, 103lnα26Mg/24Mg between dolomite and calcite dramatically increases with decreasing Mg/(Mg+Ca) in calcite [1] and it reaches a constant value when it is lower than 1/48. 103lnα44Ca/40Ca between opx and cpx significantly increases with decreasing Ca content in opx when Ca/(Ca+Mg+Fe) ranges from 2/16 to 1/48 [2]. If Ca/(Ca+Mg+Fe) is below 1/48, 103lnα44Ca/40Ca is not sensitive to Ca content. Based on our results, we conclude that the concentration effect on equilibrium isotope fractionation could be significant within a certain range of chemical composition of minerals, which should be a ubiquitous phenomenon in solid solution systems. [1] Wang, W., Qin, T., Zhou, C., Huang, S., Wu, Z., Huang, F., 2017. GCA 208, 185-197. [2] Feng, C., Qin, T., Huang, S., Wu, Z., Huang, F., 2014. GCA 143, 132-142.

Finite Temperature Densities via the S-Function Method with Application to Electron Screening in Plasmas

NASA Astrophysics Data System (ADS)

Watrous, Mitchell James

1997-12-01

A new approach to the Green's-function method for the calculation of equilibrium densities within the finite temperature, Kohn-Sham formulation of density functional theory is presented, which extends the method to all temperatures. The contour of integration in the complex energy plane is chosen such that the density is given by a sum of Green's function differences evaluated at the Matsubara frequencies, rather than by the calculation and summation of Kohn-Sham single-particle wave functions. The Green's functions are written in terms of their spectral representation and are calculated as the solutions of their defining differential equations. These differential equations are boundary value problems as opposed to the standard eigenvalue problems. For large values of the complex energy, the differential equations are further simplified from second to first-order by writing the Green's functions in terms of logarithmic derivatives. An asymptotic expression for the Green's functions is derived, which allows the sum over Matsubara poles to be approximated. The method is applied to the screening of nuclei by electrons in finite temperature plasmas. To demonstrate the method's utility, and to illustrate its advantages, the results of previous wave function type calculations for protons and neon nuclei are reproduced. The method is also used to formulate a new screening model for fusion reactions in the solar core, and the predicted reaction rate enhancements factors are compared with existing models.

Uniform electron gases. III. Low-density gases on three-dimensional spheres

DOE Office of Scientific and Technical Information (OSTI.GOV)

Agboola, Davids; Knol, Anneke L.; Gill, Peter M. W., E-mail: peter.gill@anu.edu.au

2015-08-28

By combining variational Monte Carlo (VMC) and complete-basis-set limit Hartree-Fock (HF) calculations, we have obtained near-exact correlation energies for low-density same-spin electrons on a three-dimensional sphere (3-sphere), i.e., the surface of a four-dimensional ball. In the VMC calculations, we compare the efficacies of two types of one-electron basis functions for these strongly correlated systems and analyze the energy convergence with respect to the quality of the Jastrow factor. The HF calculations employ spherical Gaussian functions (SGFs) which are the curved-space analogs of Cartesian Gaussian functions. At low densities, the electrons become relatively localized into Wigner crystals, and the natural SGFmore » centers are found by solving the Thomson problem (i.e., the minimum-energy arrangement of n point charges) on the 3-sphere for various values of n. We have found 11 special values of n whose Thomson sites are equivalent. Three of these are the vertices of four-dimensional Platonic solids — the hyper-tetrahedron (n = 5), the hyper-octahedron (n = 8), and the 24-cell (n = 24) — and a fourth is a highly symmetric structure (n = 13) which has not previously been reported. By calculating the harmonic frequencies of the electrons around their equilibrium positions, we also find the first-order vibrational corrections to the Thomson energy.« less

Importance of the Electron Correlation and Dispersion Corrections in Calculations Involving Enamines, Hemiaminals, and Aminals. Comparison of B3LYP, M06-2X, MP2, and CCSD Results with Experimental Data.

PubMed

Castro-Alvarez, Alejandro; Carneros, Héctor; Sánchez, Dani; Vilarrasa, Jaume

2015-12-18

While B3LYP, M06-2X, and MP2 calculations predict the ΔG° values for exchange equilibria between enamines and ketones with similar acceptable accuracy, the M06-2X/6-311+G(d,p) and MP2/6-311+G(d,p) methods are required for enamine formation reactions (for example, for enamine 5a, arising from 3-methylbutanal and pyrrolidine). Stronger disagreement was observed when calculated energies of hemiaminals (N,O-acetals) and aminals (N,N-acetals) were compared with experimental equilibrium constants, which are reported here for the first time. Although it is known that the B3LYP method does not provide a good description of the London dispersion forces, while M06-2X and MP2 may overestimate them, it is shown here how large the gaps are and that at least single-point calculations at the CCSD(T)/6-31+G(d) level should be used for these reaction intermediates; CCSD(T)/6-31+G(d) and CCSD(T)/6-311+G(d,p) calculations afford ΔG° values in some cases quite close to MP2/6-311+G(d,p) while in others closer to M06-2X/6-311+G(d,p). The effect of solvents is similarly predicted by the SMD, CPCM, and IEFPCM approaches (with energy differences below 1 kcal/mol).

Thermobarometry of mafic igneous rocks based on clinopyroxene-liquid equilibria, 0 30 kbar

NASA Astrophysics Data System (ADS)

Putirka, K.; Johnson, Marie; Kinzler, Rosamond; Longhi, John; Walker, David

1996-02-01

Models for estimating the pressure and temperature of igneous rocks from co-existing clino-pyroxene and liquid compositions are calibrated from existing data and from new data obtained from experiments performed on several mafic bulk compositions (from 8 30 kbar and 1100 1475° C). The resulting geothermobarometers involve thermodynamic expressions that relate temperature and pressure to equilibrium constants. Specifically, the jadeite (Jd; NaAlSi2O6) diopside/hedenbergite (DiHd; Ca(Mg, Fe) Si2O6) exchange equilibrium between clinopyroxene and liquid is temperature sensitive. When compositional corrections are made to the calibrated equilibrium constant the resulting geothermometer is (i) 104 T=6.73-0.26* ln [Jdpx*Caliq*FmliqDiHdpx*Naliq*Alliq] -0.86* ln [MgliqMgliq+Feliq]+0.52*ln [Caliq] an expression which estimates temperature to ±27 K. Compared to (i), the equilibrium constant for jadeite formation is more sensitive to pressure resulting in a thermobarometer (ii) P=-54.3+299* T104+36.4* T104 ln [Jdpx[Siliq]2*Naliq*Alliq] +367*[Naliq*Alliq] which estimates pressure to ± 1.4 kbar. Pressure is in kbar, T is in Kelvin. Quantities such as Naliq represent the cation fraction of the given oxide (NaO0.5) in the liquid and Fm=MgO+FeO. The mole fractions of Jd and diopside+hedenbergite (DiHd) components are calculated from a normative scheme which assigns the lesser of Na or octahedral Al to form Jd; any excess AlVI forms Calcium Tschermak’s component (CaTs; CaAlAlSiO6); Ca remaining after forming CaTs and CaTiAl2O6 is taken as DiHd. Experimental data not included in the regressions were used to test models (i) and (ii). Error on predictions of T using model (i) is ±40 K. A pressure-dependent form of (i) reduces this error to ±30 K. Using model (ii) to predict pressures, the error on mean values of 10 isobaric data sets (0 25 kbar, 118 data) is ±0.3 kbar. Calculating thermodynamic properties from regression coefficients in (ii) gives VJd f of 23.4 ±1.3 cm3/mol, close to the value anticipated from bar molar volume data (23.5 cm3/mol). Applied to clinopyroxene phenocrysts from Mauna Kea, Hawaii lavas, the expressions estimate equilibration depths as great as 40 km. This result indicates that transport was sufficiently rapid that at least some phenocrysts had insufficient time to re-equilibrate at lower pressures.

On the ortho-para equilibrium of H2 in the atmospheres of the Jovian planets

NASA Technical Reports Server (NTRS)

Smith, W. H.

1978-01-01

The ratio for the equivalent widths for the unsaturated H2 quadrupole transitions observed in the Jovian planets is calculated and compared with a large number of observations. The comparison indicates that equilibrium hydrogen may be present in Jupiter and Saturn, while Uranus and Neptune exhibit ratios not in accord with equilibrium hydrogen. Observations which can differentiate among the possible states of H2 are proposed.

Statistical equilibrium in cometary C2. II - Swan/Phillips band ratios

NASA Technical Reports Server (NTRS)

Swamy, K. S. K.; Odell, C. R.

1979-01-01

Statistical equilibrium calculations have been made for both the triplet and ground state singlets for C2 in comets, using the exchange rate as a free parameter. The predictions of the results are consistent with optical observations and may be tested definitively by accurate observations of the Phillips and Swan band ratios. Comparison with the one reported observation indicates compatibility with a low exchange rate and resonance fluorescence statistical equilibrium.

A combined spectroscopic, molecular docking and molecular dynamic simulation study on the interaction of quercetin with β-casein nanoparticles.

PubMed

Mehranfar, Fahimeh; Bordbar, Abdol-Khalegh; Parastar, Hadi

2013-10-05

The interaction of quercetin with β-casein nanoparticle micelle was studied at various temperatures in order to do a complete thermodynamic and molecular analysis on the binding process. The results of fluorescence studies showed the possibility of fluorescence energy transfer between excited tryptophan and quercetin. The determined values of critical transfers distance and the mean distance of ligand from Trp-143 residues in β-casein micelle represents a non-radiative energy transfer mechanism for quenching and the existence of a significant interaction between this flavonoid and β-casein nanoparticle. The equilibrium binding of quercetin with β-casein micelle at different temperatures was studied by using UV-Vis absorption spectroscopy. The chemometric analysis (principal component analysis (PCA) and multivariate curve resolution-alternating least squares (MCR-ALS) methods) on spectrophotometric data revealed the existence of two components in solution (quercetin and β-casein-quercetin complex) and resolved their pure concentration and spectral profiles. This information let us to calculate the equilibrium binding constant at various temperatures and the relevant thermodynamic parameters of interaction (enthalpy, entropy and Gibbs free energy) with low uncertainty. The negative values of entropy and enthalpy changes represent the predominate role of hydrogen binding and van der Waals interactions in the binding process. Docking calculations showed the probable binding site of quercetin is located in the hydrophobic core of β-casein where the quercetin molecule is lined by hydrophobic residues and make five hydrogen bonds and several van der Waals contacts with them. Moreover, molecular dynamic (MD) simulation results suggested that this flavonoid can interact with β-casein, without affecting the secondary structure of β-casein. Simulations, molecular docking and experimental data reciprocally supported each other. Copyright © 2013 Elsevier B.V. All rights reserved.

Unfolding of Ubiquitin Studied by Picosecond Time-Resolved Fluorescence of the Tyrosine Residue

PubMed Central

Noronha, Melinda; Lima, João C.; Bastos, Margarida; Santos, Helena; Maçanita, António L.

2004-01-01

The photophysics of the single tyrosine in bovine ubiquitin (UBQ) was studied by picosecond time-resolved fluorescence spectroscopy, as a function of pH and along thermal and chemical unfolding, with the following results: First, at room temperature (25°C) and below pH 1.5, native UBQ shows single-exponential decays. From pH 2 to 7, triple-exponential decays were observed and the three decay times were attributed to the presence of tyrosine, a tyrosine-carboxylate hydrogen-bonded complex, and excited-state tyrosinate. Second, at pH 1.5, the water-exposed tyrosine of either thermally or chemically unfolded UBQ decays as a sum of two exponentials. The double-exponential decays were interpreted and analyzed in terms of excited-state intramolecular electron transfer from the phenol to the amide moiety, occurring in one of the three rotamers of tyrosine in UBQ. The values of the rate constants indicate the presence of different unfolded states and an increase in the mobility of the tyrosine residue during unfolding. Finally, from the pre-exponential coefficients of the fluorescence decays, the unfolding equilibrium constants (KU) were calculated, as a function of temperature or denaturant concentration. Despite the presence of different unfolded states, both thermal and chemical unfolding data of UBQ could be fitted to a two-state model. The thermodynamic parameters Tm = 54.6°C, ΔHTm = 56.5 kcal/mol, and ΔCp = 890 cal/mol//K, were determined from the unfolding equilibrium constants calculated accordingly, and compared to values obtained by differential scanning calorimetry also under the assumption of a two-state transition, Tm = 57.0°C, ΔHm= 51.4 kcal/mol, and ΔCp = 730 cal/mol//K. PMID:15454455

13C 12C exchange between calcite and graphite: A possible thermometer in Grenville marbles

USGS Publications Warehouse

Valley, J.W.; O'Neil, J.R.

1981-01-01

The fractionation of 13C between calcite and graphite, ??(Cc-Gr). is consistently small (2.6-4.8 permil) in 34 assemblages from upper amphibolite- and granulite-facies marbles of the Grenville Province. In 25 samples from the Adirondack Mountains, New York, it decreases regularly with increasing metamorphic temperature. The fractionations are independent of absolute ??13C values of calcite (-2.9 to +5.0). For T = 600-800??C, the Adirondack data are described by ??(Cc-Gr) = -0.00748T (??C) + 8.68. This good correlation between ?? and T suggests that carbon isotope equilibrium was attained in these high-grade marbles and that the theoretical calculations of this fractionation by Bottinga are approximately 2 permil too large in this temperature range. Because of the relatively high temperature sensitivity suggested by these results and by Bottinga's calculations, and the pressure independence of isotope fractionation, ??(Cc-Gr) may provide a very good thermometer for high-grade marbles. Comparison of this field calibration for ??(Cc-Gr) vs temperature with results from other terranes supports the utility of ??(Cc-Gr) for geothermometry and suggests that graphite is much more sluggish to exchange than calcite, that exchange between calcite and graphite occurs at temperatures as low as 300??C, and that equilibrium may normally be attained only when peak metamorphic temperatures are greater than 500-600??C. Because 13C exchange is an unavoidable metamorphic process at temperatures above 300??C, high values of ??13C(Gr) in moderate- to high-grade carbonate-bearing rocks do not provide a sufficient criterion to infer an abiogenic origin for the graphite. ?? 1981.

Atomic charge transfer-counter polarization effects determine infrared CH intensities of hydrocarbons: a quantum theory of atoms in molecules model.

PubMed

Silva, Arnaldo F; Richter, Wagner E; Meneses, Helen G C; Bruns, Roy E

2014-11-14

Atomic charge transfer-counter polarization effects determine most of the infrared fundamental CH intensities of simple hydrocarbons, methane, ethylene, ethane, propyne, cyclopropane and allene. The quantum theory of atoms in molecules/charge-charge flux-dipole flux model predicted the values of 30 CH intensities ranging from 0 to 123 km mol(-1) with a root mean square (rms) error of only 4.2 km mol(-1) without including a specific equilibrium atomic charge term. Sums of the contributions from terms involving charge flux and/or dipole flux averaged 20.3 km mol(-1), about ten times larger than the average charge contribution of 2.0 km mol(-1). The only notable exceptions are the CH stretching and bending intensities of acetylene and two of the propyne vibrations for hydrogens bound to sp hybridized carbon atoms. Calculations were carried out at four quantum levels, MP2/6-311++G(3d,3p), MP2/cc-pVTZ, QCISD/6-311++G(3d,3p) and QCISD/cc-pVTZ. The results calculated at the QCISD level are the most accurate among the four with root mean square errors of 4.7 and 5.0 km mol(-1) for the 6-311++G(3d,3p) and cc-pVTZ basis sets. These values are close to the estimated aggregate experimental error of the hydrocarbon intensities, 4.0 km mol(-1). The atomic charge transfer-counter polarization effect is much larger than the charge effect for the results of all four quantum levels. Charge transfer-counter polarization effects are expected to also be important in vibrations of more polar molecules for which equilibrium charge contributions can be large.

Diverse origins of Arctic and Subarctic methane point source emissions identified with multiply-substituted isotopologues

NASA Astrophysics Data System (ADS)

Douglas, P. M. J.; Stolper, D. A.; Smith, D. A.; Walter Anthony, K. M.; Paull, C. K.; Dallimore, S.; Wik, M.; Crill, P. M.; Winterdahl, M.; Eiler, J. M.; Sessions, A. L.

2016-09-01

Methane is a potent greenhouse gas, and there are concerns that its natural emissions from the Arctic could act as a substantial positive feedback to anthropogenic global warming. Determining the sources of methane emissions and the biogeochemical processes controlling them is important for understanding present and future Arctic contributions to atmospheric methane budgets. Here we apply measurements of multiply-substituted isotopologues, or clumped isotopes, of methane as a new tool to identify the origins of ebullitive fluxes in Alaska, Sweden and the Arctic Ocean. When methane forms in isotopic equilibrium, clumped isotope measurements indicate the formation temperature. In some microbial methane, however, non-equilibrium isotope effects, probably related to the kinetics of methanogenesis, lead to low clumped isotope values. We identify four categories of emissions in the studied samples: thermogenic methane, deep subsurface or marine microbial methane formed in isotopic equilibrium, freshwater microbial methane with non-equilibrium clumped isotope values, and mixtures of deep and shallow methane (i.e., combinations of the first three end members). Mixing between deep and shallow methane sources produces a non-linear variation in clumped isotope values with mixing proportion that provides new constraints for the formation environment of the mixing end-members. Analyses of microbial methane emitted from lakes, as well as a methanol-consuming methanogen pure culture, support the hypothesis that non-equilibrium clumped isotope values are controlled, in part, by kinetic isotope effects induced during enzymatic reactions involved in methanogenesis. Our results indicate that these kinetic isotope effects vary widely in microbial methane produced in Arctic lake sediments, with non-equilibrium Δ18 values spanning a range of more than 5‰.

Hawking radiation and nonequilibrium quantum critical current noise.

PubMed

Sonner, Julian; Green, A G

2012-08-31

The dynamical scaling of quantum critical systems in thermal equilibrium may be inherited in the driven steady state, leading to universal out-of-equilibrium behavior. This attractive notion has been demonstrated in just a few cases. We demonstrate how holography-a mapping between the quantum critical system and a gravity dual-provides an illuminating perspective and new results. Nontrivial out-of-equilibrium universality is particularly apparent in current noise, which is dual to Hawking radiation in the gravitational system. We calculate this in a two-dimensional system driven by a strong in-plane electric field and deduce a universal scaling function interpolating between previously established equilibrium and far-from-equilibrium current noise. Since this applies at all fields, out-of-equilibrium experiments no longer require very high fields for comparison with theory.

Free energy landscape from path-sampling: application to the structural transition in LJ38

NASA Astrophysics Data System (ADS)

Adjanor, G.; Athènes, M.; Calvo, F.

2006-09-01

We introduce a path-sampling scheme that allows equilibrium state-ensemble averages to be computed by means of a biased distribution of non-equilibrium paths. This non-equilibrium method is applied to the case of the 38-atom Lennard-Jones atomic cluster, which has a double-funnel energy landscape. We calculate the free energy profile along the Q4 bond orientational order parameter. At high or moderate temperature the results obtained using the non-equilibrium approach are consistent with those obtained using conventional equilibrium methods, including parallel tempering and Wang-Landau Monte Carlo simulations. At lower temperatures, the non-equilibrium approach becomes more efficient in exploring the relevant inherent structures. In particular, the free energy agrees with the predictions of the harmonic superposition approximation.

An experimental investigation of the internal methane pressure in hydrogen attack

NASA Technical Reports Server (NTRS)

Natan, M.; Johnson, H. H.

1983-01-01

An experimental investigation of the internal methane pressure that is the driving force for bubble growth in hydrogen attack (HA) was done on pure iron (204 ppm C) and on two low carbon steels of slightly different compositions. The methane content N (c.c gas/g. material) in attacked specimens was measured by a vacuum extraction technique. The total void volume V (c.c) was determined from density measurements before and after HA exposure. The two values, N and V, were then used in an equation of state to calculate an average methane pressure P for the attack stages beyond a density loss (d.l.) greater than 0.05 pct. It was determined that N and P depend on hydrogen exposure conditions and the presence of traces of strong carbide forming alloying elements (in steel). They are independent of specimen size and grain size over a limited range. P varies as the bubble volume increases, showing a generally decreasing trend which brings it to values lower than calculated equilibrium pressures, although well within the same order of magnitude. Possible reasons for this behavior are discussed.

Influence of alkane and perfluorocarbon vapors on adsorbed surface layers and spread insoluble monolayers of surfactants, proteins and lipids.

PubMed

Fainerman, V B; Aksenenko, E V; Miller, R

2017-06-01

The influence of hexane vapor in the air atmosphere on the surface tension of water and solutions of C 10 EO 8 , C n TAB and proteins are presented. For dry air, a fast and strong decrease of surface tension of water was observed. In humid air, the process is slower and the surface tension higher. There are differences between the results obtained by the maximum bubble pressure, pendant drop and emerging bubble methods, which are discussed in terms of depletion and initial surface load. The surface tension of aqueous solutions of β-сasein (BCS), β-lactoglobulin (BLG) and human serum albumin (HSA) at the interfaces with air and air-saturated hexane vapor were measured. The results indicate that the equilibrium surface tension in the hexane vapor atmosphere is considerably lower (at 13-20mN/m) as compared to the values at the interface with pure air. A reorientation model is proposed assuming several states of adsorbed molecules with different molar area values. The newly developed theoretical model is used to describe the effect of alkane vapor in the gas phase on the surface tension. This model assumes that the first layer is composed of surfactant (or protein) molecules mixed with alkane, and the second layer is formed by alkane molecules only. The processing of the experimental data for the equilibrium surface tension for the C 10 EO 8 and BCS solutions results in a perfect agreement between the observed and calculated values. The co-adsorption mechanism of dipalmitoyl phosphatidyl choline (DPPC) and the fluorocarbon molecules leads to remarkable differences in the surface pressure term of cohesion Π coh . This in turn leads to a very efficient fluidization of the monolayer. It was found that the adsorption equilibrium constant for dioctanoyl phosphatidyl choline is increased in the presence of perfluorohexane, and the intermolecular interaction of the components is strong. Copyright © 2015 Elsevier B.V. All rights reserved.

Non-equilibrium effects in steady relativistic e^+e^-gamma winds

NASA Astrophysics Data System (ADS)

Grimsrud, Ole M.; Wasserman, Ira

1998-11-01

We consider an ultrarelativistic wind consisting of electron-positron pairs and photons with the principal goal of finding the asymptotic Lorentz factor gamma_∞ for zero baryon number. The wind is assumed to originate at radius r_i where it has a Lorentz factor gamma_i and a temperature T_i sufficiently high to maintain pair equilibrium. As r increases, T decreases and becomes less than the temperature corresponding to the electron mass m_e, after which non-equilibrium effects become important. The pairs, which carry only a small fraction of the total energy, may be accelerated by the photons until tau falls below ~2x10^-5gamma^3/4_i. Radiative transfer calculations show that only at this point do the radiation flux and pressure start to deviate significantly from their blackbody values. The acceleration of the pairs increases gamma by a factor ~45 compared with its value at the photosphere; it is shown to approach gamma_∞~1.4x10^3(r^6_i/10cm)^1/4gamma^{3/4}_iT_i/m_e. The limit of zero baryon number is a good approximation when the mass injection rate Msolar in the flow is below a critical value corresponding to (Esolar/MsolarM)_c,0~5x10^7(r^6_i/10cm)T_i/m_e for fixed energy injection rate E/E. For large baryon loading, (Esolar/Msolar<~Esolar/Msolar)_c,M~350(r_i/10^6cm)^1/4gamma^3/4_iT_i/ m_e, the asymptotic Lorentz factor is gamma_∞~Esolar/Msolar. Surprisingly, increasing Esolar/Msolar from (Esolar/Msolar)_c,M to ∞ only increases gamma_∞ by a factor ~(m_p/m_e)^1/4~6.5, less than an order of magnitude. As Esolar/Msolar increases, the fraction of the energy carried by pairs decreases, reaching ~10^-5gamma^3/4_i as Esolar/Msolar to ∞.

Bounded energy states in homogeneous turbulent shear flow: An alternative view

NASA Technical Reports Server (NTRS)

Bernard, Peter S.; Speziale, Charles G.

1990-01-01

The equilibrium structure of homogeneous turbulent shear flow is investigated from a theoretical standpoint. Existing turbulence models, in apparent agreement with physical and numerical experiments, predict an unbounded exponential time growth of the turbulent kinetic energy and dissipation rate; only the anisotropy tensor and turbulent time scale reach a structural equilibrium. It is shown that if vortex stretching is accounted for in the dissipation rate transport equation, then there can exist equilibrium solutions, with bounded energy states, where the turbulence production is balanced by its dissipation. Illustrative calculations are present for a k-epsilon model modified to account for vortex stretching. The calculations indicate an initial exponential time growth of the turbulent kinetic energy and dissipation rate for elapsed times that are as large as those considered in any of the previously conducted physical or numerical experiments on homogeneous shear flow. However, vortex stretching eventually takes over and forces a production-equals-dissipation equilibrium with bounded energy states. The validity of this result is further supported by an independent theoretical argument. It is concluded that the generally accepted structural equilibrium for homogeneous shear flow with unbounded component energies is in need of re-examination.

Optimized norm-conserving Hartree-Fock pseudopotentials for plane-wave calculations

NASA Astrophysics Data System (ADS)

Al-Saidi, W. A.; Walter, E. J.; Rappe, A. M.

2008-02-01

We report Hartree-Fock (HF)-based pseudopotentials suitable for plane-wave calculations. Unlike typical effective core potentials, the present pseudopotentials are finite at the origin and exhibit rapid convergence in a plane-wave basis; the optimized pseudopotential method [A. M. Rappe , Phys. Rev. B 41, 1227 (1990)] improves plane-wave convergence. Norm-conserving HF pseudopotentials are found to develop long-range non-Coulombic behavior which does not decay faster than 1/r , and is nonlocal. This behavior, which stems from the nonlocality of the exchange potential, is remedied using a recently developed self-consistent procedure [J. R. Trail and R. J. Needs, J. Chem. Phys. 122, 014112 (2005)]. The resulting pseudopotentials slightly violate the norm conservation of the core charge. We calculated several atomic properties using these pseudopotentials, and the results are in good agreement with all-electron HF values. The dissociation energies, equilibrium bond lengths, and frequencies of vibration of several dimers obtained with these HF pseudopotentials and plane waves are also in good agreement with all-electron results.

Calculated emission rates for barium releases in space

NASA Technical Reports Server (NTRS)

Stenbaek-Nielsen, H. C.

1989-01-01

The optical emissions from barium releases in space are caused by resonance and fluorescent scattering of sunlight. Emission rates for the dominant ion and neutral lines are calculated assuming the release to be optically thin and the barium to be in radiative equilibrium with the solar radiation. The solar spectrum has deep Fraunhofer absorption lines at the primary barium ion resonances. A velocity component toward or away from the sun will Doppler shift the emission lines relative to the absorption lines and the emission rates will increase many-fold over the rest value. The Doppler brightening is important in shaped charge or satellite releases where the barium is injected at high velocities. Emission rates as a function of velocity are calculated for the 4554, 4934, 5854, 6142 and 6497 A ion emission lines and the dominant neutral line at 5535 A. Results are presented for injection parallel to the ambient magnetic field, B, and for injection at an angle to B.

The guanidine and maleic acid (1:1) complex. The additional theoretical and experimental studies.

PubMed

Drozd, Marek; Dudzic, Damian

2012-04-01

On the basis of experimental literature data the theoretical studies for guanidinium and maleic acid complex with using DFT method are performed. In these studies the experimental X-ray data for two different forms of investigated crystal were used. During the geometry optimization process one equilibrium structure was found, only. According to this result the infrared spectrum for one theoretical molecule was calculated. On the basis of potential energy distribution (PED) analysis the clear-cut assignments of observed bands were performed. For the calculated molecule with energy minimum the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) were obtained and graphically illustrated. The energy difference (GAP) between HOMO and LUMO was analyzed. Additionally, the nonlinear properties of this molecule were calculated. The α and β (first and second order) hyperpolarizability values are obtained. On the basis of these results the title crystal was classified as new second order NLO generator. Copyright © 2011 Elsevier B.V. All rights reserved.

Molecular structure and ring tunneling of phenyl formate as observed by microwave spectroscopy and quantum chemistry

NASA Astrophysics Data System (ADS)

Ferres, Lynn; Mouhib, Halima; Stahl, Wolfgang; Schwell, Martin; Nguyen, Ha Vinh Lam

2017-07-01

Phenyl formate has been investigated by molecular jet Fourier-transform microwave spectroscopy in the frequency range from 2 to 26.5 GHz. Quantum chemical calculations at the MP2/6-311++G(d,p) level of theory indicate that this molecule does not have a plane of symmetry at equilibrium, and that the phenyl ring performs a large amplitude tunneling motion from one side of the Cs configuration to the other. The tilt angle of the ring out of the Hsbnd (Cdbnd O)O plane is ±70° and the calculated tunneling barrier is only 28 cm-1. The two lowest torsional states vt = 0 and 1 are assigned in the experimental spectrum and fitted using the program SPFIT/SPCAT. The Coriolis splitting ΔE between these states is 46.2231(25) GHz, very close to the value of 48.24 GHz calculated using a simple two-top torsional Hamiltonian of the formate group and the phenyl ring.

Multiscale calculations of thermoelectric properties of n-type Mg2Si1-xSnx solid solutions

NASA Astrophysics Data System (ADS)

Tan, X. J.; Liu, W.; Liu, H. J.; Shi, J.; Tang, X. F.; Uher, C.

2012-05-01

The band structure of Mg2Si1-xSnx solid solutions with 0.250 ⩽ x ⩽ 0.875 is calculated using the first-principles pseudopotential method. It is found that the low-lying light and heavy conduction bands converge and the effective mass reaches a maximum value near x = 0.625. Using the semiclassical Boltzmann transport theory and relaxation-time approximation, we find that the system with x = 0.625 exhibits both higher Seebeck coefficient and higher electrical conductivity than other solid solutions at intermediate temperatures. By fitting first-principles total energy calculations, a modified Morse potential is constructed, which is used to predicate the lattice thermal conductivity via equilibrium molecular dynamics simulations. Due to relatively higher power factor and lower thermal conductivity, the Mg2Si0.375Sn0.625 is found to exhibit enhanced thermoelectric performance at 800 K, and additional Sb doping is considered in order to make a better comparison with experiment results.

Spectral signatures of polar stratospheric clouds and sulfate aerosol

NASA Technical Reports Server (NTRS)

Massie, S. T.; Bailey, P. L.; Gille, J. C.; Lee, E. C.; Mergenthaler, J. L.; Roche, A. E.; Kumer, J. B.; Fishbein, E. F.; Waters, J. W.; Lahoz, W. A.

1994-01-01

Multiwavelength observations of Antarctic and midlatitude aerosol by the Cryogenic Limb Array Etalon Spectrometer (CLAES) experiment on the Upper Atmosphere Research Satellite (UARS) are used to demonstrate a technique that identifies the location of polar stratospheric clouds. The technique discussed uses the normalized area of the triangle formed by the aerosol extinctions at 925, 1257, and 1605/cm (10.8, 8.0, and 6.2 micrometers) to derive a spectral aerosol measure M of the aerosol spectrum. Mie calculations for spherical particles and T-matrix calculations for spheriodal particles are used to generate theoretical spectral extinction curves for sulfate and polar stratospheric cloud particles. The values of the spectral aerosol measure M for the sulfate and polar stratospheric cloud particles are shown to be different. Aerosol extinction data, corresponding to temperatures between 180 and 220 K at a pressure of 46 hPa (near 21-km altitude) for 18 August 1992, are used to demonstrate the technique. Thermodynamic calculations, based upon frost-point calculations and laboratory phase-equilibrium studies of nitric acid trihydrate, are used to predict the location of nitric acid trihydrate cloud particles.

Infinitely Dilute Partial Molar Properties of Proteins from Computer Simulation

PubMed Central

2015-01-01

A detailed understanding of temperature and pressure effects on an infinitely dilute protein’s conformational equilibrium requires knowledge of the corresponding infinitely dilute partial molar properties. Established molecular dynamics methodologies generally have not provided a way to calculate these properties without either a loss of thermodynamic rigor, the introduction of nonunique parameters, or a loss of information about which solute conformations specifically contributed to the output values. Here we implement a simple method that is thermodynamically rigorous and possesses none of the above disadvantages, and we report on the method’s feasibility and computational demands. We calculate infinitely dilute partial molar properties for two proteins and attempt to distinguish the thermodynamic differences between a native and a denatured conformation of a designed miniprotein. We conclude that simple ensemble average properties can be calculated with very reasonable amounts of computational power. In contrast, properties corresponding to fluctuating quantities are computationally demanding to calculate precisely, although they can be obtained more easily by following the temperature and/or pressure dependence of the corresponding ensemble averages. PMID:25325571

Assessment of the radionuclide angiographic left ventricular maximum time-varying elastance calculation in man.

PubMed

Starling, M R; Gross, M D; Walsh, R A; Dell'Italia, L J; Montgomery, D G; Squicciarini, S A; Blumhardt, R

1988-08-01

This investigation was designed to determine whether left ventricular (LV) maximum time-varying elastance (Emax) calculations obtained using equilibrium radionuclide angiography (RNA) were comparable to those obtained using biplane contrast cineangiography (CINE), and whether simple, indirect P-V relations might provide reasonable, alternative estimates of Emax. Accordingly, we studied 19 patients with simultaneous high-fidelity micromanometer LV and fluid brachial artery (Ba) pressure recordings, CINE, and RNA under control conditions and during methoxamine and nitroprusside infusions. Emax was defined for CINE and RNA as the maximum slope of the linear relation of isochronal, instantaneous P-V data points obtained from each of the three loading conditions. The indirect P-V relations were similarly obtained from Ba peak (P) pressure versus minimum RNA LV volume (BaP/minV) and Ba dicrotic notch (di) pressure versus minimum RNA LV volume (Badi/minV) data points. The mean heart rates and LV (+)dP/dtmax values were minimally altered during the three loading conditions. The isochronal Emax values ranged from 1.40 to 6.73 mmHg/ml (mean 4.13 +/- 1.99 s.d. mmHg/ml) for CINE and from 1.48 to 7.25 (mean 4.35 +/- 1.81 mmHg/ml) for RNA (p = N.S.). Similarly, the unstressed volumes ranged from -10 to 80 ml (mean 30 +/- 23 ml) for CINE and from -8 to 77 ml (29 +/- 21 ml) for RNA (p = N.S.). The individual, isochronal Emax values by RNA correlated with those by CINE (r = 0.86). In 14 of the 19 patients, the BaP/minV and Badi/minV relations correlated with the isochronal Emax values calculated by RNA (r = 0.83 and 0.82, respectively), and these relations also correlated with the Emax values calculated by CINE (r = 0.82 and 0.78, respectively). The slope and V0 values for the BaP/minV and Badi/minV relations underestimated those for Emax by RNA and CINE (p less than 0.01 and p less than 0.05, respectively, for both). Thus, the isochronal Emax values calculated using RNA are comparable to those obtained using CINE in man. Moreover, indirect P-V relations underestimate these Emax values, but they are linearly related with the isochronal Emax values calculated by RNA and CINE. Consequently, these indirect P-V relations may provide a more simple, alternative estimate of LV contractile function in man.

The Navy/NASA Engine Program (NNEP89): Interfacing the program for the calculation of complex Chemical Equilibrium Compositions (CEC)

NASA Technical Reports Server (NTRS)

Gordon, Sanford

1991-01-01

The NNEP is a general computer program for calculating aircraft engine performance. NNEP has been used extensively to calculate the design and off-design (matched) performance of a broad range of turbine engines, ranging from subsonic turboprops to variable cycle engines for supersonic transports. Recently, however, there has been increased interest in applications for which NNEP is not capable of simulating, such as the use of alternate fuels including cryogenic fuels and the inclusion of chemical dissociation effects at high temperatures. To overcome these limitations, NNEP was extended by including a general chemical equilibrium method. This permits consideration of any propellant system and the calculation of performance with dissociation effects. The new extended program is referred to as NNEP89.

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

NASA Technical Reports Server (NTRS)

1976-01-01

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

Implications of the dependence of the elastic properties of DNA on nucleotide sequence.

PubMed

Olson, Wilma K; Swigon, David; Coleman, Bernard D

2004-07-15

Recent advances in structural biochemistry have provided evidence that not only the geometric properties but also the elastic moduli of duplex DNA are strongly dependent on nucleotide sequence in a way that is not accounted for by classical rod models of the Kirchhoff type. A theory of sequence-dependent DNA elasticity is employed here to calculate the dependence of the equilibrium configurations of circular DNA on the binding of ligands that can induce changes in intrinsic twist at a single base-pair step. Calculations are presented of the influence on configurations of the assumed values and distribution along the DNA of intrinsic roll and twist and a modulus coupling roll to twist. Among the results obtained are the following. For minicircles formed from intrinsically straight DNA, the distribution of roll-twist coupling strongly affects the dependence of the total elastic energy Psi on the amount alpha of imposed untwisting, and that dependence can be far from quadratic. (In fact, for a periodic distribution of roll-twist coupling with a period equal to the intrinsic helical repeat length, Psi can be essentially independent of alpha for -90 degrees < alpha <90 degrees.) When the minicircle is homogeneous and without roll-twist coupling, but with uniform positive intrinsic roll, the point at which Psi attains its minimum value shifts towards negative values of alpha. It is remarked that there are cases in which one can relate graphs of Psi versus alpha to the 'effective values' of bending and twisting moduli and helical repeat length obtained from measurements of equilibrium distributions of topoisomers and probabilities of ring closure. For a minicircle formed from DNA that has an 'S' shape when stress-free, the graphs of Psi versus alpha have maxima at alpha = 0. As the binding of a twisting agent to such a minicircle results in a net decrease in Psi, the affinity of the twisting agent for binding to the minicircle is greater than its affinity for binding to unconstrained DNA with the same sequence.

Derivation of Hamaker Dispersion Energy of Amorphous Carbon Surfaces in Contact with Liquids Using Photoelectron Energy-Loss Spectra

NASA Astrophysics Data System (ADS)

Godet, Christian; David, Denis

2017-12-01

Hamaker interaction energies and cutoff distances have been calculated for disordered carbon films, in contact with purely dispersive (diiodomethane) or polar (water) liquids, using their experimental dielectric functions ɛ ( q, ω) obtained over a broad energy range. In contrast with previous works, a q-averaged < ɛ ( q, ω) > q is derived from photoelectron energy-loss spectroscopy (XPS-PEELS) where the energy loss function (ELF) < Im[-1/ ɛ ( q, ω)] > q is a weighted average over allowed transferred wave vector values, q, given by the physics of bulk plasmon excitation. For microcrystalline diamond and amorphous carbon films with a wide range of (sp3/sp2 + sp3) hybridization, non-retarded Hamaker energies, A 132 ( L < 1 nm), were calculated in several configurations, and distance and wavenumber cutoff values were then calculated based on A 132 and the dispersive work of adhesion obtained from contact angles. A geometric average approximation, H 0 CVL = ( H 0 CVC H 0 LVL )1/2, holds for the cutoff separation distances obtained for carbon-vacuum-liquid (CVL), carbon-vacuum-carbon (CVC) and liquid-vacuum-liquid (LVL) equilibrium configurations. The linear dependence found for A CVL, A CLC and A CLV values as a function of A CVC, for each liquid, allows predictive relationships for Hamaker energies (in any configuration) using experimental determination of the dispersive component of the surface tension, {γ}_{CV}^d , and a guess value of the cutoff distance H 0 CVC of the solid. [Figure not available: see fulltext.

Density Functional Theory Investigation of Proton Diffusion in Tungsten Oxide And Its Hydrates

NASA Astrophysics Data System (ADS)

Lin, Hao

Fast proton conduction mechanism is of key importance for achieving high performance in fuel cell membranes, batteries, supercapacitors, and electrochromic materials. Enhanced proton diffusion is often observed in hydrated materials where it is thought to occur via the famous Grotthuss mechanism through pathways formed by structural water. Using first-principles calculations, we demonstrate that proton diffusion in tungsten oxide dihydrate (WO3·2H 2O), a known good proton conductor, takes place within the layers of corner-sharing WO6 octahedra without direct involvement of structural water. The calculated proton migration barrier in WO3·2H 2O is in good agreement with the experimental value inferred from the temperature dependence of conductivity. The preferred proton diffusion path in WO3·2H2O is essentially the same as in gamma-WO 3. In contrast to the small intercalation voltages calculated for WO 3 and WO3·2H2O, we find that proton absorption in the monohydrate WO3·H2O is energetically highly favorable. However, strong proton-proton repulsion limits the equilibrium H content at zero voltage. We find a fast one-dimensional diffusion channel in WO3·H2O at dilute proton concentrations, but much higher barriers are expected at near-equilibrium concentrations due to strong repulsive interactions with other protons. Our results illustrate that low proton diffusion barriers and low insertion voltages both contribute to fast proton transport in bulk WO3·2H2O and gamma-WO 3.

First-principles investigations of equilibrium Ca, Mg, Si and O isotope fractionations between silicate melts and minerals

NASA Astrophysics Data System (ADS)

Qi, Y.; Liu, X.; Kang, J.; He, L.

2017-12-01

Equilibrium isotope fractionation factors are essential for using stable isotope data to study many geosciences processes such as planetary differentiation and mantle evolution. The mass-dependent equilibrium isotope fractionation is primarily controlled by the difference in bond energies triggered by the isotope substitution. With the recent advances in computational capabilities, first-principles calculation has become a reliable tool to investigate equilibrium isotopic fractionations, greatly improving our understanding of the factors controlling isotope fractionations. It is important to understand the isotope fractionation between melts and minerals because magmatism is critical for creating and shaping the Earth. However, because isotope fractionation between melts and minerals is small at high temperature, it is difficult to experimentally calibrate such small signature. Due to the disordered and dynamic character of melts, calculations of equilibrium isotope fractionation of melts are more challenging than that for gaseous molecules or minerals. Here, we apply first-principles molecular dynamics method to calculate equilibrium Ca, Mg, Si, and O isotope fractionations between silicate melts and minerals. Our results show that equilibrium Mg, Si, and O isotope fractionations between olivine and pure Mg2SiO4 melt are close to zero at high temperature (e.g. δ26Mgmelt-ol = 0.03 ± 0.04‰, δ30Simelt-ol = -0.06 ± 0.07‰, δ18Omelt-ol = 0.07‰ ± 0.08 at 1500 K). Equilibrium Ca, Mg, Si, and O isotope fractionations between diopside and basalt melt (67% CaMgSi2O6 + 33% CaAl2Si2O8) are also negligible at high temperature (e.g. δ44/40Camelt-cpx = -0.01 ± 0.02‰, δ26Mgmelt-cpx = -0.05 ± 0.14‰, δ30Simelt-cpx = 0.04 ± 0.04‰, δ18Omelt-cpx = 0.03 ± 0.07‰ at 1500 K). These results are consistent with the observations in natural samples that there is no significant Ca, Mg, Si, and O isotope fractionation during mantle partial melting, demonstrating the reliability of our methods. Thus, our results can be used to understand stable isotope fractionation during partial melting of mantle peridotite or fractional crystallization during magmatic differentiation. The first-principles molecular dynamics method is a promising tool to obtain equilibrium fractionation of more isotope systems for complicate liquids.

Microwave spectra and molecular structures of (Z)-pent-2-en-4-ynenitrile and maleonitrile.

PubMed

Halter, R J; Fimmen, R L; McMahon, R J; Peebles, S A; Kuczkowski, R L; Stanton, J F

2001-12-12

Accurate equilibrium structures have been determined for (Z)-pent-2-en-4-ynenitrile (8) and maleonitrile (9) by combining microwave spectroscopy data and ab initio quantum chemistry calculations. The microwave spectra of 10 isotopomers of 8 and 5 isotopomers of 9 were obtained using a pulsed nozzle Fourier transform microwave spectrometer. The ground-state rotational constants were adjusted for vibration-rotation interaction effects calculated from force fields obtained from ab initio calculations. The resultant equilibrium rotational constants were used to determine structures that are in very good agreement with those obtained from high-level ab initio calculations (CCSD(T)/cc-pVTZ). The geometric parameters in 8 and 9 are very similar; they also do not differ significantly from the all-carbon analogue, (Z)-hex-3-ene-1,5-diyne (7), the parent molecule for the Bergman cyclization. A small deviation from linearity about the alkyne and cyano linkages is observed for 7-9 and several related species where accurate equilibrium parameters are available. The data on 7-9 should be of interest to radioastronomy and may provide insights on the formation and interstellar chemistry of unsaturated species such as the cyanopolyynes.

Assessment of two-temperature kinetic model for dissociating and weakly-ionizing nitrogen

NASA Technical Reports Server (NTRS)

Park, C.

1986-01-01

The validity of the author's two-temperature, chemical/kinetic model which the author has recently improved is assessed by comparing the calculated results with the existing experimental data for nitrogen in the dissociating and weakly ionizing regime produced behind a normal shock wave. The computer program Shock Tube Radiation Program (STRAP) based on the two-temperature model is used in calculating the flow properties behind the shock wave and the Nonequilibrium Air Radiation (NEQAIR) program, in determining the radiative characteristics of the flow. Both programs were developed earlier. Comparison is made between the calculated and the existing shock tube data on (1) spectra in the equilibrium region, (2) rotational temperature of the N2(+) B state, (3) vibrational temperature of the N2(+) B state, (4) electronic excitation temperature of the N2 B state, (5) the shape of time-variation of radiation intensities, (6) the times to reach the peak in radiation intensity and equilibrium, and (7) the ratio of nonequilibrium to equilibrium radiative heat fluxes. Good agreement is seen between the experimental data and the present calculation except for the vibrational temperature. A possible reason for the discrepancy is given.

A thermochemical model of radiation damage and annealing applied to GaAs solar cells

NASA Technical Reports Server (NTRS)

Conway, E. J.; Walker, G. H.; Heinbockel, J. H.

1981-01-01

Calculations of the equilibrium conditions for continuous radiation damage and thermal annealing are reported. The calculations are based on a thermochemical model developed to analyze the incorporation of point imperfections in GaAs, and modified by introducing the radiation to produce native lattice defects rather than high-temperature and arsenic atmospheric pressure. The concentration of a set of defects, including vacancies, divacancies, and impurity vacancy complexes, are calculated as a function of temperature. Minority carrier lifetimes, short circuit current, and efficiency are deduced for a range of equilibrium temperatures. The results indicate that GaAs solar cells could have a mission life which is not greatly limited by radiation damage.

Fine-particle pH for Beijing winter haze as inferred from different thermodynamic equilibrium models

NASA Astrophysics Data System (ADS)

Song, Shaojie; Gao, Meng; Xu, Weiqi; Shao, Jingyuan; Shi, Guoliang; Wang, Shuxiao; Wang, Yuxuan; Sun, Yele; McElroy, Michael B.

2018-05-01

pH is an important property of aerosol particles but is difficult to measure directly. Several studies have estimated the pH values for fine particles in northern China winter haze using thermodynamic models (i.e., E-AIM and ISORROPIA) and ambient measurements. The reported pH values differ widely, ranging from close to 0 (highly acidic) to as high as 7 (neutral). In order to understand the reason for this discrepancy, we calculated pH values using these models with different assumptions with regard to model inputs and particle phase states. We find that the large discrepancy is due primarily to differences in the model assumptions adopted in previous studies. Calculations using only aerosol-phase composition as inputs (i.e., reverse mode) are sensitive to the measurement errors of ionic species, and inferred pH values exhibit a bimodal distribution, with peaks between -2 and 2 and between 7 and 10, depending on whether anions or cations are in excess. Calculations using total (gas plus aerosol phase) measurements as inputs (i.e., forward mode) are affected much less by these measurement errors. In future studies, the reverse mode should be avoided whereas the forward mode should be used. Forward-mode calculations in this and previous studies collectively indicate a moderately acidic condition (pH from about 4 to about 5) for fine particles in northern China winter haze, indicating further that ammonia plays an important role in determining this property. The assumed particle phase state, either stable (solid plus liquid) or metastable (only liquid), does not significantly impact pH predictions. The unrealistic pH values of about 7 in a few previous studies (using the standard ISORROPIA model and stable state assumption) resulted from coding errors in the model, which have been identified and fixed in this study.

High-accuracy calculations of the ground, 1 1A1', and the 2 1A1', 2 3A1', and 1 1E' excited states of H3+.

PubMed

Pavanello, Michele; Adamowicz, Ludwik

2009-01-21

Accurate variational Born-Oppenheimer calculations of the 1 (1)A(1) ('), 2 (1)A(1) ('), 2 (3)A(1) ('), and 1 (1)E(') states of the H(3) (+) ion at the ground-state equilibrium geometry are reported. The wave functions of the states are expanded in terms of explicitly correlated spherical Gaussian functions with shifted centers. In the variational optimization the analytical gradient of the energy with respect to the nonlinear exponential parameters of the Gaussians has been employed. The energies obtained in the calculations are the best variational estimates ever calculated for the four states. One-electron densities for the states, as well as a D(3h)-restricted potential energy surface of the ground state calculated around the equilibrium geometry, are also presented and discussed.

A comparison of three algebraic stress closures for combustor flow calculations

NASA Technical Reports Server (NTRS)

Nikjooy, M.; So, R. M. C.; Hwang, B. C.

1985-01-01

A comparison is made of the performance of two locally nonequilibrium and one equilibrium algebraic stress closures in calculating combustor flows. Effects of four different pressure-strain models on these closure models are also analyzed. The results show that the pressure-strain models have a much greater influence on the calculated mean velocity and turbulence field than the algebraic stress closures, and that the best mean strain model for the pressure-strain terms is that proposed by Launder, Reece and Rodi (1975). However, the equilibrium algebraic stress closure with the Rotta return-to-isotropy model (1951) for the pressure-strain terms gives as good a correlation with measurements as when the Launder et al. mean strain model is included in the pressure-strain model. Finally, comparison of the calculations with the standard k-epsilon closure results show that the algebraic stress closures are better suited for simple turbulent flow calculations.

Precise, contactless measurements of the surface tension of picolitre aerosol droplets† †Electronic supplementary information (ESI) available: Parametrizations used to infer concentration, density, viscosity, and surface tension from refractive index for sodium chloride and glutaric acid; description of the semi-analytical T-matrix calculations; Fig. S1 and S2. See DOI: 10.1039/c5sc03184b Click here for additional data file.

PubMed Central

Bzdek, Bryan R.; Power, Rory M.; Simpson, Stephen H.; Royall, C. Patrick

2016-01-01

The surface composition and surface tension of aqueous droplets can influence key aerosol characteristics and processes including the critical supersaturation required for activation to form cloud droplets in the atmosphere. Despite its fundamental importance, surface tension measurements on droplets represent a considerable challenge owing to their small volumes. In this work, we utilize holographic optical tweezers to study the damped surface oscillations of a suspended droplet (<10 μm radius) following the controlled coalescence of a pair of droplets and report the first contactless measurements of the surface tension and viscosity of droplets containing only 1–4 pL of material. An advantage of performing the measurement in aerosol is that supersaturated solute states (common in atmospheric aerosol) may be accessed. For pairs of droplets starting at their equilibrium surface composition, surface tensions and viscosities are consistent with bulk equilibrium values, indicating that droplet surfaces respond to changes in surface area on microsecond timescales and suggesting that equilibrium values can be assumed for growing atmospheric droplets. Furthermore, droplet surfaces are shown to be rapidly modified by trace species thereby altering their surface tension. This equilibration of droplet surface tension to the local environmental conditions is illustrated for unknown contaminants in laboratory air and also for droplets exposed to gas passing through a water–ethanol solution. This approach enables precise measurements of surface tension and viscosity over long time periods, properties that currently are poorly constrained. PMID:28758004

Topography at the inner core boundary

NASA Astrophysics Data System (ADS)

Lasbleis, M.; Forquenot, Q.; Deguen, R.

2017-12-01

Topography at the inner core boundary has been proposed to explain surprising seismic observations of some regional studies. Such observations are still debatted, and numerical values of possible inner core topography have been proposed ranging from no topography to "inner core mountains" (10km heigth over lengthscales of 20km, as in Dai et al. 2012). The inner core boundary is a peculiar boundary, as it is the place where the iron alloy constituting the core freezes. The existence of a significant topography on such a boundary is possible, but unlikely. At thermodynamic equilibrium, no topography is expected, as any material above the equilibrium radius would have melted and any below would have freezed. However, mechanical forcing may push the system out of equilibrium. Dynamical topography could be forced by convective flows in the inner core or by outer core heterogeneities. A topography induced by outer core convection would be short-lived when compared to geodynamical processes in the bulk of the inner core (τ ≈ 10-100 Myears), but long-lived compared to observations. Here, we would like to give a geodynamical perspective over inner core topography. We constrain plausible amplitude of inner core topography, and discuss the implications for seismic observations. We consider topography created by viscous flows in the bulk of the inner core and by variations of growth rate on regional lengthscale due to outer core convection. This approach allows us to consider both internal and external forcings on the topography. We treat topography forcings as stochastic processes, and calculate the probability of observing a given topography. Based on preliminary results, the high values for observed topography can not be interpreted as a normal behavior of core dynamics. If confirmed, the regions are likely to be anomalous and originated from outliers in the distribution of stochastic processes.

Linearized theory of inhomogeneous multiple 'water-bag' plasmas

NASA Technical Reports Server (NTRS)

Bloomberg, H. W.; Berk, H. L.

1973-01-01

Equations are derived for describing the inhomogeneous equilibrium and small deviations from the equilibrium, giving particular attention to systems with trapped particles. An investigation is conducted of periodic systems with a single trapped-particle water bag, taking into account the behavior of the perturbation equations at the turning points. An outline is provided concerning a procedure for obtaining the eigenvalues. The results of stability calculations connected with the sideband effects are considered along with questions regarding the general applicability of the multiple water-bag approach in stability calculations.

The procedure and results of calculations of the equilibrium isotopic composition of a demonstration subcritical molten salt reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nevinitsa, V. A., E-mail: Neviniza-VA@nrcki.ru; Dudnikov, A. A.; Blandinskiy, V. Yu.

2015-12-15

A subcritical molten salt reactor with an external neutron source is studied computationally as a facility for incineration and transmutation of minor actinides from spent nuclear fuel of reactors of VVER-1000 type and for producing {sup 233}U from {sup 232}Th. The reactor configuration is chosen, the requirements to be imposed on the external neutron source are formulated, and the equilibrium isotopic composition of heavy nuclides and the key parameters of the fuel cycle are calculated.

Thermodynamic equilibrium-air correlations for flowfield applications

NASA Technical Reports Server (NTRS)

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

1981-01-01

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

Applications of Programmable Calculators in Chemistry Classes

ERIC Educational Resources Information Center

Holdsworth, David

1977-01-01

Described is the use of calculators in two experiments. In the first, students determine the relative atomic mass of magnesium. In the second, students use a calculator to determine a constant for gaseous concentrations of two reactants and the product at equilibrium. (AJ)

Computational study of Ca, Sr and Ba under pressure

NASA Astrophysics Data System (ADS)

Jona, F.; Marcus, P. M.

2006-05-01

A first-principles procedure for the calculation of equilibrium properties of crystals under hydrostatic pressure is applied to Ca, Sr and Ba. The procedure is based on minimizing the Gibbs free energy G (at zero temperature) with respect to the structure at a given pressure p, and hence does not require the equation of state to fix the pressure. The calculated lattice constants of Ca, Sr and Ba are shown to be generally closer to measured values than previous calculations using other procedures. In particular for Ba, where careful and extensive pressure data are available, the calculated lattice parameters fit measurements to about 1% in three different phases, both cubic and hexagonal. Rigid-lattice transition pressures between phases which come directly from the crossing of G(p) curves are not close to measured transition pressures. One reason is the need to include zero-point energy (ZPE) of vibration in G. The ZPE of cubic phases is calculated with a generalized Debye approximation and applied to Ca and Sr, where it produces significant shifts in transition pressures. An extensive tabulation is given of structural parameters and elastic constants from the literature, including both theoretical and experimental results.

Calculations of critical misfit and thickness: An overview

NASA Technical Reports Server (NTRS)

Vandermerwe, Jan H.; Jesser, W. A.

1988-01-01

This overview stresses the equilibrium/nonequilibrium nature of the physical properties, as well as the basic properties of the models, used to calculate critical misfit and critical thickness in epitaxy.

The prediction of mineral solubilities in natural waters: A chemical equilibrium model for the Na-Ca-Cl-SO 4-H 2O system, to high temperature and concentration

NASA Astrophysics Data System (ADS)

Møller, Nancy

1988-04-01

This paper describes a chemical equilibrium model for the Na-Ca-Cl-SO 4-H 2O system which calculates solubilities from 25°C to 250°C and from zero to high concentration ( I ~ 18. m) within experimental uncertainty. The concentration and temperature dependence of the model were established by fitting available activity (solubility, osmotic and emf) data. A single ion complex, CaSO 04, which increases in strength with temperature, is included explicitly in the model. The validation of model accuracy by comparison to laboratory and field solubility data is included. Applications of the model are also given. Phase diagrams constructed for the Na-Ca-Cl-SO 4-H 2O system and predicted solubilities of anhydrite and hemihydrate in concentrated seawater at high temperature are in very good agreement with the data. Calculations of the temperature of gypsum-anhydrite coexistence as a function of water activity are compared to reported values, and are used to estimate the composition-temperature relation for gypsum-anhydrite transition in a natural brine evaporation. A preliminary model for barite solubility in sodium chloride solutions at high temperature (100°C to 250°C), based on this parameterization of the CaSO 4-NaCl-H 2O system, gives good agreement with the data.

Determining pH at elevated pressure and temperature using in situ ¹³C NMR.

PubMed

Surface, J Andrew; Wang, Fei; Zhu, Yanzhe; Hayes, Sophia E; Giammar, Daniel E; Conradi, Mark S

2015-02-03

We have developed an approach for determining pH at elevated pressures and temperatures by using (13)C NMR measurements of inorganic carbon species together with a geochemical equilibrium model. The approach can determine in situ pH with precision better than 0.1 pH units at pressures, temperatures, and ionic strengths typical of geologic carbon sequestration systems. A custom-built high pressure NMR probe was used to collect (13)C NMR spectra of (13)C-labeled CO2 reactions with NaOH solutions and Mg(OH)2 suspensions at pressures up to 107 bar and temperatures of 80 °C. The quantitative nature of NMR spectroscopy allows the concentration ratio [CO2]/[HCO3(-)] to be experimentally determined. This ratio is then used with equilibrium constants calculated for the specific pressure and temperature conditions and appropriate activity coefficients for the solutes to calculate the in situ pH. The experimentally determined [CO2]/[HCO3(-)] ratios agree well with the predicted values for experiments performed with three different concentrations of NaOH and equilibration with multiple pressures of CO2. The approach was then applied to experiments with Mg(OH)2 slurries in which the change in pH could track the dissolution of CO2 into solution, rapid initial Mg(OH)2 dissolution, and onset of magnesium carbonate precipitation.

Quantum size effects on the (0001) surface of double hexagonal close packed americium

NASA Astrophysics Data System (ADS)

Gao, D.; Ray, A. K.

2007-01-01

Electronic structures of double hexagonal close-packed americium and the (0001) surface have been studied via full-potential all-electron density-functional calculations with a mixed APW+lo/LAPW basis. The electronic and geometric properties of bulk dhcp Am as well as quantum size effects in the surface energies and the work functions of the dhcp Am (0001) ultra thin films up to seven layers have been examined at nonmagnetic, ferromagnetic, and antiferromagnetic configurations with and without spin orbit coupling. The anti-ferromagnetic state including spin-orbit coupling is found to be the ground state of dhcp Am with the 5f electrons primarily localized. Our results show that both magnetic configurations and spin-orbit coupling play important roles in determining the equilibrium lattice constant, the bulk modulus as well as the localized feature of 5f electrons for dhcp Am. Our calculated equilibrium lattice constant and bulk modulus at the ground state are in good agreement with the experimental values respectively. The work function of dhcp Am (0001) 7-layer surface at the ground state is predicted to be 2.90 eV. The surface energy for dhcp Am (0001) semi-infinite surface energy at the ground state is predicted to be 0.84 J/m2. Quantum size effects are found to be more pronounced in work functions than in surface energies.

Dose calculation for electron therapy using an improved LBR method.

PubMed

Gebreamlak, Wondesen T; Tedeschi, David J; Alkhatib, Hassaan A

2013-07-01

To calculate the percentage depth dose (PDD) of any irregularly shaped electron beam using a modified lateral build-up ratio (LBR) method. Percentage depth dose curves were measured using 6, 9, 12, and 15 MeV electron beam energies for applicator cone sizes of 6 × 6, 10 × 10, 14 × 14, and 20 × 20 cm(2). Circular cutouts for each cone were prepared from 2.0 cm diameter to the maximum possible size for each cone. In addition, three irregular cutouts were prepared. The LBR for each circular cutout was calculated from the measured PDD curve using the open field of the 14 × 14 cm(2) cone as the reference field. Using the LBR values and the radius of the circular cutouts, the corresponding lateral spread parameter [σR(z)] of the electron shower was calculated. Unlike the commonly accepted assumption that σR(z) is independent of cutout size, it is shown that its value increases linearly with circular cutout size (R). Using this characteristic of the lateral spread parameter, the PDD curves of irregularly shaped cutouts were calculated. Finally, the calculated PDD curves were compared with measured PDD curves. In this research, it is shown that the lateral spread parameter σR(z) increases with cutout size. For radii of circular cutout sizes up to the equilibrium range of the electron beam, the increase of σR(z) with the cutout size is linear. The percentage difference of the calculated PDD curve from the measured PDD data for irregularly shaped cutouts was under 1.0% in the region between the surface and therapeutic range of the electron beam. Similar results were obtained for four electron beam energies (6, 9, 12, and 15 MeV).

Equivalences between refractive index and equilibrium water content of conventional and silicone hydrogel soft contact lenses from automated and manual refractometry.

PubMed

González-Méijome, José M; López-Alemany, Antonio; Lira, Madalena; Almeida, José B; Oliveira, M Elisabete C D Real; Parafita, Manuel A

2007-01-01

The purpose of the present study was to develop mathematical relationships that allow obtaining equilibrium water content and refractive index of conventional and silicone hydrogel soft contact lenses from refractive index measures obtained with automated refractometry or equilibrium water content measures derived from manual refractometry, respectively. Twelve HEMA-based hydrogels of different hydration and four siloxane-based polymers were assayed. A manual refractometer and a digital refractometer were used. Polynomial models obtained from the sucrose curves of equilibrium water content against refractive index and vice-versa were used either considering the whole range of sucrose concentrations (16-100% equilibrium water content) or a range confined to the equilibrium water content of current soft contact lenses (approximately 20-80% equilibrium water content). Values of equilibrium water content measured with the Atago N-2E and those derived from the refractive index measurement with CLR 12-70 by the applications of sucrose-based models displayed a strong linear correlation (r2 = 0.978). The same correlations were obtained when the models are applied to obtain refractive index values from the Atago N-2E and compared with those (values) given by the CLR 12-70 (r2 = 0.978). No significantly different results are obtained between models derived from the whole range of the sucrose solution or the model limited to the normal range of soft contact lens hydration. Present results will have implications for future experimental and clinical research regarding normal hydration and dehydration experiments with hydrogel polymers, and particularly in the field of contact lenses. 2006 Wiley Periodicals, Inc.

Interfacial free energy and stiffness of aluminum during rapid solidification

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, Nicholas T.; Martinez, Enrique; Qu, Jianmin

Using molecular dynamics simulations and the capillary fluctuation method, we have calculated the anisotropic crystal-melt interfacial free energy and stiffness of aluminum in a rapid solidification system where a temperature gradient is applied to enforce thermal non-equilibrium. To calculate these material properties, the standard capillary fluctuation method typically used for systems in equilibrium has been modified to incorporate a second-order Taylor expansion of the interfacial free energy term. The result is a robust method for calculating interfacial energy, stiffness and anisotropy as a function of temperature gradient using the fluctuations in the defined interface height. This work includes the calculationmore » of interface characteristics for temperature gradients ranging from 11 to 34 K/nm. The captured results are compared to a thermal equilibrium case using the same model and simulation technique with a zero gradient definition. We define the temperature gradient as the change in temperature over height perpendicular to the crystal-melt interface. The gradients are applied in MD simulations using defined thermostat regions on a stable solid-liquid interface initially in thermal equilibrium. The results of this work show that the interfacial stiffness and free energy for aluminum are dependent on the magnitude of the temperature gradient, however the anisotropic parameters remain independent of the non-equilibrium conditions applied in this analysis. As a result, the relationships of the interfacial free energy/stiffness are determined to be linearly related to the thermal gradient, and can be interpolated to find material characteristics at additional temperature gradients.« less

Interfacial free energy and stiffness of aluminum during rapid solidification

DOE PAGES

Brown, Nicholas T.; Martinez, Enrique; Qu, Jianmin

2017-05-01

Using molecular dynamics simulations and the capillary fluctuation method, we have calculated the anisotropic crystal-melt interfacial free energy and stiffness of aluminum in a rapid solidification system where a temperature gradient is applied to enforce thermal non-equilibrium. To calculate these material properties, the standard capillary fluctuation method typically used for systems in equilibrium has been modified to incorporate a second-order Taylor expansion of the interfacial free energy term. The result is a robust method for calculating interfacial energy, stiffness and anisotropy as a function of temperature gradient using the fluctuations in the defined interface height. This work includes the calculationmore » of interface characteristics for temperature gradients ranging from 11 to 34 K/nm. The captured results are compared to a thermal equilibrium case using the same model and simulation technique with a zero gradient definition. We define the temperature gradient as the change in temperature over height perpendicular to the crystal-melt interface. The gradients are applied in MD simulations using defined thermostat regions on a stable solid-liquid interface initially in thermal equilibrium. The results of this work show that the interfacial stiffness and free energy for aluminum are dependent on the magnitude of the temperature gradient, however the anisotropic parameters remain independent of the non-equilibrium conditions applied in this analysis. As a result, the relationships of the interfacial free energy/stiffness are determined to be linearly related to the thermal gradient, and can be interpolated to find material characteristics at additional temperature gradients.« less

Lead sorption by waste biomass of hazelnut and almond shell.

PubMed

Pehlivan, Erol; Altun, Türkan; Cetin, Serpil; Iqbal Bhanger, M

2009-08-15

The potential to remove Pb(2+) ion from aqueous solutions using the shells of hazelnut (HNS) (Corylus avellana) and almond (AS) (Prunus dulcis) through biosorption was investigated in batch experiments. The main parameters influencing Pb(2+) ion sorption on HNS and AS were: initial metal ion concentration, amount of adsorbent, contact time and pH value of solution. The influences of initial Pb(2+) ion concentration (0.1-1.0mM), pH (2-9), contact time (10-240 min) and adsorbent amount (0.1-1.0 g) have been investigated. Equilibrium isotherms have been measured and modelled. Adsorption of Pb(2+) ions was in all cases pH-dependent showing a maximum at equilibrium pH values between 6.0 and 7.0, depending on the biomaterial, that corresponded to equilibrium pH values of 6.0 for HNS and 7.0 for AS. The equilibrium sorption capacities of HNS and AS were 28.18 and 8.08 mg/g for lead, respectively after equilibrium time of 2h. The adsorption data fit well with the Langmuir isotherm model and the experimental result inferred that adsorption, chelation and ion exchange are major adsorption mechanisms for binding Pb(2+) ion to the sorbents.

Wigner distribution function and entropy of the damped harmonic oscillator within the theory of the open quantum systems

NASA Technical Reports Server (NTRS)

Isar, Aurelian

1995-01-01

The harmonic oscillator with dissipation is studied within the framework of the Lindblad theory for open quantum systems. By using the Wang-Uhlenbeck method, the Fokker-Planck equation, obtained from the master equation for the density operator, is solved for the Wigner distribution function, subject to either the Gaussian type or the delta-function type of initial conditions. The obtained Wigner functions are two-dimensional Gaussians with different widths. Then a closed expression for the density operator is extracted. The entropy of the system is subsequently calculated and its temporal behavior shows that this quantity relaxes to its equilibrium value.

Critical Frequency in Nuclear Chiral Rotation

NASA Astrophysics Data System (ADS)

Olbratowski, P.; Dobaczewski, J.; Dudek, J.; Płóciennik, W.

2004-07-01

Self-consistent solutions for the so-called planar and chiral rotational bands in 132La are obtained for the first time within the Skyrme-Hartree-Fock cranking approach. It is suggested that the chiral rotation cannot exist below a certain critical frequency which under the approximations used is estimated as ℏωcrit≈0.5 0.6 MeV. However, the exact values of ℏωcrit may vary, to an extent, depending on the microscopic model used, in particular, through the pairing correlations and/or calculated equilibrium deformations. The existence of the critical frequency is explained in terms of a simple classical model of two gyroscopes coupled to a triaxial rigid body.

Influence of the Fluid on the Parameters and Limits of Bubble Detonation

NASA Astrophysics Data System (ADS)

Pinaev, A. V.; Prokhorov, E. S.

2017-12-01

The compression and inflammation of reactive gas bubbles in bubble detonation waves have been studied, and the considerable influence of the fluid (liquid or vapor) on the detonation parameters has been found. It has been shown numerically that the final values of the pressure and temperature significantly decrease if the temperature dependence of the adiabatic index is taken into account at the compression stage. The parameters of reactive gas combustion products in the bubble have been calculated in terms of an equilibrium model, and the influence of the fluid that remains in the bubble in the form of microdroplets and vapor on these parameters has been investigated.

Shapes and stability of algebraic nuclear models

NASA Technical Reports Server (NTRS)

Lopez-Moreno, Enrique; Castanos, Octavio

1995-01-01

A generalization of the procedure to study shapes and stability of algebraic nuclear models introduced by Gilmore is presented. One calculates the expectation value of the Hamiltonian with respect to the coherent states of the algebraic structure of the system. Then equilibrium configurations of the resulting energy surface, which depends in general on state variables and a set of parameters, are classified through the Catastrophe theory. For one- and two-body interactions in the Hamiltonian of the interacting Boson model-1, the critical points are organized through the Cusp catastrophe. As an example, we apply this Separatrix to describe the energy surfaces associated to the Rutenium and Samarium isotopes.