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Sample records for model rate constants

  1. Using the pseudophase kinetic model to interpret chemical reactivity in ionic emulsions: determining antioxidant partition constants and interfacial rate constants.

    Science.gov (United States)

    Gu, Qing; Bravo-Díaz, Carlos; Romsted, Laurence S

    2013-06-15

    Kinetic results obtained in cationic and anionic emulsions show for the first time that pseudophase kinetic models give reasonable estimates of the partition constants of reactants, here t-butylhydroquinone (TBHQ) between the oil and interfacial region, P(O)(I), and the water and interfacial region, P(W)(I), and of the interfacial rate constant, k(I), for the reaction with an arenediazonium ion in emulsions containing a 1:1 volume ratio of a medium chain length triglyceride, MCT, and aqueous acid or buffer. The results provide: (a) an explanation for the large difference in pH, >4 pH units, required to run the reaction in CTAB (pH 1.54, added HBr) and SDS (pH 5.71, acetate buffer) emulsions; (b) reasonable estimates of PO(I) and k(I) in the CTAB emulsions; (c) a sensible interpretation of added counterion effects based on ion exchange in SDS emulsions (Na(+)/H3O(+) ion exchange in the interfacial region) and Donnan equilibrium in CTAB emulsions (Br(-) increasing the interfacial H3O(+)); and (d) the significance of the effect of the much greater solubility of TBHQ in MCT versus octane, 1000/1, as the oil. These results should aid in interpreting the effects of ionic surfactants on chemical reactivity in emulsions in general and in selecting the most efficient antioxidant for particular food applications.

  2. USE OF ROUGH SETS AND SPECTRAL DATA FOR BUILDING PREDICTIVE MODELS OF REACTION RATE CONSTANTS

    Science.gov (United States)

    A model for predicting the log of the rate constants for alkaline hydrolysis of organic esters has been developed with the use of gas-phase min-infrared library spectra and a rule-building software system based on the mathematical theory of rough sets. A diverse set of 41 esters ...

  3. The ruin probability of a discrete time risk model under constant interest rate with heavy tails

    NARCIS (Netherlands)

    Tang, Q.

    2004-01-01

    This paper investigates the ultimate ruin probability of a discrete time risk model with a positive constant interest rate. Under the assumption that the gross loss of the company within one year is subexponentially distributed, a simple asymptotic relation for the ruin probability is derived and co

  4. A model for turbulent dissipation rate in a constant pressure boundary layer

    Indian Academy of Sciences (India)

    J DEY; P PHANI KUMAR

    2016-04-01

    Estimation of the turbulent dissipation rate in a boundary layer is a very involved process.Experimental determination of either the dissipation rate or the Taylor microscale, even in isotropic turbulence,which may occur in a portion of the turbulent boundary layer, is known to be a difficult task. For constant pressure boundary layers, a model for the turbulent dissipation rate is proposed here in terms of the local mean flow quantities. Comparable agreement between the estimated Taylor microscale and Kolmogorov length scale with other data in the logarithmic region suggests usefulness of this model in obtaining these quantitiesexperimentally

  5. Structural model for the dynamic buckling of a column under constant rate compression

    CERN Document Server

    Kuzkin, Vitaly A

    2015-01-01

    Dynamic buckling behavior of a column (rod, beam) under constant rate compression is considered. The buckling is caused by prescribed motion of column ends toward each other with constant velocity. Simple model with one degree of freedom simulating static and dynamic buckling of a column is derived. In the case of small initial disturbances the model yields simple analytical dependencies between the main parameters of the problem: critical force, compression rate, and initial disturbance. It is shown that the time required for buckling is inversely proportional to cubic root of compression velocity and logarithmically depends on the initial disturbance. Analytical expression for critical buckling force as a function of compression velocity is derived. It is shown that in a range of compression rates typical for laboratory experiments the dependence is accurately approximated by a power law with exponent equal to $2/3$. Theoretical findings are supported by available results of laboratory experiments. Keywords...

  6. A generalized Forchheimer radial flow model for constant-rate tests

    Science.gov (United States)

    Liu, Ming-Ming; Chen, Yi-Feng; Zhan, Hongbin; Hu, Ran; Zhou, Chuang-Bing

    2017-09-01

    Models used for data interpretation of constant-rate tests (CRTs) are commonly derived with the assumption of Darcian flow in an idealized integer flow dimension, where the non-Darcian nature of fluid flow and the complexity of flow geometry are disregarded. In this study, a Forchheimer's law-based analytical model is proposed with the assumption of buildup (or drawdown) decomposition for characterizing the non-Darcian flow in a generalized radial formation where the flow dimension n may become non-integer. The proposed model immediately reduces to Barker's (1988) model for Darcian flow in the generalized radial formation and to Mathias et al.'s (2008) model for non-Darcian flow in a two-dimensional confined aquifer. A comparison with numerical simulations shows that the proposed model behaves well at late times for flow dimension n > 1.5. The proposed model is finally applied for data interpretation of the constant-rate pumping tests performed at Ploemeur (Le Borgne et al., 2004), showing that the intrinsic hydraulic conductivity of formations will be underestimated and the specific storage will be overestimated if the non-Darcian effect is ignored. The proposed model is an extension of the generalized radial flow (GRF) model based on Forchheimer's law, which would be of significance for data interpretation of CRTs in aquifers of complex flow geometry in which non-Darcian flow occurs.

  7. A finite horizon production model with variable production rates and constant demand rate

    OpenAIRE

    2002-01-01

    In this paper we present a finite horizon single product single machine production problem. Demand rate and all the cost patterns do not change over time. However, end of horizon effects may require production rate adjustments at the beginning of each cycle. It is found that no such adjustments are required. The machine should be operated either at minimum speed (i.e. production rate = demand rate; shortage is not allowed), avoiding the buildup of any inventory, or at maximum s...

  8. Extension of the master sintering curve for constant heating rate modeling

    Science.gov (United States)

    McCoy, Tammy Michelle

    The purpose of this work is to extend the functionality of the Master Sintering Curve (MSC) such that it can be used as a practical tool for predicting sintering schemes that combine both a constant heating rate and an isothermal hold. Rather than just being able to predict a final density for the object of interest, the extension to the MSC will actually be able to model a sintering run from start to finish. Because the Johnson model does not incorporate this capability, the work presented is an extension of what has already been shown in literature to be a valuable resource in many sintering situations. A predicted sintering curve that incorporates a combination of constant heating rate and an isothermal hold is more indicative of what is found in real-life sintering operations. This research offers the possibility of predicting the sintering schedule for a material, thereby having advanced information about the extent of sintering, the time schedule for sintering, and the sintering temperature with a high degree of accuracy and repeatability. The research conducted in this thesis focuses on the development of a working model for predicting the sintering schedules of several stabilized zirconia powders having the compositions YSZ (HSY8), 10Sc1CeSZ, 10Sc1YSZ, and 11ScSZ1A. The compositions of the four powders are first verified using x-ray diffraction (XRD) and the particle size and surface area are verified using a particle size analyzer and BET analysis, respectively. The sintering studies were conducted on powder compacts using a double pushrod dilatometer. Density measurements are obtained both geometrically and using the Archimedes method. Each of the four powders is pressed into ¼" diameter pellets using a manual press with no additives, such as a binder or lubricant. Using a double push-rod dilatometer, shrinkage data for the pellets is obtained over several different heating rates. The shrinkage data is then converted to reflect the change in relative

  9. CORAL: QSPR modeling of rate constants of reactions between organic aromatic pollutants and hydroxyl radical.

    Science.gov (United States)

    Toropov, A A; Toropova, A P; Rasulev, B F; Benfenati, E; Gini, G; Leszczynska, D; Leszczynski, J

    2012-09-05

    The rate constants (K(OH)) of reactions between 78 organic aromatic pollutants and hydroxyl radical were examined. Simplified molecular input line entry system was used as representation of the molecular structure of the pollutants. Quantitative structure-property relationships was developed using CORAL software (http://www.insilico.eu/CORAL) for four random splits of the data into the subtraining, calibration, and test sets. The obtained results reveal good predictive potential of the applied approach: correlation coefficients (r(2)) for the test sets of the four random splits are 0.75, 0.91, 0.84, and 0.80. Using the Monte Carlo method CORAL software generated the optimal descriptors for one-variable models. The reproducibility of each model was tested performing three runs of the Monte Carlo optimization. The current data were compared to previous results and discussed. Copyright © 2012 Wiley Periodicals, Inc.

  10. Exponential Bounds for Ruin Probability in Two Moving Average Risk Models with Constant Interest Rate

    Institute of Scientific and Technical Information of China (English)

    Ding Jun YAO; Rong Ming WANG

    2008-01-01

    The authors consider two discrete-time insurance risk models. Two moving average risk models are introduced to model the surplus process, and the probabilities of ruin are examined in models with a constant interest force. Exponential bounds for ruin probabilities of an infinite time horizon are derived by the martingale method.

  11. Kinetics analysis for development of a rate constant estimation model for ultrasonic degradation reaction of methylene blue.

    Science.gov (United States)

    Kobayashi, Daisuke; Honma, Chiemi; Matsumoto, Hideyuki; Takahashi, Tomoki; Kuroda, Chiaki; Otake, Katsuto; Shono, Atsushi

    2014-07-01

    Ultrasound has been used as an advanced oxidation method for wastewater treatment. Sonochemical degradation of organic compounds in aqueous solution occurs by pyrolysis and/or reaction with hydroxyl radicals. Moreover, kinetics of sonochemical degradation has been proposed. However, the effect of ultrasonic frequency on degradation rate has not been investigated. In our previous study, a simple model for estimating the apparent degradation rate of methylene blue was proposed. In this study, sonochemical degradation of methylene blue was performed at various frequencies. Apparent degradation rate constant was evaluated assuming that sonochemical degradation of methylene blue was a first-order reaction. Specifically, we focused on effects of ultrasonic frequency and power on rate constant, and the applicability of our proposed model was demonstrated. Using this approach, maximum sonochemical degradation rate was observed at 490 kHz, which agrees with a previous investigation into the effect of frequency on the sonochemical efficiency value evaluated by KI oxidation dosimetry. Degradation rate increased with ultrasonic power at every frequency. It was also observed that threshold power must be reached for the degradation reaction to progress. The initial methylene blue concentration and the apparent degradation rate constant have a relation of an inverse proportion. Our proposed model for estimating the apparent degradation rate constant using ultrasonic power and sonochemical efficiency value can apply to this study which extended the frequency and initial concentration range.

  12. The saddle-node-transcritical bifurcation in a population model with constant rate harvesting

    CERN Document Server

    Saputra, K V I; Quispel, G R W

    2010-01-01

    We study the interaction of saddle-node and transcritical bifurcations in a Lotka-Volterra model with a constant term representing harvesting or migration. Because some of the equilibria of the model lie on an invariant coordinate axis, both the saddle-node and the transcritical bifurcations are of codimension one. Their interaction can be associated with either a single or a double zero eigenvalue. We show that in the former case, the local bifurcation diagram is given by a nonversal unfolding of the cusp bifurcation whereas in the latter case it is a nonversal unfolding of a degenerate Bogdanov-Takens bifurcation. We present a simple model for each of the two cases to illustrate the possible unfoldings. We analyse the consequences of the generic phase portraits for the Lotka-Volterra system.

  13. An economic order quantity model with ramp type demand rate, constant deterioration rate and unit production cost

    Directory of Open Access Journals (Sweden)

    Manna Prasenjit

    2016-01-01

    Full Text Available We have developed an order level inventory system for deteriorating items with demand rate as a ramp type function of time. The finite production rate is proportional to the demand rate and the deterioration rate is independent of time. The unit production cost is inversely proportional to the demand rate. The model with no shortages case is discussed considering that: (a the demand rate is stabilized after the production stopping time and (b the demand is stabilized before the production stopping time. Optimal costs are determined for two different cases.

  14. Inflation with a constant rate of roll

    Science.gov (United States)

    Motohashi, Hayato; Starobinsky, Alexei A.; Yokoyama, Jun'ichi

    2015-09-01

    We consider an inflationary scenario where the rate of inflaton roll defined by ̈phi/H dot phi remains constant. The rate of roll is small for slow-roll inflation, while a generic rate of roll leads to the interesting case of 'constant-roll' inflation. We find a general exact solution for the inflaton potential required for such inflaton behaviour. In this model, due to non-slow evolution of background, the would-be decaying mode of linear scalar (curvature) perturbations may not be neglected. It can even grow for some values of the model parameter, while the other mode always remains constant. However, this always occurs for unstable solutions which are not attractors for the given potential. The most interesting particular cases of constant-roll inflation remaining viable with the most recent observational data are quadratic hilltop inflation (with cutoff) and natural inflation (with an additional negative cosmological constant). In these cases even-order slow-roll parameters approach non-negligible constants while the odd ones are asymptotically vanishing in the quasi-de Sitter regime.

  15. Combination of poroelasticity theory and constant strain rate test in modelling land subsidence due to groundwater extraction

    Science.gov (United States)

    Pham, Tien Hung; Rühaak, Wolfram; Sass, Ingo

    2017-04-01

    Extensive groundwater extraction leads to a drawdown of the ground water table. Consequently, soil effective stress increases and can cause land subsidence. Analysis of land subsidence generally requires a numerical model based on poroelasticity theory, which was first proposed by Biot (1941). In the review of regional land subsidence accompanying groundwater extraction, Galloway and Burbey (2011) stated that more research and application is needed in coupling of stress-dependent land subsidence process. In geotechnical field, the constant rate of strain tests (CRS) was first introduced in 1969 (Smith and Wahls 1969) and was standardized in 1982 through the designation D4186-82 by American Society for Testing and Materials. From the reading values of CRS tests, the stress-dependent parameters of poroelasticity model can be calculated. So far, there is no research to link poroelasticity theory with CRS tests in modelling land subsidence due to groundwater extraction. One dimensional CRS tests using conventional compression cell and three dimension CRS tests using Rowe cell were performed. The tests were also modelled by using finite element method with mixed elements. Back analysis technique is used to find the suitable values of hydraulic conductivity and bulk modulus that depend on the stress or void ratio. Finally, the obtained results are used in land subsidence models. Biot, M. A. (1941). "General theory of three-dimensional consolidation." Journal of applied physics 12(2): 155-164. Galloway, D. L. and T. J. Burbey (2011). "Review: Regional land subsidence accompanying groundwater extraction." Hydrogeology Journal 19(8): 1459-1486. Smith, R. E. and H. E. Wahls (1969). "Consolidation under constant rates of strain." Journal of Soil Mechanics & Foundations Div.

  16. Model system-bath Hamiltonian and nonadiabatic rate constants for proton-coupled electron transfer at electrode-solution interfaces.

    Science.gov (United States)

    Navrotskaya, Irina; Soudackov, Alexander V; Hammes-Schiffer, Sharon

    2008-06-28

    An extension of the Anderson-Newns-Schmickler model for electrochemical proton-coupled electron transfer (PCET) is presented. This model describes reactions in which electron transfer between a solute complex in solution and an electrode is coupled to proton transfer within the solute complex. The model Hamiltonian is derived in a basis of electron-proton vibronic states defined within a double adiabatic approximation for the electrons, transferring proton, and bath modes. The interaction term responsible for electronic transitions between the solute complex and the electrode depends on the proton donor-acceptor vibrational mode within the solute complex. This model Hamiltonian is used to derive the anodic and cathodic rate constants for nonadiabatic electrochemical PCET. The derivation is based on the master equations for the reduced density matrix of the electron-proton subsystem, which includes the electrons of the solute complex and the electrode, as well as the transferring proton. The rate constant expressions differ from analogous expressions for electrochemical electron transfer because of the summation over electron-proton vibronic states and the dependence of the couplings on the proton donor-acceptor vibrational motion. These differences lead to additional contributions to the total reorganization energy, an additional exponential temperature-dependent prefactor, and a temperature-dependent term in the effective activation energy that has different signs for the anodic and cathodic processes. This model can be generalized to describe both nonadiabatic and adiabatic electrochemical PCET reactions and provides the framework for the inclusion of additional effects, such as the breaking and forming of other chemical bonds.

  17. Kinetics of the transformation of phenyl-urea herbicides during ozonation of natural waters: rate constants and model predictions.

    Science.gov (United States)

    Benitez, F Javier; Real, Francisco J; Acero, Juan L; Garcia, Carolina

    2007-10-01

    Oxidation of four phenyl-urea herbicides (isoproturon, chlortoluron, diuron, and linuron) was studied by ozone at pH=2, and by a combination of O3/H2O2 at pH=9. These experiments allowed the determination of the rate constants for their reactions with ozone and OH radicals. For reactions with ozone, the following rate constants were obtained: 1.9 +/- 0.2, 16.5 +/- 0.6, 393.5 +/- 8.4, and 2191 +/- 259 M(-1) s(-1) for linuron, diuron, chlortoluron, and isoproturon, respectively. The rate constants for the reaction with OH radicals were (7.9 +/- 0.1) x 10(9) M(-1) s(-1) for isoproturon, (6.9 +/- 0.2) x 10(9) M(-1) s(-1) for chlortoluron, (6.6 +/- 0.1) x 10(5) M(-1) s(-1) for diuron, and (5.9 +/- 0.1) x 10(9) M(-1) s(-1) for linuron. Furthermore, the simultaneous ozonation of these selected herbicides in some natural water systems (a commercial mineral water, a groundwater, and surface water from a reservoir) was studied. The influence of operating conditions (initial ozone dose, nature of herbicides, and type of water systems) on herbicide removal efficiency was established, and the parameter Rct (proposed by Elovitz, M.S., von Gunten, U., 1999. Hydroxyl radical/ozone ratios during ozonation processes. I. The Rct concept. Ozone Sci. Eng. 21, 239-260) was evaluated from simultaneous measurement of ozone and OH radicals. A kinetic model was proposed for the prediction of the elimination rate of herbicides in these natural waters, and application of this model revealed that experimental results and predicted values agreed fairly well. Finally, the partial contributions of direct ozone and radical pathways were evaluated, and the results showed that reaction with OH radicals was the major pathway for the oxidative transformation of diuron and linuron, even when conventional ozonation was applied, while for chlortoluron and isoproturon, direct ozonation was the major pathway.

  18. A quasi-QSPR modelling for the photocatalytic decolourization rate constants and cellular viability (CV%) of nanoparticles by CORAL.

    Science.gov (United States)

    Toropova, A P; Toropov, A A; Benfenati, E

    2015-01-01

    Most quantitative structure-property/activity relationships (QSPRs/QSARs) predict various endpoints related to organic compounds. Gradually, the variety of organic compounds has been extended to inorganic, organometallic compounds and polymers. However, the so-called molecular descriptors cannot be defined for super-complex substances such as different nanomaterials and peptides, since there is no simple and clear representation of their molecular structure. Some possible ways to define approaches for a predictive model in the case of super-complex substances are discussed. The basic idea of the approach is to change the traditionally used paradigm 'the endpoint is a mathematical function of the molecular structure' with another paradigm 'the endpoint is a mathematical function of available eclectic information'. The eclectic data can be (i) conditions of a synthesis, (ii) technological attributes, (iii) size of nanoparticles, (iv) concentration, (v) attributes related to cell membranes, and so on. Two examples of quasi-QSPR/QSAR analyses are presented and discussed. These are (i) photocatalytic decolourization rate constants (DRC) (10(-5)/s) of different nanopowders; and (ii) the cellular viability under the effect of nano-SiO(2).

  19. Spiral growth and dissolution models with rate constants related to the frequency of partial dehydration of cations and to the surface tension

    Science.gov (United States)

    Christoffersen, J.; Christoffersen, M. R.

    1988-01-01

    A rate expression is developed for spiral dissolution, similar to the Nielsen expression for spiral growth, with the rate constant expressed in terms of frequencies related to dehydration frequencies. These models for spiral growth and dissolution are applied to growth and dissolution of brushite, DCPD.

  20. Modeling the downward transport of {sup 210}Pb in Peatlands: Initial Penetration‐Constant Rate of Supply (IP-CRS) model

    Energy Technology Data Exchange (ETDEWEB)

    Olid, Carolina, E-mail: olid.carolina@gmail.com [Department of Ecology and Environmental Science, Umeå University, SE-90187, Umeå (Sweden); Diego, David [Department of Earth Science, University of Bergen, NO-5020 Bergen (Norway); Garcia-Orellana, Jordi [Departament de Física, Universitat Autònoma de Barcelona, E-08193 Bellaterra (Spain); Institut de Ciència i Tecnologia Ambientals (ICTA), Universitat Autònoma de Barcelona, E-08193 Bellaterra (Spain); Cortizas, Antonio Martínez [Departamento de Edafoloxía e Química Agrícola, Universidade de Santiago de Compostela, E-15782 Santiago de Compostela (Spain); Klaminder, Jonatan [Department of Ecology and Environmental Science, Umeå University, SE-90187, Umeå (Sweden)

    2016-01-15

    The vertical distribution of {sup 210}Pb is commonly used to date peat deposits accumulated over the last 100–150 years. However, several studies have questioned this method because of an apparent post-depositional mobility of {sup 210}Pb within some peat profiles. In this study, we introduce the Initial Penetration–Constant Rate of Supply (IP-CRS) model for calculating ages derived from {sup 210}Pb profiles that are altered by an initial migration of the radionuclide. This new, two-phased, model describes the distribution of atmospheric-derived {sup 210}Pb ({sup 210}Pb{sub xs}) in peat taking into account both incorporation of {sup 210}Pb into the accumulating peat matrix as well as an initial flushing of {sup 210}Pb through the uppermost peat layers. The validity of the IP-CRS model is tested in four anomalous {sup 210}Pb peat records that showed some deviations from the typical exponential decay profile not explained by variations in peat accumulation rates. Unlike the most commonly used {sup 210}Pb-dating model (Constant Rate of Supply (CRS)), the IP-CRS model estimates peat accumulation rates consistent with typical growth rates for peatlands from the same areas. Confidence in the IP-CRS chronology is also provided by the good agreement with independent chronological markers (i.e. {sup 241}Am and {sup 137}Cs). Our results showed that the IP-CRS can provide chronologies from peat records where {sup 210}Pb mobility is evident, being a valuable tool for studies reconstructing past environmental changes using peat archives during the Anthropocene. - Highlights: • Accurate age dating of peat and sediment cores is critical for evaluating change. • A new {sup 210}Pb dating model that includes vertical transport of {sup 210}Pb was developed. • The IP-CRS model provided consistent peat accumulation rates. • The IP-CRS ages were consistent with independent chronological markers. • The IP-CRS model derives peat ages where downward {sup 210}Pb transport is

  1. Ratiometric analysis in hyperpolarized NMR (I): test of the two-site exchange model and the quantification of reaction rate constants.

    Science.gov (United States)

    Li, Lin Z; Kadlececk, Stephen; Xu, He N; Daye, Dania; Pullinger, Benjamin; Profka, Harrilla; Chodosh, Lewis; Rizi, Rahim

    2013-10-01

    Conventional methods for the analysis of in vivo hyperpolarized (13) C NMR data from the lactate dehydrogenase (LDH) reaction usually make assumptions on the stability of rate constants and/or the validity of the two-site exchange model. In this study, we developed a framework to test the validity of the assumption of stable reaction rate constants and the two-site exchange model in vivo via ratiometric fitting of the time courses of the signal ratio L(t)/P(t). Our analysis provided evidence that the LDH enzymatic kinetics observed by hyperpolarized NMR are in near-equilibrium and satisfy the two-site exchange model for only a specific time window. In addition, we quantified both the forward and reverse exchange rate constants of the LDH reaction for the transgenic and mouse xenograft models of breast cancer using the ratio fitting method developed, which includes only two modeling parameters and is less sensitive to the influence of instrument settings/protocols, such as flip angles, degree of polarization and tracer dosage. We further compared the ratio fitting method with a conventional two-site exchange modeling method, i.e. the differential equation fitting method, using both the experimental and simulated hyperpolarized NMR data. The ratio fitting method appeared to fit better than the differential equation fitting method for the reverse rate constant on the mouse tumor data, with less relative errors on average, whereas the differential equation fitting method also resulted in a negative reverse rate constant for one tumor. The simulation results indicated that the accuracy of both methods depends on the width of the transport function, noise level and rate constant ratio; one method may be more accurate than the other based on the experimental/biological conditions aforementioned. We were able to categorize our tumor models into specific conditions of the computer simulation and to estimate the errors of rate quantification. We also discussed possible

  2. Determination of rate constants and branching ratios for TCE degradation by zero-valent iron using a chain decay multispecies model

    Science.gov (United States)

    Hwang, Hyoun-Tae; Jeen, Sung-Wook; Sudicky, Edward A.; Illman, Walter A.

    2015-06-01

    The applicability of a newly-developed chain-decay multispecies model (CMM) was validated by obtaining kinetic rate constants and branching ratios along the reaction pathways of trichloroethene (TCE) reduction by zero-valent iron (ZVI) from column experiments. Changes in rate constants and branching ratios for individual reactions for degradation products over time for two columns under different geochemical conditions were examined to provide ranges of those parameters expected over the long-term. As compared to the column receiving deionized water, the column receiving dissolved CaCO3 showed higher mean degradation rates for TCE and all of its degradation products. However, the column experienced faster reactivity loss toward TCE degradation due to precipitation of secondary carbonate minerals, as indicated by a higher value for the ratio of maximum to minimum TCE degradation rate observed over time. From the calculated branching ratios, it was found that TCE and cis-dichloroethene (cis-DCE) were dominantly dechlorinated to chloroacetylene and acetylene, respectively, through reductive elimination for both columns. The CMM model, validated by the column test data in this study, provides a convenient tool to determine simultaneously the critical design parameters for permeable reactive barriers and natural attenuation such as rate constants and branching ratios.

  3. QSAR models for oxidation of organic micropollutants in water based on ozone and hydroxyl radical rate constants and their chemical classification

    KAUST Repository

    Sudhakaran, Sairam

    2013-03-01

    Ozonation is an oxidation process for the removal of organic micropollutants (OMPs) from water and the chemical reaction is governed by second-order kinetics. An advanced oxidation process (AOP), wherein the hydroxyl radicals (OH radicals) are generated, is more effective in removing a wider range of OMPs from water than direct ozonation. Second-order rate constants (kOH and kO3) are good indices to estimate the oxidation efficiency, where higher rate constants indicate more rapid oxidation. In this study, quantitative structure activity relationships (QSAR) models for O3 and AOP processes were developed, and rate constants, kOH and kO3, were predicted based on target compound properties. The kO3 and kOH values ranged from 5 * 10-4 to 105 M-1s-1 and 0.04 to 18 * (109) M-1 s-1, respectively. Several molecular descriptors which potentially influence O3 and OH radical oxidation were identified and studied. The QSAR-defining descriptors were double bond equivalence (DBE), ionisation potential (IP), electron-affinity (EA) and weakly-polar component of solvent accessible surface area (WPSA), and the chemical and statistical significance of these descriptors was discussed. Multiple linear regression was used to build the QSAR models, resulting in high goodness-of-fit, r2 (>0.75). The models were validated by internal and external validation along with residual plots. © 2012 Elsevier Ltd.

  4. Do Insect Populations Die at Constant Rates as They Become Older? Contrasting Demographic Failure Kinetics with Respect to Temperature According to the Weibull Model.

    Directory of Open Access Journals (Sweden)

    Petros Damos

    Full Text Available Temperature implies contrasting biological causes of demographic aging in poikilotherms. In this work, we used the reliability theory to describe the consistency of mortality with age in moth populations and to show that differentiation in hazard rates is related to extrinsic environmental causes such as temperature. Moreover, experiments that manipulate extrinsic mortality were used to distinguish temperature-related death rates and the pertinence of the Weibull aging model. The Newton-Raphson optimization method was applied to calculate parameters for small samples of ages at death by estimating the maximum likelihoods surfaces using scored gradient vectors and the Hessian matrix. The study reveals for the first time that the Weibull function is able to describe contrasting biological causes of demographic aging for moth populations maintained at different temperature regimes. We demonstrate that at favourable conditions the insect death rate accelerates as age advances, in contrast to the extreme temperatures in which each individual drifts toward death in a linear fashion and has a constant chance of passing away. Moreover, slope of hazard rates shifts towards a constant initial rate which is a pattern demonstrated by systems which are not wearing out (e.g. non-aging since the failure, or death, is a random event independent of time. This finding may appear surprising, because, traditionally, it was mostly thought as rule that in aging population force of mortality increases exponentially until all individuals have died. Moreover, in relation to other studies, we have not observed any typical decelerating aging patterns at late life (mortality leveling-off, but rather, accelerated hazard rates at optimum temperatures and a stabilized increase at the extremes.In most cases, the increase in aging-related mortality was simulated reasonably well according to the Weibull survivorship model that is applied. Moreover, semi log- probability hazard

  5. Prediction of Rate Constants for Catalytic Reactions with Chemical Accuracy.

    Science.gov (United States)

    Catlow, C Richard A

    2016-08-01

    Ex machina: A computational method for predicting rate constants for reactions within microporous zeolite catalysts with chemical accuracy has recently been reported. A key feature of this method is a stepwise QM/MM approach that allows accuracy to be achieved while using realistic models with accessible computer resources.

  6. Coupling constant in dispersive model

    Indian Academy of Sciences (India)

    R Saleh-Moghaddam; M E Zomorrodian

    2013-11-01

    The average of the moments for event shapes in + - → hadrons within the context of next-to-leading order (NLO) perturbative QCD prediction in dispersive model is studied. Moments used in this article are $\\langle 1 - T \\rangle, \\langle ρ \\rangle, \\langle B_{T} \\rangle$ and $\\langle B_{W} \\rangle$. We extract , the coupling constant in perturbative theory and α0 in the non-perturbative theory using the dispersive model. By fitting the experimental data, the values of $(M_{Z^{°}})$ = 0.1171 ± 0.00229 and 0 ($_{I} = 2{\\text{GeV}}$) = 0.5068 ± 0.0440 are found. Our results are consistent with the above model. Our results are also consistent with those obtained from other experiments at different energies. All these features are explained in this paper.

  7. An Inventory Model for Two Warehouses with Constant Deterioration and Quadratic Demand Rate under Inflation and Permissible Delay in Payments

    Directory of Open Access Journals (Sweden)

    U. B. Gothi

    2016-07-01

    Full Text Available In this paper, we have analysed a two-warehouse inventory model for deteriorating items with quadratic demand with time varying holding cost. The effect of permissible delay in payments is also considered, which is usual practice in most of the businesses i.e. purchasers are allowed a period to pay back for the goods brought without paying any interest. To make it more suitable to the present environment the effect of inflation is also considered. Our objective is to minimize the average total cost per time unit under the influence of inflation. Numerical examples are provided to illustrate the model and sensitivity analysis is also carried out for the parameters

  8. Evaluation of antioxidants using oxidation reaction rate constants

    Institute of Scientific and Technical Information of China (English)

    SHI Yan; ZHAN Xiancheng; MA Lie; LI Linli; LI Chengrong

    2007-01-01

    An evaluation method for the capacity of antioxidants to protect drugs against oxidation is presented.As a new viewpoint,to determine the priority of the competitive oxidations between the antioxidant and the protected drug,and to compare the drug-protection capacity of antioxidants,it is important to determine their oxidation rate constants using chemical kinetics instead of standard oxidation (or reduction) potentials.Sodium sulfite,sodium bisulfite and sodium pyrosulfite were used as models for the determination of oxidation reaction rate constants in aqueous solutions.In the experiments,sufficient air was continually infused into the solution to keep the concentration of dissolved oxygen constant.The residual concentrations of the antioxidants were determined by iodimetry,and the concentration of dissolved oxygen by oxygen electrode.The data were fitted by linear regressions to obtain the reaction rate constants.It was found that the degradation of sodium sulfite,sodium bisulfite or sodium pyrosulfite obeyed pseudo zero-order kinetics in the buffer solutions.Because of the ionization equilibrium,these three antioxidants have the same ion form in solutions at a definite pH value and therefore their apparent rate constants were essentially the same.The average apparent rate constants of the three antioxidants at 25~C are (1.34±0.03)×10-3 at pH 6.8,(1.20±0.02) x 10-3 at pH 4.0 and (6.58±0.02)×10-3 mol.L-1.h-1 at pH 9.2,respectively.

  9. Application of a Genetic Algorithm to the Optimization of Rate Constants in Chemical Kinetic Models for Combustion Simulation of HCCI Engines

    Science.gov (United States)

    Kim, Sang-Kyu; Ito, Kazuma; Yoshihara, Daisuke; Wakisaka, Tomoyuki

    For numerically predicting the combustion processes in homogeneous charge compression ignition (HCCI) engines, practical chemical kinetic models have been explored. A genetic algorithm (GA) has been applied to the optimization of the rate constants in detailed chemical kinetic models, and a detailed kinetic model (592 reactions) for gasoline reference fuels with arbitrary octane number between 60 and 100 has been obtained from the detailed reaction schemes for iso-octane and n-heptane proposed by Golovitchev. The ignition timing in a gasoline HCCI engine has been predicted reasonably well by zero-dimensional simulation using the CHEMKIN code with this detailed kinetic model. An original reduced reaction scheme (45 reactions) for dimethyl ether (DME) has been derived from Curran’s detailed scheme, and the combustion process in a DME HCCI engine has been predicted reasonably well in a practical computation time by three-dimensional simulation using the authors’ GTT code, which has been linked to the CHEMKIN subroutines with the proposed reaction scheme and also has adopted a modified eddy dissipation combustion model.

  10. Discrete-state representation of ion permeation coupled to fast gating in a model of CLC-chloride channels: analytic estimation of the state-to-state rate constants.

    Science.gov (United States)

    Coalson, Rob D; Cheng, Mary Hongying

    2011-09-01

    Analytical estimation of state-to-state rate constants is carried out for a recently developed discrete state model of chloride ion motion in a CLC chloride channel (Coalson and Cheng, J. Phys. Chem. B 2010, 114, 1424). In the original presentation of this model, the same rate constants were evaluated via three-dimensional Brownian dynamics simulations. The underlying dynamical theory is an appropriate single- or multiparticle three-dimensional Smoluchowski equation. Taking advantage of approximate geometric symmetries (based on the details of the model channel geometry), well-known formulas for state-to-state transition rates are appealed to herein and adapted as necessary to the problem at hand. Rates of ionic influx from a bulk electrolyte reservoir to the nearest binding site within the channel pore are particularly challenging to compute analytically because they reflect multi-ion interactions (as opposed to single-ion dynamics). A simple empirical correction factor is added to the single-ion rate constant formula in this case to account for the saturation of influx rate constants with increasing bulk Cl(-) concentration. Overall, the agreement between all analytically estimated rate constants is within a factor of 2 of those computed via three-dimensional Brownian dynamics simulations, and often better than this. Current-concentration curves obtained using rate constants derived from these two different computational approaches agree to within 25%.

  11. Rate Constant Calculation for Thermal Reactions Methods and Applications

    CERN Document Server

    DaCosta, Herbert

    2011-01-01

    Providing an overview of the latest computational approaches to estimate rate constants for thermal reactions, this book addresses the theories behind various first-principle and approximation methods that have emerged in the last twenty years with validation examples. It presents in-depth applications of those theories to a wide range of basic and applied research areas. When doing modeling and simulation of chemical reactions (as in many other cases), one often has to compromise between higher-accuracy/higher-precision approaches (which are usually time-consuming) and approximate/lower-preci

  12. Dependence of Reaction Rate Constants on Density in Supercritical Fluids

    Institute of Scientific and Technical Information of China (English)

    WANGTao; SHENZhongyao

    2002-01-01

    A new method,which correlates rate constants of chemical reactions and density or pressure in supercritical fluids,was developed.Based on the transition state theory and thermodynamic principles, the rate constant can be reasonably correlated with the density of the supercritical fluid,and a correlation equation was obtained. Coupled with the equation of state (EOS) of a supercritical solvent,the effect of pressure on reaction rate constant could be represented.Two typical systems were used to test this method.The result indicates that this method is suitable for dilute supercritical fluid solutions.

  13. Neural estimation of kinetic rate constants from dynamic PET-scans

    DEFF Research Database (Denmark)

    Fog, Torben L.; Nielsen, Lars Hupfeldt; Hansen, Lars Kai;

    1994-01-01

    A feedforward neural net is trained to invert a simple three compartment model describing the tracer kinetics involved in the metabolism of [18F]fluorodeoxyglucose in the human brain. The network can estimate rate constants from positron emission tomography sequences and is about 50 times faster ...... than direct fitting of rate constants using the parametrized transients of the compartment model...

  14. Multivariate curve resolution-alternating least squares and kinetic modeling applied to near-infrared data from curing reactions of epoxy resins: mechanistic approach and estimation of kinetic rate constants.

    Science.gov (United States)

    Garrido, M; Larrechi, M S; Rius, F X

    2006-02-01

    This study describes the combination of multivariate curve resolution-alternating least squares with a kinetic modeling strategy for obtaining the kinetic rate constants of a curing reaction of epoxy resins. The reaction between phenyl glycidyl ether and aniline is monitored by near-infrared spectroscopy under isothermal conditions for several initial molar ratios of the reagents. The data for all experiments, arranged in a column-wise augmented data matrix, are analyzed using multivariate curve resolution-alternating least squares. The concentration profiles recovered are fitted to a chemical model proposed for the reaction. The selection of the kinetic model is assisted by the information contained in the recovered concentration profiles. The nonlinear fitting provides the kinetic rate constants. The optimized rate constants are in agreement with values reported in the literature.

  15. Biodegradation testing of chemicals with high Henry’s constants – separating mass and effective concentration reveals higher rate constants

    DEFF Research Database (Denmark)

    Birch, Heidi; Andersen, Henrik Rasmus; Comber, Mike

    During simulation-type biodegradation tests, volatile chemicals will continuously partition between water phase and headspace. This study addressed how (1) this partitioning affects biodegradation test results and (2) it can be accounted for by combining mass balance and dynamic biodegradation...... Microextraction (HS-SPME) was applied directly on the test systems to measure substrate depletion by biodegradation relative to abiotic controls. HS-SPME was also applied to determine air to water partitioning ratios. Water phase biodegradation rate constants, kwater, were up to 72 times higher than test system...... biodegradation rate constants, ksystem. True water phase degradation rate constants facilitate extrapolation to other air-water systems and are more suitable input parameters for aquatic exposure and fate models. As such, they should be considered more appropriate for risk assessments than test system rate...

  16. QSAR model reproducibility and applicability: a case study of rate constants of hydroxyl radical reaction models applied to polybrominated diphenyl ethers and (benzo-)triazoles.

    Science.gov (United States)

    Roy, Partha Pratim; Kovarich, Simona; Gramatica, Paola

    2011-08-01

    The crucial importance of the three central OECD principles for quantitative structure-activity relationship (QSAR) model validation is highlighted in a case study of tropospheric degradation of volatile organic compounds (VOCs) by OH, applied to two CADASTER chemical classes (PBDEs and (benzo-)triazoles). The application of any QSAR model to chemicals without experimental data largely depends on model reproducibility by the user. The reproducibility of an unambiguous algorithm (OECD Principle 2) is guaranteed by redeveloping MLR models based on both updated version of DRAGON software for molecular descriptors calculation and some freely available online descriptors. The Genetic Algorithm has confirmed its ability to always select the most informative descriptors independently on the input pool of variables. The ability of the GA-selected descriptors to model chemicals not used in model development is verified by three different splittings (random by response, K-ANN and K-means clustering), thus ensuring the external predictivity of the new models, independently of the training/prediction set composition (OECD Principle 5). The relevance of checking the structural applicability domain becomes very evident on comparing the predictions for CADASTER chemicals, using the new models proposed herein, with those obtained by EPI Suite. Copyright © 2011 Wiley Periodicals, Inc.

  17. Kinetic performance limits of constant pressure versus constant flow rate gradient elution separations. Part I: theory.

    Science.gov (United States)

    Broeckhoven, K; Verstraeten, M; Choikhet, K; Dittmann, M; Witt, K; Desmet, G

    2011-02-25

    We report on a general theoretical assessment of the potential kinetic advantages of running LC gradient elution separations in the constant-pressure mode instead of in the customarily used constant-flow rate mode. Analytical calculations as well as numerical simulation results are presented. It is shown that, provided both modes are run with the same volume-based gradient program, the constant-pressure mode can potentially offer an identical separation selectivity (except from some small differences induced by the difference in pressure and viscous heating trajectory), but in a significantly shorter time. For a gradient running between 5 and 95% of organic modifier, the decrease in analysis time can be expected to be of the order of some 20% for both water-methanol and water-acetonitrile gradients, and only weakly depending on the value of V(G)/V₀ (or equivalently t(G)/t₀). Obviously, the gain will be smaller when the start and end composition lie closer to the viscosity maximum of the considered water-organic modifier system. The assumptions underlying the obtained results (no effects of pressure and temperature on the viscosity or retention coefficient) are critically reviewed, and can be inferred to only have a small effect on the general conclusions. It is also shown that, under the adopted assumptions, the kinetic plot theory also holds for operations where the flow rate varies with the time, as is the case for constant-pressure operation. Comparing both operation modes in a kinetic plot representing the maximal peak capacity versus time, it is theoretically predicted here that both modes can be expected to perform equally well in the fully C-term dominated regime (where H varies linearly with the flow rate), while the constant pressure mode is advantageous for all lower flow rates. Near the optimal flow rate, and for linear gradients running from 5 to 95% organic modifier, time gains of the order of some 20% can be expected (or 25-30% when accounting for

  18. Dependence of rate constants on vibrational temperatures - An Arrhenius description

    Science.gov (United States)

    Ford, D. I.; Johnson, R. E.

    1988-01-01

    An interpretation of the variation of rate constants with vibrational temperature is proposed which introduces parameters analogous to those of the classical Arrhenius expression. The constancy of vibrational activation energy is studied for the dissociaton of NO, the ion-molecular reaction of O(+) with N2, and the atom exchange reaction of I with H2. It is found that when a Boltzmann distribution for vibrational states is applicable, the variation of the rate constant with the vibrational temperature can be used to define a vibrational activation energy. The method has application to exchange reactions where a vibrational energy threshold exists.

  19. Hemoglobin glycation rate constant in non-diabetic Individuals.

    Science.gov (United States)

    Ladyżyński, Piotr; Wójcicki, Jan M; Bąk, Marianna I; Sabalińska, Stanisława; Kawiak, Jerzy; Foltyński, Piotr; Krzymień, Janusz; Karnafel, Waldemar

    2011-11-01

    The objectives were as follows: (1) estimating mean value of the overall hemoglobin glycation rate constant (k); (2) analyzing inter-individual variability of k; (3) verifying ability of the hemoglobin A1c (HbA1c) formation model to predict changes of HbA1c during red blood cells cultivation in vitro and to reproduce the clinical data. The mean k estimated in a group of 10 non-diabetic subjects was equal to 1.257 ± 0.114 × 10(-9) L mmol(-1) s(-1). The mean k was not affected by a way of estimation of glycemia. The mean k differed less than 20% from values reported earlier and it was almost identical to the mean values calculated on basis of the selected published data. Analysis of variability of k suggests that inter-individual heterogeneity of HbA1c formation is limited or rare. The HbA1c mathematical model was able to predict changes of HbA1c in vitro resulting from different glucose levels and to reproduce a linear relationship of HbA1c and average glucose obtained in the A1C-Derived Average Glucose Study. This study demonstrates that the glycation model with the same k value might be used in majority of individuals as a tool supporting interpretation of HbA1c in different clinical situations.

  20. VMATc: VMAT with constant gantry speed and dose rate

    Science.gov (United States)

    Peng, Fei; Jiang, Steve B.; Romeijn, H. Edwin; Epelman, Marina A.

    2015-04-01

    This article considers the treatment plan optimization problem for Volumetric Modulated Arc Therapy (VMAT) with constant gantry speed and dose rate (VMATc). In particular, we consider the simultaneous optimization of multi-leaf collimator leaf positions and a constant gantry speed and dose rate. We propose a heuristic framework for (approximately) solving this optimization problem that is based on hierarchical decomposition. Specifically, an iterative algorithm is used to heuristically optimize dose rate and gantry speed selection, where at every iteration a leaf position optimization subproblem is solved, also heuristically, to find a high-quality plan corresponding to a given dose rate and gantry speed. We apply our framework to clinical patient cases, and compare the resulting VMATc plans to idealized IMRT, as well as full VMAT plans. Our results suggest that VMATc is capable of producing treatment plans of comparable quality to VMAT, albeit at the expense of long computation time and generally higher total monitor units.

  1. Cosmological models with constant deceleration parameter

    Energy Technology Data Exchange (ETDEWEB)

    Berman, M.S.; de Mello Gomide, F.

    1988-02-01

    Berman presented elsewhere a law of variation for Hubble's parameter that yields constant deceleration parameter models of the universe. By analyzing Einstein, Pryce-Hoyle and Brans-Dicke cosmologies, we derive here the necessary relations in each model, considering a perfect fluid.

  2. Biodegradation testing of chemicals with high Henry's constants - Separating mass and effective concentration reveals higher rate constants.

    Science.gov (United States)

    Birch, Heidi; Andersen, Henrik R; Comber, Mike; Mayer, Philipp

    2017-05-01

    During simulation-type biodegradation tests, volatile chemicals will continuously partition between water phase and headspace. This study addressed how (1) this partitioning affects test results and (2) can be accounted for by combining equilibrium partition and dynamic biodegradation models. An aqueous mixture of 9 (semi)volatile chemicals was first generated using passive dosing and then diluted with environmental surface water producing concentrations in the ng/L to μg/L range. After incubation for 2 h to 4 weeks, automated Headspace Solid Phase Microextraction (HS-SPME) was applied directly on the test systems to measure substrate depletion by biodegradation relatively to abiotic controls. HS-SPME was also applied to determine air to water partitioning ratios. Biodegradation rate constants relating to the chemical in the water phase, kwater, were generally a factor 1 to 11 times higher than biodegradation rate constants relating to the total mass of chemical in the test system, ksystem, with one exceptional factor of 72 times for a long chain alkane. True water phase degradation rate constants were found (i) more appropriate for risk assessment than test system rate constants, (ii) to facilitate extrapolation to other air-water systems and (iii) to be better defined input parameters for aquatic exposure and fate models.

  3. Fractional constant elasticity of variance model

    OpenAIRE

    Ngai Hang Chan; Chi Tim Ng

    2007-01-01

    This paper develops a European option pricing formula for fractional market models. Although there exist option pricing results for a fractional Black-Scholes model, they are established without accounting for stochastic volatility. In this paper, a fractional version of the Constant Elasticity of Variance (CEV) model is developed. European option pricing formula similar to that of the classical CEV model is obtained and a volatility skew pattern is revealed.

  4. High-temperature rate constant measurements for OH+xylenes

    KAUST Repository

    Elwardani, Ahmed Elsaid

    2015-06-01

    The overall rate constants for the reactions of hydroxyl (OH) radicals with o-xylene (k 1), m-xylene (k 2), and p-xylene (k 3) were measured behind reflected shock waves over 890-1406K at pressures of 1.3-1.8atm using OH laser absorption near 306.7nm. Measurements were performed under pseudo-first-order conditions. The measured rate constants, inferred using a mechanism-fitting approach, can be expressed in Arrhenius form as:k1=2.93×1013exp(-1350.3/T)cm3mol-1s-1(890-1406K)k2=3.49×1013exp(-1449.3/T)cm3mol-1s-1(906-1391K)k3=3.5×1013exp(-1407.5/T)cm3mol-1s-1(908-1383K)This paper presents, to our knowledge, first high-temperature measurements of the rate constants of the reactions of xylene isomers with OH radicals. Low-temperature rate-constant measurements by Nicovich et al. (1981) were combined with the measurements in this study to obtain the following Arrhenius expressions, which are applicable over a wider temperature range:k1=2.64×1013exp(-1181.5/T)cm3mol-1s-1(508-1406K)k2=3.05×109exp(-400/T)cm3mol-1s-1(508-1391K)k3=3.0×109exp(-440/T)cm3mol-1s-1(526-1383K) © 2015 The Combustion Institute.

  5. Reaction rate constant for radiative association of CF{sup +}

    Energy Technology Data Exchange (ETDEWEB)

    Öström, Jonatan, E-mail: jonatan.ostrom@gmail.com; Gustafsson, Magnus, E-mail: magnus.gustafsson@ltu.se [Applied Physics, Division of Materials Science, Department of Engineering Science and Mathematics, Luleå University of Technology, 97187 Luleå (Sweden); Bezrukov, Dmitry S. [Department of Chemistry, M. V. Lomonosov Moscow State University, Moscow, 119991 (Russian Federation); Nyman, Gunnar [Department of Chemistry and Molecular Biology, University of Gothenburg, 41296 Gothenburg (Sweden)

    2016-01-28

    Reaction rate constants and cross sections are computed for the radiative association of carbon cations (C{sup +}) and fluorine atoms (F) in their ground states. We consider reactions through the electronic transition 1{sup 1}Π → X{sup 1}Σ{sup +} and rovibrational transitions on the X{sup 1}Σ{sup +} and a{sup 3}Π potentials. Semiclassical and classical methods are used for the direct contribution and Breit–Wigner theory for the resonance contribution. Quantum mechanical perturbation theory is used for comparison. A modified formulation of the classical method applicable to permanent dipoles of unequally charged reactants is implemented. The total rate constant is fitted to the Arrhenius–Kooij formula in five temperature intervals with a relative difference of <3%. The fit parameters will be added to the online database KIDA. For a temperature of 10–250 K, the rate constant is about 10{sup −21} cm{sup 3} s{sup −1}, rising toward 10{sup −16} cm{sup 3} s{sup −1} for a temperature of 30 000 K.

  6. Reaction Rate Constant for Radiative Association of CF$^+$

    CERN Document Server

    Öström, Jonatan; Nyman, Gunnar; Gustafsson, Magnus

    2015-01-01

    Reaction rate constants and cross sections are computed for the radiative association of carbon cations ($\\text{C}^+$) and fluorine atoms ($\\text{F}$) in their ground states. We consider reactions through the electronic transition $1^1\\Pi \\rightarrow X^1\\Sigma^+$ and rovibrational transitions on the $X^1\\Sigma^+$ and $a^3\\Pi$ potentials. Semiclassical and classical methods are used for the direct contribution and Breit--Wigner theory for the resonance contribution. Quantum mechanical perturbation theory is used for comparison. A modified formulation of the classical method applicable to permanent dipoles of unequally charged reactants is implemented. The total rate constant is fitted to the Arrhenius--Kooij formula in five temperature intervals with a relative difference of $<3\\:\\%$. The fit parameters will be added to the online database KIDA. For a temperature of $10$ to $250\\:\\text{K}$, the rate constant is about $10^{-21}\\:\\text{cm}^3\\text{s}^{-1}$, rising toward $10^{-16}\\:\\text{cm}^3\\text{s}^{-1}$ fo...

  7. Uniaxial tension test on Rubber at constant true strain rate

    Directory of Open Access Journals (Sweden)

    Sourne H.L.

    2012-08-01

    Full Text Available Elastomers are widely used for damping parts in different industrial contexts because of their remarkable dissipation properties. Indeed, they can undergo severe mechanical loading conditions, i.e., high strain rates and large strains. Nevertheless, the mechanical response of these materials can vary from purely rubber-like to glassy depending on the strain rate undergone. Classically, uniaxial tension tests are made in order to find a relation between the stress and the strain in the material at various strain rates. However, even if the strain rate is searched to be constant, it is the nominal strain rate that is considered. Here we develop a test at constant true strain rate, i.e. the strain rate that is experienced by the material. In order to do such a test, the displacement imposed by the machine is an exponential function of time. This test has been performed with a high speed hydraulic machine for strain rates between 0.01/s and 100/s. A specific specimen has been designed, yielding a uniform strain field (and so a uniform stress field. Furthermore, an instrumented aluminum bar has been used to take into account dynamic effects in the measurement of the applied force. A high speed camera enables the determination of strain in the sample using point tracking technique. Using this method, the stress-strain curve of a rubber-like material during a loading-unloading cycle has been determined, up to a stretch ratio λ = 2.5. The influence of the true strain rate both on stiffness and on dissipation of the material is then discussed.

  8. Lattice Boltzmann model with nearly constant density.

    Science.gov (United States)

    Fang, Hai-ping; Wan, Rong-zheng; Lin, Zhi-fang

    2002-09-01

    An improved lattice Boltzmann model is developed to simulate fluid flow with nearly constant fluid density. The ingredient is to incorporate an extra relaxation for fluid density, which is realized by introducing a feedback equation in the equilibrium distribution functions. The pressure is dominated by the moving particles at a node, while the fluid density is kept nearly constant and explicit mass conservation is retained as well. Numerical simulation based on the present model for the (steady) plane Poiseuille flow and the (unsteady) two-dimensional Womersley flow shows a great improvement in simulation results over the previous models. In particular, the density fluctuation has been reduced effectively while achieving a relatively large pressure gradient.

  9. Development of a group contribution method to predict aqueous phase hydroxyl radical (HO*) reaction rate constants.

    Science.gov (United States)

    Minakata, Daisuke; Li, Ke; Westerhoff, Paul; Crittenden, John

    2009-08-15

    The hydroxyl radical (HO*) is a strong oxidant that reacts with electron-rich sites of organic compounds and initiates complex chain mechanisms. In order to help understand the reaction mechanisms, a rule-based model was previously developed to predict the reaction pathways. For a kinetic model, there is a need to develop a rate constant estimator that predicts the rate constants for a variety of organic compounds. In this study, a group contribution method (GCM) is developed to predict the aqueous phase HO* rate constants for the following reaction mechanisms: (1) H-atom abstraction, (2) HO* addition to alkenes, (3) HO* addition to aromatic compounds, and (4) HO* interaction with sulfur (S)-, nitrogen (N)-, or phosphorus (P)-atom-containing compounds. The GCM hypothesizes that an observed experimental rate constant for a given organic compound is the combined rate of all elementary reactions involving HO*, which can be estimated using the Arrhenius activation energy, E(a), and temperature. Each E(a) for those elementary reactions can be comprised of two parts: (1) a base part that includes a reactive bond in each reaction mechanism and (2) contributions from its neighboring functional groups. The GCM includes 66 group rate constants and 80 group contribution factors, which characterize each HO* reaction mechanism with steric effects of the chemical structure groups and impacts of the neighboring functional groups, respectively. Literature-reported experimental HO* rate constants for 310 and 124 compounds were used for calibration and prediction, respectively. The genetic algorithms were used to determine the group rate constants and group contribution factors. The group contribution factors for H-atom abstraction and HO* addition to the aromatic compounds were found to linearly correlate with the Taft constants, sigma*, and electrophilic substituent parameters, sigma+, respectively. The best calibrations for 83% (257 rate constants) and predictions for 62% (77

  10. Standard-model coupling constants from compositeness

    CERN Document Server

    Besprosvany, J

    2003-01-01

    A coupling-constant definition is given based on the compositeness property of some particle states with respect to the elementary states of other particles. It is applied in the context of the vector-spin-1/2-particle interaction vertices of a field theory, and the standard model. The definition reproduces Weinberg's angle in a grand-unified theory. One obtains coupling values close to the experimental ones for appropriate configurations of the standard-model vector particles, at the unification scale within grand-unified models, and at the electroweak breaking scale.

  11. Electron-ion dissociative recombination rate constants relevant to the Titan atmosphere and the Interstellar Medium

    Energy Technology Data Exchange (ETDEWEB)

    Osborne, David; Lawson, Patrick; Adams, Nigel, E-mail: ngadams@uga.edu [University of Georgia, Department of Chemistry, 101 Cedar St., Athens, Georgia 30602 (United States)

    2014-01-21

    Following the arrival of Cassini at Titan in 2004, the Titan atmosphere has been shown to contain large complex polycyclic-aromatic hydrocarbons. Since Cassini has provided a great deal of data, there exists a need for kinetic rate data to help with modeling this atmosphere. One type of kinetic data needed is electron-ion dissociative recombination (e-IDR) rate constants. These data are not readily available for larger compounds, such as naphthalene, or oxygen containing compounds, such as 1,4 dioxane or furan. Here, the rate constants for naphthalene, 1,4 dioxane, and furan have been measured and their temperature dependencies are determined when possible, using the University of Georgia's Variable Temperature Flowing Afterglow. The rate constants are compared with those previously published for other compounds; these show trends which illustrate the effects which multi-rings and oxygen heteroatoms substitutions have upon e-IDR rate constants.

  12. Insurance Calculation of Bankruptcy Probability of Constant Interest Rate Model under Dependent Negative%负相依下带常数利率模型的破产概率的保险计算

    Institute of Scientific and Technical Information of China (English)

    李明倩

    2014-01-01

    本文研究了负相依索赔条件下带常数利率的风险模型在随机区间上的破产问题,最终得到了该模型破产概率的渐进表达式。%This paper studies the risk model under conditions of constant interest rates negatively correlated claims in the bankruptcy issue random intervals, and finally get the asymptotic expression of the model the probability of bankruptcy.

  13. Statistical Modelling of the Soil Dielectric Constant

    Science.gov (United States)

    Usowicz, Boguslaw; Marczewski, Wojciech; Bogdan Usowicz, Jerzy; Lipiec, Jerzy

    2010-05-01

    The dielectric constant of soil is the physical property being very sensitive on water content. It funds several electrical measurement techniques for determining the water content by means of direct (TDR, FDR, and others related to effects of electrical conductance and/or capacitance) and indirect RS (Remote Sensing) methods. The work is devoted to a particular statistical manner of modelling the dielectric constant as the property accounting a wide range of specific soil composition, porosity, and mass density, within the unsaturated water content. Usually, similar models are determined for few particular soil types, and changing the soil type one needs switching the model on another type or to adjust it by parametrization of soil compounds. Therefore, it is difficult comparing and referring results between models. The presented model was developed for a generic representation of soil being a hypothetical mixture of spheres, each representing a soil fraction, in its proper phase state. The model generates a serial-parallel mesh of conductive and capacitive paths, which is analysed for a total conductive or capacitive property. The model was firstly developed to determine the thermal conductivity property, and now it is extended on the dielectric constant by analysing the capacitive mesh. The analysis is provided by statistical means obeying physical laws related to the serial-parallel branching of the representative electrical mesh. Physical relevance of the analysis is established electrically, but the definition of the electrical mesh is controlled statistically by parametrization of compound fractions, by determining the number of representative spheres per unitary volume per fraction, and by determining the number of fractions. That way the model is capable covering properties of nearly all possible soil types, all phase states within recognition of the Lorenz and Knudsen conditions. In effect the model allows on generating a hypothetical representative of

  14. ESTIMATION OF PHOSPHATE ESTER HYDROLYSIS RATE CONSTANTS. II. ACID AND GENERAL BASE CATALYZED HYDROLYSIS

    Science.gov (United States)

    SPARC (SPARC Performs Automated Reasoning in Chemistry) chemical reactivity models were extended to calculate acid and neutral hydrolysis rate constants of phosphate esters in water. The rate is calculated from the energy difference between the initial and transition states of a ...

  15. Universality of thermodynamic constants governing biological growth rates.

    Directory of Open Access Journals (Sweden)

    Ross Corkrey

    Full Text Available BACKGROUND: Mathematical models exist that quantify the effect of temperature on poikilotherm growth rate. One family of such models assumes a single rate-limiting 'master reaction' using terms describing the temperature-dependent denaturation of the reaction's enzyme. We consider whether such a model can describe growth in each domain of life. METHODOLOGY/PRINCIPAL FINDINGS: A new model based on this assumption and using a hierarchical Bayesian approach fits simultaneously 95 data sets for temperature-related growth rates of diverse microorganisms from all three domains of life, Bacteria, Archaea and Eukarya. Remarkably, the model produces credible estimates of fundamental thermodynamic parameters describing protein thermal stability predicted over 20 years ago. CONCLUSIONS/SIGNIFICANCE: The analysis lends support to the concept of universal thermodynamic limits to microbial growth rate dictated by protein thermal stability that in turn govern biological rates. This suggests that the thermal stability of proteins is a unifying property in the evolution and adaptation of life on earth. The fundamental nature of this conclusion has importance for many fields of study including microbiology, protein chemistry, thermal biology, and ecological theory including, for example, the influence of the vast microbial biomass and activity in the biosphere that is poorly described in current climate models.

  16. Quantum Mechanics Rate Constant for the N+ND Reaction

    Institute of Scientific and Technical Information of China (English)

    Ai-jie Zhang; Guo-zhong He

    2011-01-01

    We present nonadiabatic quantum dynamical calculations on the two coupled potential energy surfaces (12A' and 22A') [J.Theor.Comput.Chem.8,849 (2009)] for the reaction.Initial state-resolved reaction probabilities and cross sections for the N+ND→N2+D reaction and N'+ND→N+N'D reaction for collision energies of 5 meV to 1.0 eV are determined,respectively.It is found that the N+ND→N2+D reaction is dominated in the N+ND reaction.In addition,we obtained the rate constants for the N+ND→N2+D reaction which demand further experimental investigations.

  17. Efficient calculation of rate constants: Downhill versus uphill sampling

    Science.gov (United States)

    Klenin, Konstantin V.

    2014-08-01

    The classical transition state theory (TST), together with the notion of transmission coefficient, provides a useful tool for calculation of rate constants for rare events. However, in complex biomolecular reactions, such as protein folding, it is difficult to find a good reaction coordinate, so the transition state is ill-defined. In this case, other approaches are more popular, such as the transition interface sampling (TIS) and the forward flux sampling (FFS). Here, we show that the algorithms developed in the frames of TIS and FFS can be successfully applied, after a modification, for calculation of the transmission coefficient. The new procedure (which we call "downhill sampling") is more efficient in comparison with the traditional TIS and FFS ("uphill sampling") even if the reaction coordinate is bad. We also propose a new computational scheme that combines the advantages of TST, TIS, and FFS.

  18. DILATANCY BEHAVIOR IN CONSTANT STRAIN RATE CONSOLIDATION TEST

    Directory of Open Access Journals (Sweden)

    Berty Sompie

    2006-01-01

    Full Text Available Subjected to remolded young clay, this paper shows that a lot of time dependent behavior in the standard consolidation (SC and constant strain rate consolidation (CSRC tests is represented systematically by a simple assumption concerning the time dependency of dilatancy. In the SC test, at the first stage of each loading step little dilatancy takes place and dilatancy begins to occur several minutes after step loading. In CSRC test, some time period after the stress state has entered the normally consolidated region, dilatancy tends to occur rapidly with the increase in stress ratio. Since most of dilatancy has taken place at the earlier stage of consolidation, little dilatancy occurs at the latter stage of CSRC process. This tendency makes the specimen stiffer with the passage of time, and makes the vertical pressure and pore pressure increase substantially at the last stage of CSRC process. Consideration to such behavior may be effective to correctly interpret the result of CSRC test.

  19. Extraction of elementary rate constants from global network analysis of E. coli central metabolism

    Directory of Open Access Journals (Sweden)

    Broderick Gordon

    2008-05-01

    Full Text Available Abstract Background As computational performance steadily increases, so does interest in extending one-particle-per-molecule models to larger physiological problems. Such models however require elementary rate constants to calculate time-dependent rate coefficients under physiological conditions. Unfortunately, even when in vivo kinetic data is available, it is often in the form of aggregated rate laws (ARL that do not specify the required elementary rate constants corresponding to mass-action rate laws (MRL. There is therefore a need to develop a method which is capable of automatically transforming ARL kinetic information into more detailed MRL rate constants. Results By incorporating proteomic data related to enzyme abundance into an MRL modelling framework, here we present an efficient method operating at a global network level for extracting elementary rate constants from experiment-based aggregated rate law (ARL models. The method combines two techniques that can be used to overcome the difficult properties in parameterization. The first, a hybrid MRL/ARL modelling technique, is used to divide the parameter estimation problem into sub-problems, so that the parameters of the mass action rate laws for each enzyme are estimated in separate steps. This reduces the number of parameters that have to be optimized simultaneously. The second, a hybrid algebraic-numerical simulation and optimization approach, is used to render some rate constants identifiable, as well as to greatly narrow the bounds of the other rate constants that remain unidentifiable. This is done by incorporating equality constraints derived from the King-Altman and Cleland method into the simulated annealing algorithm. We apply these two techniques to estimate the rate constants of a model of E. coli glycolytic pathways. The simulation and statistical results show that our innovative method performs well in dealing with the issues of high computation cost, stiffness, local

  20. Empirical correlation for prediction of the elutriation rate constant

    Directory of Open Access Journals (Sweden)

    Stojkovski Valentino

    2003-01-01

    Full Text Available In vessels containing fluidized solids, the gas leaving carries some suspended particles. This flux of solids is called entrainment, E or carryover and the bulk density of solids on this leaving gas stream is called the holdup. For design we need to know the rate of this entrainment and the size distribution of these entrained particles Rim in relation to the size distribution in the bed, Rib, as well as the variation of both these quantities with gas and solids properties, gas flow rate, bed geometry and location of the leaving gas stream. Steady-state elutriation experiments have been done in a fluidized bed 0,2 m diameter by 2,94 m high freeboard with superficial gas velocities up to 1 m/s using solids ranging in mean size from 0,15 to 0,58 mm and with particle density 2660 kg/m3. When the fine and coarse particles were mixed, the total entrainment flux above the freeboard was increased. None of the published correlations for estimating the elutriation rate constant were useful. A new simple equation, which is developed on the base of experimental results and theory of dimensional analyses, is presented.

  1. Systematic Angle Random Walk Estimation of the Constant Rate Biased Ring Laser Gyro

    Directory of Open Access Journals (Sweden)

    Guohu Feng

    2013-02-01

    Full Text Available An actual account of the angle random walk (ARW coefficients of gyros in the constant rate biased rate ring laser gyro (RLG inertial navigation system (INS is very important in practical engineering applications. However, no reported experimental work has dealt with the issue of characterizing the ARW of the constant rate biased RLG in the INS. To avoid the need for high cost precise calibration tables and complex measuring set-ups, the objective of this study is to present a cost-effective experimental approach to characterize the ARW of the gyros in the constant rate biased RLG INS. In the system, turntable dynamics and other external noises would inevitably contaminate the measured RLG data, leading to the question of isolation of such disturbances. A practical observation model of the gyros in the constant rate biased RLG INS was discussed, and an experimental method based on the fast orthogonal search (FOS for the practical observation model to separate ARW error from the RLG measured data was proposed. Validity of the FOS-based method was checked by estimating the ARW coefficients of the mechanically dithered RLG under stationary and turntable rotation conditions. By utilizing the FOS-based method, the average ARW coefficient of the constant rate biased RLG in the postulate system is estimated. The experimental results show that the FOS-based method can achieve high denoising ability. This method estimate the ARW coefficients of the constant rate biased RLG in the postulate system accurately. The FOS-based method does not need precise calibration table with high cost and complex measuring set-up, and Statistical results of the tests will provide us references in engineering application of the constant rate biased RLG INS.

  2. Rate constants for 1,5- and 1,6-hydrogen atom transfer reactions of mono-, di-, and tri-aryl-substituted donors, models for hydrogen atom transfers in polyunsaturated fatty acid radicals.

    Science.gov (United States)

    DeZutter, Christopher B; Horner, John H; Newcomb, Martin

    2008-03-06

    Rate constants for 1,5- and 1,6-hydrogen atom transfer reactions in models of polyunsaturated fatty acid radicals were measured via laser flash photolysis methods. Photolyses of PTOC (pyridine-2-thioneoxycarbonyl) ester derivatives of carboxylic acids gave primary alkyl radicals that reacted by 1,5-hydrogen transfer from mono-, di-, and tri-aryl-substituted positions or 1,6-hydrogen transfer from di- and tri-aryl-substituted positions to give UV-detectable products. Rate constants for reactions in acetonitrile at room temperature ranged from 1 x 10(4) to 4 x 10(6) s(-1). The activation energies for a matched pair of 1,5- and 1,6-hydrogen atom transfers giving tri-aryl-substituted radicals were approximately equal, as were the primary kinetic isotope effects, but the 1,5-hydrogen atom transfer reaction was 1 order of magnitude faster at room temperature than the 1,6-hydrogen atom transfer reaction due to a less favorable entropy of activation for the 1,6-transfer reaction. Solvent effects on the rate constants for the 1,5-hydrogen atom transfer reaction of the 2-[2-(diphenylmethyl)phenyl]ethyl radical at ambient temperature were as large as a factor of 2 with the reaction increasing in rate in lower polarity solvents. Hybrid density functional theory computations for the 1,5- and 1,6-hydrogen atom transfers of the tri-aryl-substituted donors were in qualitative agreement with the experimental results.

  3. Reaction mechanisms and rate constants of waste degradation in landfill bioreactor systems with enzymatic-enhancement.

    Science.gov (United States)

    Jayasinghe, P A; Hettiaratchi, J P A; Mehrotra, A K; Kumar, S

    2014-06-01

    Augmenting leachate before recirculation with peroxidase enzymes is a novel method to increase the available carbon, and therefore the food supply to microorganisms at the declining phase of the anaerobic landfill bioreactor operation. In order to optimize the enzyme-catalyzed leachate recirculation process, it is necessary to identify the reaction mechanisms and determine rate constants. This paper presents a kinetic model developed to ascertain the reaction mechanisms and determine the rate constants for enzyme catalyzed anaerobic waste degradation. The maximum rate of reaction (Vmax) for MnP enzyme-catalyzed reactors was 0.076 g(TOC)/g(DS).day. The catalytic turnover number (k(cat)) of the MnP enzyme-catalyzed was 506.7 per day while the rate constant (k) of the un-catalyzed reaction was 0.012 per day.

  4. In vivo Target Residence Time and Kinetic Selectivity: The Association Rate Constant as Determinant.

    Science.gov (United States)

    de Witte, Wilhelmus E A; Danhof, Meindert; van der Graaf, Piet H; de Lange, Elizabeth C M

    2016-10-01

    It is generally accepted that, in conjunction with pharmacokinetics, the first-order rate constant of target dissociation is a major determinant of the time course and duration of in vivo target occupancy. Here we show that the second-order rate constant of target association can be equally important. On the basis of the commonly used mathematical models for drug-target binding, it is shown that a high target association rate constant can increase the (local) concentration of the drug, which decreases the rate of decline of target occupancy. The increased drug concentration can also lead to increased off-target binding and decreased selectivity. Therefore, the kinetics of both target association and dissociation need to be taken into account in the selection of drug candidates with optimal pharmacodynamic properties. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Requirement of Working Stably of Compound Negative Binomial Risk Model with Constant Interest rate%常利率复合负二项风险模型下稳定经营的必要条件

    Institute of Scientific and Technical Information of China (English)

    乔克林; 高渊; 张宁

    2015-01-01

    Assume that insurance companies began to hold capital to u,with constane δ is accumulation of interest rates,and policy number always obey hegative binomia process,manage compensate total number follows poisson process. we give the compound negative binomial risk model with constant interest rate and the requirement of insur-ance company working stably.%假设保险公司刚开始持有的资本为u,以常数δ为利率积累,并且保单总份数服从负二项过程,理赔总次数服从Poisson过程,给出常利率复合负二项风险模型以及稳定经营的必要条件。

  6. Measurements of Creep Internal Stress Based on Constant Strain Rate and Its Application to Engineering

    Institute of Scientific and Technical Information of China (English)

    TAO Wen-liang; WEI Tao

    2006-01-01

    This research is carried out on the basis of Constant Strain Rate(CSR) to measure creep internal stress. Measurements of creep internal stress are conducted on the material test machine by using the CSR method. A mathematical model of creep internal stress is also proposed and its application is presented in this paper.

  7. Modelling heart rate kinetics.

    Science.gov (United States)

    Zakynthinaki, Maria S

    2015-01-01

    The objective of the present study was to formulate a simple and at the same time effective mathematical model of heart rate kinetics in response to movement (exercise). Based on an existing model, a system of two coupled differential equations which give the rate of change of heart rate and the rate of change of exercise intensity is used. The modifications introduced to the existing model are justified and discussed in detail, while models of blood lactate accumulation in respect to time and exercise intensity are also presented. The main modification is that the proposed model has now only one parameter which reflects the overall cardiovascular condition of the individual. The time elapsed after the beginning of the exercise, the intensity of the exercise, as well as blood lactate are also taken into account. Application of the model provides information regarding the individual's cardiovascular condition and is able to detect possible changes in it, across the data recording periods. To demonstrate examples of successful numerical fit of the model, constant intensity experimental heart rate data sets of two individuals have been selected and numerical optimization was implemented. In addition, numerical simulations provided predictions for various exercise intensities and various cardiovascular condition levels. The proposed model can serve as a powerful tool for a complete means of heart rate analysis, not only in exercise physiology (for efficiently designing training sessions for healthy subjects) but also in the areas of cardiovascular health and rehabilitation (including application in population groups for which direct heart rate recordings at intense exercises are not possible or not allowed, such as elderly or pregnant women).

  8. Modelling heart rate kinetics.

    Directory of Open Access Journals (Sweden)

    Maria S Zakynthinaki

    Full Text Available The objective of the present study was to formulate a simple and at the same time effective mathematical model of heart rate kinetics in response to movement (exercise. Based on an existing model, a system of two coupled differential equations which give the rate of change of heart rate and the rate of change of exercise intensity is used. The modifications introduced to the existing model are justified and discussed in detail, while models of blood lactate accumulation in respect to time and exercise intensity are also presented. The main modification is that the proposed model has now only one parameter which reflects the overall cardiovascular condition of the individual. The time elapsed after the beginning of the exercise, the intensity of the exercise, as well as blood lactate are also taken into account. Application of the model provides information regarding the individual's cardiovascular condition and is able to detect possible changes in it, across the data recording periods. To demonstrate examples of successful numerical fit of the model, constant intensity experimental heart rate data sets of two individuals have been selected and numerical optimization was implemented. In addition, numerical simulations provided predictions for various exercise intensities and various cardiovascular condition levels. The proposed model can serve as a powerful tool for a complete means of heart rate analysis, not only in exercise physiology (for efficiently designing training sessions for healthy subjects but also in the areas of cardiovascular health and rehabilitation (including application in population groups for which direct heart rate recordings at intense exercises are not possible or not allowed, such as elderly or pregnant women.

  9. Modelling Heart Rate Kinetics

    Science.gov (United States)

    Zakynthinaki, Maria S.

    2015-01-01

    The objective of the present study was to formulate a simple and at the same time effective mathematical model of heart rate kinetics in response to movement (exercise). Based on an existing model, a system of two coupled differential equations which give the rate of change of heart rate and the rate of change of exercise intensity is used. The modifications introduced to the existing model are justified and discussed in detail, while models of blood lactate accumulation in respect to time and exercise intensity are also presented. The main modification is that the proposed model has now only one parameter which reflects the overall cardiovascular condition of the individual. The time elapsed after the beginning of the exercise, the intensity of the exercise, as well as blood lactate are also taken into account. Application of the model provides information regarding the individual’s cardiovascular condition and is able to detect possible changes in it, across the data recording periods. To demonstrate examples of successful numerical fit of the model, constant intensity experimental heart rate data sets of two individuals have been selected and numerical optimization was implemented. In addition, numerical simulations provided predictions for various exercise intensities and various cardiovascular condition levels. The proposed model can serve as a powerful tool for a complete means of heart rate analysis, not only in exercise physiology (for efficiently designing training sessions for healthy subjects) but also in the areas of cardiovascular health and rehabilitation (including application in population groups for which direct heart rate recordings at intense exercises are not possible or not allowed, such as elderly or pregnant women). PMID:25876164

  10. Likelihood inference of non-constant diversification rates with incomplete taxon sampling.

    Directory of Open Access Journals (Sweden)

    Sebastian Höhna

    Full Text Available Large-scale phylogenies provide a valuable source to study background diversification rates and investigate if the rates have changed over time. Unfortunately most large-scale, dated phylogenies are sparsely sampled (fewer than 5% of the described species and taxon sampling is not uniform. Instead, taxa are frequently sampled to obtain at least one representative per subgroup (e.g. family and thus to maximize diversity (diversified sampling. So far, such complications have been ignored, potentially biasing the conclusions that have been reached. In this study I derive the likelihood of a birth-death process with non-constant (time-dependent diversification rates and diversified taxon sampling. Using simulations I test if the true parameters and the sampling method can be recovered when the trees are small or medium sized (fewer than 200 taxa. The results show that the diversification rates can be inferred and the estimates are unbiased for large trees but are biased for small trees (fewer than 50 taxa. Furthermore, model selection by means of Akaike's Information Criterion favors the true model if the true rates differ sufficiently from alternative models (e.g. the birth-death model is recovered if the extinction rate is large and compared to a pure-birth model. Finally, I applied six different diversification rate models--ranging from a constant-rate pure birth process to a decreasing speciation rate birth-death process but excluding any rate shift models--on three large-scale empirical phylogenies (ants, mammals and snakes with respectively 149, 164 and 41 sampled species. All three phylogenies were constructed by diversified taxon sampling, as stated by the authors. However only the snake phylogeny supported diversified taxon sampling. Moreover, a parametric bootstrap test revealed that none of the tested models provided a good fit to the observed data. The model assumptions, such as homogeneous rates across species or no rate shifts, appear

  11. Rapid estimation of glucosinolate thermal degradation rate constants in leaves of Chinese kale and broccoli (Brassica oleracea) in two seasons.

    Science.gov (United States)

    Hennig, Kristin; Verkerk, Ruud; Bonnema, Guusje; Dekker, Matthijs

    2012-08-15

    Kinetic modeling was used as a tool to quantitatively estimate glucosinolate thermal degradation rate constants. Literature shows that thermal degradation rates differ in different vegetables. Well-characterized plant material, leaves of broccoli and Chinese kale plants grown in two seasons, was used in the study. It was shown that a first-order reaction is appropriate to model glucosinolate degradation independent from the season. No difference in degradation rate constants of structurally identical glucosinolates was found between broccoli and Chinese kale leaves when grown in the same season. However, glucosinolate degradation rate constants were highly affected by the season (20-80% increase in spring compared to autumn). These results suggest that differences in glucosinolate degradation rate constants can be due to variation in environmental as well as genetic factors. Furthermore, a methodology to estimate rate constants rapidly is provided to enable the analysis of high sample numbers for future studies.

  12. The C(3P) + NH3 reaction in interstellar chemistry: II. Low temperature rate constants and modeling of NH, NH2 and NH3 abundances in dense interstellar clouds

    CERN Document Server

    Hickson, Kevin M; Bourgalais, Jérémy; Capron, Michael; Picard, Sebastien D Le; Goulay, Fabien; Wakelam, Valentine

    2016-01-01

    A continuous supersonic flow reactor has been used to measure rate constants for the C + NH3 reaction over the temperature range 50 to 296 K. C atoms were created by the pulsed laser photolysis of CBr4. The kinetics of the title reaction were followed directly by vacuum ultra-violet laser induced fluorescence (VUV LIF) of C loss and through H formation. The experiments show unambiguously that the reaction is rapid at 296 K, becoming faster at lower temperatures, reaching a value of 1.8 10-10 cm3 molecule-1 s-1 at 50 K. As this reaction is not currently included in astrochemical networks, its influence on interstellar nitrogen hydride abundances is tested through a dense cloud model including gas-grain interactions. In particular, the effect of the ortho-to-para ratio of H2 which plays a crucial role in interstellar NH3 synthesis is examined.

  13. On the Temperature Dependence of the Rate Constant of the Bimolecular Reaction of two Hydrated Electrons

    Directory of Open Access Journals (Sweden)

    S.L. Butarbutar

    2013-08-01

    Full Text Available It has been a longstanding issue in the radiation chemistry of water that, even though H2 is a molecular product, its “escape” yield g(H2 increases with increasing temperature. A main source of H2 is the bimolecular reaction of two hydrated electrons (eaq. The temperature dependence of the rate constant of this reaction (k1, measured under alkaline conditions, reveals that the rate constant drops abruptly above ~150°C. Recently, it has been suggested that this temperature dependence should be regarded as being independent of pH and used in high-temperature modeling of near-neutral water radiolysis. However, when this drop in the eaq self-reaction rate constant is included in low (isolated spurs and high (cylindrical tracks linear energy transfer (LET modeling calculations, g(H2 shows a marked downward discontinuity at ~150°C which is not observed experimentally. The consequences of the presence of this discontinuity in g(H2 for both low and high LET radiation are briefly discussed in this communication. It is concluded that the applicability of the sudden drop in k1 observed at ~150°C in alkaline water to near-neutral water is questionable and that further measurements of the rate constant in pure water are highly desirable.

  14. Exergy analysis of integrated photovoltaic thermal solar water heater under constant flow rate and constant collection temperature modes

    NARCIS (Netherlands)

    Tiwari, Arvind; Dubey, Swapnil; Sandhu, G.S.; Sodha, M.S.; Anwar, S.I.

    2009-01-01

    In this communication, an analytical expression for the water temperature of an integrated photovoltaic thermal solar (IPVTS) water heater under constant flow rate hot water withdrawal has been obtained. Analysis is based on basic energy balance for hybrid flat plate collector and storage tank, resp

  15. Exergy analysis of integrated photovoltaic thermal solar water heater under constant flow rate and constant collection temperature modes

    NARCIS (Netherlands)

    Tiwari, A.; Dubey, Swapnil; Sandhu, G.S.; Sodha, M.S.; Anwar, S.I.

    2009-01-01

    In this communication, an analytical expression for the water temperature of an integrated photovoltaic thermal solar (IPVTS) water heater under constant flow rate hot water withdrawal has been obtained. Analysis is based on basic energy balance for hybrid flat plate collector and storage tank, resp

  16. Exergy analysis of integrated photovoltaic thermal solar water heater under constant flow rate and constant collection temperature modes

    NARCIS (Netherlands)

    Tiwari, A.; Dubey, Swapnil; Sandhu, G.S.; Sodha, M.S.; Anwar, S.I.

    2009-01-01

    In this communication, an analytical expression for the water temperature of an integrated photovoltaic thermal solar (IPVTS) water heater under constant flow rate hot water withdrawal has been obtained. Analysis is based on basic energy balance for hybrid flat plate collector and storage tank,

  17. Endo- and exocytic rate constants for spontaneous and protein kinase C-activated T cell receptor cycling

    DEFF Research Database (Denmark)

    Menné, Charlotte; Møller Sørensen, Tine; Siersma, Volkert

    2002-01-01

    To determine the rate constants of spontaneous and activated TCR cycling, we examined TCR endo- and exocytosis in the human T cell line Jurkat by three different methods. Using a simple kinetic model for TCR cycling and non-linear regression analyses, we found that the spontaneous endocytic rate......)) whereas the exocytic rate constant was unaffected. Thus, the TCR becomes a rapidly cycling receptor with kinetics similar to classical cycling receptors subsequent to PKC activation. This results in a reduction of the half-life of cell surface expressed TCR from approximately 58 to 6 min and allows rapid...... constant of the TCR was low (approximately 0.012 min(-1)) whereas the spontaneous exocytic rate constant was similar to that of other cycling receptors (approximately 0.055 min(-1)). Following protein kinase C activation (PKC) the endocytic rate constant was increased tenfold (to approximately 0.128 min(-1...

  18. KABAM Version 1.0 User's Guide and Technical Documentation - Appendix H - Methods for Estimating Metabolism Rate Constant

    Science.gov (United States)

    Appendix H of KABAM Version 1.0 documentation related to estimating the metabolism rate constant. KABAM is a simulation model used to predict pesticide concentrations in aquatic regions for use in exposure assessments.

  19. EOQ Model for Deteriorating Items with non-constant Deteriorating Rate under Inflation%通货膨胀下非常数变质率的易变质商品的EOQ模型

    Institute of Scientific and Technical Information of China (English)

    文晓巍

    2011-01-01

    Inventory of deteriorating items has been one of the optimal EOQ model problems challenged by many researchers for several decades.An EOQ model with non-constant deteriorating rate under inflation and permissible delay payments is constructed,and the total cost of the inventory of deteriorating items is analyzed.Then an optimal inventory replenishment policy and algorithms are proposed.Numerical examples are provided to illustrate the theory.%易变质商品的库存问题成为最近几十年中备受学者们关注的EOQ模型优化问题。本文构建了通货膨胀下允许延期支付的非常数变质率的易变质商品的EOQ模型,并分析了对应的总成本函数,同时,给出了总库存成本最小的最优库存补充决策和算法。最后给出了算例进行说明。

  20. On the multi-compound Poisson-Geometric risk model of multi-type-insurance with a constant interest rate%多险种多复合Poisson-Geometric过程的常利率风险模型

    Institute of Scientific and Technical Information of China (English)

    李碧云; 余国胜

    2015-01-01

    A multi-compound Poisson-Geometric risk model of multi-type-insurance with a constant interest rate was constructed,and the integral-differential equation of the survival probability under this model was derived.Using the integral-differential equation we established,we got the explicit expression about the Laplace transforms of the survival probability and the exact solution was given when the initial surplus was zero and there were no premium incomes. Finally,we gave a numerical example to illustrate our results.%建立多险种多复合Poisson-Geometric过程的常利率风险模型,得到该模型的生存概率所满足的积分-微分方程.当无保费收入时,由所得到的积分-微分方程推出生存概率的Laplace变换的表达式,对于初始盈余为0时,得到生存概率的精确解.并给出具体的数值计算的实例以解释我们的结果.①

  1. Exergy analysis of integrated photovoltaic thermal solar water heater under constant flow rate and constant collection temperature modes

    Energy Technology Data Exchange (ETDEWEB)

    Tiwari, Arvind [Department of Design, Production and Management, University of Twente, Enschede (Netherlands); Dubey, Swapnil; Sandhu, G.S. [Centre for Energy Studies, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016 (India); Sodha, M.S. [Department of Education and Physics, Lucknow University, Lucknow 226007 (India); Anwar, S.I. [Indian Institute of Sugar-cane Research, Lucknow, U.P. (India)

    2009-12-15

    In this communication, an analytical expression for the water temperature of an integrated photovoltaic thermal solar (IPVTS) water heater under constant flow rate hot water withdrawal has been obtained. Analysis is based on basic energy balance for hybrid flat plate collector and storage tank, respectively, in the terms of design and climatic parameters. Further, an analysis has also been extended for hot water withdrawal at constant collection temperature. Numerical computations have been carried out for the design and climatic parameters of the system used by Huang et al. [Huang BJ, Lin TH, Hung WC, Sun FS. Performance evaluation of solar photovoltaic/thermal systems. Sol Energy 2001; 70(5): 443-8]. It is observed that the daily overall thermal efficiency of IPVTS system increases with increase constant flow rate and decrease with increase of constant collection temperature. The exergy analysis of IPVTS system has also been carried out. It is further to be noted that the overall exergy and thermal efficiency of an integrated photovoltaic thermal solar system (IPVTS) is maximum at the hot water withdrawal flow rate of 0.006 kg/s. The hourly net electrical power available from the system has also been evaluated. (author)

  2. Absolute rate constants for the reaction of hypochlorous acid with protein side chains and peptide bonds

    DEFF Research Database (Denmark)

    Pattison, D I; Davies, Michael Jonathan

    2001-01-01

    , absolute second-order rate constants for the reactions of HOCl with protein side chains, model compounds, and backbone amide (peptide) bonds have been determined at physiological pH values. The reactivity of HOCl with potential reactive sites in proteins is summarized by the series: Met (3.8 x 10(7) M(-1......) x s(-1)) > backbone amides (10-10(-3) M(-1) x s(-1)) > Gln(0.03 M(-1) x s(-1)) approximately Asn (0.03 M(-1) x s(-1)). The rate constants for reaction of HOCl with backbone amides (peptide bonds) vary by 4 orders of magnitude with uncharged peptide bonds reacting more readily with HOCl than those...

  3. Rate constant for the reaction SO + BrO yields SO2 + Br

    Science.gov (United States)

    Brunning, J.; Stief, L.

    1986-01-01

    The rate of the radical-radical reaction SO + BrO yields SO2 + Br has been determined at 298 K in a discharge flow system near 1 torr pressure with detection of SO and BrO via collision-free sampling mass spectrometry. The rate constant was determined using two different methods: measuring the decay of SO radicals in the presence of an excess of BrO and measuring the decay of BrO radicals in excess SO. The results from the two methods are in reasonable agreement and the simple mean of the two values gives the recommended rate constant at 298 K, k = (5.7 + or - 2.0) x 10 to the -11th cu cm/s. This represents the first determination of this rate constant and it is consistent with a previously derived lower limit based on SO2 formation. Comparison is made with other radical-radical reactions involving SO or BrO. The reaction SO + BrO yields SO2 + Br is of interest for models of the upper atmosphere of the earth and provides a potential coupling between atmospheric sulfur and bromine chemistry.

  4. Ab-Initio Based Computation of Rate Constants for Spin Forbidden Metalloprotein-Substrate Reactions

    Science.gov (United States)

    Ozkanlar, Abdullah; Rodriguez, Jorge H.

    2007-03-01

    Some chemical and biochemical reactions are non-adiabatic processes whereby the total spin angular momentum, before and after the reaction, is not conserved. These are named spin- forbidden reactions. The application of ab-initio methods, such as spin density functional theory (SDFT), to the prediction of rate constants is a challenging task of fundamental and practical importance. We apply non-adiabatic transition state theory (NA-TST) in conjuntion with SDFT to predict the rate constant of the spin- forbidden recombination of carbon monoxide with iron tetracarbonyl. To model the surface hopping probability between singlet and triplet states, the Landau-Zener formalism is used. The lowest energy point for singlet-triplet crossing, known as minimum energy crossing point (MECP), was located and used to compute, in a semi-quantum approach, reaction rate constants at 300 K. The predicted rates are in very good agreement with experiment. In addition, we present results for the spin- forbidden ligand binding reactions of iron-containing heme proteins such as myoglobin.

  5. Characteristic thermal constant and dimensionless heating rate. The links to optimum heating rate in GC

    Science.gov (United States)

    Blumberg; Klee

    2000-09-01

    An initial step in the quest of deriving a generalized approach to optimization of a temperature program in gas chromatography is presented. Central to this is the introduction of a dimensionless heating rate, r. As a first step to defining r, a characteristic thermal constant, thetachar, defined as thetachar = -dT/dk at k = 1, where T and k are, respectively, column temperature and solute retention factor, is introduced and evaluated for our own experimental data and for thermodynamic data from the literature. It was determined that, for silicone stationary phases with a phase ratio of 250, thetachar ranged from about 23 degrees C for low molecular weight hydrocarbons such as dimethylpropane to about 45 degrees C for high molecular weight pesticides such as mirex. It was also found that, for a particular solute and a stationary phase type, a 2 orders of magnitude increase in the film thickness caused only about a 2-fold increase in the characteristic thermal constant. Using thetachar as a fundamental temperature unit in GC and void time as a fundamental time unit, a dimensionless heating rate is introduced and its potential utility for the evaluation of the separation-speed tradeoffs in a temperature-programmed GC is demonstrated.

  6. THE C({sup 3}P) + NH{sub 3} REACTION IN INTERSTELLAR CHEMISTRY. II. LOW TEMPERATURE RATE CONSTANTS AND MODELING OF NH, NH{sub 2}, AND NH{sub 3} ABUNDANCES IN DENSE INTERSTELLAR CLOUDS

    Energy Technology Data Exchange (ETDEWEB)

    Hickson, Kevin M.; Loison, Jean-Christophe [Université de Bordeaux, Institut des Sciences Moléculaires, UMR 5255, F-33400 Talence (France); Bourgalais, Jérémy; Capron, Michael; Picard, Sébastien D. Le [Institut de Physique de Rennes, Astrophysique de Laboratoire, UMR CNRS 6251, Université de Rennes 1, Campus de Beaulieu, F-35042 Rennes Cedex (France); Goulay, Fabien [Department of Chemistry, West Virginia University, Morgantown, WV 26506 (United States); Wakelam, Valentine, E-mail: kevin.hickson@u-bordeaux.fr [Université de Bordeaux, Laboratoire d’Astrophysique de Bordeaux, UMR 5804, F-33270 Floirac (France)

    2015-10-20

    A continuous supersonic flow reactor has been used to measure rate constants for the C({sup 3}P) + NH{sub 3} reaction over the temperature range 50–296 K. C({sup 3}P) atoms were created by the pulsed laser photolysis of CBr{sub 4}. The kinetics of the title reaction were followed directly by vacuum ultra-violet laser induced fluorescence of C({sup 3}P) loss and through H({sup 2}S) formation. The experiments show unambiguously that the reaction is rapid at 296 K, becoming faster at lower temperatures, reaching a value of (1.8 ± 0.2) × 10{sup −10} cm{sup 3} molecule{sup −1} s{sup −1} at 50 K. As this reaction is not currently included in astrochemical networks, its influence on interstellar nitrogen hydride abundances is tested through a dense cloud model including gas–grain interactions. In particular, the effect of the ortho-to-para ratio of H{sub 2}, which plays a crucial role in interstellar NH{sub 3} synthesis, is examined.

  7. Rate constants of reactions of {kappa}-carrageenan with hydrated electron and hydroxyl radical

    Energy Technology Data Exchange (ETDEWEB)

    Abad, L.V. [Nuclear Professional School, School of Engineering Laboratory, University of Tokyo, 2-22 Shirakata-Shirane, Tokai, Naka, Ibaraki 319-1188 (Japan); Philippine Nuclear Research Institute, Commonwealth Avenue, Diliman, Quezon City (Philippines)], E-mail: lvabad@pnri.dost.gov.ph; Saiki, S.; Kudo, H.; Muroya, Y.; Katsumura, Y. [Nuclear Professional School, School of Engineering Laboratory, University of Tokyo, 2-22 Shirakata-Shirane, Tokai, Naka, Ibaraki 319-1188 (Japan); Rosa, A.M. de la [Philippine Nuclear Research Institute, Commonwealth Avenue, Diliman, Quezon City (Philippines)

    2007-12-15

    The rate constants for the reactions of {kappa}-carrageenan with hydrated electron and hydroxyl radical was investigated by pulse radiolysis and laser photolysis. The kinetics of the reaction of hydrated electron indicates no seeming reaction with {kappa}-carrageenan. On the other hand, hydroxyl radical reacts very rapidly with {kappa}-carrageenan at a rate constant of approximately 1.2 x 10{sup 9} M{sup -1} s{sup -1}. This rate constant varies with pH.

  8. Mark-recapture models with parameters constant in time.

    Science.gov (United States)

    Jolly, G M

    1982-06-01

    The Jolly-Seber method, which allows for both death and immigration, is easy to apply but often requires a larger number of parameters to be estimated tha would otherwise be necessary. If (i) survival rate, phi, or (ii) probability of capture, p, or (iii) both phi and p can be assumed constant over the experimental period, models with a reduced number of parameters are desirable. In the present paper, maximum likelihood (ML) solutions for these three situations are derived from the general ML equations of Jolly [1979, in Sampling Biological Populations, R. M. Cormack, G. P. Patil and D. S. Robson (eds), 277-282]. A test is proposed for heterogeneity arising from a breakdown of assumptions in the general Jolly-Seber model. Tests for constancy of phi and p are provided. An example is given, in which these models are fitted to data from a local butterfly population.

  9. Rate constants for the formation of SiO by radiative association

    Science.gov (United States)

    Cairnie, M.; Forrey, R. C.; Babb, J. F.; Stancil, P. C.; McLaughlin, B. M.

    2017-10-01

    Accurate molecular data for the low-lying states of SiO are computed and used to calculate rate constants for radiative association (RA) of Si and O. Einstein A-coefficients are also calculated for transitions between all of the bound and quasi-bound levels for each molecular state. The radiative widths are used together with elastic tunnelling widths to define effective RA rate constants which include both direct and indirect (inverse pre-dissociation) formation processes. The indirect process is evaluated for two kinetic models which represent limiting cases for astrophysical environments. The first case scenario assumes an equilibrium distribution of quasi-bound states and would be applicable whenever collisional and/or radiative excitation mechanisms are able to maintain the population. The second case scenario assumes that no excitation mechanisms are available which corresponds to the limit of zero radiation temperature and zero atomic density. Rate constants for SiO formation in realistic astrophysical environments would presumably lie between these two limiting cases.

  10. Biotransformation of trace organic chemicals during groundwater recharge: How useful are first-order rate constants?

    KAUST Repository

    Regnery, J.

    2015-05-29

    This study developed relationships between the attenuation of emerging trace organic chemicals (TOrC) during managed aquifer recharge (MAR) as a function of retention time, system characteristics, and operating conditions using controlled laboratory-scale soil column experiments simulating MAR. The results revealed that MAR performance in terms of TOrC attenuation is primarily determined by key environmental parameters (i.e. redox, primary substrate). Soil columns with suboxic and anoxic conditions performed poorly (i.e. less than 30% attenuation of moderately degradable TOrC) in comparison to oxic conditions (on average between 70-100% attenuation for the same compounds) within a residence time of three days. Given this dependency on redox conditions, it was investigated if key parameter-dependent rate constants are more suitable for contaminant transport modeling to properly capture the dynamic TOrC attenuation under field-scale conditions. Laboratory-derived first-order removal kinetics were determined for 19 TOrC under three different redox conditions and rate constants were applied to MAR field data. Our findings suggest that simplified first-order rate constants will most likely not provide any meaningful results if the target compounds exhibit redox dependent biotransformation behavior or if the intention is to exactly capture the decline in concentration over time and distance at field-scale MAR. However, if the intention is to calculate the percent removal after an extended time period and subsurface travel distance, simplified first-order rate constants seem to be sufficient to provide a first estimate on TOrC attenuation during MAR.

  11. Constant diversification rates of endemic gastropods in ancient Lake Ohrid: ecosystem resilience likely buffers environmental fluctuations

    Science.gov (United States)

    Föller, K.; Stelbrink, B.; Hauffe, T.; Albrecht, C.; Wilke, T.

    2015-12-01

    Ancient lakes represent key ecosystems for endemic freshwater species. This high endemic biodiversity has been shown to be mainly the result of intra-lacustrine diversification. Whereas the principle role of this mode of diversification is generally acknowledged, actual diversification rates in ancient lakes remain little understood. At least four types are conceivable. Diversification rates may be constant over time, they may fluctuate, rates may be higher in the initial phase of diversification, or there may be a pronounced lag phase between colonization and subsequent diversification. As understanding the tempo of diversification in ancient lake environments may help reveal the underlying processes that drive speciation and extinction, we here use the Balkan Lake Ohrid as a model system and the largest species flock in the lake, the non-pyrgulinid Hydrobiidae, as a model taxon to study changes in diversification rates over time together with the respective drivers. Based on phylogenetic, molecular-clock, lineage-through-time plot, and diversification-rate analyses we found that this potentially monophyletic group is comparatively old and that it most likely evolved with a constant diversification rate. Preliminary data of the SCOPSCO (Scientific Collaboration On Past Speciation Conditions in Lake Ohrid) deep-drilling program do indicate signatures of severe environmental/climatic perturbations in Lake Ohrid. However, so far there is no evidence for the occurrence of catastrophic environmental events. We therefore propose that the constant diversification rate observed in endemic gastropods has been caused by two factors: (i) a potential lack of catastrophic environmental events in Lake Ohrid and/or (ii) a probably high ecosystem resilience, buffering environmental changes. Parameters potentially contributing to the lake's high ecosystem resilience are its distinct bathymetry, ongoing tectonic activities, and karst hydrology. The current study not only

  12. Determination of Constitutive Model Constants from Cylinder Impact Tests

    Science.gov (United States)

    1987-12-01

    HONEYWELL, INC./ARMAMENT SYSTEMS DIVISION) FOR NAVAL SURFACE WARFARE CENTER RESEARCH AND TECHNOLOGY DEPARTMENT DECEMBER 1988 Approved for public release...primary application is for higher strain rates, and the strain rate constant was therefore selected to give better correlation with the higher strain...to that of the test data. The new constants (C and C2) were obtained in conjunction with the previous values of C. and C4, as talen from Reference 2

  13. Apparent Rate Constant for Diffusion-Controlled Three molecular (catalytic) reaction

    OpenAIRE

    Burlatsky, S. F.; Moreau, M

    1996-01-01

    We present simple explicit estimates for the apparent reaction rate constant for three molecular reactions, which are important in catalysis. For small concentrations and $d> 1$, the apparent reaction rate constant depends only on the diffusion coefficients and sizes of the particles. For small concentrations and $d\\le 1$, it is also time -- dependent. For large concentrations, it gains the dependence on concentrations.

  14. Competitive kinetics as a tool to determine rate constants for reduction of ferrylmyoglobin by food components

    DEFF Research Database (Denmark)

    Jongberg, Sisse; Lund, Marianne Nissen; Pattison, David I.

    2016-01-01

    . This approach allows determination of apparent rate constants for the oxidation of proteins by haem proteins of relevance to food oxidation and should be applicable to other systems. A similar approach has provided approximate apparent rate constants for the reduction of MbFe(IV)=O by catechin and green tea...

  15. Stability Analysis of GI/G/c/K Retrial Queue with Constant Retrial Rate

    CERN Document Server

    Avrachenkov, Konstantin

    2010-01-01

    We consider a GI/G/c/K-type retrial queueing system with constant retrial rate. The system consists of a primary queue and an orbit queue. The primary queue has $c$ identical servers and can accommodate the maximal number of $K$ jobs. If a newly arriving job finds the full primary queue, it joins the orbit. The original primary jobs arrive to the system according to a renewal process. The jobs have general i.i.d. service times. A job in front of the orbit queue retries to enter the primary queue after an exponentially distributed time independent of the orbit queue length. Telephone exchange systems, Medium Access Protocols and short TCP transfers are just some applications of the proposed queueing system. For this system we establish minimal sufficient stability conditions. Our model is very general. In addition, to the known particular cases (e.g., M/G/1/1 or M/M/c/c systems), the proposed model covers as particular cases the deterministic service model and the Erlang model with constant retrial rate. The l...

  16. Determination of the alpha-tocopherol inhibition rate constant for peroxidation in low-density lipoprotein.

    Science.gov (United States)

    Culbertson, Sean M; Antunes, Fernando; Havrilla, Christine M; Milne, Ginger L; Porter, Ned A

    2002-06-01

    This work reports an estimate of the inhibition rate constant (k(inh)) for alpha-tocopherol (alpha-TOH) in low-density lipoproteins (LDL) based on cholesteryl linoleate hydroperoxide products formed during autoxidation of intact lipoproteins. The ratio of cis,trans/trans,trans product hydroperoxides was determined during the consumption of the antioxidant. For a reasonable determination of k(inh) in LDL, the pro-oxidant behavior of alpha-TOH was minimized by oxidizing LDL with an unsymmetrical amphiphilic azo initiator which significantly reduces phase-transfer mediated pro-oxidant effects of alpha-TOH. This initiator delivers a more constant flux of initiator radicals into LDL lipid regions and permits determination of alpha-TOH k(inh) in LDL. Development of a tocopherol-mediated peroxidation (TMP) model and analysis of cholesteryl linoleate hydroperoxide cis,trans/trans,trans product ratios provided an estimated value for the inhibition rate constant of alpha-TOH in a lipoprotein of k(inh) = 5.9 +/- 0.5 x 10(5) M(-)(1) s(-)(1)

  17. Periods of constant and falling-rate for infrared drying of carrot slices Períodos de secagem constante e decrescente de fatias de cenoura por infravermelho

    Directory of Open Access Journals (Sweden)

    Fernando M. Botelho

    2011-08-01

    Full Text Available The aim of this work was to study the infrared drying process of carrot slices and to determine coefficients related to the heat and mass transfer of the process. Fresh carrots were used, dried until constant weight in a dryer with infrared heating source. Different models were utilized to fit the experimental data of constant and falling drying rate periods. It was verified that the coefficients of heat and mass transfer, during the constant drying rate, significantly increased with temperature on rise. The Diffusion Approximation, Two Terms, Midili and Verna models satisfactory represented the falling period of drying rate of carrot slices. The effective diffusion coefficient increased with temperature and this relationship can be represented by the Arrhenius equation, obtaining activation energy to the drying process of 29.092 kJ mol-1.Com este trabalho objetivou-se estudar o processo de secagem por infravermelho das fatias de cenoura e determinar alguns coeficientes referentes à transferência de calor e massa do processo. Utilizaram-se cenouras frescas, secadas até massa constante em um secador com fonte de aquecimento por infravermelho. Aos dados experimentais se ajustaram diferentes modelos para os períodos de taxa de secagem constante e decrescentes. Verificou-se que os coeficientes transferência de calor e massa, referentes ao período de secagem constante, aumentaram significativamente com o aumento da temperatura e que os modelos Aproximação da Difusão, Dois Termos, Midili e Verna representaram satisfatoriamente o período de secagem decrescente das fatias de cenoura. O coeficiente de difusão efetivo aumentou com a temperatura e esta relação pode ser representada pela Equação de Arrhenius, obtendo-se uma energia de ativação para o processo de secagem de 29,092 kJ mol-1.

  18. Methane combustion kinetic rate constants determination: an ill-posed inverse problem analysis

    Directory of Open Access Journals (Sweden)

    Bárbara D. L. Ferreira

    2013-01-01

    Full Text Available Methane combustion was studied by the Westbrook and Dryer model. This well-established simplified mechanism is very useful in combustion science, for computational effort can be notably reduced. In the inversion procedure to be studied, rate constants are obtained from [CO] concentration data. However, when inherent experimental errors in chemical concentrations are considered, an ill-conditioned inverse problem must be solved for which appropriate mathematical algorithms are needed. A recurrent neural network was chosen due to its numerical stability and robustness. The proposed methodology was compared against Simplex and Levenberg-Marquardt, the most used methods for optimization problems.

  19. Laser Measurements of the H Atom + Ozone Rate Constant at Atmospheric Temperatures

    Science.gov (United States)

    Liu, Y.; Smith, G. P.; Peng, J.; Reppert, K. J.; Callahan, S. L.

    2015-12-01

    The exothermic H + O3 reaction produces OH(v) Meinel band emissions, used to derive mesospheric H concentrations and chemical heating rates. We have remeasured its rate constant to reduce resulting uncertainties and the measurement extend to lower mesospheric temperatures using modern laser techniques. H atoms are produced by pulsed ultraviolet laser trace photolysis of O3, followed by reaction of O(D) with added H2. A second, delayed, frequency-mixed dye laser measures the reaction decay rate with the remaining ozone by laser induced fluorescence. We monitor either the H atom decay by 2 photon excitation at 205 nm and detection of red fluorescence, or the OH(v=9) product time evolution with excitation of the B-X (0,9) band at 237 nm and emission in blue B-A bands. By cooling the enclosed low pressure flow cell we obtained measurements from 146-305 K. Small kinetic modeling corrections are made for secondary regeneration of H atoms. The results fully confirm the current NASA JPL recommendation for this rate constant, and establish its extrapolation down to the lower temperatures of the mesosphere. This work was supported by the NSF Aeronomy Program and an NSF Physics summer REU student grant.

  20. Constant diversification rates of endemic gastropods in ancient Lake Ohrid: ecosystem resilience likely buffers environmental fluctuations

    Directory of Open Access Journals (Sweden)

    K. Föller

    2015-08-01

    Full Text Available Ancient lakes represent key ecosystems for endemic freshwater species. This high endemic biodiversity has been shown to be mainly the result of intra-lacustrine diversification. Whereas the principle role of this mode of diversification is generally acknowledged, actual diversification rates in ancient lakes remain little understood. At least four modes are conceivable. Diversification rates may be constant over time, they may fluctuate, rates may be higher in the initial phase of diversification, or there may be a pronounced lag phase between colonization and subsequent diversification. As understanding the tempo of diversification in ancient lake environments may help unrevealing the underlying processes that drive speciation and extinction, we here use the Balkan Lake Ohrid as a model system and the largest species flock in the lake, the non-pyrgulinid Hydrobiidae, as a model taxon to study changes in diversification rates over time together with the respective drivers. Based on phylogenetic, molecular-clock, lineage-through-time plot and diversification-rate analyses we found that this monophyletic group is comparatively old and that it most likely evolved with a constant diversification rate. Preliminary data of the SCOPSCO deep-drilling program do indicate signatures of severe environmental/climatic perturbations in Lake Ohrid. However, so far there is no evidence for the occurrence of catastrophic environmental events. We therefore propose that the rate homogeneity observed in endemic gastropods has been caused by two factors: (i a potential lack of catastrophic environmental events in Lake Ohrid and/or (ii a high ecosystem resilience, buffering environmental changes. Parameters potentially contributing to the lake's high ecosystem resilience are its distinct bathymetry, ongoing tectonic activities, and karst hydrology. The current study not only contributes to one of the overall goals of the SCOPSCO deep-drilling program – inferring

  1. Rate constants for the reaction of CF3O radicals with hydrocarbons at 298 K

    DEFF Research Database (Denmark)

    Kelly, C.; Treacy, J.; Sidebottom, H.W.;

    1993-01-01

    Rate constant ratios of the reactions of CF3O radicals with a number of hydrocarbons have been determined at 298 +/- 2 K and atmospheric pressure using a relative rate method. Using a previously determined value k(CF30 + C2H6) = 1.2 x 10(-12) cm3 molecule-1 s-1 these rate constant ratios provide......-1. The importance of the reactions of CF3O radicals with hydrocarbons under atmospheric conditions is discussed....

  2. Asymptotic solution of nonlinear moment equations for constant-rate aerosol reactors

    Directory of Open Access Journals (Sweden)

    B. D. Shaw

    1998-01-01

    Full Text Available Nonlinear evolution equations based upon moments of the aerosol size distribution function are solved asymptotically for constant-rate aerosol reactors (i.e., where condensible monomer is added at a constant rate operating in the free-molecular limit. The governing equations are nondimensionalized and a large parameter that controls nucleation behavior is identified. Asymptotic analyses are developed in terms of this parameter. Comparison of the asymptotic results with direct numerical integration of the governing equations is favorable. The asymptotic results provide a simplified analytical approach to estimating average particle sizes, particle number densities, and peak supersaturation values for constant-rate aerosol reactors.

  3. Absolute level-resolved reactive and inelastic rate constants in Li+Li2*

    Science.gov (United States)

    Coppage, Steven; Matei, Paula; Stewart, Brian

    2008-06-01

    We have used nuclear parity-changing collisions to obtain absolute level-to-level rate constants for reactive scattering in a triatomic system with identical nuclei. We have determined rate constants for the system 7Li2*(A 1Σu+)(vi=2,ji=19)+7Li-->7Li+7Li2*(A 1Σu+)(vf,jf), from laser-induced fluorescence spectra of lithium vapor in a heat pipe oven. Parity-preserving collisions yielded measurements of absolute rotationally and vibrationally inelastic rate constants as well. We compare the reactive rate constants with statistical prior distributions and the inelastic results with previously measured results on the Ne+7Li2* system.

  4. DETERMINATION OF HETEROGENEOUS ELECTRON TRANSFER RATE CONSTANTS AT MICROFABRICATED IRIDIUM ELECTRODES. (R825511C022)

    Science.gov (United States)

    There has been an increasing use of both solid metal and microfabricated iridium electrodes as substrates for various types of electroanalysis. However, investigations to determine heterogeneous electron transfer rate constants on iridium, especially at an electron beam evapor...

  5. DETERMINATION OF HETEROGENEOUS ELECTRON TRANSFER RATE CONSTANTS AT MICROFABRICATED IRIDIUM ELECTRODES. (R825511C022)

    Science.gov (United States)

    There has been an increasing use of both solid metal and microfabricated iridium electrodes as substrates for various types of electroanalysis. However, investigations to determine heterogeneous electron transfer rate constants on iridium, especially at an electron beam evapor...

  6. Low-energy electron impact cross-sections and rate constants of $NH_2$

    Indian Academy of Sciences (India)

    ANAND BHARADVAJA; SAVINDER KAUR; K L BALUJA

    2017-08-01

    This systematic study reports various electron impact cross-sections, rate constants and transport properties of $NH_2$ radical in the low-energy limit. The collision study is based on $R$-matrix formalism and involves the use of various scattering models employing different active spaces. Both electron excited inelasticcross-sections and resonances are found influenced by correlation and polarization effects. The non-relativistic molecular bremsstrahlung radiation cross-section for soft photons, binary encounter Bethe model-based ionization cross-sections and a few molecular properties of the target radical are also reported. The present calculations are found to be in agreement with the available results. This theoretical study provides a pathway to understand collision dynamics and generates data required in various fields of applied physics.

  7. A model for self-tuning the cosmological constant

    CERN Document Server

    Kim, J E; Lee, H M; Kim, Jihn E.; Kyae, Bumseok; Lee, Hyun Min

    2001-01-01

    The vanishing cosmological constant in the four dimensional space-time is obtained in a 5D Randall-Sundrum model with a brane (B1) located at $y=0$. The matter fields can be located at the brane. For settling any vacuum energy generated at the brane to zero, we need a three index antisymmetric tensor field $A_{MNP}$ with a specific form for the Lagrangian. For the self-tuning mechanism, the bulk cosmological constant should be negative.

  8. Simple Model with Time-Varying Fine-Structure ``Constant''

    Science.gov (United States)

    Berman, M. S.

    2009-10-01

    Extending the original version written in colaboration with L.A. Trevisan, we study the generalisation of Dirac's LNH, so that time-variation of the fine-structure constant, due to varying electrical and magnetic permittivities is included along with other variations (cosmological and gravitational ``constants''), etc. We consider the present Universe, and also an inflationary scenario. Rotation of the Universe is a given possibility in this model.

  9. Constant rate solutions for a fractured well with an asymmetric fracture

    Energy Technology Data Exchange (ETDEWEB)

    Berumen, S.; Rodriguez, F. [PEMEX E and P and UNAM, Ciudad Universitaria, Postal 70-256, 04510 Coyoacan (Mexico); Tiab, D. [School of Petroleum and Geological Engineering, The University of Oklahoma, 100 East Boyd Street, T301 SEC Norman, OK (United States)

    2000-01-01

    This paper presents solutions for the pressure response on hydraulically fractured wells flowing at constant flow rate through an asymmetric vertical fracture. The pressure behavior of wells intercepting asymmetric fractures of both infinite and finite conductivity was investigated by solving numerically and analytically the mathematical model. The new solutions developed for the dimensionless wellbore pressure under production at constant flow rate are presented in terms of an asymmetry factor {xi}. New curves for these systems were generated and the deviation from the classical solution was readily detected. Some qualitative criteria to interpret the intensity of this effect are provided. Results of our investigation indicated that at early times for fractures of moderate conductivity (C{sub D}<5) the characteristic slope of one fourth is present, except for cases of strong asymmetry (0.85<{xi}{<=}1) where no evidence of straight line having one fourth slope was observed. However, it was also detected that at intermediate fracture conductivities (5

  10. Determination of rapid chlorination rate constants by a stopped-flow spectrophotometric competition kinetics method.

    Science.gov (United States)

    Song, Dean; Liu, Huijuan; Qiang, Zhimin; Qu, Jiuhui

    2014-05-15

    Free chlorine is extensively used for water and wastewater disinfection nowadays. However, it still remains a big challenge to determine the rate constants of rapid chlorination reactions although competition kinetics and stopped-flow spectrophotometric (SFS) methods have been employed individually to investigate fast reaction kinetics. In this work, we proposed an SFS competition kinetics method to determine the rapid chlorination rate constants by using a common colorimetric reagent, N,N-diethyl-p-phenylenediamine (DPD), as a reference probe. A kinetic equation was first derived to estimate the reaction rate constant of DPD towards chlorine under a given pH and temperature condition. Then, on that basis, an SFS competition kinetics method was proposed to determine directly the chlorination rate constants of several representative compounds including tetracycline, ammonia, and four α-amino acids. Although Cl2O is more reactive than HOCl, its contribution to the overall chlorination kinetics of the test compounds could be neglected in this study. Finally, the developed method was validated through comparing the experimentally measured chlorination rate constants of the selected compounds with those obtained or calculated from literature and analyzing with Taft's correlation as well. This study demonstrates that the SFS competition kinetics method can measure the chlorination rate constants of a test compound rapidly and accurately.

  11. On the ambiguity of the reaction rate constants in multivariate curve resolution for reversible first-order reaction systems.

    Science.gov (United States)

    Schröder, Henning; Sawall, Mathias; Kubis, Christoph; Selent, Detlef; Hess, Dieter; Franke, Robert; Börner, Armin; Neymeyr, Klaus

    2016-07-13

    If for a chemical reaction with a known reaction mechanism the concentration profiles are accessible only for certain species, e.g. only for the main product, then often the reaction rate constants cannot uniquely be determined from the concentration data. This is a well-known fact which includes the so-called slow-fast ambiguity. This work combines the question of unique or non-unique reaction rate constants with factor analytic methods of chemometrics. The idea is to reduce the rotational ambiguity of pure component factorizations by considering only those concentration factors which are possible solutions of the kinetic equations for a properly adapted set of reaction rate constants. The resulting set of reaction rate constants corresponds to those solutions of the rate equations which appear as feasible factors in a pure component factorization. The new analysis of the ambiguity of reaction rate constants extends recent research activities on the Area of Feasible Solutions (AFS). The consistency with a given chemical reaction scheme is shown to be a valuable tool in order to reduce the AFS. The new methods are applied to model and experimental data.

  12. Application of an Artificial Neural Network to the Prediction of OH Radical Reaction Rate Constants for Evaluating Global Warming Potential.

    Science.gov (United States)

    Allison, Thomas C

    2016-03-03

    Rate constants for reactions of chemical compounds with hydroxyl radical are a key quantity used in evaluating the global warming potential of a substance. Experimental determination of these rate constants is essential, but it can also be difficult and time-consuming to produce. High-level quantum chemistry predictions of the rate constant can suffer from the same issues. Therefore, it is valuable to devise estimation schemes that can give reasonable results on a variety of chemical compounds. In this article, the construction and training of an artificial neural network (ANN) for the prediction of rate constants at 298 K for reactions of hydroxyl radical with a diverse set of molecules is described. Input to the ANN consists of counts of the chemical bonds and bends present in the target molecule. The ANN is trained using 792 (•)OH reaction rate constants taken from the NIST Chemical Kinetics Database. The mean unsigned percent error (MUPE) for the training set is 12%, and the MUPE of the testing set is 51%. It is shown that the present methodology yields rate constants of reasonable accuracy for a diverse set of inputs. The results are compared to high-quality literature values and to another estimation scheme. This ANN methodology is expected to be of use in a wide range of applications for which (•)OH reaction rate constants are required. The model uses only information that can be gathered from a 2D representation of the molecule, making the present approach particularly appealing, especially for screening applications.

  13. Tempo of Diversification of Global Amphibians: One-Constant Rate, One-Continuous Shift or Multiple-Discrete Shifts?

    Directory of Open Access Journals (Sweden)

    Youhua Chen

    2014-01-01

    Full Text Available In this brief report, alternative time-varying diversification rate models were fitted onto the phylogeny of global amphibians by considering one-constant-rate (OCR, one-continuous-shift (OCS and multiplediscrete- shifts (MDS situations. The OCS diversification model was rejected by γ statistic (γ=-5.556, p⁄ 0.001, implying the existence of shifting diversification rates for global amphibian phylogeny. Through model selection, MDS diversification model outperformed OCS and OCR models using “laser” package under R environment. Moreover, MDS models, implemented using another R package “MEDUSA”, indicated that there were sixteen shifts over the internal nodes for amphibian phylogeny. Conclusively, both OCS and MDS models are recommended to compare so as to better quantify rate-shifting trends of species diversification. MDS diversification models should be preferential for large phylogenies using “MEDUSA” package in which any arbitrary numbers of shifts are allowed to model.

  14. Construction of constant-Q viscoelastic model with three parameters

    Institute of Scientific and Technical Information of China (English)

    SUN Cheng-yu; YIN Xing-yao

    2007-01-01

    The popularly used viscoelastic models have some shortcomings in describing relationship between quality factor (Q) and frequency, which is not consistent with the observation data. Based on the theory of viscoelasticity, a new approach to construct constant-Q viscoelastic model in given frequency band with three parameters is developed. The designed model describes the frequency-independence feature of quality factor very well, and the effect of viscoelasticity on seismic wave field can be studied relatively accurate in theory with this model. Furthermore, the number of required parameters in this model has been reduced fewer than that of other constant-Q models, this can simplify the solution of the viscoelastic problems to some extent. At last, the accuracy and application range have been analyzed through numerical tests. The effect of viscoelasticity on wave propagation has been briefly illustrated through the change of frequency spectra and waveform in several different viscoelastic models.

  15. [On true and apparent Michaelis constants in enzymology. III. Is it linear dependence between apparent michaelis constant and limiting rate and is it possible to determine the substrate constant value using this dependence?].

    Science.gov (United States)

    Karakhim, S A

    2012-01-01

    The Slater-Bonner method which is used for graphic determination of substrate constant (Ks) by linear dependence of apparent Michaelis constant (Km(app)) on the limiting rate (V(app)) of enzyme-catalysed reactions with activator participation has been critically analysed. It has been shown that although it is possible to record the mechanisms of such reactions as a scheme similar to Michaelis-Menten model which allow to find correlation Km(app) and V(app) as equation Km(app) = Ks + V(app)/k1[E]0 ([E]0 is a total enzyme concentration, k1 is a rate constant of enzyme-substrate complex formation from free enzyme and substrate) in order to calculate Ks and individual rate constants (k1, k(-1)), but this approach for investigation of all reactions with activator participation ought not to be used. The above equation is not obeyed in general, it may be true for some mechanisms only or under certain ratios of kinetic parameters of enzyme-catalysed reactions.

  16. The Influence of Photolysis Rate Constants in Ozone Production for the Paso del Norte Region

    Science.gov (United States)

    Becerra, Fernando; Fitzgerald, Rosa

    2012-03-01

    In this research work we are focusing on understanding the relationship between photolysis rates and the photochemical ozone changes observed in the Paso del Norte region. The city of El Paso, Texas together with Ciudad Juarez, Mexico, forms the largest contiguous bi-national metropolitan area. This region suffers year-round ozone pollution events, and a better understanding is needed to mitigate them. Previous studies have found that ambient ozone concentrations tend to be higher on weekends rather than on weekdays, this phenomenon being referred to, as the ``weekend effect.'' If the ozone standard is exceeded more frequently on weekends, then this phenomenon must be considered in the design of ozone control strategies. In this work we investigate some of the most representative weekend ozone episodes at El Paso, TX, during the years 2009, 2010 and 2011 using the ozone photolysis rates. In this research the TUV radiative-transfer model is used to calculate the local photolysis rates and a UV MFRSR instrument is used to obtain experimental parameters. Seasonal variations and the weekday-weekend effect is studied. The results of this research will help to understand the underlying behavior of the photolysis rate constants when different atmospheric conditions are present.

  17. Deuterium recycling rate constants derived from plasma implantation/desorption shots in a martensitic steel surface

    Energy Technology Data Exchange (ETDEWEB)

    Sedano, L.A. [CIEMAT/DIAE, Madrid (Spain); European Commission/JRC, H-Materials Interaction Sector, Ispra (Italy); Esteban, G.A. [UPV-EHU/ETSIIT, D. Nuc. Eng. and Fluid Mec., Bilbao (Spain); Perujo, A. [European Commission/JRC, H-Materials Interaction Sector, Ispra (Italy)

    2001-12-04

    The recombination (K{sub 2}) and dissociation rate constants (K{sub 1}) are essential magnitudes for the tracking of tritium at the first wall (FW) of fusion reactors (FR). This paper presents our plasma implantation/recycling test, the modelling of the experiment and the results obtained for K{sub 2} and K{sub 1} in the case of a deuterium (D{sub 3}{sup +}/D{sub 2}{sup +}) plasma in the martensitic steel DIN 1.4914 (MANET). Once parasitic contributions were accounted, the D{sub 2} release from the target was seen to be surface limited. The values obtained for K{sub 1} and K{sub 2} show low dispersion on impinging flux and ion energies. For K{sub 1} a roughly constant value of 7 x 10{sup -6} mol Pa{sup -1} m{sup -2} s{sup -1} is derived. The obtained K{sub 2} is written as: K{sub 2} = 2.414 exp (-1571/RT) (m{sup 4} mol{sup -1} s{sup -1}), with R = 8.314 J mol{sup -1} K{sup -1}. Our activation energies agree with those existing in the literature derived from permeation experiments. High reflection coefficients are derived, which are in good agreement with the classical theory of ion scattering at low energy. (orig.)

  18. Rate constant and reaction coordinate of Trp-cage folding in explicit water

    NARCIS (Netherlands)

    Juraszek, J.; Bolhuis, P.G.

    2008-01-01

    We report rate constant calculations and a reaction coordinate analysis of the rate-limiting folding and unfolding process of the Trp-cage mini-protein in explicit solvent using transition interface sampling. Previous transition path sampling simulations revealed that in this (un)folding process the

  19. Microscopic Rate Constants of Crystal Growth from Molecular Dynamic Simulations Combined with Metadynamics

    Directory of Open Access Journals (Sweden)

    Dániel Kozma

    2012-01-01

    Full Text Available Atomistic simulation of crystal growth can be decomposed into two steps: the determination of the microscopic rate constants and a mesoscopic kinetic Monte Carlo simulation. We proposed a method to determine kinetic rate constants of crystal growth. We performed classical molecular dynamics on the equilibrium liquid/crystal interface of argon. Metadynamics was used to explore the free energy surface of crystal growth. A crystalline atom was selected at the interface, and it was displaced to the liquid phase by adding repulsive Gaussian potentials. The activation free energy of this process was calculated as the maximal potential energy density of the Gaussian potentials. We calculated the rate constants at different interfacial structures using the transition state theory. In order to mimic real crystallization, we applied a temperature difference in the calculations of the two opposite rate constants, and they were applied in kinetic Monte Carlo simulation. The novelty of our technique is that it can be used for slow crystallization processes, while the simple following of trajectories can be applied only for fast reactions. Our method is a possibility for determination of elementary rate constants of crystal growth that seems to be necessary for the long-time goal of computer-aided crystal design.

  20. Implementation of a microcanonical variational transition state theory for direct dynamics calculations of rate constants

    Institute of Scientific and Technical Information of China (English)

    王艳; 钱英; 冯文林; 刘若庄

    2003-01-01

    An implementation of the variational quantum RRKM program is presented to utilize the direct ab initio dynamics approach for calculating k(E, J), k(E) and k(T) within the framework of the microcanonical transition state (μTST) and microcanonical variational TST (μVT) theories. An algorithm including tunneling contributions in Beyer-Swinehart method for calculating microcanonical rate constants is also proposed. An efficient piece-wise interpolation method is developed to evaluate the Boltzmann integral in calculation of thermal rate constants. Calculations on several test reactions, namely the H(D)2CO→H(D)2 + CO, CH2CO→CH2 + CO and CH4 + H→CH3 + H2 reactions, show that the results are in good agreement with the previous rate constants calculations. This approach would require much less computational resource.

  1. Feasibility of constant dose rate VMAT in the treatment of nasopharyngeal cancer patients

    OpenAIRE

    Yu, Wenliang; Shang, Haijiao; Xie, Congying; Han, CE; Yi, Jinling; Zhou, Yongqiang; Jin, Xiance

    2014-01-01

    Purpose To investigate the feasibility of constant dose rate volumetric modulated arc therapy (CDR-VMAT) in the treatment of nasopharyngeal cancer (NPC) patients and to introduce rotational arc radiotherapy for linacs incapable of dose rate variation. Materials and methods Twelve NPC patients with various stages treated previously using variable dose rate (VDR) VMAT were enrolled in this study. CDR-VMAT, VDR-VMAT and mutlicriteria optimization (MCO) VMAT plans were generated for each patient ...

  2. Reply to the comment of S. Rayne on "QSAR model reproducibility and applicability: A case study of rate constants of hydroxyl radical reaction models applied to polybrominated diphenyl ethers and (benzo-)triazoles".

    Science.gov (United States)

    Gramatica, Paola; Kovarich, Simona; Roy, Partha Pratim

    2013-07-30

    We appreciate the interest of Dr. Rayne on our article and we completely agree that the dataset of (benzo-)triazoles, which were screened by the hydroxyl radical reaction quantitative structure-activity relationship (QSAR) model, was not only composed of benzo-triazoles but also included some simpler triazoles (without the condensed benzene ring), such as the chemicals listed by Dr. Rayne, as well as some related heterocycles (also few not aromatic). We want to clarify that in this article (as well as in other articles in which the same dataset was screened), for conciseness, the abbreviations (B)TAZs and BTAZs were used as general (and certainly too simplified) notations meaning an extended dataset of benzo-triazoles, triazoles, and related compounds. Copyright © 2013 Wiley Periodicals, Inc.

  3. Accurate quantum thermal rate constants for the three-dimensional H+H2 reaction

    Science.gov (United States)

    Park, Tae Jun; Light, J. C.

    1989-07-01

    The rate constants for the three-dimensional H+H2 reaction on the Liu-Siegbahn-Truhlar-Horowitz (LSTH) surface are calculated using Pack-Parker hyperspherical (APH) coordinates and a C2v symmetry adapted direct product discrete variable representation (DVR). The C2v symmetry decomposition and the parity decoupling on the basis are performed for the internal coordinate χ. The symmetry decomposition results in a block diagonal representation of the flux and Hamiltonian operators. The multisurface flux is introduced to represent the multichannel reactive flux. The eigenvalues and eigenvectors of the J=0 internal Hamiltonian are obtained by sequential diagonalization and truncation. The individual symmetry blocks of the flux operator are propagated by the corresponding blocks of the Hamiltonian, and the J=0 rate constant k0(T) is obtained as a sum of the rate constants calculated for each block. k0(T) is compared with the exact k0(T) obtained from thermal averaging of the J=0 reaction probabilities; the errors are within 5%-20% up to T=1500 K. The sequential diagonalization-truncation method reduces the size of the Hamiltonian greatly, but the resulting Hamiltonian matrix still describes the time evolution very accurately. For the J≠0 rate constant calculations, the truncated internal Hamiltonian eigenvector basis is used to construct reduced (JKJ) blocks of the Hamiltonian. The individual (JKJ) blocks are diagonalized neglecting Coriolis coupling and treating the off-diagonal KJ±2 couplings by second order perturbation theory. The full wave function is parity decoupled. The rate constant is obtained as a sum over J of (2J+1)kJ(T). The time evolution of the flux for J≠0 is again very accurately described to give a well converged rate constant.

  4. Prediction and dissection of widely-varying association rate constants of actin-binding proteins.

    Directory of Open Access Journals (Sweden)

    Xiaodong Pang

    Full Text Available Actin is an abundant protein that constitutes a main component of the eukaryotic cytoskeleton. Its polymerization and depolymerization are regulated by a variety of actin-binding proteins. Their functions range from nucleation of actin polymerization to sequestering G-actin in 1∶1 complexes. The kinetics of forming these complexes, with rate constants varying at least three orders of magnitude, is critical to the distinct regulatory functions. Previously we have developed a transient-complex theory for computing protein association mechanisms and association rate constants. The transient complex refers to an intermediate in which the two associating proteins have near-native separation and relative orientation but have yet to form short-range specific interactions of the native complex. The association rate constant is predicted as k(a = k(a0 e(-ΔG(el*/k(BT, where k(a0 is the basal rate constant for reaching the transient complex by free diffusion, and the Boltzmann factor captures the bias of long-range electrostatic interactions. Here we applied the transient-complex theory to study the association kinetics of seven actin-binding proteins with G-actin. These proteins exhibit three classes of association mechanisms, due to their different molecular shapes and flexibility. The 1000-fold k(a variations among them can mostly be attributed to disparate electrostatic contributions. The basal rate constants also showed variations, resulting from the different shapes and sizes of the interfaces formed by the seven actin-binding proteins with G-actin. This study demonstrates the various ways that actin-binding proteins use physical properties to tune their association mechanisms and rate constants to suit distinct regulatory functions.

  5. Exacerbating the Cosmological Constant Problem with Interacting Dark Energy Models

    Science.gov (United States)

    Marsh, M. C. David

    2017-01-01

    Future cosmological surveys will probe the expansion history of the Universe and constrain phenomenological models of dark energy. Such models do not address the fine-tuning problem of the vacuum energy, i.e., the cosmological constant problem (CCP), but can make it spectacularly worse. We show that this is the case for "interacting dark energy" models in which the masses of the dark matter states depend on the dark energy sector. If realized in nature, these models have far-reaching implications for proposed solutions to the CCP that require the number of vacua to exceed the fine-tuning of the vacuum energy density. We show that current estimates of the number of flux vacua in string theory, Nvac˜O (1 0272 000) , are far too small to realize certain simple models of interacting dark energy and solve the cosmological constant problem anthropically. These models admit distinctive observational signatures that can be targeted by future gamma-ray observatories, hence making it possible to observationally rule out the anthropic solution to the cosmological constant problem in theories with a finite number of vacua.

  6. Predicting reaction rate constants of ozone with organic compounds from radical structures

    Science.gov (United States)

    Yu, Xinliang; Yi, Bing; Wang, Xueye; Chen, Jianfang

    2012-05-01

    The reaction rate constants of ozone with organic compounds in the atmosphere were predicted by a quantitative structure-activity relationship (QSAR) model. Density functional theory (DFT) calculations, for the first time, were carried out on the radicals from organic compounds, at the UB3LYP level of theory with 6-31G(d) basis set. A set of quantum chemical descriptors calculated from the radicals, the energy of the highest occupied molecular orbital of beta spin states (EβHOMO), the molecular average polarizability (α), and the total energy (ET), were used to build the general QSAR model for aliphatic compounds, applying the genetic algorithm (GA) technique and support vector machine (SVM) regression. The root mean square errors (RMSE) are 0.680 for the training set (68 compounds), 0.777 for the validation set (36 compounds) and 0.709 for the test set (35 compounds). Investigated results indicate that the SVM model given here has good predictivity for aliphatic compounds.

  7. Lapse Rate Modeling

    DEFF Research Database (Denmark)

    De Giovanni, Domenico

    prepayment models for mortgage backed securities, this paper builds a Rational Expectation (RE) model describing the policyholders' behavior in lapsing the contract. A market model with stochastic interest rates is considered, and the pricing is carried out through numerical approximation...... of the corresponding two-space-dimensional parabolic partial differential equation. Extensive numerical experiments show the differences in terms of pricing and interest rate elasticity between the ACC and RE approaches as well as the sensitivity of the contract price with respect to changes in the policyholders...

  8. Lapse rate modeling

    DEFF Research Database (Denmark)

    De Giovanni, Domenico

    2010-01-01

    prepayment models for mortgage backed securities, this paper builds a Rational Expectation (RE) model describing the policyholders' behavior in lapsing the contract. A market model with stochastic interest rates is considered, and the pricing is carried out through numerical approximation...... of the corresponding two-space-dimensional parabolic partial differential equation. Extensive numerical experiments show the differences in terms of pricing and interest rate elasticity between the ACC and RE approaches as well as the sensitivity of the contract price with respect to changes in the policyholders...

  9. Separating the effect of respiration from the heart rate variability for cases of constant harmonic breathing

    Directory of Open Access Journals (Sweden)

    Kircher Michael

    2015-09-01

    Full Text Available Heart Rate Variability studies are a known measure for the autonomous control of the heart rate. In special situations, its interpretation can be ambiguous, since the respiration has a major influence on the heart rate variability. For this reason it has often been proposed to measure Heart Rate Variability, while the subjects are breathing at a constant respiration rate. That way the spectral influence of the respiration is known. In this work we propose to remove this constant respiratory influence from the heart rate and the Heart Rate Variability parameters to gain respiration free autonomous controlled heart rate signal. The spectral respiratory component in the heart rate signal is detected and characterized. Subsequently the respiratory effect on Heart Rate Variability is removed using spectral filtering approaches, such as the Notch filter or the Raised Cosine filter. As a result new decoupled Heart Variability parameters are gained, which could lead to new additional interpretations of the autonomous control of the heart rate.

  10. A streamwise constant model of turbulence in plane Couette flow

    OpenAIRE

    Gayme, D. F.; McKeon, B. J.; Papachristodoulou, A.; Bamieh, B; Doyle, J. C.

    2010-01-01

    Streamwise and quasi-streamwise elongated structures have been shown to play a significant role in turbulent shear flows. We model the mean behaviour of fully turbulent plane Couette flow using a streamwise constant projection of the Navier–Stokes equations. This results in a two-dimensional three-velocity-component (2D/3C) model. We first use a steady-state version of the model to demonstrate that its nonlinear coupling provides the mathematical mechanism that shapes the turbulent velocity p...

  11. The Cosmological Constant for the Crystalline Vacuum Cosmic Space Model

    CERN Document Server

    Montemayor-Aldrete, J A; Morales-Mori, A; Mendoza-Allende, A; Montemayor-Varela, A; Castillo-Mussot, M; Vazquez, G J

    2005-01-01

    The value of the cosmological constant arising from a crystalline model for vacuum cosmic space with lattice parameter of the order of the neutron radius [1] has been calculated. The model allows to solve, in an easy way, the problem of the cosmological constant giving the right order of magnitude, which corresponds very well with the mean value of matter density in the universe. The obtained value is about 10-48 Km-2. Diffraction experiments with non-thermal neutron beam in cosmic space are proposed to search for the possibility of crystalline structure of vacuum space and to measure the lattice parameter. PACS numbers: 98.80.Es, 04.20.-q, 03.65.-w, 61.50.-f, 98.80.Ft

  12. Power consumption analysis of constant bit rate data transmission over 3G mobile wireless networks

    DEFF Research Database (Denmark)

    Wang, Le; Ukhanova, Ann; Belyaev, Evgeny

    2011-01-01

    This paper presents the analysis of the power consumption of data transmission with constant bit rate over 3G mobile wireless networks. Our work includes the description of the transition state machine in 3G networks, followed by the detailed energy consumption analysis and measurement results...

  13. Estimate Of The Decay Rate Constant of Hydrogen Sulfide Generation From Landfilled Drywall

    Science.gov (United States)

    Research was conducted to investigate the impact of particle size on H2S gas emissions and estimate a decay rate constant for H2S gas generation from the anaerobic decomposition of drywall. Three different particle sizes of regular drywall and one particle size of paperless drywa...

  14. Stress relaxation of entangled polystyrene solution after constant-rate, uniaxial elongation

    DEFF Research Database (Denmark)

    Matsumiya, Yumi; Masubuchi, Yuichi; Watanabe, Hiroshi

    For an entangled solution of linear polystyrene (PS 545k; M = 545k) in dibutyl phthalate (DBP), the stress relaxation after constant-rate uniaxial elongation was examined with an extensional viscosity fixture mounted on ARES (TA Instruments). The PS concentration, c = 52 wt%, was chosen in a way...

  15. The Reaction Mechanism and Rate Constants in the Radiolysis of Fe2+-Cu2+ Solutions

    DEFF Research Database (Denmark)

    Bjergbakke, Erling; Sehested, Knud; Rasmussen, O. Lang

    1976-01-01

    Pulse radiolysis and gamma radiolysis have been used to study the reaction mechanism in the radiolysis of aqueous solutions of Fe2+ and Cu2+. A reaction scheme has been developed and confirmed by computation of the corresponding complete set of differential equations. The rate constants for some...

  16. Formulation of a universal first-order rate constant for enzymatic reactions.

    Science.gov (United States)

    Imoto, Taiji

    2013-01-01

    It is a common practice to employ k(cat)[E]₀/K(m) as a first-order rate constant for the analysis of an enzymatic reaction, where [E]₀ is the total enzyme concentration. I describe in this report a serious shortcoming in analyzing enzymatic reactions when kcat[E]₀/K(m) is employed and show that k(cat)[E]₀/K(m) can only be applied under very limited conditions. I consequently propose the use of a more universal first-order rate constant, k(cat)[ES](K)/[S]₀, where [ES](K) is the initial equilibrium concentration of the ES-complex derived from [E]₀, [S]₀ and K(m). Employing k(cat)[ES](K)/[S]₀ as the first-order rate constant enables all enzymatic reactions to be reasonably simulated under a wide range of conditions, and the catalytic and binding contributions to the rate constant of any enzyme can be determined under any and all conditions.

  17. Theoretical and Shock Tube Study of the Rate Constants for Hydrogen Abstraction Reactions of Ethyl Formate

    KAUST Repository

    Wu, Junjun

    2017-08-03

    We report a systematic chemical kinetics study of the H-atom abstractions from ethyl formate (EF) by H, O(3P), CH3, OH, and HO2 radicals. The geometry optimization and frequency calculation of all the species were conducted using the M06 method and the cc-pVTZ basis set. The one-dimensional hindered rotor treatment of the reactants and transition states and the intrinsic reaction coordinate analysis were also performed at the M06/cc-pVTZ level of theory. The relative electronic energies were calculated at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory and further extrapolated to the complete basis set limit. Rate constants for the tittle reactions were calculated over the temperature range of 500‒2500 K by the transition state theory (TST) in conjunction with asymmetric Eckart tunneling effect. In addition, the rate constants of H-abstraction by hydroxyl radical were measured in shock tube experiments at 900‒1321 K and 1.4‒2.0 atm. Our theoretical rate constants of OH + EF → Products agree well with the experimental results within 15% over the experimental temperature range of 900‒1321 K. Branching ratios for the five types of H-abstraction reactions were also determined from their individual site-specific rate constants.

  18. Stress relaxation of entangled polystyrene solution after constant-rate, uniaxial elongation

    DEFF Research Database (Denmark)

    Matsumiya, Yumi; Masubuchi, Yuichi; Watanabe, Hiroshi;

    For an entangled solution of linear polystyrene (PS 545k; M = 545k) in dibutyl phthalate (DBP), the stress relaxation after constant-rate uniaxial elongation was examined with an extensional viscosity fixture mounted on ARES (TA Instruments). The PS concentration, c = 52 wt%, was chosen in a way...

  19. Perturbations of Kantowski-Sachs models with a cosmological constant

    CERN Document Server

    Keresztes, Zoltán; Bradley, Michael; Dunsby, Peter K S; Gergely, László Á

    2013-01-01

    We investigate perturbations of Kantowski-Sachs models with a positive cosmological constant, using the gauge invariant 1+3 and 1+1+2 covariant splits of spacetime together with a harmonic decomposition. The perturbations are assumed to be vorticity-free and of perfect fluid type, but otherwise include general scalar, vector and tensor modes. In this case the set of equations can be reduced to six evolution equations for six harmonic coefficients.

  20. Regularized learning of linear ordered-statistic constant false alarm rate filters (Conference Presentation)

    Science.gov (United States)

    Havens, Timothy C.; Cummings, Ian; Botts, Jonathan; Summers, Jason E.

    2017-05-01

    The linear ordered statistic (LOS) is a parameterized ordered statistic (OS) that is a weighted average of a rank-ordered sample. LOS operators are useful generalizations of aggregation as they can represent any linear aggregation, from minimum to maximum, including conventional aggregations, such as mean and median. In the fuzzy logic field, these aggregations are called ordered weighted averages (OWAs). Here, we present a method for learning LOS operators from training data, viz., data for which you know the output of the desired LOS. We then extend the learning process with regularization, such that a lower complexity or sparse LOS can be learned. Hence, we discuss what 'lower complexity' means in this context and how to represent that in the optimization procedure. Finally, we apply our learning methods to the well-known constant-false-alarm-rate (CFAR) detection problem, specifically for the case of background levels modeled by long-tailed distributions, such as the K-distribution. These backgrounds arise in several pertinent imaging problems, including the modeling of clutter in synthetic aperture radar and sonar (SAR and SAS) and in wireless communications.

  1. Unimolecular reaction rate constants of NO{sub 2} just above D{sub 0}

    Energy Technology Data Exchange (ETDEWEB)

    Bezel, I.; Stolyarov, D.; Wittig, C.

    1999-12-09

    Photoinitiated unimolecular decomposition on a barrierless potential energy surface (PES) has been studied for the reaction NO{sub 2} {yields} O({sup 3}P{sub 2}) + NO(X{sup 2}{Pi}{sub 1/2}, {nu} = 0) for excess energies up to approximately 17 cm{sup {minus}1} above the dissociation threshold (i.e., D{sub 0} for nonrotating molecules) by using expansion-cooled samples and the time-resolved pump-probe technique. To examine the threshold region with enough energy resolution to discern abrupt changes in the rate constant, should they occur, a pump-probe cross-correlation temporal width of {approximately}25 ps and a pump line width {le}2 cm{sup {minus}1} has been used. These are the first direct observations of the reaction rate constants in this energy regime. The rate constant was found to increase by an order of magnitude, varying from {approximately}2 x 10{sup 10} s{sup {minus}1} to {ge}10{sup 11} s{sup {minus}1}, the latter being a rough lower bound imposed by the experimental arrangement. The rate constant does not display the energy dependence predicted by using phase space theory, at least in detail. Rather, it appears to reflect the highly complex nature of the levels and the multiple PESs that are believed to be responsible for the anomalously high vibronic level density which has been observed just below D{sub 0}. These results bridge the gap between spectroscopic studies which have been carried out at energies just above D{sub 0} and ultrafast experiments which have measured rate constants in this energy region with pump laser spectral widths of {approximately}30 cm{sup {minus}1}.

  2. A Streamwise Constant Model of Turbulence in Plane Couette Flow

    CERN Document Server

    Gayme, D F; Papachristodoulou, A; Bamieh, B; Doyle, J C

    2010-01-01

    There is a consensus that turbulent flow is characterized by coherent structures. In particular, streamwise and quasi-streamwise elongated structures have been observed in both numerical simulations and experiments. Using this idea the mean behavior of fully turbulent plane Couette flow is modeled using a streamwise constant projection of the Navier Stokes equations. This assumption results in a two dimensional, three velocity component (2D/3C) model. We first use a steady state version of this 2D/3C model to demonstrate that the nonlinear coupling in the equations provides the mathematical mechanisms associated with the shape of the turbulent velocity profile. In simulating the full model we borrow some ideas from robust control and represent uncertainty as well as modeling errors using small amplitude noise forcing. Simulations of the 2D/3C model under small amplitude Gaussian forcing of the cross stream components is compared to DNS data. The results indicate that a streamwise constant projection of the Na...

  3. Validation of models with constant bias: an applied approach

    Directory of Open Access Journals (Sweden)

    Salvador Medina-Peralta

    2014-06-01

    Full Text Available Objective. This paper presents extensions to the statistical validation method based on the procedure of Freese when a model shows constant bias (CB in its predictions and illustrate the method with data from a new mechanistic model that predict weight gain in cattle. Materials and methods. The extensions were the hypothesis tests and maximum anticipated error for the alternative approach, and the confidence interval for a quantile of the distribution of errors. Results. The model evaluated showed CB, once the CB is removed and with a confidence level of 95%, the magnitude of the error does not exceed 0.575 kg. Therefore, the validated model can be used to predict the daily weight gain of cattle, although it will require an adjustment in its structure based on the presence of CB to increase the accuracy of its forecasts. Conclusions. The confidence interval for the 1-α quantile of the distribution of errors after correcting the constant bias, allows determining the top limit for the magnitude of the error of prediction and use it to evaluate the evolution of the model in the forecasting of the system. The confidence interval approach to validate a model is more informative than the hypothesis tests for the same purpose.

  4. Fine-structure constant constraints on Bekenstein-type models

    CERN Document Server

    Leal, P M M; Ventura, L B

    2014-01-01

    Astrophysical tests of the stability of dimensionless fundamental couplings, such as the fine-structure constant $\\alpha$, are an area of much increased recent activity, following some indications of possible spacetime variations at the few parts per million level. Here we obtain updated constraints on the Bekenstein-Sandvik-Barrow-Magueijo model, which is arguably the simplest model allowing for $\\alpha$ variations. Recent accurate spectroscopic measurements allow us to improve previous constraints by about an order of magnitude. We briefly comment on the dependence of the results on the data sample, as well as on the improvements expected from future facilities.

  5. Efficient quantum-classical method for computing thermal rate constant of recombination: application to ozone formation.

    Science.gov (United States)

    Ivanov, Mikhail V; Babikov, Dmitri

    2012-05-14

    Efficient method is proposed for computing thermal rate constant of recombination reaction that proceeds according to the energy transfer mechanism, when an energized molecule is formed from reactants first, and is stabilized later by collision with quencher. The mixed quantum-classical theory for the collisional energy transfer and the ro-vibrational energy flow [M. Ivanov and D. Babikov, J. Chem. Phys. 134, 144107 (2011)] is employed to treat the dynamics of molecule + quencher collision. Efficiency is achieved by sampling simultaneously (i) the thermal collision energy, (ii) the impact parameter, and (iii) the incident direction of quencher, as well as (iv) the rotational state of energized molecule. This approach is applied to calculate third-order rate constant of the recombination reaction that forms the (16)O(18)O(16)O isotopomer of ozone. Comparison of the predicted rate vs. experimental result is presented.

  6. Rate constants for H abstraction from benzo(a)pyrene and chrysene: a theoretical study.

    Science.gov (United States)

    Semenikhin, A S; Savchenkova, A S; Chechet, I V; Matveev, S G; Liu, Z; Frenklach, M; Mebel, A M

    2017-09-12

    Density functional B3LYP/6-31G(d) and ab initio G3(MP2,CC) calculations have been carried out to determine thermal rate constants of direct H abstraction reactions from four- and five-ring polycyclic aromatic hydrocarbons (PAH) chrysene and benzo[a]pyrene by various radicals abundant in combustion flames, such as H, CH3, C3H3, and OH, using transition state theory. The results show that the H abstraction reactions with OH have the lowest barriers of ∼4 kcal mol(-1), followed by those with H and CH3 with barriers of 16-17 kcal mol(-1), and then with propargyl radicals with barriers of 24-26 kcal mol(-1). Thus, the OH radical is predicted to be the fastest H abstractor from PAH. Even at 2500 K, the rate constant for H abstraction by H is still 34% lower than the rate constant for H abstraction by OH. The reaction with H is calculated to have rate constants 35-19 times higher than those for the reaction with CH3 due to a more favorable entropic factor. The reactions of H abstraction by C3H3 are predicted to be orders of magnitude slower than the other reactions considered and their equilibrium is strongly shifted toward the reactants, making propargyl an inefficient H abstractor from the aromatics. The calculations showed strong similarity of the reaction energetics in different H abstraction positions of benzo[a]pyrene and chrysene within armchair and zigzag edges in these molecules, but clear distinction between the armchair and zigzag sites. The zigzag sites appear to be more reactive, with H abstraction rate constants by H, CH3, and OH being respectively 37-42%, a factor of 2.1, and factors of 8-9 higher than the corresponding rate constants for the H abstraction reactions from armchair sites. Although the barrier heights for the two types of edges are similar, the entropic factor makes zigzag sites more favorable for H abstraction. Rate expressions have been generated for all studied reactions with the goal to rectify current combustion kinetics mechanisms.

  7. Determination of the kinetic rate constant of cyclodextrin supramolecular systems by high performance affinity chromatography.

    Science.gov (United States)

    Li, Haiyan; Ge, Jingwen; Guo, Tao; Yang, Shuo; He, Zhonggui; York, Peter; Sun, Lixin; Xu, Xu; Zhang, Jiwen

    2013-08-30

    It is challenging and extremely difficult to measure the kinetics of supramolecular systems with extensive, weak binding (Kahigh performance affinity chromatography (HPAC) was established to determine the dissociation rate constant of cyclodextrin supramolecular systems. The interactions of β-cyclodextrin with acetaminophen and sertraline were used to exemplify the method. The retention times, variances and the plate heights of the peaks for acetaminophen or sertraline, conventional non-retained substance (H2O) on the β-cyclodextrin bonded column and a control column were determined at four flow rates under linear elution conditions. Then, plate heights for the theoretical non-retained substance were estimated by the modified HPAC method, in consideration of the diffusion and stagnant mobile phase mass transfer. As a result, apparent dissociation rate constants of 1.82 (±0.01)s(-1) and 3.55 (±0.37)s(-1) were estimated for acetaminophen and sertraline respectively at pH 6.8 and 25°C with multiple flow rates. Following subtraction of the non-specific binding with the support, dissociation rate constants were estimated as 1.78 (±0.00) and 1.91 (±0.02)s(-1) for acetaminophen and sertraline, respectively. These results for acetaminophen and sertraline were in good agreement with the magnitude of the rate constants for other drugs determined by capillary electrophoresis reported in the literature and the peak fitting method we performed. The method described in this work is thought to be suitable for other supramolecules, with relatively weak, fast and extensive interactions.

  8. BRS structure of simple model of cosmological constant and cosmology

    Science.gov (United States)

    Mori, Taisaku; Nitta, Daisuke; Nojiri, Shin'ichi

    2017-07-01

    In Mod. Phys. Lett. A 31, 1650213 (2016, 10.1142/S0217732316502138), Nojiri proposed a simple model in order to solve one of the problems related to the cosmological constant. The model is induced from a topological field theory, and the model has an infinite number of BRS symmetries. The BRS symmetries are, in general, spontaneously broken, however. We investigate the BRS symmetry in detail and show that there is one and only one BRS symmetry which is not broken, and the unitarity can be guaranteed. In the model, the quantum problem of the vacuum energy, which may be identified with the cosmological constant, reduces to the classical problem of the initial condition. We investigate the cosmology given by the model and specify the region of the initial conditions, which could be consistent with the evolution of the Universe. We also show that there is a stable solution describing the de Sitter space-time, which may explain the accelerating expansion in the current Universe.

  9. Lapse rate modeling

    DEFF Research Database (Denmark)

    De Giovanni, Domenico

    2010-01-01

    prepayment models for mortgage backed securities, this paper builds a Rational Expectation (RE) model describing the policyholders' behavior in lapsing the contract. A market model with stochastic interest rates is considered, and the pricing is carried out through numerical approximation......The surrender option embedded in many life insurance products is a clause that allows policyholders to terminate the contract early. Pricing techniques based on the American Contingent Claim (ACC) theory are often used, though the actual policyholders' behavior is far from optimal. Inspired by many......' behavior....

  10. Monte Carlo-based revised values of dose rate constants at discrete photon energies

    Directory of Open Access Journals (Sweden)

    T Palani Selvam

    2014-01-01

    Full Text Available Absorbed dose rate to water at 0.2 cm and 1 cm due to a point isotropic photon source as a function of photon energy is calculated using the EDKnrc user-code of the EGSnrc Monte Carlo system. This code system utilized widely used XCOM photon cross-section dataset for the calculation of absorbed dose to water. Using the above dose rates, dose rate constants are calculated. Air-kerma strength S k needed for deriving dose rate constant is based on the mass-energy absorption coefficient compilations of Hubbell and Seltzer published in the year 1995. A comparison of absorbed dose rates in water at the above distances to the published values reflects the differences in photon cross-section dataset in the low-energy region (difference is up to 2% in dose rate values at 1 cm in the energy range 30-50 keV and up to 4% at 0.2 cm at 30 keV. A maximum difference of about 8% is observed in the dose rate value at 0.2 cm at 1.75 MeV when compared to the published value. S k calculations based on the compilation of Hubbell and Seltzer show a difference of up to 2.5% in the low-energy region (20-50 keV when compared to the published values. The deviations observed in the values of dose rate and S k affect the values of dose rate constants up to 3%.

  11. Constant-load versus heart rate-targeted exercise - Responses of systolic intervals

    Science.gov (United States)

    Lance, V. Q.; Spodick, D. H.

    1975-01-01

    Various systolic intervals were measured prior to and during heart rate-targeted bicycle ergometer exercise. There were striking similarities within each matched exercise set for Q-Im, isovolumetric contraction time, preejection period (PEP), and PEP/left ventricular ejection time (LVET). LVET was significantly shorter for rate-targeted exercise. It is concluded that either constant-load or rate-targeted bicycle ergometry may be used with the choice of method determined by the purpose of the protocol, and that systolic intervals (except LVET) should not be much altered owing to the method chosen.

  12. Degradation of bisphenol A by ozonation: rate constants, influence of inorganic anions, and by-products

    Directory of Open Access Journals (Sweden)

    Kheng Soo Tay

    2012-02-01

    Full Text Available The second-order rate constants for the reaction between bisphenol A (BPA and ozonewere evaluated over the pH range of 2-12. The rate constants showed minimum values (×104 M-1s-1under acidic condition (pH 10. From pH 4 to 7, the second-order rate constants were found to increase by a magnitudeof almost 102 and this was due to the increase in anionic BPA species in the solution. The rateconstants increased almost twofold when pH increased from 9.6 to 10.2. The presence of commoninorganic anions at levels commonly found in the environment did not affect the rate of degradationof BPA.The degradation by-products from the ozonation of BPA were identified as 4-(prop-1-en-2-ylphenol, hydroquinone, 4-hydroxyacetophenone, 2-(2-(4-hydroxyphenylpropan-2-ylsuccinaldehyde,2-(1-(4-hydroxyphenylvinylpent-2-enal, 3-formyl-4-(4-hydroxyphenyl-4-methylpent-2-enoic acid, monohydroxy-BPA and dihydroxy-BPA. In conclusion, ozonation was found to be aneffective method for the removal of BPA even in the presence of common inorganic anions atenvironmental concentrations. However, incomplete treatment of BPA might produce a variety ofdegradation by-products.

  13. Determination of Methane and Carbon Dioxide Formation Rate Constants for Semi-Continuously Fed Anaerobic Digesters

    Directory of Open Access Journals (Sweden)

    Jan Moestedt

    2015-01-01

    Full Text Available To optimize commercial-scale biogas production, it is important to evaluate the performance of each microbial step in the anaerobic process. Hydrolysis and methanogenesis are usually the rate-limiting steps during digestion of organic waste and by-products. By measuring biogas production and methane concentrations on-line in a semi-continuously fed reactor, gas kinetics can be evaluated. In this study, the rate constants of the fermentative hydrolysis step (kc and the methanogenesis step (km were determined and evaluated in a continuously stirred tank laboratory-scale reactor treating food and slaughterhouse waste and glycerin. A process additive containing Fe2+, Co2+ and Ni2+ was supplied until day 89, after which Ni2+ was omitted. The omission resulted in a rapid decline in the methanogenesis rate constant (km to 70% of the level observed when Ni2+ was present, while kc remained unaffected. This suggests that Ni2+ mainly affects the methanogenic rather than the hydrolytic microorganisms in the system. However, no effect was initially observed when using conventional process monitoring parameters such as biogas yield and volatile fatty acid concentration. Hence, formation rate constants can reveal additional information on process performance and km can be used as a complement to conventional process monitoring tools for semi-continuously fed anaerobic digesters.

  14. Properties of human motor units after prolonged activity at a constant firing rate.

    Science.gov (United States)

    Johnson, K V B; Edwards, S C; Van Tongeren, C; Bawa, P

    2004-02-01

    The primary purpose of this study was to examine if there are changes in the intrinsic properties of spinal motoneurons after prolonged submaximal contractions. To do this, we assessed whether or not the synaptic drive to motoneurons needs to increase in order to maintain a constant firing rate of a motor unit. Recruitment of new units and an increase in total electromyographic (EMG) activity of the muscle of interest were taken as estimates of an increase in synaptic drive. Subjects were asked to maintain a constant firing rate of a clearly identifiable (targeted) motor unit from the first dorsal interosseous muscle for approximately 10 min, while surface EMG and force were recorded simultaneously. For the 60 units studied, the duration of the constant-firing-rate period ranged from 73 to 1,140 s (448 +/- 227 s; mean +/- SD). There was a significant increase ( t-test, prate suggesting an increase in the net excitatory input to the motoneuron pool. Changes occurring simultaneously in other parameters, namely, variability in interspike interval, magnitude of force fluctuations, the duration of motor unit action potentials, and the median power frequency of surface EMG were also computed. The firing rates of 16 concurrently firing motoneurons, not controlled by the subject, remained constant. The key finding of this study is that after prolonged activity, a motoneuron requires a stronger excitatory input to maintain its firing rate. Additional results are indicative of significant changes in the characteristics of the synaptic inputs, changes at the neuromuscular junction (both pre- and postsynaptic regions) and the sarcolemma.

  15. ESTIMATION OF HYDROLYSIS RATE CONSTANTS OF CARBOXYLIC ACID ESTER AND PHOSPHATE ESTER COMPOUNDS IN AQUEOUS SYSTEMS FROM MOLECULAR STRUCTURE BY SPARC

    Science.gov (United States)

    SPARC (SPARC Performs Automated Reasoning in Chemistry) chemical reactivity models were extended to calculate hydrolysis rate constants for carboxylic acid ester and phosphate ester compounds in aqueous non- aqueous and systems strictly from molecular structure. The energy diffe...

  16. Calculated third order rate constants for interpreting the mechanisms of hydrolyses of chloroformates, carboxylic Acid halides, sulfonyl chlorides and phosphorochloridates

    National Research Council Canada - National Science Library

    Bentley, T William

    2015-01-01

    .... Third order rate constants (k3) are calculated for solvolytic reactions in a wide range of compositions of acetone-water mixtures, and are shown to be either approximately constant or correlated with the Grunwald-Winstein Y parameter...

  17. Bianchi Type-Ⅲ Cosmological Models with Gravitational Constant G and the Cosmological Constant Λ

    Institute of Scientific and Technical Information of China (English)

    J.P.Singh; R.K.Tiwari; Pratibha Shukla

    2007-01-01

    Einstein field equations with variable gravitational and cosmological constants are considered in the presence of perfect fluid for the Bianchi type-Ⅲ universe by assuming conservation law for the energy-momentum tensor.Exact solutions of the field equations are obtained by using the scalar of expansion proportional to the shear scalar θχσ,which leads to a relation between metric potential B=Cn,where n is a constant.The corresponding physical interpretation of the cosmological solutions are also discussed.

  18. Photolysis of ketene at 193 nm and the rate constant for H + HCCO at 297 K.

    Energy Technology Data Exchange (ETDEWEB)

    Glass, G. P.; Kumaran, S. S.; Michael, J. V.; Chemistry

    2000-01-01

    The 193 nm photolysis of ketene was studied by measuring the amount of atomic hydrogen produced when very dilute ketene/Ar and ketene/H{sub 2} mixtures were irradiated by a single pulse from an ArF excimer laser. Absolute concentrations of atomic hydrogen were monitored over a time interval of 0-2.5 ms by using Lyman-{alpha} atomic resonance absorption spectroscopy (ARAS). Four different photodissociation channels of ketene were identified: H{sub 2}CCO + hv gives (a) CH{sub 2}({sup 3}B1) + CO; (b) CH{sub 2}({sup 1}A{sub 1}) + CO; (c) HCCO + H; and (d) C{sub 2}O(b{sup -1}{Sigma}{sup +}) + H{sub 2}. The quantum yields for each channel were measured as {phi}{sub a} = 0.628, {phi}{sub b} = 0.193, {phi}{sub 3}= 0.107, and {phi}{sub d} = 0.072, respectively. To explore the secondary chemistry that occurred when using higher pressure H{sub 2}CCO/Ar mixtures, a mechanism was constructed that used well-documented reactions and, for most processes, rate constants that had already been accurately determined. Modeling studies using this mechanism showed the [H] profile to be determined largely by the rate of the reaction H + HCCO {yields} CH{sub 2} + CO. An excellent fit to all of the experimental data was obtained when k{sub 2} = (1.7 {+-} 0.3) x 10{sup -10} cm{sup 3} molecule{sup -1} s{sup -1}.

  19. Ab Initio Calculation of Rate Constants for Molecule–Surface Reactions with Chemical Accuracy

    Science.gov (United States)

    Piccini, GiovanniMaria; Alessio, Maristella

    2016-01-01

    Abstract The ab initio prediction of reaction rate constants for systems with hundreds of atoms with an accuracy that is comparable to experiment is a challenge for computational quantum chemistry. We present a divide‐and‐conquer strategy that departs from the potential energy surfaces obtained by standard density functional theory with inclusion of dispersion. The energies of the reactant and transition structures are refined by wavefunction‐type calculations for the reaction site. Thermal effects and entropies are calculated from vibrational partition functions, and the anharmonic frequencies are calculated separately for each vibrational mode. This method is applied to a key reaction of an industrially relevant catalytic process, the methylation of small alkenes over zeolites. The calculated reaction rate constants (free energies), pre‐exponential factors (entropies), and enthalpy barriers show that our computational strategy yields results that agree with experiment within chemical accuracy limits (less than one order of magnitude). PMID:27008460

  20. I. Determination of chemical reaction rate constants by numerical nonlinear analysis: differential methods

    CERN Document Server

    Jesudason, Christopher G

    2011-01-01

    The primary emphasis of this work on kinetics is to illustrate the a posteriori approach to applications, where focus on data leads to novel outcomes, rather than the a priori tendencies of applied analysis which imposes constructs on the nature of the observable. The secondary intention is the development of appropriate methods consonant with experimental definitions. By focusing on gradients, it is possible to determine both the average and instantaneous rate constants that can monitor changes in the rate constant with concentration changes as suggested by this theory. Here, methods are developed and discussed utilizing nonlinear analysis which does not require exact knowledge of initial concentrations. These methods are compared with those derived from standard methodology. These gradient methods are shown to be consistent with the ones from standard methods and could readily serve as alternatives for studies where there are limits or unknowns in the initial conditions, such as in the burgeoning fields of ...

  1. The rate constant for the CO + H2O2 reaction

    DEFF Research Database (Denmark)

    Glarborg, Peter; Marshall, Paul

    2009-01-01

    The rate constant for the reaction CO + H2O2 -> HOCO + OH (R1) at 713 K is determined based on the batch reactor experiments of Baldwin et al. [ R. R. Baldwin, R. W. Walker, S. J. Webster, Combust. Flame 15 (1970) 167] on decomposition of H2O2 sensitized by CO. The value, k(1) (713 K) = 8.1 x 10...... in combustion. The present analysis reconciles the batch reactor data of Baldwin et al. with recent high-level theoretical work on the CO + HO2 reaction.......(2) cm(3) mol(-1) s(-1), is consistent with spin-unrestricted density functional theory. Extrapolation to a wider temperature range through ab initio calculations yields the rate constant k(1) = 3.6 x 10(4)T(2.5) exp(-14425[K]/T) cm(3) mol(-1) s(-1). The reaction is probably of minor importance...

  2. Reaction rate constants of H-abstraction by OH from large ketones: Measurements and site-specific rate rules

    KAUST Repository

    Badra, Jihad

    2014-01-01

    Reaction rate constants of the reaction of four large ketones with hydroxyl (OH) are investigated behind reflected shock waves using OH laser absorption. The studied ketones are isomers of hexanone and include 2-hexanone, 3-hexanone, 3-methyl-2-pentanone, and 4-methl-2-pentanone. Rate constants are measured under pseudo-first-order kinetics at temperatures ranging from 866 K to 1375 K and pressures near 1.5 atm. The reported high-temperature rate constant measurements are the first direct measurements for these ketones under combustion-relevant conditions. The effects of the position of the carbonyl group (CO) and methyl (CH3) branching on the overall rate constant with OH are examined. Using previously published data, rate constant expressions covering, low-to-high temperatures, are developed for acetone, 2-butanone, 3-pentanone, and the hexanone isomers studied here. These Arrhenius expressions are used to devise rate rules for H-abstraction from various sites. Specifically, the current scheme is applied with good success to H-abstraction by OH from a series of n-ketones. Finally, general expressions for primary and secondary site-specific H-abstraction by OH from ketones are proposed as follows (the subscript numbers indicate the number of carbon atoms bonded to the next-nearest-neighbor carbon atom, the subscript CO indicates that the abstraction is from a site next to the carbonyl group (CO), and the prime is used to differentiate different neighboring environments of a methylene group):P1,CO = 7.38 × 10-14 exp(-274 K/T) + 9.17 × 10-12 exp(-2499 K/T) (285-1355 K)S10,CO = 1.20 × 10-11 exp(-2046 K/T) + 2.20 × 10-13 exp(160 K/T) (222-1464 K)S11,CO = 4.50 × 10-11 exp(-3000 K/T) + 8.50 × 10-15 exp(1440 K/T) (248-1302 K)S11′,CO = 3.80 × 10-11 exp(-2500 K/T) + 8.50 × 10-15 exp(1550 K/T) (263-1370 K)S 21,CO = 5.00 × 10-11 exp(-2500 K/T) + 4.00 × 10-13 exp(775 K/T) (297-1376 K) © 2014 the Partner Organisations.

  3. Study on improving the turbidity measurement of the absolute coagulation rate constant.

    Science.gov (United States)

    Sun, Zhiwei; Liu, Jie; Xu, Shenghua

    2006-05-23

    The existing theories dealing with the evaluation of the absolute coagulation rate constant by turbidity measurement were experimentally tested for different particle-sized (radius = a) suspensions at incident wavelengths (lambda) ranging from near-infrared to ultraviolet light. When the size parameter alpha = 2pi a/lambda > 3, the rate constant data from previous theories for fixed-sized particles show significant inconsistencies at different light wavelengths. We attribute this problem to the imperfection of these theories in describing the light scattering from doublets through their evaluation of the extinction cross section. The evaluations of the rate constants by all previous theories become untenable as the size parameter increases and therefore hampers the applicable range of the turbidity measurement. By using the T-matrix method, we present a robust solution for evaluating the extinction cross section of doublets formed in the aggregation. Our experiments show that this new approach is effective in extending the applicability range of the turbidity methodology and increasing measurement accuracy.

  4. Shock Tube Measurement for the Dissociation Rate Constant of Acetaldehyde Using Sensitive CO Diagnostics.

    Science.gov (United States)

    Wang, Shengkai; Davidson, David F; Hanson, Ronald K

    2016-09-08

    The rate constant of acetaldehyde thermal dissociation, CH3CHO = CH3 + HCO, was measured behind reflected shock waves at temperatures of 1273-1618 K and pressures near 1.6 and 0.34 atm. The current measurement utilized sensitive CO diagnostics to track the dissociation of CH3CHO via oxygen atom balance and inferred the title rate constant (k1) from CO time histories obtained in pyrolysis experiments of 1000 and 50 ppm of CH3CHO/Ar mixtures. By using dilute test mixtures, the current study successfully suppressed the interferences from secondary reactions and directly determined the title rate constant as k1(1.6 atm) = 1.1 × 10(14) exp(-36 700 K/T) s(-1) over 1273-1618 K and k1(0.34 atm) = 5.5 × 10(12) exp(-32 900 K/T) s(-1) over 1377-1571 K, with 2σ uncertainties of approximately ±30% for both expressions. Example simulations of existing reaction mechanisms updated with the current values of k1 demonstrated substantial improvements with regards to the acetaldehyde pyrolysis chemistry.

  5. Shock Tube Measurement of the High-Temperature Rate Constant for OH + CH3 → Products.

    Science.gov (United States)

    Wang, Shengkai; Li, Sijie; Davidson, David F; Hanson, Ronald K

    2015-08-20

    The reaction between hydroxyl (OH) and methyl radicals (CH3) is critical to hydrocarbon oxidation. Motivated by the sparseness of its high-temperature rate constant data and the large uncertainties in the existing literature values, the current study has remeasured the overall rate constant of the OH + CH3 reaction and extended the measurement temperature range to 1214-1933 K, using simultaneous laser absorption diagnostics for OH and CH3 radicals behind incident and reflected shock waves. tert-Butyl hydroperoxide and azomethane were used as pyrolytic sources for the OH and CH3 radicals, respectively. The current study bridged the temperature ranges of existing experimental data, and good agreement is seen between the current measurement and some previous experimental and theoretical high-temperature studies. A recommendation for the rate constant expression of the title reaction, based on the weighted average of the high-temperature data from selected studies, is given by k1 = 4.19 × 10(1)(T/K)(3.15) exp(5270 K/T) cm(3) mol(-1) s(-1) ±30%, which is valid over 1000-2500 K.

  6. Mechanism of tension generation in muscle: an analysis of the forward and reverse rate constants.

    Science.gov (United States)

    Davis, Julien S; Epstein, Neal D

    2007-04-15

    Tension generation in muscle occurs during the attached phase of the ATP-powered cyclic interaction of myosin heads with thin filaments. The transient nature of tension-generating intermediates and the complexity of the mechanochemical cross-bridge cycle have impeded a quantitative description of tension generation. Recent experiments performed under special conditions yielded a sigmoidal dependence of fiber tension on temperature--a unique case that simplifies the system to a two-state transition. We have applied this two-state analysis to kinetic data obtained from biexponential laser temperature-jump tension transients. Here we present the forward and reverse rate constants for de novo tension generation derived from analysis of the kinetics of the fast laser temperature-jump phase tau(2) (equivalent of the length-jump phase 2(slow)). The slow phase tau(3) is temperature-independent indicating coupling to rather than a direct role in, de novo tension generation. Increasing temperature accelerates the forward, and slows the reverse, rate constant for the creation of the tension-generating state. Arrhenius behavior of the forward and anti-Arrhenius behavior of the reverse rate constant is a kinetic signature of multistate multipathway protein-folding reactions. We conclude that locally unfolded tertiary and/or secondary structure of the actomyosin cross-bridge mediates the power stroke.

  7. Calculating rate constants with updated Hessians using variational transition state theory with multidimensional tunneling.

    Science.gov (United States)

    Chuang, Yao-Yuan

    2007-08-01

    Variational transition state theory with multidimensional tunneling (VTST/MT) has been used for calculating the rate constants of reactions. The updated Hessians have been used to reduce the computational costs for both geometry optimization and trajectory following procedures. In this paper, updated Hessians are used to reduce the computational costs while calculating the rate constants applying VTST/MT. Although we found that directly applying the updated Hessians will not generate good vibrational frequencies along the minimum energy path (MEP), however, we can either re-compute the full Hessian matrices at fixed intervals or calculate the Block Hessians, which is constructed by numerical one-side difference for the Hessian elements in the "critical" region and Bofill updating scheme for the rest of the Hessian elements. Due to the numerical instability of the Bofill update method near the saddle point region, we have suggested a simple strategy in which we follow the MEP until certain percentage of the classical barrier height from the barrier top with full Hessians computed and then performing rate constant calculation with the extended MEP using Block Hessians. This strategy results a mean unsigned percentage deviation (MUPD) around 10% with full Hessians computed till the point with 80% classical barrier height for four studied reactions. This proposed strategy is attractive not only it can be implemented as an automatic procedure but also speeds up the VTST/MT calculation via embarrassingly parallelization to a personal computer cluster.

  8. Theory and Experiment on the Measurement of Kinetic Rate Constants for Surfactant Exchange at an Air/Water Interface.

    Science.gov (United States)

    Pan; Green; Maldarelli

    1998-09-15

    The paper focuses on the measurement of the rate constants for the kinetic steps of adsorption and desorption of surfactant between an air/water surface and the aqueous bulk sublayer adjacent to the surface. Kinetic constants are determined in nonequilibrium experiments in which either a clean surface is contacted with a bulk solution and surfactant diffuses toward and adsorbs onto the interface, or the area of an established monolayer in equilibrium with an underlying solution is changed, and surfactant exchanges between the surface and bulk. The dynamic tension change due to the surfactant exchange is measured, and compared to predictions of kinetic-diffusive transport models in order to infer the kinetic coefficients as well the diffusion coefficients. Model comparisons for highly surface active surfactants have resolved only the diffusion coefficient as the transport was found to be diffusion controlled; kinetic constants have only been established for less active materials such as alcohols or bolaform surfactants. In this study, we demonstrate that kinetics can be differentiated from diffusion in clean interface adsorption and re-equilibration if high bulk concentrations of the surfactant are used, or in re-equilibration, if the surface is compressed sufficiently. We first establish theoretically that mass transfer shifts from diffusion-limited to mixed as the bulk concentration increases in clean interface adsorption, or the surface compression is increased in re-equilibration. We then experimentally verify this idea by using the polyethoxylated surfactant C12E6 (C12H25 (OCH2CH2)6-OH) and by measuring dynamic surface tensions in clean interface adsorption and re-equilibration, respectively by the shape analysis of pendant bubbles. We find values of 6 x 10(-10) m2/s for the diffusion coefficient, and 1.4 x 10(-5) m/sec and 1.4 x 10(-4) s-1 for the adsorption and desorption rate constants, respectively, in a Frumkin kinetic formulation. While the adsorption

  9. An optimal policy for deteriorating items with time-proportional deterioration rate and constant and time-dependent linear demand rate

    Science.gov (United States)

    Singh, Trailokyanath; Mishra, Pandit Jagatananda; Pattanayak, Hadibandhu

    2017-04-01

    In this paper, an economic order quantity (EOQ) inventory model for a deteriorating item is developed with the following characteristics: (i) The demand rate is deterministic and two-staged, i.e., it is constant in first part of the cycle and linear function of time in the second part. (ii) Deterioration rate is time-proportional. (iii) Shortages are not allowed to occur. The optimal cycle time and the optimal order quantity have been derived by minimizing the total average cost. A simple solution procedure is provided to illustrate the proposed model. The article concludes with a numerical example and sensitivity analysis of various parameters as illustrations of the theoretical results.

  10. Petri nets extension to model state-varying failure rates

    DEFF Research Database (Denmark)

    Lazarova-Molnar, Sanja

    2013-01-01

    One of the most common assumptions in reliability modeling is the constant failure rate. This has been increasingly changing lately, yielding significant research towards abandoning simulation results based on this assumption; thus, deeming constant failure rates as inadequate to model failures......-varying failure rates and extend the formalism of Petri nets to model them. To illustrate our approach we provide an example model that features state-varying failure rates....

  11. A constant air flow rate control of blower for residential applications

    Energy Technology Data Exchange (ETDEWEB)

    Yang, S.M. [Tamkang Univ., Taipei (Taiwan, Province of China). Dept. of Mechanical Engineering

    1998-03-01

    This paper presents a technique to control a blower for residential applications at constant air flow rate using an induction motor drive. The control scheme combines a variable volt/hertz ratio inverter drive and an average motor current regulation loop to achieve control of the motor torque-speed characteristics, consequently controlling the air flow rate of the blower which the motor is driving. The controller is simple to implement and practical for commercialization. It is also reliable, since no external pressure or air flow sensor is required. Both a theoretical derivation and an experimental verification for the control scheme are presented in this paper.

  12. Evaluation of the reaction rate constants for the gas-phase Al-CH4-air combustion chemistry

    Science.gov (United States)

    Sharipov, A. S.; Titova, N. S.; Starik, A. M.

    2012-10-01

    The most likely reaction pathways and reaction products in the Al-CH4-O2-N2 system are investigated using density functional theory and ab initio calculations. The B3LYP functional with extended 6-311+G(3df,2p) basis set as well as the CBS-QB3 composite method are mainly utilised. Theoretical analysis of corresponding reaction rate constants is also performed with the use of simple theoretical models. A critical overview of current knowledge on combustion-relevant reactions with aluminium compounds is given. On the basis of critical comparison of available experimental kinetic data with theoretical calculations, the approximations for rate constants for 44 reversible elementary reactions involving Al-containing species are recommended for use in combustion issues.

  13. Theoretical Prediction of Rate Constants for Hydrogen Abstraction by OH, H, O, CH3, and HO2 Radicals from Toluene.

    Science.gov (United States)

    Li, Shu-Hao; Guo, Jun-Jiang; Li, Rui; Wang, Fan; Li, Xiang-Yuan

    2016-05-26

    Hydrogen abstraction from toluene by OH, H, O, CH3, and HO2 radicals are important reactions in oxidation process of toluene. Geometries and corresponding harmonic frequencies of the reactants, transition states as well as products involved in these reactions are determined at the B3LYP/6-31G(2df,p) level. To achieve highly accurate thermochemical data for these stationary points on the potential energy surfaces, the Gaussian-4(G4) composite method was employed. Torsional motions are treated either as free rotors or hindered rotors in calculating partion functions to determine thermodynamic properties. The obtained standard enthalpies of formation for reactants and some prodcuts are shown to be in excellent agreement with experimental data with the largest error of 0.5 kcal mol(-1). The conventional transition state theory (TST) with tunneling effects was adopted to determine rate constants of these hydrogen abstraction reactions based on results from quantum chemistry calculations. To faciliate its application in kinetic modeling, the obtained rate constants are given in Arrhenius expression: k(T) = AT(n) exp(-EaR/T). The obtained reaction rate constants also agree reasonably well with available expermiental data and previous theoretical values. Branching ratios of these reactions have been determined. The present reaction rates for these reactions have been used in a toluene combustion mechanism, and their effects on some combustion properties are demonstrated.

  14. Ab-Initio Based Computation of Rate Constants of Spin Forbidden Transitions in (Bio)inorganic Complexes and Metalloproteins

    Science.gov (United States)

    Ozkanlar, Abdullah; Rodriguez, Jorge H.

    2009-03-01

    Some (bio)chemical reactions are non-adiabatic processes whereby the total spin angular momentum, before and after the reaction, is not conserved. These are named spin- forbidden reactions. The application of spin density functional theory (SDFT) to the prediction of rate constants is a challenging task of fundamental and practical importance. We apply non-adiabatic transition state theory in conjunction with SDFT to predict the rate constant of the spin- forbidden dihydrogen binding to iron tetracarbonyl. To model the surface hopping probability between singlet and triplet states, the Landau-Zener formalism is used. The lowest energy point for singlet-triplet crossing, known as minimum energy crossing point (MECP), was located and used to compute, in a semi-quantum approach, reaction rate constants at 300 K. The predicted rates are in good agreement with experiment. In addition, we present results which are relevant to the ligand binding reactions of metalloproteins. This work is supported in part by NSF via CAREER award CHE-0349189 (JHR).

  15. Comparison of ultrasonic degradation rates constants of methylene blue at 22.8 kHz, 127 kHz, and 490 kHz.

    Science.gov (United States)

    Kobayashi, Daisuke; Honma, Chiemi; Suzuki, Atsushi; Takahashi, Tomoki; Matsumoto, Hideyuki; Kuroda, Chiaki; Otake, Katsuto; Shono, Atsushi

    2012-07-01

    Techniques such as solvent extraction, incineration, chemical dehalogenation, and biodegradation have been investigated for the degradation of hazardous organic compounds. We found ultrasound to be an attractive technology for the degradation of hazardous organic compounds in water. However, the effects of ultrasonic frequency on degradation rate constants were not investigated quantitatively. In this study, the degradation process of a model for hazardous organic compound methylene blue was investigated using ultrasonic irradiation. The study focused on the effects of ultrasonic frequency and ultrasonic power on the degradation rate constant. The apparent degradation rate constants were estimated based on time dependence of methylene blue concentration assuming pseudo-first-order kinetics for the decomposition. A linear relationship between the apparent degradation rate constant and ultrasonic power was identified. In addition, the apparent degradation rate constants at frequencies of 127 and 490 kHz were much larger than those at 22.8 kHz. A relationship between the apparent degradation rate constant and the sonochemical efficiency value (SE value) was also found. Based on these results, a simple model for estimating the apparent degradation rate constant of methylene blue based on the ultrasonic power and the SE value is proposed in this study.

  16. Mathematical Model of Seasonal Influenza with Treatment in Constant Population

    Science.gov (United States)

    Kharis, M.; Arifudin, R.

    2017-04-01

    Seasonal Influenza is one of disease that outbreaks periodically at least once every year. This disease caused many people hospitalized. Many hospitalized people as employers would infect production quantities, distribution time, and some economic aspects. It will infect economic growth. Infected people need treatments to reduce infection period and cure the infection. In this paper, we discussed about a mathematical model of seasonal influenza with treatment. Factually, the disease was held in short period, less than one year. Hence, we can assume that the population is constant at the disease outbreak time. In this paper, we analyzed the existence of the equilibrium points of the model and their stability. We also give some simulation to give a geometric image about the results of the analysis process.

  17. Application of the compensated Arrhenius formalism to explain the dielectric constant dependence of rates for Menschutkin reactions.

    Science.gov (United States)

    Petrowsky, Matt; Glatzhofer, Daniel T; Frech, Roger

    2013-11-21

    The dependence of the reaction rate on solvent dielectric constant is examined for the reaction of trihexylamine with 1-bromohexane in a series of 2-ketones over the temperature range 25-80 °C. The rate constant data are analyzed using the compensated Arrhenius formalism (CAF), where the rate constant assumes an Arrhenius-like equation that also contains a dielectric constant dependence in the exponential prefactor. The CAF activation energies are substantially higher than those obtained using the simple Arrhenius equation. A master curve of the data is observed by plotting the prefactors against the solvent dielectric constant. The master curve shows that the reaction rate has a weak dependence on dielectric constant for values approximately less than 10 and increases more rapidly for dielectric constant values greater than 10.

  18. In situ and laboratory determined first-order degradation rate constants of specific organic compounds in an aerobic aquifer

    DEFF Research Database (Denmark)

    Nielsen, P.H.; Bjerg, P.L.; Nielsen, P.;

    1996-01-01

    experiments. First-order degradation rate constants for aromatic and phenolic hydrocarbons ranged between 0.01 and 0.9 day(-1). Local variations in first-order degradation rates and variations between rate constants determined by ISM and LBM were generally with in a factor of 5, but no systematic differences...

  19. Theoretical study of the mechanism and rate constant of the B + CO2 reaction.

    Science.gov (United States)

    Poully, Benjamin; Bergeat, Astrid; Hannachi, Yacine

    2008-09-04

    The different stationary points on the potential energy surface relative to the title reaction have been reinvestigated at the B3LYP/aug-cc-pVDZ level with relative energies computed at the CCSD(T)/aug-cc-pVTZ level with B3LYP/aug-cc-pVDZ optimized geometries and by using the G3B3 composite method. Two entrance channels have been identified. The first one corresponds to boron addition at one of the oxygen atoms of the CO 2 molecule leading to trans-BOCO, which is found to be about 27 kcal/mol exothermic with a potential energy barrier of 16.4 kcal/mol (G3B3). The second channel, which has not been identified in previous theoretical works, corresponds to a direct insertion of the boron atom into a CO bond and leads to OBCO. The B + CO 2 --> OBCO step is found to be about 84 kcal/mol exothermic and needs to overcome a potential energy barrier of only 3.6 kcal/mol (G3B3). The rate constant at 300 K of the insertion step, calculated by using TST theory with G3B3 calculated activation energy value, is 5.4 10 (-14) cm (3) molecule (-1) s (-1), in very good agreement with the experimental data ((7.0 +/- 2.8) 10 (-14) cm (3) molecule (-1) s (-1), DiGiuseppe, T. G.; Davidovits, P. J. Chem. Phys. 1981, 74, 3287). The one corresponding to the addition process is found to be several orders of magnitude smaller because of a much higher potential energy barrier. The addition channel would not contribute to the title reaction even at high temperature. A modified Arrhenius equation has been fitted in the 300-1000 K temperature range, which might be useful for chemical models.

  20. Shock tube measurements of the rate constants for seven large alkanes+OH

    KAUST Repository

    Badra, Jihad

    2015-01-01

    Reaction rate constants for seven large alkanes + hydroxyl (OH) radicals were measured behind reflected shock waves using OH laser absorption. The alkanes, n-hexane, 2-methyl-pentane, 3-methyl-pentane, 2,2-dimethyl-butane, 2,3-dimethyl-butane, 2-methyl-heptane, and 4-methyl-heptane, were selected to investigate the rates of site-specific H-abstraction by OH at secondary and tertiary carbons. Hydroxyl radicals were monitored using narrow-line-width ring-dye laser absorption of the R1(5) transition of the OH spectrum near 306.7 nm. The high sensitivity of the diagnostic enabled the use of low reactant concentrations and pseudo-first-order kinetics. Rate constants were measured at temperatures ranging from 880 K to 1440 K and pressures near 1.5 atm. High-temperature measurements of the rate constants for OH + n-hexane and OH + 2,2-dimethyl-butane are in agreement with earlier studies, and the rate constants of the five other alkanes with OH, we believe, are the first direct measurements at combustion temperatures. Using these measurements and the site-specific H-abstraction measurements of Sivaramakrishnan and Michael (2009) [1,2], general expressions for three secondary and two tertiary abstraction rates were determined as follows (the subscripts indicate the number of carbon atoms bonded to the next-nearest-neighbor carbon): S20=1.58×10-11exp(-1550K/T)cm3molecule-1s-1(887-1327K)S30=2.37×10-11exp(-1850K/T)cm3molecule-1s-1(887-1327K)S21=4.5×10-12exp(-793.7K/T)cm3molecule-1s-1(833-1440K)T100=2.85×10-11exp(-1138.3K/T)cm3molecule-1s-1(878-1375K)T101=7.16×10-12exp(-993K/T)cm3molecule-1s-1(883-1362K) © 2014 The Combustion Institute.

  1. Size dependence of surface thermodynamic properties of nanoparticles and its determination method by reaction rate constant

    Energy Technology Data Exchange (ETDEWEB)

    Li, Wenjiao; Xue, Yongqiang, E-mail: xyqlw@126.com; Cui, Zixiang

    2016-08-15

    Surface thermodynamic properties are the fundamental properties of nanomaterials, and these properties depend on the size of nanoparticles. In this paper, relations of molar surface thermodynamic properties and surface heat capacity at constant pressure of nanoparticles with particle size were derived theoretically, and the method of obtaining the surface thermodynamic properties by reaction rate constant was put forward. The reaction of nano-MgO with sodium bisulfate solution was taken as a research system. The influence regularities of the particle size on the surface thermodynamic properties were discussed theoretically and experimentally, which show that the experimental regularities are in accordance with the corresponding theoretical relations. With the decreasing of nanoparticle size, the molar surface thermodynamic properties increase, while the surface heat capacity decreases (the absolute value increases). In addition, the surface thermodynamic properties are linearly related to the reciprocal of nanoparticle diameter, respectively.

  2. Acclimation to constant and variable temperatures in plethodontid salamanders--I. Rates of oxygen consumption.

    Science.gov (United States)

    Feder, M E

    1985-01-01

    In preliminary experiments, salamanders of three species (Desmognathus ochrophaeus, Plethodon cinereus and Plethodon jordani) required 5-11 days to complete metabolic acclimation to a constant warm temperature; the rate of oxygen consumption (VO2) decreased 16-28% during acclimation. Unfed animals of each species underwent cyclic exposure to 5 and 21 degrees C at three different cycle periods (12 hr, 4-5 days, 51 days), or constant exposure to 14 degrees C for 102 days. The experimental treatments significantly affected the VO2 measured at 5, 14, 17.5 and 21 degrees C. The direction and magnitude of the acclimatory effects upon VO2 were inconsistent among species and among experimental temperatures, and resulted in little energy saving. The VO2 during exposure to cyclic temperatures averaged only 83% of that during preliminary experiments, perhaps as a response to starvation.

  3. A Method for Achieving Constant Rotation Rates in a Micro-Orthogonal Linkage System

    Energy Technology Data Exchange (ETDEWEB)

    Dickey, F.M.; Holswade, S.C.; Romero, L.A.

    1999-05-12

    Silicon micromachine designs include engines that consist of orthog- onally oriented linear comb drive actuators mechanically connected to a rotating gear. These gears are as small as 50 {micro}m in diameter and can be driven at rotation rates exceeding 300,000 rpm. Generally, these en- gines will run with non-uniform rotation rates if the drive signals are not properly designed and maintained over a range of system parameters. We present a method for producing constant rotation rates in a micro-engine driven by an orthogonal linkage system. We show that provided the val- ues of certain masses, springs, damping factors, and lever arms are in the right proportions, the system behaves as though it were symmetrical. We will refer to systems built in this way as being quasi-symmetrical. We show that if a system is built quasi-symmetrically , then it is possible to achieve constant rotation rates even if one does not know the form of the friction function, or the value of the friction. We analyze this case in some detail.

  4. Measured dose rate constant from oncology patients administered 18F for positron emission tomography

    Energy Technology Data Exchange (ETDEWEB)

    Quinn, Brian; Holahan, Brian; Aime, Jean; Humm, John; St Germain, Jean; Dauer, Lawrence T. [Department of Medical Physics, Memorial Sloan-Kettering Cancer Center, 1275 York Avenue, New York, New York 10065 (United States); Department of Radiology, Memorial Sloan-Kettering Cancer Center, 1275 York Avenue, New York, New York 10065 (United States); Department of Medical Physics, Memorial Sloan-Kettering Cancer Center, 1275 York Avenue, New York, New York 10065 (United States) and Department of Radiology, Memorial Sloan-Kettering Cancer Center, 1275 York Avenue, New York, New York 10065 (United States); Department of Medical Physics, Memorial Sloan-Kettering Cancer Center, 1275 York Avenue, New York, New York 10065 (United States); Department of Medical Physics, Memorial Sloan-Kettering Cancer Center, 1275 York Avenue, New York, New York 10065 (United States) and Department of Radiology, Memorial Sloan-Kettering Cancer Center, 1275 York Avenue, New York, New York 10065 (United States)

    2012-10-15

    Purpose: Patient exposure rate measurements verify published patient dose rate data and characterize dose rates near 2-18-fluorodeoxyglucose ({sup 18}F-FDG) patients. A specific dose rate constant based on patient exposure rate measurements is a convenient quantity that can be applied to the desired distance, injection activity, and time postinjection to obtain an accurate calculation of cumulative external radiation dose. This study reports exposure rates measured at various locations near positron emission tomography (PET) {sup 18}F-FDG patients prior to PET scanning. These measurements are normalized for the amount of administered activity, measurement distance, and time postinjection and are compared with other published data. Methods: Exposure rates were measured using a calibrated ionization chamber at various body locations from 152 adult oncology patients postvoid after a mean uptake time of 76 min following injection with a mean activity of 490 MBq {sup 18}F-FDG. Data were obtained at nine measurement locations for each patient: three near the head, four near the chest, and two near the feet. Results: On contact with, 30 cm superior to and 30 cm lateral to the head, the mean (75th percentile) dose rates per unit injected activity at 60 min postinjection were 0.482 (0.511), 0.135 (0.155), and 0.193 (0.223) {mu}Sv/MBq h, respectively. On contact with, 30 cm anterior to, 30 cm lateral to and 1 m anterior to the chest, the mean (75th percentile) dose rates per unit injected activity at 60 min postinjection were 0.623 (0.709), 0.254 (0.283), 0.190 (0.218), and 0.067 (0.081) {mu}Sv/MBq h respectively. 30 cm inferior and 30 cm lateral to the feet, the mean (75th percentile) dose rates per unit injected activity at 60 min postinjection were 0.024 (0.022) and 0.039 (0.044) {mu}Sv/MBq h, respectively. Conclusions: The measurements for this study support the use of 0.092 {mu}Sv m{sup 2}/MBq h as a reasonable representation of the dose rate anterior from the chest of

  5. Calorimetric determination of rate constants and enthalpy changes for zero-order reactions.

    Science.gov (United States)

    Almeida e Sousa, Luis; Beezer, Anthony E; Hansen, Lee D; Clapham, David; Connor, Joseph A; Gaisford, Simon

    2012-06-07

    Calorimetry is a general method for determination of the rates of zero-order processes, but analysis of the data for the rate constant and reaction enthalpy is difficult because these occur as a product in the rate equation so evaluation of one requires knowledge of the other. Three methods for evaluation of both parameters, without prior knowledge, are illustrated with examples and compared with literature data. Method 1 requires the reaction to be studied in two buffers with different enthalpies of ionization. Method 2 is based on calculation of reaction enthalpy from group additivity functions. Method 3 applies when reaction progresses to completion. The methods are applied to the enzymatic hydrolysis of urea, the hydrolysis of acetylsalicylic acid, and the photodegradation of nifedipine, respectively.

  6. Evaluation and comparison of diffusion MR methods for measuring apparent transcytolemmal water exchange rate constant

    Science.gov (United States)

    Tian, Xin; Li, Hua; Jiang, Xiaoyu; Xie, Jingping; Gore, John C.; Xu, Junzhong

    2017-02-01

    Two diffusion-based approaches, CG (constant gradient) and FEXI (filtered exchange imaging) methods, have been previously proposed for measuring transcytolemmal water exchange rate constant kin, but their accuracy and feasibility have not been comprehensively evaluated and compared. In this work, both computer simulations and cell experiments in vitro were performed to evaluate these two methods. Simulations were done with different cell diameters (5, 10, 20 μm), a broad range of kin values (0.02-30 s-1) and different SNR's, and simulated kin's were directly compared with the ground truth values. Human leukemia K562 cells were cultured and treated with saponin to selectively change cell transmembrane permeability. The agreement between measured kin's of both methods was also evaluated. The results suggest that, without noise, the CG method provides reasonably accurate estimation of kin especially when it is smaller than 10 s-1, which is in the typical physiological range of many biological tissues. However, although the FEXI method overestimates kin even with corrections for the effects of extracellular water fraction, it provides reasonable estimates with practical SNR's and more importantly, the fitted apparent exchange rate AXR showed approximately linear dependence on the ground truth kin. In conclusion, either CG or FEXI method provides a sensitive means to characterize the variations in transcytolemmal water exchange rate constant kin, although the accuracy and specificity is usually compromised. The non-imaging CG method provides more accurate estimation of kin, but limited to large volume-of-interest. Although the accuracy of FEXI is compromised with extracellular volume fraction, it is capable of spatially mapping kin in practice.

  7. Shock tube measurements of the rate constant for the reaction ethanol + OH.

    Science.gov (United States)

    Stranic, Ivo; Pang, Genny A; Hanson, Ronald K; Golden, David M; Bowman, Craig T

    2014-02-06

    The overall rate constant for the reaction ethanol + OH → products was determined experimentally from 900 to 1270 K behind reflected shock waves. Ethan(18)ol was utilized for these measurements in order to avoid the recycling of OH radicals following H-atom abstraction at the β-site of ethanol. Similar experiments were also performed with unlabeled ethan(16)ol in order to infer the rate constant that excludes reactivity at the β-site. The two data sets were used to directly infer the branching ratio for the reaction at the β-site. Experimental data in the current study and in previous low-temperature studies for the overall rate constant are best fit by the expression koverall = 5.07 × 10(5) T[K](2.31) exp(608/T[K]) cm(3) mol(-1) s(-1), valid from 300 to 1300 K. Measurements indicate that the branching ratio of the β-site is between 20 and 25% at the conditions studied. Pseudo-first-order reaction conditions were generated using tert-butylhydroperoxide (TBHP) as a fast source of (16)OH with ethanol in excess. (16)OH mole fraction time-histories were measured using narrow-line width laser absorption near 307 nm. Measurements were performed at the linecenter of the R22(5.5) transition in the A-X(0,0) band of (16)OH that does not overlap with any absorption features of (18)OH, thus producing a measurement of the (16)OH mole fraction that is insensitive to the presence of (18)OH.

  8. The constant work rate critical power protocol overestimates ramp incremental exercise performance.

    Science.gov (United States)

    Black, Matthew I; Jones, Andrew M; Kelly, James A; Bailey, Stephen J; Vanhatalo, Anni

    2016-12-01

    The parameters of the power-duration relationship (i.e., the critical power, CP, and the curvature constant, W') may theoretically predict maximal performance capability for exercise above the CP. The CP and W' are associated with the parameters of oxygen uptake ([Formula: see text]O2) kinetics, which can be altered by manipulation of the work-rate forcing function. We tested the hypothesis that the CP and W' derived from constant work-rate (CWR) prediction trials would overestimate ramp incremental exercise performance. Thirty subjects (males, n = 28; females, n = 2) performed a ramp incremental test, and 3-5 CWR prediction trials for the determination of the CP and W'. Multiple ramp incremental tests and corresponding CP and W' estimates were available for some subjects such that in total 51 ramp test performances were predicted. The ramp incremental test performance (729 ± 113 s) was overestimated by the CP and W' estimates derived from the best (751 ± 114 s, P incremental performance suggests that the CP and W' derived from different work-rate forcing functions, thus resulting in different [Formula: see text]O2 kinetics, cannot be used interchangeably. The present findings highlight a potential source of error in performance prediction that is of importance to both researchers and applied practitioners.

  9. Subcritical crack growth in oxide and non-oxide ceramics using the Constant Stress Rate Test

    Directory of Open Access Journals (Sweden)

    Agnieszka Wojteczko

    2015-12-01

    Full Text Available Fracture toughness is one of the most important parameters for ceramics description. In some cases, material failure occurs at lower stresses than described by KIc parameter. In these terms, determination of fracture toughness only, proves to be insufficient. This may be due to environmental factors, such as humidity, which might cause subcritical crack propagation in a material. Therefore, it is very important to estimate crack growth velocities to predict lifetime of ceramics used under specific conditions. Constant Stress Rate Test is an indirect method of subcritical crack growth parameters estimation. Calculations are made by using strength data, thus avoiding crack measurement. The expansion of flaws causes reduction of material strength. If subcritical crack growth phenomenon occurs, critical value of crack lengths increases with decreasing stress rate due to longer time for flaw to grow before the critical crack propagation at KIc takes place. Subcritical crack growth phenomenon is particularly dangerous for oxide ceramics due to chemical interactions occurring as a result of exposure to humidity. This paper presents results of Constant Stress Rate Test performed for alumina, zirconia, silicon carbide and silicon nitride in order to demonstrate the differences in subcritical crack propagation phenomenon course.

  10. Perturbation theory in the catalytic rate constant of the Henri-Michaelis-Menten enzymatic reaction.

    Science.gov (United States)

    Bakalis, Evangelos; Kosmas, Marios; Papamichael, Emmanouel M

    2012-11-01

    The Henry-Michaelis-Menten (HMM) mechanism of enzymatic reaction is studied by means of perturbation theory in the reaction rate constant k (2) of product formation. We present analytical solutions that provide the concentrations of the enzyme (E), the substrate (S), as well as those of the enzyme-substrate complex (C), and the product (P) as functions of time. For k (2) small compared to k (-1), we properly describe the entire enzymatic activity from the beginning of the reaction up to longer times without imposing extra conditions on the initial concentrations E ( o ) and S ( o ), which can be comparable or much different.

  11. Application guide for source PM10 measurement with constant sampling rate

    Energy Technology Data Exchange (ETDEWEB)

    Farthing, W.E.; Dawes, S.S.

    1989-05-01

    The manual presents a method, Constant Sampling Rate (CSR), which allows determination of stationary source PM-10 emissions with hardware similar to that used for Methods 5 or 17. The operating principle of the method is to extract a multipoint sample so that errors due to spatial variation of particle size and anisokinetic sampling are kept within predetermined limits. The manual specifically addresses the use of the CSR methodology for determination of stationary source PM-10 emissions. Material presented in the manual includes calibration of sampling train components, pretest setup calculations, sample recovery, test data reduction, and routine equipment maintenance.

  12. Power consumption analysis of constant bit rate video transmission over 3G networks

    DEFF Research Database (Denmark)

    Ukhanova, Ann; Belyaev, Evgeny; Wang, Le

    2012-01-01

    for the 3GPP transition state machine that allows to decrease power consumption on a mobile device taking signaling traffic, buffer size and latency restrictions into account. Furthermore, we discuss the gain in power consumption vs. PSNR for transmitted video and show the possibility of performing power......This paper presents an analysis of the power consumption of video data transmission with constant bit rate over 3G mobile wireless networks. The work includes the description of the radio resource control transition state machine in 3G networks, followed by a detailed power consumption analysis...... consumption management based on the requirements for the video quality....

  13. Electron attachment rate constant measurement by photoemission electron attachment ion mobility spectrometry (PE-EA-IMS)

    Science.gov (United States)

    Su, Desheng; Niu, Wenqi; Liu, Sheng; Shen, Chengyin; Huang, Chaoqun; Wang, Hongmei; Jiang, Haihe; Chu, Yannan

    2012-12-01

    Photoemission electron attachment ion mobility spectrometry (PE-EA-IMS), with a source of photoelectrons induced by vacuum ultraviolet radiation on a metal surface, has been developed to study electron attachment reaction at atmospheric pressure using nitrogen as the buffer gas. Based on the negative ion mobility spectra, the rate constants for electron attachment to tetrachloromethane and chloroform were measured at ambient temperature as a function of the average electron energy in the range from 0.29 to 0.96 eV. The experimental results are in good agreement with the data reported in the literature.

  14. Rate constants for chemical reactions in high-temperature nonequilibrium air

    Science.gov (United States)

    Jaffe, R. L.

    1986-01-01

    In the nonequilibrium atmospheric chemistry regime that will be encountered by the proposed Aeroassisted Orbital Transfer Vehicle in the upper atmosphere, where air density is too low for thermal and chemical equilibrium to be maintained, the detailed high temperature air chemistry plays a critical role in defining radiative and convective heating loads. Although vibrational and electronic temperatures remain low (less than 15,000 K), rotational and translational temperatures may reach 50,000 K. Attention is presently given to the effects of multiple temperatures on the magnitudes of various chemical reaction rate constants, for the cases of both bimolecular exchange reactions and collisional excitation and dissociation reactions.

  15. Feature analysis of the scale factor variation on a constant rate biased ring laser gyro

    Institute of Scientific and Technical Information of China (English)

    Shiqiao Qin; Zongsheng Huang; Xingshu Wang

    2007-01-01

    Scale factor of a constant rate biased ring laser gyro (RLG) is studied both theoretically and experimentally.By analyzing experimental data, we find that there are three main terms contributing to the scale factor deviation. One of them is independent of time, the second varies linearly with time and the third varies exponentially with time. Theoretical analyses show that the first term is caused by experimental setup,the second and the third are caused by un-uniform thermal expension and cavity loss variation of the RLG.

  16. The WiggleZ Dark Energy Survey: constraining the evolution of Newton's constant using the growth rate of structure

    CERN Document Server

    Nesseris, Savvas; Davis, Tamara; Parkinson, David

    2011-01-01

    We constrain the evolution of Newton's constant using the growth rate of large-scale structure measured by the WiggleZ Dark Energy Survey in the redshift range $0.1 < z < 0.9$. We use this data in two ways. Firstly we constrain the matter density of the Universe, $\\Omega_m$ (assuming General Relativity), and use this to construct a diagnostic to detect the presence of an evolving Newton's constant. Secondly we directly measure the evolution of Newton's constant, $G_{eff}$, that appears in Modified Gravity theories, without assuming General Relativity to be true. The novelty of these approaches are that, contrary to other methods, they do not require knowledge of the expansion history of the Universe, $H(z)$, making them model independent tests. Our constraints for the second derivative of Newton's constant at the present day, assuming it is slowly evolving as suggested by Big Bang Nucleosynthesis constraints, using the WiggleZ data is $\\ddotGeff(t_0)=-1.19\\pm 0.95\\cdot 10^{-20}h^2 yr^{-2}$, where $h$ is...

  17. Flowing afterglow: construction of an apparatus, measurement of rate constants, and consideration of the diffusive behavior of charges

    Energy Technology Data Exchange (ETDEWEB)

    Matsuoka, Shingo; Nakamura, Hirone; Tamura, Takaaki (Tokyo Univ., Tokai, Ibaraki (Japan). Nuclear Engineering Research Lab.); Fujii, Toshihiro

    1984-06-01

    A flowing afterglow apparatus was constructed and the operation of the afterglow system including data analysis was tested by measuring the rate constants for the reactions N/sup +/ + NO, N/sub 2//sup +/ + NO, He/sup +/ + N/sub 2/, and SF/sub 6/ + e; the results were 5.8 x 10/sup -10/, 3.9 x 10/sup -10/, 1.20 x 10/sup -9/, and 2.1 x 10/sup -7/ cm/sup 3/s/sup -1/ respectively. In the measurements an extraction voltage for ion sampling was not applied to the nose cone in order not to introduce an electric field into the reaction region. A ''non-ambipolar'' model developed by us was used for the data analysis of the ion/molecule reactions. For the data analysis of the electron attachment, a typical curve fit mehtod to the product ion signal was used. However, no theoretical curves fit the experimental points. This disagreement is attributed to a change of the ion-sampling efficiency through the nose-cone aperture arising from a change of the electron-dominated plasma to a negative-ion-dominated plasma with an increasing flow rate of SF/sub 6/. Nevertheless, the attachment rate could be determined by fitting the theoretical and experimantal curves in the limited region of the SF/sub 6/ flow rate where the negative-ion-dominated plasma is established at the sampling aperture. All the rate constants obtained here agree reasonably well with literature values. Next, errors in the positive ion/molecule reaction rate constants, which would occur if the diffusion coefficients of the ions and neutrals each have a + 10 % error were calculated for the flow model to be -0.4 and +1.2 % respectively, demonstrating that these parameters are not important in the analysis of data. This insensitivity explains why the nose-cone voltage applied in a typical flowing afterglow operation has not caused a significant error in the published rate constants although it disturbs the ion diffusive behavior.

  18. Comments to "Analysis of constant rate period of spray drying of slurry" by Liang et al., 2001

    DEFF Research Database (Denmark)

    Jørgensen, Kåre; Jensen, Anker Degn; Sloth, Jakob;

    2006-01-01

    In the study by Liang et al. [2001. Analysis of constant rate period of spray drying of slurry. Chemical Engineering Science 56, 2205-2213] the Darcy flow of liquid through a pore system of primary particles to the surface of a slurry droplet was applied for the constant rate period. Steep primary...

  19. Comments to ”Analysis of constant rate period of spray drying of slurry” by Liang et al

    DEFF Research Database (Denmark)

    Jørgensen, Kåre; Jensen, Anker; Sloth, Jakob;

    2006-01-01

    In the study by Liang et al. [2001. Analysis of constant rate period of spray drying of slurry. Chemical Engineering Science 56, 2205-2213] the Darcy flow of liquid through a pore system of primary particles to the surface of a slurry droplet was applied for the constant rate period. Steep primary...

  20. Computational study of the rate constants and free energies of intramolecular radical addition to substituted anilines

    Directory of Open Access Journals (Sweden)

    Andreas Gansäuer

    2013-08-01

    Full Text Available The intramolecular radical addition to aniline derivatives was investigated by DFT calculations. The computational methods were benchmarked by comparing the calculated values of the rate constant for the 5-exo cyclization of the hexenyl radical with the experimental values. The dispersion-corrected PW6B95-D3 functional provided very good results with deviations for the free activation barrier compared to the experimental values of only about 0.5 kcal mol−1 and was therefore employed in further calculations. Corrections for intramolecular London dispersion and solvation effects in the quantum chemical treatment are essential to obtain consistent and accurate theoretical data. For the investigated radical addition reaction it turned out that the polarity of the molecules is important and that a combination of electrophilic radicals with preferably nucleophilic arenes results in the highest rate constants. This is opposite to the Minisci reaction where the radical acts as nucleophile and the arene as electrophile. The substitution at the N-atom of the aniline is crucial. Methyl substitution leads to slower addition than phenyl substitution. Carbamates as substituents are suitable only when the radical center is not too electrophilic. No correlations between free reaction barriers and energies (ΔG‡ and ΔGR are found. Addition reactions leading to indanes or dihydrobenzofurans are too slow to be useful synthetically.

  1. Computational study of the rate constants and free energies of intramolecular radical addition to substituted anilines

    Science.gov (United States)

    Seddiqzai, Meriam; Dahmen, Tobias; Sure, Rebecca

    2013-01-01

    Summary The intramolecular radical addition to aniline derivatives was investigated by DFT calculations. The computational methods were benchmarked by comparing the calculated values of the rate constant for the 5-exo cyclization of the hexenyl radical with the experimental values. The dispersion-corrected PW6B95-D3 functional provided very good results with deviations for the free activation barrier compared to the experimental values of only about 0.5 kcal mol−1 and was therefore employed in further calculations. Corrections for intramolecular London dispersion and solvation effects in the quantum chemical treatment are essential to obtain consistent and accurate theoretical data. For the investigated radical addition reaction it turned out that the polarity of the molecules is important and that a combination of electrophilic radicals with preferably nucleophilic arenes results in the highest rate constants. This is opposite to the Minisci reaction where the radical acts as nucleophile and the arene as electrophile. The substitution at the N-atom of the aniline is crucial. Methyl substitution leads to slower addition than phenyl substitution. Carbamates as substituents are suitable only when the radical center is not too electrophilic. No correlations between free reaction barriers and energies (ΔG ‡ and ΔG R) are found. Addition reactions leading to indanes or dihydrobenzofurans are too slow to be useful synthetically. PMID:24062821

  2. Quantum-instanton evaluation of the isotopic effects on the rate constants

    Science.gov (United States)

    Vanicek, Jiri; Miller, William H.

    2004-03-01

    We present a general quantum-mechanical method suitable for numerical evaluation of the isotopic effects on the rate constants of chemical reactions. Our method is based on the quantum instanton approximation [1-3] and on the path-integral Metropolis Monte-Carlo evaluation of the Boltzmann operator matrix elements. The method is more accurate than existing transition-state theory or semiclassical instanton method since we do not assume a single reaction path and do not use a semiclassical approximation of the Boltzmann operator. In order to calculate the isotopic effect we use a "charging algoritm," whereby the mass of the isotope is continuously changed from the initial to the final value. Direct calculation of the isotopic ratio turns out to be much more efficient than finding the absolute rate constants first and then calculating their ratio. While the Monte-Carlo implementation should make the method accessible to systems with a larger number of atoms, we present numerical results for the Eckart barrier and for the reactions H + H2 arrow H2 + H and H + DH arrow HD + H. [1] W.H. Miller, Y. Zhao, M. Ceotto, and Sandy Yang, J. Chem. Phys. 119, 1329 (2003). [2] T. Yamamoto and W.H. Miller, J. Chem. Phys. (in press). [3] Y. Zhao, T. Yamamoto, and W.H. Miller, J. Chem. Phys. (in press).

  3. Rate constants of chemical reactions from semiclassical transition state theory in full and one dimension.

    Science.gov (United States)

    Greene, Samuel M; Shan, Xiao; Clary, David C

    2016-06-28

    Semiclassical Transition State Theory (SCTST), a method for calculating rate constants of chemical reactions, offers gains in computational efficiency relative to more accurate quantum scattering methods. In full-dimensional (FD) SCTST, reaction probabilities are calculated from third and fourth potential derivatives along all vibrational degrees of freedom. However, the computational cost of FD SCTST scales unfavorably with system size, which prohibits its application to larger systems. In this study, the accuracy and efficiency of 1-D SCTST, in which only third and fourth derivatives along the reaction mode are used, are investigated in comparison to those of FD SCTST. Potential derivatives are obtained from numerical ab initio Hessian matrix calculations at the MP2/cc-pVTZ level of theory, and Richardson extrapolation is applied to improve the accuracy of these derivatives. Reaction barriers are calculated at the CCSD(T)/cc-pVTZ level. Results from FD SCTST agree with results from previous theoretical and experimental studies when Richardson extrapolation is applied. Results from our implementation of 1-D SCTST, which uses only 4 single-point MP2/cc-pVTZ energy calculations in addition to those for conventional TST, agree with FD results to within a factor of 5 at 250 K. This degree of agreement and the efficiency of the 1-D method suggest its potential as a means of approximating rate constants for systems too large for existing quantum scattering methods.

  4. Direct evaluation of the temperature dependence of the rate constant based on the quantum instanton approximation

    CERN Document Server

    Buchowiecki, Marcin

    2010-01-01

    A general method for the direct evaluation of the temperature dependence of the quantum-mechanical reaction rate constant in many-dimensional systems is described. The method is based on the quantum instanton approximation for the rate constant, thermodynamic integration with respect to the inverse temperature, and the path integral Monte Carlo evaluation. It can describe deviations from the Arrhenius law due to the coupling of rotations and vibrations, zero-point energy, tunneling, corner-cutting, and other nuclear quantum effects. The method is tested on the Eckart barrier and the full-dimensional H + H_2 -> H_2 + H reaction. In the temperature range from 300K to 1500K, the error of the present method remains within 13% despite the very large deviations from the Arrhenius law. The direct approach makes the calculations much more efficient, and the efficiency is increased even further (by up to two orders of magnitude in the studied reactions) by using optimal estimators for reactant and transition state the...

  5. Determination of the epimerization rate constant of amygdalin by microemulsion electrokinetic chromatography.

    Science.gov (United States)

    Yu, Lishuang; Ye, Hongzhi; Zheng, Lili; Chen, Lidian; Chu, Kedan; Liu, Xianxiang; Xu, Xueqin; Chen, Guonan

    2011-01-01

    A new method for separation and determination of amygdalin and its epimer (neoamygdalin) in the epimerization of amygdalin by MEEKC is proposed. For the chiral separation of amygdalin and neoamygdalin, a running buffer composed of 80 mM sodium cholate, 5.0% v/v butan-1-ol, 0.5% v/v heptane and 94.5% v/v 30 mM Na(2) B(4) O(7) buffer (pH 9.00) is proposed. Under optimum conditions, the basic separation of amygdalin and neoamygdalin can be achieved within 7 min. The calibration curve for amygdalin showed excellent linearity in the concentration range of 20-1000 μg/mL with a detection limit of 5.0 μg/mL (S/N=3). The epimerization rate constant of amygdalin in basic microemulsion was first determined by monitoring the concentration changes of amygdalin, and the epimerization rate constant of amygdalin was found to be 2×10(-3) min(-1) at 25°C under the above optimum microemulsion conditions. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Rate constant for the reaction of atomic oxygen with phosphine at 298 K

    Science.gov (United States)

    Stief, L. J.; Payne, W. A.; Nava, D. F.

    1987-01-01

    The rate constant for the reaction of atomic oxygen with phosphine has been measured at 298 K using flash photolysis combined with time-resolved detection of O(3P) via resonance fluorescence. Atomic oxygen was produced by flash photolysis of N2O or NO highly diluted in argon. The results were shown to be independent of (PH3), (O), total pressure and the source of O(3P). The mean value of all the experiments is k1 = (3.6 + or -0.8) x 10 to the -11th cu cm/s (1 sigma). Two previous measurements of k1 differed by more than an order of magnitude, and the results support the higher value obtained in a discharge flow-mass spectrometry study. A comparison with rate data for other atomic and free radical reactions with phosphine is presented, and the role of these reactions in the aeronomy or photochemistry of Jupiter and Saturn is briefly considered.

  7. Rate Constant and Branching Fraction for the NH2 + NO2 Reaction

    DEFF Research Database (Denmark)

    Klippenstein, Stephen J.; Harding, Lawrence B.; Glarborg, Peter

    2013-01-01

    The NH2 + NO2 reaction has been studied experimentally and theoretically. On the basis of laser photolysis/LIF experiments, the total rate constant was determined over the temperature range 295–625 K as k1,exp(T) = 9.5 × 10–7(T/K)−2.05 exp(−404 K/T) cm3 molecule–1 s–1. This value is in the upper...... may facilitate a small flux between the adducts. High- and low-pressure limit rate coefficients for the various product channels of NH2 + NO2 are determined from the ab initio TST-based master equation calculations for the temperature range 300–2000 K. The theoretical predictions are in good agreement...

  8. Protein balance and evaluation of velocity constant k (drained rate on syneresis of milk

    Directory of Open Access Journals (Sweden)

    Migena Hoxha

    2013-12-01

    Full Text Available The syneresis process is influenced by various factors such as milk pH, curd incubation temperature, fat content, heat treatment of milk, acidity, salt, curd dimension and gel firmness at cutting time. The aim of this study was to investigate balance of protein, the syneresis kinetic of whey drainage and evaluation of velocity constant k (drained rate on curd incubation temperature (25 and 30oC and heat treatment (at 70oC for 5 minutes. Milk was sampled from cow, sheep and goat breeds. The milk samples were analyzed for physical and chemical properties (pH, acidity, protein, casein, fat and lactose, coagulation parameters (R coagulation time in minutes, curd firmness measured in volt after 20 minutes (A20 or 30 minutes (A30 and the rate of firming K20 in minutes as well as for whey volume drained after 30, 50, 70, 90, 110, 130 and 150 minutes. During this study it was observed that the curd incubation temperature is the major factor affecting syneresis. Velocity constant k value (drained rate is increased with higher temperature, but can be decrease significantly at low temperature. The syneresis rate differs between breed’s milk and is influenced by their coagulation properties. Regarding balance of protein, protein recovery and curd yield results to be higher at incubation temperature of 25oC, in spite of breed. Whey protein loss result to be higher for goat’s milk on two incubation temperature (41.05–58.35%, while the whey loss on sheep’s milk result to be lower (14.01–37.61%.

  9. Non-steady state mass action dynamics without rate constants: dynamics of coupled reactions using chemical potentials

    Science.gov (United States)

    Cannon, William R.; Baker, Scott E.

    2017-10-01

    Comprehensive and predictive simulation of coupled reaction networks has long been a goal of biology and other fields. Currently, metabolic network models that utilize enzyme mass action kinetics have predictive power but are limited in scope and application by the fact that the determination of enzyme rate constants is laborious and low throughput. We present a statistical thermodynamic formulation of the law of mass action for coupled reactions at both steady states and non-stationary states. The formulation uses chemical potentials instead of rate constants. When used to model deterministic systems, the method corresponds to a rescaling of the time dependent reactions in such a way that steady states can be reached on the same time scale but with significantly fewer computational steps. The relationships between reaction affinities, free energy changes and generalized detailed balance are central to the discussion. The significance for applications in systems biology are discussed as is the concept and assumption of maximum entropy production rate as a biological principle that links thermodynamics to natural selection.

  10. Fast proton exchange in histidine: measurement of rate constants through indirect detection by NMR spectroscopy.

    Science.gov (United States)

    Sehgal, Akansha Ashvani; Duma, Luminita; Bodenhausen, Geoffrey; Pelupessy, Philippe

    2014-05-19

    Owing to its imidazole side chain, histidine participates in various processes such as enzyme catalysis, pH regulation, metal binding, and phosphorylation. The determination of exchange rates of labile protons for such a system is important for understanding its functions. However, these rates are too fast to be measured directly in an aqueous solution by using NMR spectroscopy. We have obtained the exchange rates of the NH3(+) amino protons and the labile NH(ε2) and NH(δ1) protons of the imidazole ring by indirect detection through nitrogen-15 as a function of temperature (272 KExchange rates up to 8.5×10(4) s(-1) could be determined (i.e., lifetimes as short as 12 μs). The three chemical shifts δH(i) of the invisible exchanging protons H(i) and the three one-bond scalar coupling constants (1)J(N,H(i)) could also be determined accurately.

  11. Model test study of evaporation mechanism of sand under constant atmospheric condition

    OpenAIRE

    Cui, Yu Jun; Ding, Wenqi; SONG, Weikang

    2014-01-01

    The evaporation mechanism of Fontainebleau sand using a large-scale model chamber is studied. First, the evaporation test on a layer of water above sand surface is performed under various atmospheric conditions, validating the performance of the chamber and the calculation method of actual evaporation rate by comparing the calculated and measured cumulative evaporations. Second,the evaporation test on sand without water layer is conducted under constant atmospheric condition. Both the evoluti...

  12. Uptake rate constants and partition coefficients for vapor phase organic chemicals using semipermeable membrane devices (SPMDs)

    Science.gov (United States)

    Cranor, W.L.; Alvarez, D.A.; Huckins, J.N.; Petty, J.D.

    2009-01-01

    To fully utilize semipermeable membrane devices (SPMDs) as passive samplers in air monitoring, data are required to accurately estimate airborne concentrations of environmental contaminants. Limited uptake rate constants (kua) and no SPMD air partitioning coefficient (Ksa) existed for vapor-phase contaminants. This research was conducted to expand the existing body of kinetic data for SPMD air sampling by determining kua and Ksa for a number of airborne contaminants including the chemical classes: polycyclic aromatic hydrocarbons, organochlorine pesticides, brominated diphenyl ethers, phthalate esters, synthetic pyrethroids, and organophosphate/organosulfur pesticides. The kuas were obtained for 48 of 50 chemicals investigated and ranged from 0.03 to 3.07??m3??g-1??d-1. In cases where uptake was approaching equilibrium, Ksas were approximated. Ksa values (no units) were determined or estimated for 48 of the chemicals investigated and ranging from 3.84E+5 to 7.34E+7. This research utilized a test system (United States Patent 6,877,724 B1) which afforded the capability to generate and maintain constant concentrations of vapor-phase chemical mixtures. The test system and experimental design employed gave reproducible results during experimental runs spanning more than two years. This reproducibility was shown by obtaining mean kua values (n??=??3) of anthracene and p,p???-DDE at 0.96 and 1.57??m3??g-1??d-1 with relative standard deviations of 8.4% and 8.6% respectively.

  13. The Constant Growth Rate of the Bound-Zone Peculiar Velocity Profile

    CERN Document Server

    Lee, Jounghun

    2016-01-01

    We present a numerical evidence that the amplitude and slope of the bound-zone peculiar velocity profile grow at the constant rates in a LambdaCDM universe. Analyzing the friends-of-friends halo catalogs from the Millennium-II simulations at various redshifts, we measure the average peculiar velocity profile of the objects located in the bound zone around massive group-size halos and compare it to an analytic formula characterized by the amplitude and slope parameters. It is shown that the amplitude and slope of the bound-zone peculiar velocity profile remain constant in the dark matter dominated epoch but begin to grow linearly with redshift after the onset of the Lambda-domination. Our explanation for this phenomenon is that as the balance between the gravitational attraction of the massive groups and the repulsive force of the Hubble expansion cracks up in the Lambda-dominated epoch, the gravitational influence on the bound-zone halos diminishes more rapidly with the increment of the radial distances. Spec...

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

    DEFF Research Database (Denmark)

    Sorvajärvi, Tapio; Viljanen, Jan; Toivonen, Juha;

    2015-01-01

    The addition reaction of potassium atoms with oxygen has been studied using the collinear photofragmentation and atomic absorption spectroscopy (CPFAAS) method. KCl vapor was photolyzed with 266 nm pulses and the absorbance by K atoms at 766.5 nm was measured at various delay times with a narrow...... line width diode laser. Experiments were carried out with O2/N2 mixtures at a total pressure of 1 bar, over 748-1323 K. At the lower temperatures single exponential decays of [K] yielded the third-order rate constant for addition, kR1, whereas at higher temperatures equilibration was observed...... in the form of double exponential decays of [K], which yielded both kR1 and the equilibrium constant for KO2 formation. kR1 can be summarized as 1.07 × 10-30(T/1000 K)-0.733 cm6 molecule-2 s-1. Combination with literature values leads to a recommended kR1 of 5.5 × 10-26T-1.55 exp(-10/T) cm6 molecule-2 s-1...

  15. Critical evaluation and rate constants of chemoselective ligation reactions for stoichiometric conjugations in water.

    Science.gov (United States)

    Saito, Fumito; Noda, Hidetoshi; Bode, Jeffrey W

    2015-04-17

    Chemoselective ligation reactions have contributed immensely to the development of organic synthesis and chemical biology. However, the ligation of stoichiometric amounts of large molecules for applications such as protein-protein conjugates is still challenging. Conjugation reactions need to be fast enough to proceed under dilute conditions and chemoselective in the presence of unprotected functional groups; the starting materials and products must be stable under the reaction conditions. To compare known ligation reactions for their suitability under these conditions, we determined the second-order rate constants of ligation reactions using peptide substrates with unprotected functional groups. The reaction conditions, the chemoselectivity of the reactions, and the stability of the starting materials and products were carefully evaluated. In some cases, the stability could be improved by modifying the substrate structure. These data obtained under the ligation conditions provide a useful guide to choose an appropriate ligation reaction for synthesis of large molecules by covalent ligation reactions of unprotected substrates in water.

  16. Temperature dependence of the absolute rate constant for the reaction of ozone with dimethyl sulfide

    Institute of Scientific and Technical Information of China (English)

    WANG Hai-tao; ZHANG Yu-jie; MU Yu-jing

    2007-01-01

    Absolute rate constants for the reaction of ozone with dimethyl sulfide (DMS) were measured in a 200-L Teflon chamber over the temperature range of 283-353 K. Measurements were carried out using DMS in large excess over ozone of 10 to 1 or greater. Over the indicated temperature range,the data could be fit to the simple Arrhenius expression as KDMS = (9.96±3.61)×10-11exp(-(7309.7±1098.2)/T)cm3/(molecule·s). A compared investigation of the reaction between ozone and ethene had a kc2H4 value of(1.35±0.11)×10-18 cm3/(molecule·s) at room temperature.

  17. Determination of ultimate carbonaceous BOD and the specific rate constant (K1)

    Science.gov (United States)

    Stamer, J.K.; Bennett, J.P.; McKenzie, Stuart W.

    1982-01-01

    Ultimate carbonaceous biochemical oxygen demand (BODu) and the specific rate constant (K1) at which the demand is exerted are important parameters in designing biological wastewater treatment plants and in assessing the impact of wastewater on receiving streams. An analytical method is presented which uses time-series concentrations of BOD, defined as the calculated sum of dissolved oxygen (DO) losses at each time of measurement, for determining BODu and K1. Time-series DO measurements are obtained from a water sample that is incubated in darkness at 20 degrees Celsius in the presence of nitrapyrin, a chemical nitrification inhibitor. Time-series concentrations of BOD that approximate first order kinetics can be analyzed graphically or mathematically to compute BODu and K1.

  18. Consideration of demand rate in overall equipment effetiveness (OEE on equipment with constant process time

    Directory of Open Access Journals (Sweden)

    Tay C.C.

    2013-06-01

    research should be conducted to test the possibility and to verify the definition of such performance ratio including Takt time on those processes of which its operating time is possibly to be reduced, especially those are not constant and fixed. This piece of research is temporarily done on the process where its operating time is constant from time to time and there is no ideal cycle time possible.Practical implications: The awareness of the overproduction should be emphasized and raised in the intention of pursuing higher OEE value. As the definition proposed such, the process with constant cycle time could even be defined in different performance ratio from time to time regarding to the customer demands and corresponding production rate. These two variables can be adjusted and balanced to increase the OEE value through optimization of average cycle time. Over this, optimization of average cycle time on equipment with constant operating time can be achieved through the optimization of loading number per each processing.Originality/value: The novelty of the paper is the inclusion of customer demand in obtaining OEE value of any particular equipment. Besides that, the equipment without ideal cycle time, which means those processes carried out in constant cycle time are possibly to be evaluated with performance ratio. As consequence of that, the machine utilization and capability used could be quantified and visualized using the performance ratio data of the OEE proposed.

  19. EFRT M-12 Issue Resolution: Caustic Leach Rate Constants from PEP and Laboratory-Scale Tests

    Energy Technology Data Exchange (ETDEWEB)

    Mahoney, Lenna A.; Rassat, Scot D.; Eslinger, Paul W.; Aaberg, Rosanne L.; Aker, Pamela M.; Golovich, Elizabeth C.; Hanson, Brady D.; Hausmann, Tom S.; Huckaby, James L.; Kurath, Dean E.; Minette, Michael J.; Sundaram, S. K.; Yokuda, Satoru T.

    2009-08-14

    concentrated to nominally 20 wt% solids using cross-flow ultrafiltration before adding caustic. The work described in this report addresses the kinetics of caustic leach under WTP conditions, based on tests performed with a Hanford waste simulant. The tests were completed at the lab-scale and in the PEP, which is a 1/4.5-scale mock-up of key PTF process equipment. The purpose of this report is to summarize the results from both scales that are related to caustic leach chemistry to support a scale-up factor for the submodels to be used in the G2 model, which predicts WTP operating performance. The scale-up factor will take the form of an adjustment factor for the rate constant in the boehmite leach kinetic equation in the G2 model.

  20. Quantification of in Situ Biodegradation Rate Constants Using a Novel Combined Isotope Approach

    Science.gov (United States)

    Blum, P.; Sültenfuß, J.; Martus, P.

    2014-12-01

    Numerous studies have shown the enormous potential of the compound-specific isotope analysis (CSIA) for studying the biodegradation of organic compounds such as monoaromatic hydrocarbons (BTEX), polyaromatic hydrocarbons (PAH), chlorinated solvents and other organic contaminants and environmental transformation mechanisms in groundwater. In addition, two-dimensional isotope analysis such as carbon and hydrogen have been successfully studied indicating the potential to also investigate site-specific reaction mechanisms. The main objective of the current study however is to quantify real effective in situ biodegradation rate constants in a coal-tar contaminated aquifer by combining compound-specific isotope analysis (CSIA) and tracer-based (3H-3He) ground-water dating (TGD). Hence, groundwater samples are used to determine groundwater residence times, and carbon and hydrogen stable isotopes are analyzed for selected BTEX and PAH. The results of the hydrogen stable isotopes surprisingly indicate no isotope fractionation and therefore no biodegradation. In contrast, for stable carbon isotopes of selected BTEX such as o-xylene and toluene, isotope shifts are detected indicating active biodegradation under sulfate-reducing conditions. These and previous results of stable carbon isotopes show that only for o-xylene a clear evidence for biodegradation is possible for the studied site. Nevertheless, in combining these results with the groundwater residence times, which range between 1 year for the shallow wells (20 m below surface) and 41 years for the deeper wells (40 m below surface), it is feasible to effectively determine in situ biodegradation rate constants for o-xylene. Conversely, the outcome also evidently demonstrate the major limitations of the novel combined isotope approach for a successful implementation of monitored natural attenuation (MNA) at such field sites.

  1. Feasibility study of volumetric modulated arc therapy with constant dose rate for endometrial cancer

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ruijie [Department of Radiation Oncology, Peking University Third Hospital, Beijing (China); Wang, Junjie, E-mail: junjiewang47@yahoo.com [Department of Radiation Oncology, Peking University Third Hospital, Beijing (China); Xu, Feng [Department of Biomedical Engineering, Peking University Third Hospital, Beijing (China); Li, Hua [Department of Obstetrics and Gynecology, Peking University Third Hospital, Beijing (China); Zhang, Xile [Department of Radiation Oncology, Peking University Third Hospital, Beijing (China)

    2013-10-01

    To investigate the feasibility, efficiency, and delivery accuracy of volumetric modulated arc therapy with constant dose rate (VMAT-CDR) for whole-pelvic radiotherapy (WPRT) of endometrial cancer. The nine-field intensity-modulated radiotherapy (IMRT), VMAT with variable dose-rate (VMAT-VDR), and VMAT-CDR plans were created for 9 patients with endometrial cancer undergoing WPRT. The dose distribution of planning target volume (PTV), organs at risk (OARs), and normal tissue (NT) were compared. The monitor units (MUs) and treatment delivery time were also evaluated. For each VMAT-CDR plan, a dry run was performed to assess the dosimetric accuracy with MatriXX from IBA. Compared with IMRT, the VMAT-CDR plans delivered a slightly greater V{sub 20} of the bowel, bladder, pelvis bone, and NT, but significantly decreased the dose to the high-dose region of the rectum and pelvis bone. The MUs decreased from 1105 with IMRT to 628 with VMAT-CDR. The delivery time also decreased from 9.5 to 3.2 minutes. The average gamma pass rate was 95.6% at the 3%/3 mm criteria with MatriXX pretreatment verification for 9 patients. VMAT-CDR can achieve comparable plan quality with significant shorter delivery time and smaller number of MUs compared with IMRT for patients with endometrial cancer undergoing WPRT. It can be accurately delivered and be an alternative to IMRT on the linear accelerator without VDR capability.

  2. A sequence-specific threading tetra-intercalator with an extremely slow dissociation rate constant

    Science.gov (United States)

    Holman, Garen G.; Zewail-Foote, Maha; Smith, Amy Rhoden; Johnson, Kenneth A.; Iverson, Brent L.

    2011-11-01

    A long-lived and sequence-specific ligand-DNA complex would make possible the modulation of biological processes for extended periods. For this purpose, we are investigating a polyintercalation approach to DNA recognition in which flexible chains of aromatic units thread back and forth repeatedly through the double helix. Here we describe the DNA-binding behaviour of a threading tetra-intercalator. Specific binding was observed on a relatively long DNA strand that strongly favoured a predicted 14 base-pair sequence. Kinetic studies revealed a multistep association process, with sequence specificity that primarily derives from large differences in dissociation rates. The rate-limiting dissociation rate constant of the tetra-intercalator complex dissociating from its preferred binding site was extremely slow, corresponding to a half-life of 16 days. This is one of the longest non-covalent complex half-lives yet reported and, to the best of our knowledge, the longest for a DNA-binding molecule.

  3. [Determination of rate constants of gas-phase reactions of alpha-pinene and beta-pinene with ozone].

    Science.gov (United States)

    Liu, Z R; Hu, D

    2001-10-01

    alpha-pinene and beta-pinene are the most dominating species among natural terpenes. Terpenes are mainly emitted from forest trees, flowers and grass. In the lower troposphere terpenes can react fast with OH radical, ozone, NO3 radical and ground state oxygen atom. These reactions may contribute to the occurring of aerosols, peroxides (hydrogen peroxide and organic peroxide), carbon cycle (mainly CO), acid rain (organic acids, NO3- and SO4(2-), ozone and active radicals such as OH radical. Reactions with ozone occur both in the daytime and in the night. The study in this field in China began in the late 1980. The main work focus on the source emission and the experimental simulation has just started. It is most of our group's work. In this paper preliminary experimental simulation of the gas-phase reactions of alpha-pinene and beta-pinene with ozone were carried out in the quartz chamber. The rate constants of these reactions were measured using long-path Fourier transform infra-red combined with relative rate constant method. And the rate constants for the gas-phase reactions of alpha-pinene, beta-pinene with ozone were determined as 2.83 x 10(17) cm3.molecule-1.s-1 and 1.48 x 10(17) cm3.molecule-1.s-1 at 1.0 x 10(5) Pa and 296 +/- 3 K. The results are quite similar to the data from Atkinson group. No cyclohexane was added to the reaction system during the measurement to restrain the formation of OH radical. The formation of OH radical could not be quantified, so that the effect of subsidiary reactions induced by OH radical has not been calculated. In the later simulation study and model this effect should be considered.

  4. An initial-abstraction, constant-loss model for unit hydrograph modeling for applicable watersheds in Texas

    Science.gov (United States)

    Asquith, William H.; Roussel, Meghan C.

    2007-01-01

    Estimation of representative hydrographs from design storms, which are known as design hydrographs, provides for cost-effective, riskmitigated design of drainage structures such as bridges, culverts, roadways, and other infrastructure. During 2001?07, the U.S. Geological Survey (USGS), in cooperation with the Texas Department of Transportation, investigated runoff hydrographs, design storms, unit hydrographs,and watershed-loss models to enhance design hydrograph estimation in Texas. Design hydrographs ideally should mimic the general volume, peak, and shape of observed runoff hydrographs. Design hydrographs commonly are estimated in part by unit hydrographs. A unit hydrograph is defined as the runoff hydrograph that results from a unit pulse of excess rainfall uniformly distributed over the watershed at a constant rate for a specific duration. A time-distributed, watershed-loss model is required for modeling by unit hydrographs. This report develops a specific time-distributed, watershed-loss model known as an initial-abstraction, constant-loss model. For this watershed-loss model, a watershed is conceptualized to have the capacity to store or abstract an absolute depth of rainfall at and near the beginning of a storm. Depths of total rainfall less than this initial abstraction do not produce runoff. The watershed also is conceptualized to have the capacity to remove rainfall at a constant rate (loss) after the initial abstraction is satisfied. Additional rainfall inputs after the initial abstraction is satisfied contribute to runoff if the rainfall rate (intensity) is larger than the constant loss. The initial abstraction, constant-loss model thus is a two-parameter model. The initial-abstraction, constant-loss model is investigated through detailed computational and statistical analysis of observed rainfall and runoff data for 92 USGS streamflow-gaging stations (watersheds) in Texas with contributing drainage areas from 0.26 to 166 square miles. The analysis is

  5. Dynamics of a Ivlev-type predator-prey system with constant rate harvesting

    Energy Technology Data Exchange (ETDEWEB)

    Ling Li [Institute of Nonlinear Analysis, College of Mathematics and Information Science, Wenzhou University, Wenzhou 325035 (China); Wang Weiming [Institute of Nonlinear Analysis, College of Mathematics and Information Science, Wenzhou University, Wenzhou 325035 (China)], E-mail: weimingwang2003@163.com

    2009-08-30

    In this paper, by using the analysis of qualitative method and bifurcation theory, we investigate the dynamical properties of the Ivlev-type predator-prey model with nonzero constant prey harvesting and with or without time delay, respectively. It is shown that the system we considered can exhibit the subcritical and supercritical Hopf bifurcation. We also study the effect of the time delay on the dynamics of the system. By choosing the delay {tau} as a bifurcation parameter, we show that Hopf bifurcation can occur as the delay {tau} crosses some critical values. The direction and stability of the Hopf bifurcation are investigated by following the procedure of deriving normal form given by Faria and Magalhaes. Finally, numerical simulations are performed to illustrate the obtained results.

  6. An Analytical Formula for Potential Water Vapor in an Atmosphere of Constant Lapse Rate

    Directory of Open Access Journals (Sweden)

    Ali Varmaghani

    2012-01-01

    Full Text Available Accurate calculation of precipitable water vapor (PWV in the atmosphere has always been a matter of importance for meteorologists. Potential water vapor (POWV or maximum precipitable water vapor can be an appropriate base for estimation of probable maximum precipitation (PMP in an area, leading to probable maximum flood (PMF and flash flood management systems. PWV and POWV have miscellaneously been estimated by means of either discrete solutions such as tables, diagrams or empirical methods; however, there is no analytical formula for POWV even in a particular atmospherical condition. In this article, fundamental governing equations required for analytical calculation of POWV are first introduced. Then, it will be shown that this POWV calculation relies on a Riemann integral solution over a range of altitude whose integrand is merely a function of altitude. The solution of the integral gives rise to a series function which is bypassed by approximation of saturation vapor pressure in the range of -55 to 55 degrees Celsius, and an analytical formula for POWV in an atmosphere of constant lapse rate is proposed. In order to evaluate the accuracy of the suggested equation, exact calculations of saturated adiabatic lapse rate (SALR at different surface temperatures were performed. The formula was compared with both the diagrams from the US Weather Bureau and SALR. The results demonstrated unquestionable capability of analytical solutions and also equivalent functions.

  7. An Analytical Formula for Potential Water Vapor in an Atmosphere of Constant Lapse Rate

    Directory of Open Access Journals (Sweden)

    Ali Varmaghani

    2012-01-01

    Full Text Available Accurate calculation of precipitable water vapor (PWV in the atmosphere has always been a matter of importance for meteorologists. Potential water vapor (POWV or maximum precipitable water vapor can be an appropriate base for estimation of probable maximum precipitation (PMP in an area, leading to probable maximum flood (PMF and flash flood management systems. PWV and POWV have miscellaneously been estimated by means of either discrete solutions such as tables, diagrams or empirical methods; however, there is no analytical formula for POWV even in a particular atmospherical condition. In this article, fundamental governing equations required for analytical calculation of POWV are first introduced. Then, it will be shown that this POWV calculation relies on a Riemann integral solution over a range of altitude whose integrand is merely a function of altitude. The solution of the integral gives rise to a series function which is bypassed by approximation of saturation vapor pressure in the range of -55 to 55 degrees Celsius, and an analytical formula for POWV in an atmosphere of constant lapse rate is proposed. In order to evaluate the accuracy of the suggested equation, exact calculations of saturated adiabatic lapse rate (SALR at different surface temperatures were performed. The formula was compared with both the diagrams from the US Weather Bureau and SALR. The results demonstrated unquestionable capability of analytical solutions and also equivalent functions.

  8. Stress corrosion cracking of alloy 600 using the constant strain rate test

    Energy Technology Data Exchange (ETDEWEB)

    Bulischeck, T. S.; van Rooyen, D.

    1980-01-01

    The most recent corrosion problems experienced in nuclear steam generators tubed with Inconel alloy 600 is a phenomenon labeled ''denting''. Denting has been found in various degrees of severity in many operating pressurized water reactors. Laboratory investigations have shown that Inconel 600 exhibits intergranular SCC when subjected to high stresses and exposed to deoxygenated water at elevated temperatures. A research project was initiated at Brookhaven National Laboratory in an attempt to improve the qualitative and quantitative understanding of factors influencing SCC in high temperature service-related environments. An effort is also being made to develop an accelerated test method which could be used to predict the service life of tubes which have been deformed or are actively denting. Several heats of commercial Inconel 600 tubing were procured for testing in deaerated pure and primary water at temperatures from 290 to 365/sup 0/C. U-bend type specimens were used to determine crack initiation times which may be expected for tubes where denting has occurred but is arrested and provide baseline data for judging the accelerating effects of the slow strain rate method. Constant extension rate tests were employed to determine the crack velocities experienced in the crack propagation stage and predict failure times of tubes which are actively denting. 8 refs., 17 figs., 5 tabs.

  9. Kinetic mechanism of phenylalanine hydroxylase: intrinsic binding and rate constants from single-turnover experiments.

    Science.gov (United States)

    Roberts, Kenneth M; Pavon, Jorge Alex; Fitzpatrick, Paul F

    2013-02-12

    Phenylalanine hydroxylase (PheH) catalyzes the key step in the catabolism of dietary phenylalanine, its hydroxylation to tyrosine using tetrahydrobiopterin (BH(4)) and O(2). A complete kinetic mechanism for PheH was determined by global analysis of single-turnover data in the reaction of PheHΔ117, a truncated form of the enzyme lacking the N-terminal regulatory domain. Formation of the productive PheHΔ117-BH(4)-phenylalanine complex begins with the rapid binding of BH(4) (K(d) = 65 μM). Subsequent addition of phenylalanine to the binary complex to form the productive ternary complex (K(d) = 130 μM) is approximately 10-fold slower. Both substrates can also bind to the free enzyme to form inhibitory binary complexes. O(2) rapidly binds to the productive ternary complex; this is followed by formation of an unidentified intermediate, which can be detected as a decrease in absorbance at 340 nm, with a rate constant of 140 s(-1). Formation of the 4a-hydroxypterin and Fe(IV)O intermediates is 10-fold slower and is followed by the rapid hydroxylation of the amino acid. Product release is the rate-determining step and largely determines k(cat). Similar reactions using 6-methyltetrahydropterin indicate a preference for the physiological pterin during hydroxylation.

  10. A new method for measuring the oxygen diffusion constant and oxygen consumption rate of arteriolar walls.

    Science.gov (United States)

    Sasaki, Nobuhiko; Horinouchi, Hirohisa; Ushiyama, Akira; Minamitani, Haruyuki

    2012-01-01

    Oxygen transport is believed to primarily occur via capillaries and depends on the oxygen tension gradient between the vessels and tissues. As blood flows along branching arterioles, the O(2) saturation drops, indicating either consumption or diffusion. The blood flow rate, the O(2) concentration gradient, and Krogh's O(2) diffusion constant (K) of the vessel wall are parameters affecting O(2)delivery. We devised a method for evaluating K of arteriolar wall in vivo using phosphorescence quenching microscopy to measure the partial pressure of oxygen in two areas almost simultaneously. The K value of arteriolar wall (inner diameter, 63.5 ± 11.9 μm; wall thickness, 18.0 ± 1.2 μm) was found to be 6.0 ± 1.2 × 10(-11) (cm(2)/s)(ml O(2)·cm(-3) tissue·mmHg(-1)). The arteriolar wall O(2) consumption rate (M) was 1.5 ± 0.1 (ml O(2)·100 cm(-3) tissue·min(-1)), as calculated using Krogh's diffusion equation. These results suggest that the arteriolar wall consumes a considerable proportion of the O(2) that diffuses through it.

  11. Toy Stories: Modeling Rates

    Science.gov (United States)

    Swanson, Patricia E.

    2015-01-01

    Elementary school mathematics is increasingly recognized for its crucial role in developing the foundational skills and understandings for algebra. In this article, the author uses a lesson to introduce the concept of "rates"--comparing two different types and units of measure--and how to graph them. Described is the lesson and shared…

  12. Adaptation of fugacity models to treat speciating chemicals with constant species concentration ratios.

    Science.gov (United States)

    Toose, Liisa K; Mackay, Donald

    2004-09-01

    A "multiplier" method is developed by which multimedia mass balance fugacity models designed to describe the fate of a single chemical species can be applied to chemicals that exist as several interconverting species. The method is applicable only when observed ratios of species concentrations in each phase are relatively constant and there is thus no need to define interspecies conversion rates. It involves the compilation of conventional transformation and intermedia transport rate expressions for a single, selected key species, and then a multiplier, Ri, is deduced for each of the other species. The total rate applicable to all species is calculated as the product of the rate for the single key species and a combined multiplier (1 + R2 + R3 + etc.). The theory is developed and illustrated by two examples. Limitations of the method are discussed, especially under conditions when conversion rates are uncertain. The advantage of this approach is that existing fugacity and concentration-based models that describe the fate of single-species chemicals can be readily adapted to estimate the fate of multispecies substances such as mercury which display relatively constant species proportions in each medium.

  13. KiSThelP: a program to predict thermodynamic properties and rate constants from quantum chemistry results.

    Science.gov (United States)

    Canneaux, Sébastien; Bohr, Frédéric; Henon, Eric

    2014-01-05

    Kinetic and Statistical Thermodynamical Package (KiSThelP) is a cross-platform free open-source program developed to estimate molecular and reaction properties from electronic structure data. To date, three computational chemistry software formats are supported (Gaussian, GAMESS, and NWChem). Some key features are: gas-phase molecular thermodynamic properties (offering hindered rotor treatment), thermal equilibrium constants, transition state theory rate coefficients (transition state theory (TST), variational transition state theory (VTST)) including one-dimensional (1D) tunnelling effects (Wigner, and Eckart) and Rice-Ramsperger-Kassel-Marcus (RRKM) rate constants, for elementary reactions with well-defined barriers. KiSThelP is intended as a working tool both for the general public and also for more expert users. It provides graphical front-end capabilities designed to facilitate calculations and interpreting results. KiSThelP enables to change input data and simulation parameters directly through the graphical user interface and to visually probe how it affects results. Users can access results in the form of graphs and tables. The graphical tool offers customizing of 2D plots, exporting images and data files. These features make this program also well-suited to support and enhance students learning and can serve as a very attractive courseware, taking the teaching content directly from results in molecular and kinetic modelling. © 2013 Wiley Periodicals, Inc.

  14. Universal Rate Model Selector: A Method to Quickly Find the Best-Fit Kinetic Rate Model for an Experimental Rate Profile

    Science.gov (United States)

    2017-08-01

    Wastewater. Chemosphere 1996, 32 (4), 769–789. 11. Namasivayam, C.; Kadirvelu, K. Agricultural Solid Wastes for the Removal of Heavy Metals: Adsorption of...fraction of site ae initial adsorption rate b constant with b < 1 be desorption constant Cons. consecutive (in-series) rate model Cd zero when diffusion

  15. Carbofuran removal in continuous-photocatalytic reactor: Reactor optimization, rate-constant determination and carbofuran degradation pathway analysis.

    Science.gov (United States)

    Vishnuganth, M A; Remya, Neelancherry; Kumar, Mathava; Selvaraju, N

    2017-02-22

    Carbofuran (CBF) removal in a continuous-flow photocatalytic reactor with granular activated carbon supported titanium dioxide (GAC-TiO2) catalyst was investigated. The effects of feed flow rate, TiO2 concentration and addition of supplementary oxidants on CBF removal were investigated. The central composite design (CCD) was used to design the experiments and to estimate the effects of feed flow rate and TiO2 concentration on CBF removal. The outcome of CCD experiments demonstrated that reactor performance was influenced mainly by feed flow rate compared to TiO2 concentration. A second-order polynomial model developed based on CCD experiments fitted the experimental data with good correlation (R(2) ∼ 0.964). The addition of 1 mL min(-1) hydrogen peroxide has shown complete CBF degradation and 76% chemical oxygen demand removal under the following operating conditions of CBF ∼50 mg L(-1), TiO2 ∼5 mg L(-1) and feed flow rate ∼82.5 mL min(-1). Rate constant of the photodegradation process was also calculated by applying the kinetic data in pseudo-first-order kinetics. Four major degradation intermediates of CBF were identified using GC-MS analysis. As a whole, the reactor system and GAC-TiO2 catalyst used could be constructive in cost-effective CBF removal with no impact to receiving environment through getaway of photocatalyst.

  16. α-Terpineol reactions with the nitrate radical: Rate constant and gas-phase products

    Science.gov (United States)

    Jones, Brian T.; Ham, Jason E.

    The bimolecular rate constant of k rad +α-terpineol (16 ± 4) × 10 -12 cm 3 molecule -1 s -1 was measured using the relative rate technique for the reaction of the nitrate radical (NO 3rad ) with α-terpineol (2-(4-methyl-1-cyclohex-3-enyl)propan-2-ol) at 297 ± 3 K and 1 atmosphere total pressure. To more clearly define part of α-terpineol's indoor environment degradation mechanism, the products of α-terpineol + NO 3rad reaction were investigated. The identified reaction products were: acetone, glyoxal (HC( dbnd O)C( dbnd O)H), and methylglyoxal (CH 3C( dbnd O)C( dbnd O)H). The use of derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N, O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) were used to propose the other major reaction products: 6-hydroxyhept-5-en-2-one, 4-(1-hydroxy-1-methylethyl)-1-methyl-2-oxocyclohexyl nitrate, 5-(1-hydroxy-1-methylethyl)-2-oxocyclohexyl nitrate, 1-formyl-5-hydroxy-4-(hydroxymethyl)-1,5-dimethylhexyl nitrate, and 1,4-diformyl-5-hydroxy-1,5-dimethylhexyl nitrate. The elucidation of these products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible α-terpineol + NO 3rad reaction mechanisms based on previously published volatile organic compound + NO 3rad gas-phase mechanisms. The additional gas-phase products (2,6,6-trimethyltetrahydro-2 H-pyran-2,5-dicarbaldehyde and 2,2-dimethylcyclohexane-1,4-dicarbaldehyde) are proposed to be the result of cyclization through a reaction intermediate.

  17. Variable dose rate single-arc IMAT delivered with a constant dose rate and variable angular spacing.

    Science.gov (United States)

    Tang, Grace; Earl, Matthew A; Yu, Cedric X

    2009-11-07

    Single-arc intensity-modulated arc therapy (IMAT) has gained worldwide interest in both research and clinical implementation due to its superior plan quality and delivery efficiency. Single-arc IMAT techniques such as the Varian RapidArc deliver conformal dose distributions to the target in one single gantry rotation, resulting in a delivery time in the order of 2 min. The segments in these techniques are evenly distributed within an arc and are allowed to have different monitor unit (MU) weightings. Therefore, a variable dose-rate (VDR) is required for delivery. Because the VDR requirement complicates the control hardware and software of the linear accelerators (linacs) and prevents most existing linacs from delivering IMAT, we propose an alternative planning approach for IMAT using constant dose-rate (CDR) delivery with variable angular spacing. We prove the equivalence by converting VDR-optimized RapidArc plans to CDR plans, where the evenly spaced beams in the VDR plan are redistributed to uneven spacing such that the segments with larger MU weighting occupy a greater angular interval. To minimize perturbation in the optimized dose distribution, the angular deviation of the segments was restricted to single gantry sweep as in the VDR plans but each sector was delivered with a different value of CDR. For four patient cases, including two head-and-neck, one brain and one prostate, all CDR plans developed with the variable spacing scheme produced similar dose distributions to the original VDR plans. For plans with complex angular MU distributions, the number of sectors increased up to four in the CDR plans in order to maintain the original plan quality. Since each sector was delivered with a different dose rate, extra mode-up time (xMOT) was needed between the transitions of the successive sectors during delivery. On average, the delivery times of the CDR plans were approximately less than 1 min longer than the treatment times of the VDR plans, with an average of

  18. A simple biophysically plausible model for long time constants in single neurons.

    Science.gov (United States)

    Tiganj, Zoran; Hasselmo, Michael E; Howard, Marc W

    2015-01-01

    Recent work in computational neuroscience and cognitive psychology suggests that a set of cells that decay exponentially could be used to support memory for the time at which events took place. Analytically and through simulations on a biophysical model of an individual neuron, we demonstrate that exponentially decaying firing with a range of time constants up to minutes could be implemented using a simple combination of well-known neural mechanisms. In particular, we consider firing supported by calcium-controlled cation current. When the amount of calcium leaving the cell during an interspike interval is larger than the calcium influx during a spike, the overall decay in calcium concentration can be exponential, resulting in exponential decay of the firing rate. The time constant of the decay can be several orders of magnitude larger than the time constant of calcium clearance, and it could be controlled externally via a variety of biologically plausible ways. The ability to flexibly and rapidly control time constants could enable working memory of temporal history to be generalized to other variables in computing spatial and ordinal representations.

  19. Three-minute constant rate step test for detecting exertional dyspnea relief after bronchodilation in COPD

    Directory of Open Access Journals (Sweden)

    Borel B

    2016-11-01

    Full Text Available Benoit Borel,1,2 Courtney A Wilkinson-Maitland,3 Alan Hamilton,4 Jean Bourbeau,5 Hélène Perrault,6 Dennis Jensen,3,5,7 François Maltais2 1Laboratoire HAVAE, Université de Limoges, Limoges, France; 2Centre de Recherche, Institut Universitaire de Cardiologie et de Pneumologie de Québec, Université Laval, Québec, 3Clinical Exercise and Respiratory Physiology Laboratory, Department of Kinesiology and Physical Education, McGill University, Montréal, QC, 4Boehringer Ingelheim (Canada Limited, Burlington, ON, 5Respiratory Epidemiology and Clinical Research Unit, Montreal Chest Institute, McGill University Health Center, Montreal, QC, 6Faculty of Health Sciences, University of Ottawa, Ottawa, ON, 7Translational Research in Respiratory Diseases Program, Research Institute of the McGill University Health Centre, Montreal, QC, Canada Background: The aim of this study was to evaluate the responsiveness of the 3-minute constant rate step test (3-MST to detect the relief of exertional dyspnea (respiratory discomfort after acute bronchodilation in COPD patients. Patients and methods: A total of 40 patients with moderate-to-severe COPD (mean forced expiratory volume in 1 second: 45.7 (±14.7, % predicted performed four 3-MSTs at randomly assigned stepping rates of 14, 16, 20 and 24 steps/min after inhalation of nebulized ipratropium bromide (500 µg/salbutamol (2.5 mg and saline placebo, which were randomized to order. Patients rated their intensity of perceived dyspnea at the end of each 3-MST using Borg 0–10 category ratio scale. Results: A total of 37 (92.5%, 36 (90%, 34 (85% and 27 (67.5% patients completed all 3 minutes of exercise at 14, 16, 20 and 24 steps/min under both treatment conditions, respectively. Compared with placebo, ipratropium bromide/salbutamol significantly decreased dyspnea at the end of the third minute of exercise at 14 steps/min (by 0.6±1.0 Borg 0–10 scale units, P<0.01 and 16 steps/min (by 0.7±1.3 Borg 0–10 scale

  20. The modified Black-Scholes model via constant elasticity of variance for stock options valuation

    Science.gov (United States)

    Edeki, S. O.; Owoloko, E. A.; Ugbebor, O. O.

    2016-02-01

    In this paper, the classical Black-Scholes option pricing model is visited. We present a modified version of the Black-Scholes model via the application of the constant elasticity of variance model (CEVM); in this case, the volatility of the stock price is shown to be a non-constant function unlike the assumption of the classical Black-Scholes model.

  1. Modeling for Hydraulic Permeability and Kozeny-Carman Constant of Porous Nanofibers Using a Fractal Approach

    Science.gov (United States)

    Xiao, Boqi; Tu, Xing; Ren, Wen; Wang, Zongchi

    2015-06-01

    In this study, the analytical expressions for the hydraulic permeability and Kozeny-Carman (KC) constant of porous nanofibers are derived based on fractal theory. In the present approach, the permeability is explicitly related to the porosity and the area fractal dimensions of porous nanofibers. The proposed fractal models for KC constant is also found to be a function of the microstructural parameters (porosity, area fractal dimensions). Besides, the present model clearly indicates that KC constant is not a constant and increases with porosity. However, KC constant is close to a constant value which is 18 for ϕ > 0.8. Every parameter of the proposed formulas of calculating permeability and KC constant has clear physical meaning. The model predictions are compared with the existing experimental data, and fair agreement between the model predictions and experimental data is found for different porosities.

  2. Relationship between phenol-induced cytotoxicity and experimental inhibition rate constant or a theoretical parameter.

    Science.gov (United States)

    Fujisawa, S; Kadoma, Y

    2012-06-01

    We synthesized various dimer forms of 2-methoxyphenols and 2-tert-butylphenols, as dimers such as curcumin exhibit potent antioxidant and anti-inflammatory activity. We investigated the QSARs between the cytotoxicity and independent variables; kinetic parameters (inhibition rate constant (kinh/kp), stoichiometric factor (n)) or DFT-based theoretical parameters (i.e. phenolic O-H bond dissociation enthalpy (BDE), ionization potential according to Koopman's theorem (IP), LUMO, absolute hardness (η), electronegativity (χ) and electrophilicity (ω)) for 2-methoxyphenols and 2- tert- or 2,6-di-tert-butylphenols. The cytotoxicity of these phenols against human tumor cells (HSG, HL60) and/or human gingival fibroblasts (HGF) showed a marked negative linear relationship to kinh/kp, suggesting that the cytotoxicity of phenols may be related to radical reactions. By contrast, a linear relationship between the cytotoxicity and η-term was demonstrated; 2-methoxyphenols showed a negative slope, whereas 2-tert- or 2,6-di-tert-butylphenols showed a positive slope. Also, the cytotoxicity of tert-butylphenols was linearly dependent on the LUMO-term, showing a positive slope. The cytotoxicity of methoxy-substituted monophenols toward both HSG and HGF cells was related to both log P and η- terms. Also, that of X-phenols toward murine L-1210 cells was related to both log P and η or IP-terms, determined from a dataset reported by Zhang et al., 1998. It was concluded that the phenol-induced cytotoxicity was attributable to radical reactions resulting from the terms (kinh/kp, IP, η, and LUMO) in QSAR. The LUMO-dependent cytotoxicity of 2-tert- or 2,6-di-tert-butylphenols may be related to their quinone oxidation products. Experimental and theoretical parameters provide a useful approach for analysis of the cytotoxicity for phenolic compounds.

  3. 100 kV/2A three-phase constant-current repetitive-rate charging equipment

    CERN Document Server

    Tan Yu Gang; Chen Li Dong; Guo Zhi Gang; Zou Xiao Bing; Luo Min; Cao Shao Yun; Chang An Bi

    2002-01-01

    A 100 kV/2A three-phase constant-current repetitive-rate charging equipment was designed and constructed. A three-phase L-C converter is adopted as constant-current power source. Six Insulated Gate Bipolar Transistors (IGBTs) are connected in parallel to control the stop of charge. A Programmable Logical Controller (PLC) is the central element of the control unit. The equipment is used in the repetitive-rate discharge features test of the switch. It works stably under the conditions of 2A charging current, 10 Hz operating voltage, 100 kV repetitive rate and 1 mu F capacitor

  4. Selecting Constant Work Rates for Endurance Testing in COPD : The Role of the Power-Duration Relationship

    NARCIS (Netherlands)

    van der Vaart, Hester; Murgatroyd, Scott R.; Rossiter, Harry B.; Chen, Carey; Casaburi, Richard; Porszasz, Janos

    2014-01-01

    Constant work rate (CWR) exercise testing is highly responsive to therapeutic interventions and reveals physiological and functional benefits. No consensus exists, however, regarding optimal methods for selecting the pre-intervention work rate. We postulate that a CWR whose tolerated duration (t(lim

  5. Toward an understanding of the turbidity measurement of heterocoagulation rate constants of dispersions containing particles of different sizes.

    Science.gov (United States)

    Liu, Jie; Xu, Shenghua; Sun, Zhiwei

    2007-11-01

    Our previous studies have shown that the determination of coagulation rate constants by turbidity measurement becomes impossible for a certain operating wavelength (that is, its blind point) because at this wavelength the change in the turbidity of a dispersion completely loses its response to the coagulation process. Therefore, performing the turbidity measurement in the wavelength range near the blind point should be avoided. In this article, we demonstrate that the turbidity measurement of the rate constant for coagulation of a binary dispersion containing particles of two different sizes (heterocoagulation) presents special difficulties because the blind point shifts with not only particle size but also with the component fraction. Some important aspects of the turbidity measurement for the heterocoagulation rate constant are discussed and experimentally tested. It is emphasized that the T-matrix method can be used to correctly evaluate extinction cross sections of doublets formed during the heterocoagulation process, which is the key data determining the rate constant from the turbidity measurement, and choosing the appropriate operating wavelength and component fraction are important to achieving a more accurate rate constant. Finally, a simple scheme in experimentally determining the sensitivity of the turbidity changes with coagulation over a wavelength range is proposed.

  6. Modelling Australia's Retail Mortgage Rate

    OpenAIRE

    Abbas Valadkhani; Sajid Anwar

    2012-01-01

    There is an ongoing controversy over whether banks’ mortgage rates rise more readily than they fall due to their asymmetric responses to changes in the cash rate. This paper examines the dynamic interplay between the cash rate and the variable mortgage rate using monthly data in the post-1989 era. Unlike previous studies for Australia, our proposed threshold and asymmetric error-correction models account for both the amount and adjustment asymmetries. We found thatrate rises have much larger ...

  7. Two Optimization Methods to Determine the Rate Constants of a Complex Chemical Reaction Using FORTRAN and MATLAB

    Directory of Open Access Journals (Sweden)

    Abdel-Latif A. Seoud

    2010-01-01

    Full Text Available Problem statement: For chemical reactions, the determination of the rate constants is both very difficult and a time consuming process. The aim of this research was to develop computer programs for determining the rate constants for the general form of any complex reaction at a certain temperature. The development of such program can be very helpful in the control of industrial processes as well as in the study of the reaction mechanisms. Determination of the accurate values of the rate constants would help in establishing the optimum conditions of reactor design including pressure, temperature and other parameters of the chemical reaction. Approach: From the experimental concentration-time data, initial values of rate constants were calculated. Experimental data encountered several types of errors, including temperature variation, impurities in the reactants and human errors. Simulations of a second order consecutive irreversible chemical reaction of the saponification of diethyl ester were presented as an example of the complex reactions. The rate equations (system of simultaneous differential equations of the reaction were solved to get the analytical concentration versus time profiles. The simulation results were compared with experimental results at each measured point. All deviations between experimental and calculated values were squared and summed up to form a new function. This function was fed into a minimizer routine that gave the optimal rate constants. Two optimization techniques were developed using FORTRAN and MATLAB for accurately determining the rate constants of the reaction at certain temperature from the experimental data. Results: Results showed that the two proposed programs were very efficient, fast and accurate tools to determine the true rate constants of the reaction with less 1% error. The use of the MATLAB embedded subroutines for simultaneously solving the differential equations and minimization of the error function

  8. Rate Constants for Fine-structure Excitations in O-H Collisions with Error Bars Obtained by Machine Learning

    Science.gov (United States)

    Vieira, Daniel; Krems, Roman V.

    2017-02-01

    We present an approach using a combination of coupled channel scattering calculations with a machine-learning technique based on Gaussian Process regression to determine the sensitivity of the rate constants for non-adiabatic transitions in inelastic atomic collisions to variations of the underlying adiabatic interaction potentials. Using this approach, we improve the previous computations of the rate constants for the fine-structure transitions in collisions of O({}3{P}j) with atomic H. We compute the error bars of the rate constants corresponding to 20% variations of the ab initio potentials and show that this method can be used to determine which of the individual adiabatic potentials are more or less important for the outcome of different fine-structure changing collisions.

  9. Kinetics of nonstationary chemiluminescence during the inhibited oxidation of hydrocarbons and determination of the rate constants for peroxy radical decay

    Energy Technology Data Exchange (ETDEWEB)

    Rusina, I.F.; Emanuel, N.M.; Gagarina, A.B.

    1986-05-01

    This paper presents the results of a theoretical analysis of the kinetics of the nonstationary inhibited chemiluminescence and suggests a method for determining the absolute value of the rate constants for the recombination of peroxy radicals and for their removal by reaction with an inhibitor. From the rate curve for the chemiluminescence in the nonstationary regime following the introduction of an inhibitor it is possible simultaneously and independently to determine the absolute values of the rate constants for recombination of the peroxy radicals and their destruction by the inhibitor. Equations are obtained for calculating the time to establish the quasistationary concentration of peroxy radicals and of radicals formed from the inhibitor, using known values of the constants.

  10. Dark energy models with time-dependent gravitational constant

    CERN Document Server

    Ray, S; Ray, Saibal; Mukhopadhyay, Utpal

    2005-01-01

    Two phenomenological models of $\\Lambda$, viz. $\\Lambda \\sim (\\dot a/a)^2$ and $\\Lambda \\sim \\ddot a/a$ are studied under the assumption that $G$ is a time-variable parameter. Both models show that $G$ is inversely proportional to time as suggested earlier by others including Dirac. The models considered here can be matched with observational results by properly tuning the parameters of the models. Our analysis shows that $\\Lambda \\sim \\ddot a/a$ model corresponds to a repulsive situation and hence correlates with the present status of the accelerating Universe. The other model $\\Lambda \\sim (\\dot a/a)^2$ is, in general, attractive in nature. Moreover, it is seen that due to the combined effect of time-variable $\\Lambda$ and $G$ the Universe evolved with acceleration as well as deceleration. This later one indicates a Big Crunch.

  11. Dark Energy Models with a Time-Dependent Gravitational Constant

    Science.gov (United States)

    Ray, Saibal; Mukhopadhyay, Utpal; Choudhury, S. B. Dutta

    Two phenomenological models of Λ, viz. Λ ˜ (˙ a/a)2 and Λ ˜ ḋ a/a, are studied under the assumption that G is a time-variable parameter. Both models show that G is inversely proportional to time, as suggested earlier by others, including Dirac. The models considered here can be matched with observational results by properly tuning the parameters of the models. Our analysis shows that the Λ ˜ ḋ a/a model corresponds to a repulsive situation and hence correlates with the present status of the accelerating Universe. The other model, Λ ˜ (˙ a/a)2, is in general attractive in nature. Moreover, it is seen that due to the combined effect of time-variable Λ and G the Universe evolved with acceleration as well as deceleration. Deceleration indicates a "big crunch".

  12. Temperature dependence of the rate constant of hydrogen isotope interactions with a lithium capillary-porous system under reactor irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Tazhibayeva, Irina, E-mail: tazhibayeva@ntsc.kz [Institute of Atomic Energy NNC RK, Kurchatov (Kazakhstan); Kulsartov, Timur; Gordienko, Yuri [Institute of Atomic Energy NNC RK, Kurchatov (Kazakhstan); Mukanova, Aliya [Al’ Farabi Kazakh National University, Almaty (Kazakhstan); Ponkratov, Yuri; Barsukov, Nikolay; Tulubaev, Evgeniy [Institute of Atomic Energy NNC RK, Kurchatov (Kazakhstan); Platacis, Erik [University of Latvia (IPUL), Riga (Latvia); Kenzhin, Ergazy [Shakarim Semey State University, Semey (Kazakhstan)

    2013-10-15

    Highlights: • The experiments with Li CPS sample were carried out at reactor IVG-1.M. • The gas absorption technique was used to study hydrogen isotope interaction with lithium CPS. • The temperature dependence of constants of interaction rate was obtained for various power rates of the reactor. • Determination of the activation energies, and pre-exponents of Arrhenius dependence. • The effect of increase of the rate constant under reaction irradiation. -- Abstract: Experiments with a sample of a lithium capillary-porous system (CPS) were performed at the reactor IVG-1.M of the Institute of Atomic Energy NNC RK to study the effects of neutron irradiation on the parameters of hydrogen isotope interactions with a lithium CPS. The absorption technique was used during the experiments, and this technique allowed the temperature dependences of the hydrogen isotope interaction rate constants with the lithium CPS to be obtained under various reactor powers. The obtained dependencies were used to determine the main interaction parameters: the activation energies and the pre-exponents of the Arrhenius dependence of the hydrogen interaction rate constants with lithium and the lithium CPS. An increase of the hydrogen isotope interaction rate with the lithium CPS was observed under reactor irradiation.

  13. Chemical modeling of boron adsorption by humic materials using the constant capacitance model

    Science.gov (United States)

    The constant capacitance surface complexation model was used to describe B adsorption behavior on reference Aldrich humic acid, humic acids from various soil environments, and dissolved organic matter extracted from sewage effluents. The reactive surface functional groups on the humic materials wer...

  14. Voltage gating by molecular subunits of Na+ and K+ ion channels: higher-dimensional cubic kinetics, rate constants, and temperature.

    Science.gov (United States)

    Fohlmeister, Jürgen F

    2015-06-01

    The structural similarity between the primary molecules of voltage-gated Na and K channels (alpha subunits) and activation gating in the Hodgkin-Huxley model is brought into full agreement by increasing the model's sodium kinetics to fourth order (m(3) → m(4)). Both structures then virtually imply activation gating by four independent subprocesses acting in parallel. The kinetics coalesce in four-dimensional (4D) cubic diagrams (16 states, 32 reversible transitions) that show the structure to be highly failure resistant against significant partial loss of gating function. Rate constants, as fitted in phase plot data of retinal ganglion cell excitation, reflect the molecular nature of the gating transitions. Additional dimensions (6D cubic diagrams) accommodate kinetically coupled sodium inactivation and gating processes associated with beta subunits. The gating transitions of coupled sodium inactivation appear to be thermodynamically irreversible; response to dielectric surface charges (capacitive displacement) provides a potential energy source for those transitions and yields highly energy-efficient excitation. A comparison of temperature responses of the squid giant axon (apparently Arrhenius) and mammalian channel gating yields kinetic Q10 = 2.2 for alpha unit gating, whose transitions are rate-limiting at mammalian temperatures; beta unit kinetic Q10 = 14 reproduces the observed non-Arrhenius deviation of mammalian gating at low temperatures; the Q10 of sodium inactivation gating matches the rate-limiting component of activation gating at all temperatures. The model kinetics reproduce the physiologically large frequency range for repetitive firing in ganglion cells and the physiologically observed strong temperature dependence of recovery from inactivation. Copyright © 2015 the American Physiological Society.

  15. 一类推广的常利率复合 Poisson-Geometric风险模型的预警区问题∗%Duration of Negative Surplus for a Generalized Compound Poisson-Geometric Risk Model with Constant Interest Rate

    Institute of Scientific and Technical Information of China (English)

    赵明清; 尚鹂; 李田

    2015-01-01

    On the basis of the compound Poisson-Geometric risk model,by introducing interest rate and extending the Premium income from linear to compound Poisson process,this paper set up a Generalized Compound Poisson-Geometric Risk Model with Constant Interest Rate.The ability of the model to describe the realistic is more stronger.At the same time,it has more practical significance.Then taking full advantage of the strong Markov property of the surplus process,an integral differ-ential function for the first duration of negative surplus was obtained.Finally,the explicit expression was given when the Pre-mium and the claim were exponential distributions.%在复合 Poisson-Geometric 风险模型的基础上,引入利率因素,并将保费收入由线性过程推广为复合 Poisson 过程,建立了一类推广的带常利率复合 Poisson-Geometric 风险模型,该模型描述现实的能力更强,更具有实际意义。然后,利用盈余过程的强马氏性推导出了首个预警区的条件矩母函数所满足的积分方程,并进一步在保费额和索赔额都服从指数分布的情形下得出了其解析解。

  16. High-level theoretical study of the reaction between hydroxyl and ammonia: Accurate rate constants from 200 to 2500 K

    Science.gov (United States)

    Nguyen, Thanh Lam; Stanton, John F.

    2017-10-01

    Hydrogen abstraction from NH3 by OH to produce H2O and NH2—an important reaction in combustion of NH3 fuel—was studied with a theoretical approach that combines high level quantum chemistry and advanced chemical kinetics methods. Thermal rate constants calculated from first principles agree well (within 5%-20%) with available experimental data over a temperature range that extends from 200 to 2500 K. Quantum mechanical tunneling effects were found to be important; they lead to a decided curvature and non-Arrhenius behavior for the rate constant.

  17. Classical reaction probabilities, cross sections and rate constants for the O( 1D) + H2 → OH + H reaction

    Science.gov (United States)

    Alexander, A. J.; Aoiz, F. J.; Bañares, L.; Brouard, M.; Herrero, V. J.; Simons, J. P.

    1997-10-01

    Reaction probabilitiers total reaction cross sections as a function of collision energy, and rate constants have been calculated using the quasi-classical trajectory (QCT) method for the O( 1D) + H 2 reaction on several ab initio potential energy surfaces (PES), including the recent one by Ho, Hollebeck, Rabitz, Harding and Schatz. Detailed QCT results on the Schinke and Lester PES are compared with recent time-dependent wavepacket calculations on the same PES, showing good agreement. The QCT thermal rate constants calculated on the PES of Ho et al. are in better accord with the experimental determinations than those calculated on the Schinke-Lester PES.

  18. Review on optical constants of Titan aerosols: Experimental results and modeling/observational data

    Science.gov (United States)

    Brassé, Coralie; Muñoz, Olga; Coll, Patrice; Raulin, François

    2014-05-01

    During the last years many studies have been performed to improve the experimental database of optical constants of Titan aerosols. Indeed, the determination of the optical constants of these particles is essential to quantify their capacity to absorb and to scatter solar radiation, and thus to evaluate their role on Titan's radiative balance and climate. The study of optical properties is also crucial to analyze and to better interpret many of Titan's observational data, in particular those acquired during the Cassini-Huygens mission. One way to determine Titan aerosols optical constant is to measure the optical constants of analogues of Titan complex organic material synthesized in the laboratory, usually named Titan's tholins (Sagan and Khare, 1979). But the optical constants depend on the chemical composition, the size and the shape of particles (Raulin et al., 2012). Those three parameters result from the experimental conditions such as energy source, gas mixing ratio, gas pressure, flow rate and irradiation time (Cable et al., 2012). Besides the determination of the refractive index in the laboratory, there are others methods using theoretical models or observational data. Nevertheless, theoretical models are based on laboratory data or/and observational data. The visible - near infrared spectral region of optical constants has been widely studied with laboratory analogues. Comparison of the obtained results suggest that tholins synthesized by Tran et al. (2003) and Majhoub et al. (2012) are the best representative of Titan aerosols with regards to their refractive indexes in this spectral region. The mid-infrared spectral range has been studied only by Imanaka et al. (2012) and slightly by Tran et al. (2003). In that spectral range, Titan tholins do not exhibit the features displayed by Kim and Courtin (2013) from Titan's observations. For spectral region of wavelengths smaller than 0.20µm or higher than 25µm, only the data from Khare et al. (1984) are

  19. The Influence of Uncompensated Solution Resistance on the Determination and Standard Electrochemical Rate Constants Using Cyclic Voltammetry, and Some Comparisons with AC Voltammetry.

    Science.gov (United States)

    1987-09-25

    rate constants, k2r using cyclic voltametry . The res tss are expressed in terms of systematic deviations oP sapparent measured" rate constants, k~b(app...Classification) The Influence of Uncompensated Solution Resistance on the Determination and Standard Electro- - . chemical Rate Constants Using Cyclic ...Year MonhOy SAGE COUNT FIELD GROUP Sue-GROUP digital simulation analysis, uncompensated solution resis- I A tance, electrochemical rate constants, cyclic

  20. Numerical modeling of shoreline undulations part 1: Constant wave climate

    DEFF Research Database (Denmark)

    Kærgaard, Kasper Hauberg; Fredsøe, Jørgen

    2013-01-01

    This paper presents a numerical study of the non-linear development of alongshore undulations up to fully developed quasi-steady equilibrium. A numerical model which describes the longshore sediment transport along arbitrarily shaped shorelines is applied, based on a spectral wave model, a depth...... integrated flow model, a wave-phase resolving sediment transport description and a one-line shoreline model.First the length of the shoreline undulations is determined in the linear regime using a stability analysis. Next the further evolution from the linear to the fully non-linear regime is described....... In the fully non-linear regime down-drift spits and migrating shoreline undulations are described.Three different shoreline shapes are found depending on the wave conditions: undulations with no spits, undulations with shore parallel spit and undulations with reconnecting spits. © 2012 Published by Elsevier B.V....

  1. Evaluation of Johnson-Cook model constants for aluminum based particulate metal matrix composites

    Science.gov (United States)

    Hilfi, H.; Brar, N. S.

    1996-05-01

    High strain rate and high temperature response of three types of aluminum based particulate metal matrix ceramic composites is investigated by performing split Hopkinson pressure bar (SHPB) experiments. The composites are: NGP-2014 (15% SiC), NGT-6061 (15% SiC), and NGU-6061 (15% Al2O3), in which all the reinforcement materials are percentage by volume. Johnson-Cook constitutive model constants are evaluated from the high strain rate/high temperature data and implemented in a two dimensional finite element computer code (EPIC-2D) to simulate the penetration of an ogive nose tungsten projectile (23 grams) at a velocity 1.17 km/sec into the base 6061-T6 aluminum alloy and the composite NGU-6061. The simulated penetrations in the composite and in 6061-T6 aluminum agree with in 2%, in both materials, with the measured values.

  2. Dynamics of 'abc' and 'qd' constant parameters induction generator model

    DEFF Research Database (Denmark)

    Fajardo-R, L.A.; Medina, A.; Iov, F.

    2009-01-01

    In this paper, parametric sensibility effects on dynamics of the induction generator in the presence of local perturbations are investigated. The study is conducted in a 3x2 MW wind park dealing with abc, qd0 and qd reduced order, induction generator model respectively, and with fluxes as state v...

  3. The form of the rate constant for elementary reactions at equilibrium from MD: framework and proposals for thermokinetics

    CERN Document Server

    Jesudason, C G

    2006-01-01

    The rates or formation and concentration distributions of a dimer reaction showing hysteresis behavior are examined in an ab initio chemical reaction designed as elementary and where the hysteresis structure precludes the formation of transition states (TS) with pre-equilibrium and internal sub-reactions. It was discovered that the the reactivity coefficients, defined as a measure of departure from the zero density rate constant for the forward and backward steps had a ratio that was equal to the activity coefficient ratio for the product and reactant species. From the above observations, a theory is developed with the aid of some proven elementary theorems in thermodynamics, and expressions are derived whereby a feasible experimental and computational method for determining the activity coefficients from the rate constants may be obtained The theory developed is applied to ionic reactions where the standard Bronsted-Bjerrum rate equation and exceptions to this are rationalized, and by viewing ion association...

  4. Quintessence a natural model to parametrize the cosmological constant

    CERN Document Server

    Macorra, A D L

    2003-01-01

    We show how a scalar field with gravitational interaction only, i e. quintessence, can account for present day acceleration of the universe and it gives the correct acoustic scale and peaks of the CMP,R anisotropy. We show that the quintessence field can be naturally be described by the fermion condensates of a non-abelian gauge group. This gauge group is unified with the standard model gauge groups. The model has no free parameters. Even the initial energy density at the unification scale and at the condensation scale are fixed by the number of degrees of freedom of the gauge group. We study the evolution of all fields from the unification scale and we calculate the relevant cosmological quantities. (Author)

  5. Magnetized anisotropic dark energy models with constant deceleration parameter

    Indian Academy of Sciences (India)

    A Y SHAIKH; S D KATORE

    2016-12-01

    In this paper, we have studied the solutions of plane-symmetric Universe with variable $\\omega$ in the presence and the absence of magnetic field of energy density $\\rho B$. A special law of variation for Hubble’s parameterproposed by Bermann in {\\it Nuovo Cimento} B 74, 182 (1983) has been utilized to solve the field equations. Some physical and kinematical properties of the models are also discussed.

  6. Catalytic antibody light chain capable of cleaving a chemokine receptor CCR-5 peptide with a high reaction rate constant.

    Science.gov (United States)

    Mitsuda, Yukie; Hifumi, Emi; Tsuruhata, Kumi; Fujinami, Hiroko; Yamamoto, Naoki; Uda, Taizo

    2004-04-20

    A monoclonal antibody (MAb), ECL2B-2, was obtained by immunizing a peptide possessing a part of a sequence of a chemokine receptor, CCR-5, which is present as a membrane protein on the macrophage surface, and which plays an important role in human immunodeficiency virus (HIV) infection. From the DNA and the deduced amino acid sequences of the light and heavy chains of ECL2B-2 MAb, molecular modeling was conducted to calculate the steric conformation of the antibody. Modeling suggested that the structure of ECL2B-2 could possess one or two catalytic triad(s), composed of Asp(1), Ser(27a) (or Ser(27e)), and His(93) (or His(27d)), in the light chain of ECL2B-2. The three amino acid residues, Asp(1), Ser(27a), and His(93), are identical to those of catalytic antibody light chains such as VIPase and i41SL1-2. The light chain of ECL2B-2 MAb degraded the antigenic peptide CCR-5 within about 100 h. Surprisingly, the light chain had a very high catalytic reaction rate constant (k(cat)) of 2.23 min(-1), which is greater by factors of tens to hundreds than those of natural catalytic antibodies obtained previously. The heavy chain of ECL2B-2 MAb, which has no catalytic triad because of a lack of His residue, did not degrade the CCR-5 peptide.

  7. Resonant vibrational-excitation cross sections and rate constants for low-energy electron scattering by molecular oxygen

    CERN Document Server

    Laporta, V; Tennyson, J

    2016-01-01

    Resonant vibrational-excitation cross sections and rate constants for electron scattering by molecular oxygen are presented. Transitions between all 42 vibrational levels of O$_2(\\textrm{X}\\ ^3\\Sigma_g^- $) are considered. Molecular rotations are parameterized by the rotational quantum number $J$ which is considered in the range 1 to 151. The lowest four resonant states of O$_2^-$, $^2\\Pi_g$, $^2\\Pi_u$, $^4\\Sigma_u^-$ and $^2\\Sigma_u^-$, are taken into account. The calculations are performed using the fixed-nuclei R-matrix approach to determine the resonance positions and widths, and the boomerang model to characterize the nuclei motion. Two energy regions below and above 4~eV are investigated: the first one is characterized by sharp structures in the cross section, and the second by a broad resonance peaked at 10~eV. The computed cross sections are compared with theoretical and experimental results available in literature for both the energy regions, and are made available for use by modelers. The effect of ...

  8. Evolution of accretion disc flow in cataclysmic variables. 3. Outburst properties of constant and uniform-. cap alpha. model discs

    Energy Technology Data Exchange (ETDEWEB)

    Lin, D.N.C.; Faulkner, J. (Lick Observatory, Santa Cruz, CA (USA); California Univ., Santa Cruz (USA). Board of Studies in Astronomy and Astrophysics); Papaloizou, J. (Queen Mary Coll., London (UK). Dept. of Applied Mathematics)

    1985-01-01

    The investigation of accretion disc models relevant to cataclysmic-variable systems is continued. This paper examines the stability and evolution of some simple accretion disc models in which the viscosity is prescribed by an ad hoc uniform-..cap alpha.. model. It is primarily concerned with systems in which the mass-input rate from the secondary to the disc around the primary is assumed to be constant. However, initial calculations with variable mass-input rates are also performed. The time-dependent visual magnitude light-curves are constructed for cataclysmic binaries with a range of disc size, primary mass, mass-input rate, and magnitude of viscosity.

  9. Dose equivalent rate constants and barrier transmission data for nuclear medicine facility dose calculations and shielding design.

    Science.gov (United States)

    Kusano, Maggie; Caldwell, Curtis B

    2014-07-01

    A primary goal of nuclear medicine facility design is to keep public and worker radiation doses As Low As Reasonably Achievable (ALARA). To estimate dose and shielding requirements, one needs to know both the dose equivalent rate constants for soft tissue and barrier transmission factors (TFs) for all radionuclides of interest. Dose equivalent rate constants are most commonly calculated using published air kerma or exposure rate constants, while transmission factors are most commonly calculated using published tenth-value layers (TVLs). Values can be calculated more accurately using the radionuclide's photon emission spectrum and the physical properties of lead, concrete, and/or tissue at these energies. These calculations may be non-trivial due to the polyenergetic nature of the radionuclides used in nuclear medicine. In this paper, the effects of dose equivalent rate constant and transmission factor on nuclear medicine dose and shielding calculations are investigated, and new values based on up-to-date nuclear data and thresholds specific to nuclear medicine are proposed. To facilitate practical use, transmission curves were fitted to the three-parameter Archer equation. Finally, the results of this work were applied to the design of a sample nuclear medicine facility and compared to doses calculated using common methods to investigate the effects of these values on dose estimates and shielding decisions. Dose equivalent rate constants generally agreed well with those derived from the literature with the exception of those from NCRP 124. Depending on the situation, Archer fit TFs could be significantly more accurate than TVL-based TFs. These results were reflected in the sample shielding problem, with unshielded dose estimates agreeing well, with the exception of those based on NCRP 124, and Archer fit TFs providing a more accurate alternative to TVL TFs and a simpler alternative to full spectral-based calculations. The data provided by this paper should assist

  10. Weak decay constant of pseudscalar meson in a QCD-inspired model

    CERN Document Server

    Salcedo, L A M; Hadj-Michef, D; Frederico, T

    2003-01-01

    We show that a linear scaling between the weak decay constants of pseudoscalar and the vector mesons masses is supported by the available experimental data. The decay constant scale as $f_m/f_{pi}=M_V/M_{\\rho}$ (f_m is decay constant and M_V vector meson ground state mass). This simple form is justified within a renormalized light-front QCD-inpired model for quark-antiquark bound states.

  11. Online rate control in digital cameras for near-constant distortion based on minimum/maximum criterion

    Science.gov (United States)

    Lee, Sang-Yong; Ortega, Antonio

    2000-04-01

    We address the problem of online rate control in digital cameras, where the goal is to achieve near-constant distortion for each image. Digital cameras usually have a pre-determined number of images that can be stored for the given memory size and require limited time delay and constant quality for each image. Due to time delay restrictions, each image should be stored before the next image is received. Therefore, we need to define an online rate control that is based on the amount of memory used by previously stored images, the current image, and the estimated rate of future images. In this paper, we propose an algorithm for online rate control, in which an adaptive reference, a 'buffer-like' constraint, and a minimax criterion (as a distortion metric to achieve near-constant quality) are used. The adaptive reference is used to estimate future images and the 'buffer-like' constraint is required to keep enough memory for future images. We show that using our algorithm to select online bit allocation for each image in a randomly given set of images provides near constant quality. Also, we show that our result is near optimal when a minimax criterion is used, i.e., it achieves a performance close to that obtained by applying an off-line rate control that assumes exact knowledge of the images. Suboptimal behavior is only observed in situations where the distribution of images is not truly random (e.g., if most of the 'complex' images are captured at the end of the sequence.) Finally, we propose a T- step delay rate control algorithm and using the result of 1- step delay rate control algorithm, we show that this algorithm removes the suboptimal behavior.

  12. Site-specific reaction rate constant measurements for various secondary and tertiary H-abstraction by OH radicals

    KAUST Repository

    Badra, Jihad

    2015-02-01

    Reaction rate constants for nine site-specific hydrogen atom (H) abstraction by hydroxyl radicals (OH) have been determined using experimental measurements of the rate constants of Alkane+OH→Products reactions. Seven secondary (S 20, S 21, S 22, S 30, S 31, S 32, and S 33) and two tertiary (T 100 and T 101) site-specific rate constants, where the subscripts refer to the number of carbon atoms (C) connected to the next-nearest-neighbor (N-N-N) C atom, were obtained for a wide temperature range (250-1450K). This was done by measuring the reaction rate constants for H abstraction by OH from a series of carefully selected large branched alkanes. The rate constant of OH with four different alkanes, namely 2,2-dimethyl-pentane, 2,4-dimethyl-pentane, 2,2,4-trimethyl-pentane (iso-octane), and 2,2,4,4-tetramethyl-pentane were measured at high temperatures (822-1367K) using a shock tube and OH absorption diagnostic. Hydroxyl radicals were detected using the narrow-line-width ring-dye laser absorption of the R1(5) transition of OH spectrum near 306.69nm.Previous low-temperature rate constant measurements are added to the current data to generate three-parameter rate expressions that successfully represent the available direct measurements over a wide temperature range (250-1450. K). Similarly, literature values of the low-temperature rate constants for the reaction of OH with seven normal and branched alkanes are combined with the recently measured high-temperature rate constants from our group [1]. Subsequent to that, site-specific rate constants for abstractions from various types of secondary and tertiary H atoms by OH radicals are derived and have the following modified Arrhenius expressions:. S20=8.49×10-17T1.52exp(73.4K/T)cm3molecule-1s-1(250-1450K) S21=1.07×10-15T1.07exp(208.3K/T)cm3molecule-1s-1(296-1440K) S22=2.88×10-13T0.41exp(-291.5K/T)cm3molecule-1s-1(272-1311K) S30=3.35×10-18T1.97exp(323.1K/T)cm3molecule-1s-1(250-1366K) S31=1.60×10-18T2.0exp(500.0K/T)cm3

  13. The effects of a non-zero cosmological constant on the Veltmann models

    CERN Document Server

    Lingam, Manasvi

    2014-01-01

    The Veltmann models, which include the Plummer and Hernquist models as special cases, are studied in the presence of a cosmological constant. Physically relevant quantities such as the velocity dispersion profiles and the anisotropy parameter are computed through the use of the self-consistent approach. The cutoff radii for these models and the mass contained within this volume are also calculated. It is shown that the inclusion of a cosmological constant leads to many observable quantities such as the surface density, dispersion profiles and the anisotropy parameter becoming increasingly modified. In some scenarios, they are easily distinguished from the case where the cosmological constant is absent, as a result of their non-monotonic behaviour. The effects of neighbouring gravitational systems on the central system are also studied, and compared against the effects arising from the cosmological constant. Consequently, it is suggested that the effects of a cosmological constant can prove to be quite importa...

  14. Prediction model for the growth rates of short cracks based on K{sub max}-constant tests with m(t) specimens; Vorhersagemodell fuer die Wachstumsraten kurzer Risse auf der Basis von K{sub max}-konstant-Versuchen an M(T)-Proben

    Energy Technology Data Exchange (ETDEWEB)

    Tesch, A. [MAHLE International GmbH, Stuttgart (Germany); Pippan, R. [Erich-Schmid-Institut fuer Materialwissenschaft der Oesterreichischen Akademie der Wissenschaften, Loeben (Austria); Trautmann, K.H.; Doeker, H. [Deutsches Zentrum fuer Luft- und Raumfahrt, Institut fuer Werkstoff-Forschung, Koeln (Germany)

    2007-09-15

    The fatigue crack growth behaviour of short corner cracks in the Aluminium alloys Al 6013-T6 and Al 2524-T351 was investigated. The aim was to determine the crack growth rates of small corner cracks at stress ratios of R = 0.1, R = 0.7 and R = 0.8 and to develop a method to predict these crack growth rates from fatigue crack growth curves determined for long cracks. Corner cracks were introduced into short crack specimens, similar to M(T)-specimens, at one side of a hole (diameter = 4.8 mm) by cyclic compression (R = 20). The pre-cracks were smaller than 100 {mu}m (notch + precrack). A completely new method was used to cut very small notches (10-50 {mu}m) into the specimens with a Focussed Ion Beam. The results of the fatigue crack growth tests with short corner cracks were compared with long fatigue crack growth test data. The short cracks grew at {delta}K-values below the threshold for long cracks at the same stress ratio. They also grew faster than long cracks at the same {delta}K-values and the same stress ratios. A model was developed on the basis of K{sub max}-constant tests with long cracks that gives a good and conservative prediction of the short crack growth rates. (Abstract Copyright [2007], Wiley Periodicals, Inc.) [German] Das Ermuedungsrisswachstumsverhalten von kurzen Rissen in den Aluminiumlegierungen Al 6013-T6 und Al 2524-T351 wurde untersucht. Ziel war es die Ermuedungsrisswachstumsraten von kurzen Eckrissen bei Spannungsverhaeltnissen von R = 0,1, R = 0,7 und R = 0,8 zu bestimmen und einen Weg zu finden, diese Wachstumsraten auf der Grundlage von Ermuedungsrisswachstumskurven von langen Rissen vorherzusagen. In Kurzrissproben, aehnlich M(T)-Proben, wurden an einer Seite einer Bohrung (diameter = 4,8 mm) durch zyklische Druckbelastungen (R = 20) Eckrisse eingebracht. Kerbe und Anrisse zusammen waren kleiner als 100 {mu}m. Unter anderen Methoden wurde eine komplett neue Methode, ein fokussierter Ionenstrahl, verwendet, um die sehr kleinen Kerben

  15. Atmospheric reaction of Cl + methacrolein: a theoretical study on the mechanism, and pressure- and temperature-dependent rate constants.

    Science.gov (United States)

    Sun, Cuihong; Xu, Baoen; Zhang, Shaowen

    2014-05-22

    Methacrolein is a major degradation product of isoprene, the reaction of methacrolein with Cl atoms may play some roles in the degradation of isoprene where these species are relatively abundant. However, the energetics and kinetics of this reaction, which govern the reaction branching, are still not well understood so far. In the present study, two-dimensional potential energy surfaces were constructed to analyze the minimum energy path of the barrierless addition process between Cl and the C═C double bond of methacrolein, which reveals that the terminal addition intermediate is directly formed from the addition reaction. The terminal addition intermediate can further yield different products among which the reaction paths abstracting the aldehyde hydrogen atom and the methyl hydrogen atom are dominant reaction exits. The minimum reaction path for the direct aldehydic hydrogen atom abstraction is also obtained. The reaction kinetics was calculated by the variational transition state theory in conjunction with the master equation method. From the theoretical model we predicted that the overall rate constant of the Cl + methacrolein reaction at 297 K and atmospheric pressure is koverall = 2.3× 10(-10) cm(3) molecule(-1) s(-1), and the branching ratio of the aldehydic hydrogen abstraction is about 12%. The reaction is pressure dependent at P pressure limit at about 100 Torr. The calculated results could well account for the experimental observations.

  16. Constant harvest rate for the Pacific sardine (Sardinops caeruleus) fishery in the Gulf of California based on catchability-at-length estimations

    OpenAIRE

    2009-01-01

    Constant harvest rate as a management strategy for the Pacific sardine (Sardinops caeruleus) fishery in the Gulf of California is supported by an analysis of variations in the catchability coefficient (q), stock abundance and commercial catch. Catchability was analyzed based on population length-structured data standard length (SL), expressed as CPUE, for 26 fishing seasons (1972-1973 to 1997-1998). We used a deterministic model of catchability to estimate the catchability-at-length assuming ...

  17. Monte Carlo模拟在聚合反应速率常数估算中的运用%Estimation of rate constants for polymerization based on Monte Carlo simulation

    Institute of Scientific and Technical Information of China (English)

    罗正鸿; 詹晓力; 阳永荣

    2006-01-01

    The application of Monte Carlo method in estimating rate constants for polymerization was described.A general program for Monte Carlo simulation was determined first according to the elementary reactions, after which the rate constants could be automatically adjusted and optimized through comparing of experimental and simulated data with an error expression that meeted a given minimum criterion.Such a process made the rate constants to be estimated without kinetic model in advance.The technique was applied to estimate the rate constants of the bulk polymerization of styrene catalyzed by the rare earth catalyst.The estimated results showed the Monte Carlo method was feasible and effective for estimating rate constants in polymerization engineering.

  18. Constant growth rate can be supported by decreasing energy flux and increasing aerobic glycolysis

    NARCIS (Netherlands)

    Slavov, Nikolai; Budnik, Bogdan A; Schwab, David; Airoldi, Edoardo M; van Oudenaarden, Alexander

    2014-01-01

    Fermenting glucose in the presence of enough oxygen to support respiration, known as aerobic glycolysis, is believed to maximize growth rate. We observed increasing aerobic glycolysis during exponential growth, suggesting additional physiological roles for aerobic glycolysis. We investigated such ro

  19. Constant growth rate can be supported by decreasing energy flux and increasing aerobic glycolysis

    NARCIS (Netherlands)

    Slavov, Nikolai; Budnik, Bogdan A; Schwab, David; Airoldi, Edoardo M; van Oudenaarden, Alexander

    2014-01-01

    Fermenting glucose in the presence of enough oxygen to support respiration, known as aerobic glycolysis, is believed to maximize growth rate. We observed increasing aerobic glycolysis during exponential growth, suggesting additional physiological roles for aerobic glycolysis. We investigated such

  20. Use of Closed Vessel as a Constant Pressure Apparatus for the Measurement of the Rate of Burning of Propellants

    Directory of Open Access Journals (Sweden)

    D. Vittal

    1980-04-01

    Full Text Available A method for the determination of burning rates of propellants whose from function is unknown is introduced. The method consists of burning in the closed vessel, a known charge weight of the test propellant alongwith a known pressure which remains nearly constant during the burning of the test propellant whose web size is the only quantity required for the evaluation of its rate of burning. The test propellants burns at near constant pressure conditions just as in the strand burner technique. This method can be applied to any unknown propellant of any shape whose web size can be measured and very large webs also can be used. In addition, the measurement of the records and the computation are very simple.

  1. Absolute rate constants for the reaction of NO with a series of peroxy radicals in the gas at 295 K

    DEFF Research Database (Denmark)

    Sehested, J.; Nielsen, O.J.; Wallington, T.J.

    1993-01-01

    The rate constants for the reaction of NO with a series of peroxy radicals: CH3O2, C2H5O2, (CH3)3CCH2O2, (CH3)3CC(CH3)2CH2O2, CH2FO2, CH2ClO2, CH2BrO2, CHF2O2, CF2ClO2, CHF2CF2O2, CF3CF2O2, CFCl2CH2O2 and CF2ClCH2O2 were measured at 298 K and a total pressure of 1 atm. The rate constants were obt...... obtained using the absolute technique of pulse radiolysis combined with time-resolved UV-VIS spectroscopy. The results are discussed in terms of reactivity trends and the atmospheric chemistry of peroxy radicals....

  2. Recommended Henry’s Law Constants for Non-Groundwater Pathways Models in GoldSim

    Energy Technology Data Exchange (ETDEWEB)

    Dyer, J. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2017-06-20

    This memorandum documents the source and numerical value of Henry’s law constants for volatile radionuclides of interest used in the non-groundwater (air and radon) pathways models for the 2018 E-Area Performance Assessment.

  3. Equilibrium Star Formation In A Constant Q Disk: Model Optimisation and Initial Tests

    CERN Document Server

    Zheng, Zheng; Heckman, Timothy; Thilker, David; Zwaan, Martin

    2013-01-01

    We develop a model for the distribution of the ISM and star formation in galaxies based on recent studies that indicate that galactic disks stabilise to a constant stability parameter, which we combine with prescriptions of how the phases of the ISM are determined and for the Star Formation Law (SFL). The model predicts the gas surface mass density and star formation intensity of a galaxy given its rotation curve, stellar surface mass density and the gas velocity dispersion. This model is tested on radial profiles of neutral and molecular ISM surface mass density and star formation intensity of 12 galaxies selected from the THINGS sample. Our tests focus on intermediate radii. Nevertheless, the model produces reasonable agreement with ISM mass and star formation rate integrated over the central region in all but one case. To optimise the model, we evaluate four recipes for the stability parameter, three recipes for apportioning the ISM into molecular and neutral components, and eight versions of the SFL. We f...

  4. Superoxide dismutase versus ferricytochrome C: determining rate constants for the spin trapping of superoxide by cyclic nitrones.

    Science.gov (United States)

    Weaver, John; Tsai, Pei; Pou, Sovitj; Rosen, Gerald M

    2004-11-26

    Given that spin trapping/electron paramagnetic resonance (EPR) spectroscopy has become the primary technique to identify important biologically generated free radicals, such as superoxide (O(2)(*-)), in vitro and in vivo models, evaluation of the efficiency of specific spin traps to identify this free radical is paramount. Recently, a family of ester-containing nitrones has been prepared, which appears to have distinct advantages for spin trapping O(2)(*-) compared to the well-studied spin traps 5,5-dimethyl-1-pyrroline N-oxide 1 and 5-(diethoxyphosphoryl)-5-methyl-1-pyrroline N-oxide 2. An important determinant in the selection of a spin trap is the rate constant (k(app)) for its reaction with O(2)(*-), and several different methods have been employed in estimating this k(app). In this paper, the two most frequently used scavengers of O(2)(*-), ferricytochrome c and Cu/Zn-SOD, were evaluated as competitive inhibitors for spin trapping this free radical. Data presented herein demonstrate that SOD is the preferred compound when determining the k(app) for the reaction of O(2)(*-) with spin traps. Using this model, the k(app) for the reaction of nitrone 1, 5-tert-butoxycarbonyl-5-methyl-1-pyrroline N-oxide 3, and 5-methoxycarbonyl-5-methyl-1-pyrroline N-oxide 4 with O(2)(*)(-) was estimated to be 24.6 +/- 3.1, 73.0 +/- 12, and 89.4 +/- 1.0 M(-1) s(-1) at pH 7.0, respectively. Several other comparative studies between known spin traps were also undertaken.

  5. Unified equation for access to rate constants of first-order reactions in dynamic and on-column reaction chromatography.

    Science.gov (United States)

    Trapp, O

    2006-01-01

    A unified equation to evaluate elution profiles of reversible as well as irreversible (pseudo-) first-order reactions in dynamic chromatography and on-column reaction chromatography has been derived. Rate constants k1 and k(-1) and Gibbs activation energies are directly obtained from the chromatographic parameters (retention times tR(A) and tR(B) of the interconverting or reacting species A and B, the peak widths at half-height wA and wB, and the relative plateau height h(p)), the initial amounts A0 and B0 of the reacting species, and the equilibrium constant K(A/B). The calculation of rate constants requires only a few iterative steps without the need of performing a computationally extensive simulation of elution profiles. The unified equation was validated by comparison with a data set of 125,000 simulated elution profiles to confirm the quality of this equation by statistical means and to predict the minimal experimental requirements. Surprisingly, the recovery rate from a defined data set is on average 35% higher using the unified equation compared to the evaluation by iterative computer simulation.

  6. The H2 + CO ↔ H2CO Reaction: Rate Constants and Relevance to Hot and Dense Astrophysical Media

    Science.gov (United States)

    Vichietti, R. M.; Spada, R. F. K.; da Silva, A. B. F.; Machado, F. B. C.; Haiduke, R. L. A.

    2016-07-01

    A theoretical thermochemical and kinetic investigation of the thermal H2 + CO ↔ H2CO reaction was performed for a temperature range from 200 to 4000 K. Geometries and vibrational frequencies of reactants, product, and transition state (TS) were obtained at CCSD/cc-pVxZ (x = T and Q) levels and scaling factors were employed to consider anharmonicity effects on vibrational frequencies, zero-point energies, and thermal corrections provided by these methodologies. Enthalpies Gibbs energies, and rate constants for this reaction were determined by including a complete basis set extrapolation correction for the electronic properties calculated at CCSD(T)/cc-pVyZ (y = Q and 5) levels. Our study indicates that enthalpy changes for this reaction are highly dependent on temperature. Moreover, forward and reverse (high-pressure limit) rate constants were obtained from variational TS theory with quantum tunneling corrections. Thus, modified Arrhenius’ equations were fitted by means of the best forward and reverse rate constant values, which provide very reliable estimates for these quantities within the temperature range between 700 and 4000 K. To our knowledge, this is the first kinetic study done for the forward H2 + CO \\to H2CO process in a wide temperature range. Finally, these results can be used to explain the formaldehyde abundance in hot and dense interstellar media, possibly providing data about the physical conditions associated with H2CO masers close to massive star-forming regions.

  7. Computational study on the mechanisms and rate constants of the OH-initiated oxidation of ethyl vinyl ether in atmosphere.

    Science.gov (United States)

    Han, Dandan; Cao, Haijie; Li, Jing; Li, Mingyue; He, Maoxia; Hu, Jingtian

    2014-09-01

    The hydroxylation reactions of ethyl vinyl ether (EVE) in the present of O2 and NO are analyzed by using MPWB1K/6-311++G(3df,2p)//MPWB1K/6-31+G(d,p) level of theory. According to the calculated thermodynamic data, the detailed reaction mechanisms of EVE and OH are proposed. All of the ten possible reaction pathways are discussed. The major products of the title reaction are ethyl formate and formaldehyde, which is in accordance with experimental detection. The rate constants of the primary reactions over the temperature of 250-400K and the pressure range of 100-2000Torr are computed by employing MESMER program. At 298K and 760Torr, OH-addition channels are predominate and the total rate constant is ktot=4.53×10(-11)cm(3)molecule(-1)s(-1). The Arrhenius equation is obtained as ktot=6.27×10(-12)exp(611.5/T), according to the rate constants given at different temperatures. Finally, the atmospheric half life of EVE with respect to OH is estimated to be 2.13h.

  8. Cosmological-constant cold dark matter models and the cobe two-year Sky maps

    CERN Document Server

    Bunn, E F; Emory F Bunn; Naoshi Sugiyama

    1994-01-01

    Abstract. We compare the two-year COBE DMR sky maps with the predictions of cosmological-constant cold dark matter models. Using a Bayesian analysis, we find that the most likely value of the cosmological constant in such a model is Lambda = 0. The data set an upper limit on Lambda of 0.71 (0.78) at 90% confidence, and 0.78 (0.86) at 95% confidence with (without) the quadrupole anisotropy.

  9. APPROXIMATION OF BIODEGRADATION RATE CONSTANTS FOR MONOAROMATIC HYDROCARBONS (BTEX) IN GROUND WATER

    Science.gov (United States)

    Two methods were used to approximate site-specific biodegradation rates of monoaromatic hydrocarbons (benzene, toluene, ethylbenzene, and xylenes [BTEX]) dissolved in ground water. Both use data from monitoring wells and the hydrologic properties of the quifer to estimate a biode...

  10. The effect of solvation on the radiation damage rate constants for adenine

    DEFF Research Database (Denmark)

    Milhøj, Birgitte Olai; Sauer, Stephan P. A.

    2016-01-01

    in calculations of Gibbs free energies and reaction rates for the reaction between the OH radical and the DNA nucleobase adenine using Density Functional Theory at the ωB97X-D/6-311++G(2df,2pd) level with the Eckart tunneling correction. The solvent, water, has been included through either the implicit...

  11. Rate Constants and Activation Energies for Gas‐Phase Reactions of Three Cyclic Volatile Methyl Siloxanes with the Hydroxyl Radical

    Science.gov (United States)

    Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie

    2015-01-01

    ABSTRACT Reaction with hydroxyl radicals (OH) is the major pathway for removal of cyclic volatile methyl siloxanes (cVMS) from air. We present new measurements of second‐order rate constants for reactions of the cVMS octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) with OH determined at temperatures between 313 and 353 K. Our measurements were made using the method of relative rates with cyclohexane as a reference substance and were conducted in a 140‐mL gas‐phase reaction chamber with online mass spectrometry analysis. When extrapolated to 298 K, our measured reaction rate constants of D4 and D5 with the OH radical are 1.9 × 10−12 (95% confidence interval (CI): (1.7–2.2) × 10−12) and 2.6 × 10−12 (CI: (2.3–2.9) × 10−12) cm3 molecule−1 s−1, respectively, which are 1.9× and 1.7× faster than previous measurements. Our measured rate constant for D6 is 2.8 × 10−12 (CI: (2.5–3.2) × 10−12) cm3 molecule−1 s−1 and to our knowledge there are no comparable laboratory measurements in the literature. Reaction rates for D5 were 33% higher than for D4 (CI: 30–37%), whereas the rates for D6 were only 8% higher than for D5 (CI: 5–10%). The activation energies of the reactions of D4, D5, and D6 with OH were not statistically different and had a value of 4300 ± 2800 J/mol. PMID:27708500

  12. Rate Constants and Activation Energies for Gas-Phase Reactions of Three Cyclic Volatile Methyl Siloxanes with the Hydroxyl Radical.

    Science.gov (United States)

    Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie; Macleod, Matthew

    2015-07-01

    Reaction with hydroxyl radicals (OH) is the major pathway for removal of cyclic volatile methyl siloxanes (cVMS) from air. We present new measurements of second-order rate constants for reactions of the cVMS octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) with OH determined at temperatures between 313 and 353 K. Our measurements were made using the method of relative rates with cyclohexane as a reference substance and were conducted in a 140-mL gas-phase reaction chamber with online mass spectrometry analysis. When extrapolated to 298 K, our measured reaction rate constants of D4 and D5 with the OH radical are 1.9 × 10(-12) (95% confidence interval (CI): (1.7-2.2) × 10(-12)) and 2.6 × 10(-12) (CI: (2.3-2.9) × 10(-12)) cm(3) molecule(-1) s(-1), respectively, which are 1.9× and 1.7× faster than previous measurements. Our measured rate constant for D6 is 2.8 × 10(-12) (CI: (2.5-3.2) × 10(-12)) cm(3) molecule(-1) s(-1) and to our knowledge there are no comparable laboratory measurements in the literature. Reaction rates for D5 were 33% higher than for D4 (CI: 30-37%), whereas the rates for D6 were only 8% higher than for D5 (CI: 5-10%). The activation energies of the reactions of D4, D5, and D6 with OH were not statistically different and had a value of 4300 ± 2800 J/mol.

  13. Non-Constant Learning Rates in Retrospective Experience Curve Analyses and their Correlation to Deployment Programs

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Max [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Smith, Sarah J. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Sohn, Michael D. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2015-07-16

    A key challenge for policy-makers and technology market forecasters is to estimate future technology costs and in particular the rate of cost reduction versus production volume. A related, critical question is what role should state and federal governments have in advancing energy efficient and renewable energy technologies? This work provides retrospective experience curves and learning rates for several energy-related technologies, each of which have a known history of federal and state deployment programs. We derive learning rates for eight technologies including energy efficient lighting technologies, stationary fuel cell systems, and residential solar photovoltaics, and provide an overview and timeline of historical deployment programs such as state and federal standards and state and national incentive programs for each technology. Piecewise linear regimes are observed in a range of technology experience curves, and public investments or deployment programs are found to be strongly correlated to an increase in learning rate across multiple technologies. A downward bend in the experience curve is found in 5 out of the 8 energy-related technologies presented here (electronic ballasts, magnetic ballasts, compact fluorescent lighting, general service fluorescent lighting, and the installed cost of solar PV). In each of the five downward-bending experience curves, we believe that an increase in the learning rate can be linked to deployment programs to some degree. This work sheds light on the endogenous versus exogenous contributions to technological innovation and highlights the impact of exogenous government sponsored deployment programs. This work can inform future policy investment direction and can shed light on market transformation and technology learning behavior.

  14. The chemistry of bromine in the stratosphere: Influence of a new rate constant for the reaction BrO + HO2

    Science.gov (United States)

    Pirre, Michel; Marceau, Francois J.; Lebras, Georges; Maguin, Francoise; Poulet, Gille; Ramaroson, Radiela

    1994-01-01

    The impact of new laboratory data for the reaction BrO + HO2 yields HOBr + O2 in the depletion of global stratospheric ozone has been estimated using a one-dimensional photochemical model taking into account the heterogeneous reaction on sulphate aerosols which converts N2O5 into HNO3. Assuring an aerosol loading 2 times as large as the 'background' and a reaction probability of 0.1 for the above heterogeneous reaction, the 6 fold increase in the measured rate constant for the reaction of BrO with HO2 increases the computed depletion of global ozone produced by 20 ppt of total bromine from 2.01 percent to 2.36 percent. The use of the higher rate constant increases the HOBr mixing ratio and makes the bromine partitioning and the ozone depletion very sensitive to the branching ratio of the potential channel forming HBr in the BrO + HO2 reaction.

  15. Photochemistry of UV-excited trifluoroacetylacetone and hexafluoroacetylacetone II: Quantum yield and rate constants of hydrogen fluoride photoelimination forming fluorinated methylfuranones

    Science.gov (United States)

    Disselkoen, Kyle R.; Alsum, Joel R.; Thielke, Timothy A.; Muyskens, Mark A.

    2017-03-01

    The photochemistry of gas-phase 1,1,1-trifluoroacetylacetone (TFAA) and 1,1,1,5,5,5-hexafluoroacetylacetone (HFAA) excited with ultraviolet light involves a significant photoelimination channel producing HF and difluoromethylfuranone or pentafluoromethylfuranone, respectively. We report collisional self-quenching of the experimentally-determined relative quantum yield, and determine rate constants of 0.27 ± 0.03 and 0.33 ± 0.04 μs-1, for HFAA and TFAA respectively. A strong collision model is consistent with the observed quenching. The data suggest that this elimination is the primary photochemical fate at low pressure in both cases. The TFAA rate constant is larger than that for HFAA, in spite of TFAA having half as many fluorine atoms as HFAA.

  16. A methodology to study cyclic debond growth at constant mode-mixity and energy release rate

    DEFF Research Database (Denmark)

    Quispitupa, Amilcar; Berggreen, Christian; Carlsson, Leif A.

    2010-01-01

    It is well known that face/core debond crack propagation is governed by the critical energy release rate (fracture toughness) and mode-mixity at the crack tip. Thus, the current study focuses on the developing of a methodology to perform fatigue crack growth experiments of debonded sandwich...... and better control of loading conditions at the crack tip will be the most relevant outcomes of using the proposed fatigue test method....

  17. Implementation of Constant Dose Rate and Constant Angular Spacing Intensity-modulated Arc Therapy for Cervical Cancer by Using a Conventional Linear Accelerator

    Institute of Scientific and Technical Information of China (English)

    Ruo-Hui Zhang; Xiao-Mei Fan; Wen-Wen Bai; Yan-Kun Cao

    2016-01-01

    Background: Volumetric-modulated arc therapy (VMAT) can only be implemented on the new generation linacs such as the Varian Trilogy(R) and Elekta Synergy(R).This prevents most existing linacs from delivering VMAT.The purpose of this study was to investigate the feasibility of using a conventional linear accelerator delivering constant dose rate and constant angular spacing intensity-modulated arc therapy (CDR-CAS-IMAT) for treating cervical cancer.Methods: Twenty patients with cervical cancer previously treated with intensity-modulated radiation therapy (IMRT) using Varian Clinical 23EX were retreated using CDR-CAS-IMAT.The planning target volume (PTV) was set as 50.4 Gy in 28 fractions.Plans were evaluated based on the ability to meet the dose volume histogram.The homogeneity index (HI), target volume conformity index (CI), the dose to organs at risk, radiation delivery time, and monitor units (MUs) were also compared.The paired t-test was used to analyze the two data sets.All statistical analyses were performed using SPSS 19.0 software.Results: Compared to the IMRT group, the CDR-CAS-IMAT group showed better PTV CI (0.85 ± 0.03 vs.0.81 ± 0.03, P =0.001), clinical target volume CI (0.46 ± 0.05 vs.0.43 ± 0.05, P =0.001), HI (0.09±0.02 vs.0.11 ± 0.02, P =0.005) and D95 (5196.33 ± 28.24 cGy vs.5162.63 ± 31.12 cGy, P =0.000), and cord D2 (3743.8 ± 118.7 cGy vs.3806.2 ± 98.7 cGy, P =0.017) and rectum V40 (41.9 ± 6.1% vs.44.2 ± 4.8%, P =0.026).Treatment time (422.7 ± 46.7 s vs.84.6 ± 7.8 s, P =0.000) and the total plan Mus (927.4 ± 79.1 vs.787.5 ± 78.5, P =0.000) decreased by a factor of 0.8 and 0.15, respectively.The IMRT group plans were superior to the CDR-CAS-IMAT group plans considering decreasing bladder V50 (17.4 ± 4.5% vs.16.6 ± 4.2%, P =0.049), bowel V30 (39.6 ± 6.5% vs.36.6 ± 7.5%, P =0.008), and low-dose irradiation volume;there were no significant differences in other statistical indexes.Conclusions: Patients with cervical

  18. Implementation of Constant Dose Rate and Constant Angular Spacing Intensity-modulated Arc Therapy for Cervical Cancer by Using a Conventional Linear Accelerator

    Science.gov (United States)

    Zhang, Ruo-Hui; Fan, Xiao-Mei; Bai, Wen-Wen; Cao, Yan-Kun

    2016-01-01

    Background: Volumetric-modulated arc therapy (VMAT) can only be implemented on the new generation linacs such as the Varian Trilogy® and Elekta Synergy®. This prevents most existing linacs from delivering VMAT. The purpose of this study was to investigate the feasibility of using a conventional linear accelerator delivering constant dose rate and constant angular spacing intensity-modulated arc therapy (CDR-CAS-IMAT) for treating cervical cancer. Methods: Twenty patients with cervical cancer previously treated with intensity-modulated radiation therapy (IMRT) using Varian Clinical 23EX were retreated using CDR-CAS-IMAT. The planning target volume (PTV) was set as 50.4 Gy in 28 fractions. Plans were evaluated based on the ability to meet the dose volume histogram. The homogeneity index (HI), target volume conformity index (CI), the dose to organs at risk, radiation delivery time, and monitor units (MUs) were also compared. The paired t-test was used to analyze the two data sets. All statistical analyses were performed using SPSS 19.0 software. Results: Compared to the IMRT group, the CDR-CAS-IMAT group showed better PTV CI (0.85 ± 0.03 vs. 0.81 ± 0.03, P = 0.001), clinical target volume CI (0.46 ± 0.05 vs. 0.43 ± 0.05, P = 0.001), HI (0.09±0.02 vs. 0.11 ± 0.02, P = 0.005) and D95 (5196.33 ± 28.24 cGy vs. 5162.63 ± 31.12 cGy, P = 0.000), and cord D2 (3743.8 ± 118.7 cGy vs. 3806.2 ± 98.7 cGy, P = 0.017) and rectum V40 (41.9 ± 6.1% vs. 44.2 ± 4.8%, P = 0.026). Treatment time (422.7 ± 46.7 s vs. 84.6 ± 7.8 s, P = 0.000) and the total plan Mus (927.4 ± 79.1 vs. 787.5 ± 78.5, P = 0.000) decreased by a factor of 0.8 and 0.15, respectively. The IMRT group plans were superior to the CDR-CAS-IMAT group plans considering decreasing bladder V50 (17.4 ± 4.5% vs. 16.6 ± 4.2%, P = 0.049), bowel V30 (39.6 ± 6.5% vs. 36.6 ± 7.5%, P = 0.008), and low-dose irradiation volume; there were no significant differences in other statistical indexes. Conclusions

  19. Non-chiral fusion rules, structure constants of $D_{m}$ minimal models

    CERN Document Server

    Rida, A

    1999-01-01

    We present a technique to construct, for $D_{m}$ unitary minimal models, the non-chiral fusion rules which determines the operator content of the operator product algebra. Using these rules we solve the bootstrap equations and therefore determine the structure constants of these models. Through this approach we emphasize the role played by some discrete symmetries in the classification of minimal models.

  20. Nanostructured thin film polymer devices for constant-rate protein delivery.

    Science.gov (United States)

    Bernards, Daniel A; Lance, Kevin D; Ciaccio, Natalie A; Desai, Tejal A

    2012-10-10

    Herein long-term delivery of proteins from biodegradable thin film devices is demonstrated, where a nanostructured polymer membrane controls release. Protein was sealed between two poly(caprolactone) films, which generated the thin film devices. Protein release for 210 days was shown in vitro, and stable activity was established through 70 days with a model protein. These thin film devices present a promising delivery platform for biologic therapeutics, particularly for application in constrained spaces.

  1. AGGREGATE RATING MODEL IN THE TOURISM INDUSTRY

    Directory of Open Access Journals (Sweden)

    Maris Angela

    2014-07-01

    Full Text Available In the paper the authors present a model aggregate rating based on credit-scoring models, banking models and their rating model. Multi-criteria approach and an aggregate model better capture business risk of the company.

  2. Preference and resistance to change with constant- and variable-duration terminal links: independence of reinforcement rate and magnitude.

    Science.gov (United States)

    Grace, Randolph C; Bedell, Melissa A; Nevin, John A

    2002-05-01

    Pigeons responded in a three-component multiple concurrent-chains procedure in which the variable-interval reinforcement schedules were the same across components but magnitudes differed across components. The terminal links were arranged either as a variable delay followed by presentation of a reinforcer ("variable duration") or as a fixed period of access to the schedule during which a variable number of reinforcers could be earned ("constant duration"). Relative reinforcement rate was varied parametrically across both types of conditions. After baseline training in each condition, resistance to change of terminal-link responding was assessed by delivering food during the initial links according to a variable-time schedule. Both preference and resistance to change were more sensitive to reinforcement-rate differences in the constant-duration conditions. Sensitivities of preference and resistance to change to relative reinforcement rate did not change depending on relative reinforcement magnitude. Taken together, these results confirm and extend those of prior studies, and suggest that reinforcement rate and magnitude combine additively to determine preference and resistance to change. A single structural relation linking preference and resistance to change describes all the data from this and several related studies.

  3. Modeling drug release from hot-melt extruded mini-matrices with constant and non-constant diffusivities.

    Science.gov (United States)

    Verhoeven, E; Siepmann, F; De Beer, T R M; Van Loo, D; Van den Mooter, G; Remon, J P; Siepmann, J; Vervaet, C

    2009-10-01

    Different types of ethylcellulose-based mini-matrices were prepared by hot-melt extrusion and thoroughly characterized in vitro. Metoprolol tartrate was used as model drug, and various amounts and types of polyethylene glycol (PEG)/polyethylene oxide (PEO) were added as release rate modifiers. Based on the experimental results, appropriate mathematical theories were identified/developed, allowing for a better understanding of the underlying drug release mechanisms. For instance, it could be shown that at high initial PEG/PEO contents and/or intermediate initial PEG/PEO contents of low molecular weight, drug diffusion with time- and position-independent diffusivities is predominant. In contrast, at low initial PEG/PEO contents and intermediate initial PEG/PEO contents of high molecular weight, the time- and position-dependent dynamic changes in the matrix porosities significantly affect the conditions for drug and PEG/PEO diffusion. These dynamic changes must be taken into account in the mathematical model. Importantly, the proposed theories are mechanistic realistic and also allow for the quantitative prediction of the effects of the device design on the resulting drug release patterns. Interestingly, these quantitative predictions could be confirmed by independent experiments. Furthermore, Raman spectroscopy allowed for the determination of the resulting drug concentration-position profiles within the mini-matrices as a function of time and confirmed the theoretical predictions.

  4. NON-CONSTANT POSITIVE STEADY-STATES OF A PREDATOR-PREY-MUTUALIST MODEL

    Institute of Scientific and Technical Information of China (English)

    CHEN WENYAN; WANG MINGXIN

    2004-01-01

    In this paper, the authors deal with the non-constant positive steady-states of a predator-prey-mutualist model with homogeneous Neumann boundary condition. They first give a priori estimates (positive upper and lower bounds) of positive steady-states,and then study the non-existence, the global existence and bifurcation of non-constant positive steady-states as some parameters are varied. Finally the asymptotic behavior of such solutions as d3 →∞ is discussed.

  5. Theoretical determination of chemical rate constants using novel time-dependent methods

    Science.gov (United States)

    Dateo, Christopher E.

    1994-01-01

    The work completed within the grant period 10/1/91 through 12/31/93 falls primarily in the area of reaction dynamics using both quantum and classical mechanical methodologies. Essentially four projects have been completed and have been or are in preparation of being published. The majority of time was spent in the determination of reaction rate coefficients in the area of hydrocarbon fuel combustion reactions which are relevant to NASA's High Speed Research Program (HSRP). These reaction coefficients are important in the design of novel jet engines with low NOx emissions, which through a series of catalytic reactions contribute to the deterioration of the earth's ozone layer. A second area of research studied concerned the control of chemical reactivity using ultrashort (femtosecond) laser pulses. Recent advances in pulsed-laser technologies have opened up a vast new field to be investigated both experimentally and theoretically. The photodissociation of molecules adsorbed on surfaces using novel time-independent quantum mechanical methods was a third project. And finally, using state-of-the-art, high level ab initio electronic structure methods in conjunction with accurate quantum dynamical methods, the rovibrational energy levels of a triatomic molecule with two nonhydrogen atoms (HCN) were calculated to unprecedented levels of agreement between theory and experiment.

  6. Variational RRKM calculation of thermal rate constant for C–H bond fission reaction of nitro methane

    Directory of Open Access Journals (Sweden)

    Afshin Taghva Manesh

    2017-02-01

    Full Text Available The present work provides quantitative results for the rate constants of unimolecular C–H bond fission reactions in the nitro methane at elevated temperatures up to 2000 K. In fact, there are three different hydrogen atoms in the nitro methane. The potential energy surface for each C–H bond fission reaction of nitro methane was investigated by ab initio calculations. The geometry and vibrational frequencies of the species involved in this process were optimized at the MP2 level of theory, using the cc-pvdz basis set. Since C–H bond fission channel is a barrierless reaction, we have used variational RRKM theory to predict rate coefficients. By means of calculated rate coefficients at different temperatures, the Arrhenius expression of the channel over the temperature range of 100–2000 K is k(T = 5.9E19∗exp(−56274.6/T.

  7. Propagator with Positive Cosmological Constant in the 3D Euclidian Quantum Gravity Toy Model

    CERN Document Server

    Bunting, William

    2014-01-01

    We study the propagator on a single tetrahedron in a three dimensional toy model of quantum gravity with positive cosmological constant. The cosmological constant is included in the model via q-deformation of the spatial symmetry algebra, that is, we use the Tuarev-Viro amplitude. The expected repulsive effect of dark energy is recovered in numerical and analytic calculations of the propagator at large scales comparable to the infrared cutoff. However, due to the simplicity of the model we do not obtain the exact Newton limit of the propagator. This is a first step toward the similar calculation in the full 3+1 dimensional theory with larger numbers of simplicies.

  8. Simplified Burn-Rate Model for CMDB Propellants

    OpenAIRE

    Kulkarni, A. R.; Bhat, V.K.; S. P. Phadke; R.G.K. Nair

    1990-01-01

    A single model has been proposed to predict the burning rates of bimodal AP,RDX and aluminum containing CMDB propellants. This is done in terms of the respective physical constants on the basis of a recently developed model of combustion of CMDB propellants. The study has been carried out to examine the effects of changes in propellants composition, AP particle size and pressures on burning rate. Computer programs were developed for this purpose and the results obtained for typical set...

  9. Creatine kinase rate constant in the human heart measured with 3D‐localization at 7 tesla

    Science.gov (United States)

    Robson, Matthew D.; Neubauer, Stefan; Rodgers, Christopher T.

    2016-01-01

    Purpose We present a new Bloch‐Siegert four Angle Saturation Transfer (BOAST) method for measuring the creatine kinase (CK) first‐order effective rate constant kf in human myocardium at 7 tesla (T). BOAST combines a variant of the four‐angle saturation transfer (FAST) method using amplitude‐modulated radiofrequency pulses, phosphorus Bloch‐Siegert B1+‐mapping to determine the per‐voxel flip angles, and nonlinear fitting to Bloch simulations for postprocessing. Methods Optimal flip angles and repetition time parameters were determined from Monte Carlo simulations. BOAST was validated in the calf muscle of two volunteers at 3T and 7T. The myocardial CK forward rate constant was then measured in 10 volunteers at 7T in 82 min (after 1H localization). Results BOAST kfCK values were 0.281 ± 0.002 s−1 in the calf and 0.35 ± 0.05 s−1 in myocardium. These are consistent with literature values from lower fields. Using a literature values for adenosine triphosphate concentration, we computed CK flux values of 4.55 ± 1.52 mmol kg−1 s−1. The sensitive volume for BOAST depends on the B1 inhomogeneity of the transmit coil. Conclusion BOAST enables measurement of the CK rate constant in the human heart at 7T, with spatial localization in three dimensions to 5.6 mL voxels, using a 10‐cm loop coil. Magn Reson Med 78:20–32, 2017. © 2016 The Authors Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. PMID:27579566

  10. An independent constraint on the secular rate of variation of the gravitational constant from pulsating white dwarfs

    CERN Document Server

    Córsico, Alejandro H; García-Berro, Enrique; Romero, Alejandra D

    2013-01-01

    A secular variation of the gravitational constant modifies the structure and evolutionary time scales of white dwarfs. Using an state-of-the-art stellar evolutionary code and an up-to-date pulsational code we compute the effects of a secularly varying $G$ on the pulsational properties of variable white dwarfs. Comparing the the theoretical results obtained taking into account the effects of a running $G$ with the observed periods and measured rates of change of the periods of two well studied pulsating white dwarfs, G117--B15A and R548, we place constraints on the rate of variation of Newton's constant. We derive an upper bound $\\dot G/G\\sim -1.8\\times 10^{-10}$ yr$^{-1}$ using the variable white dwarf G117--B15A, and $\\dot G/G\\sim -1.3\\times 10^{-10}$ yr$^{-1}$ using R548. Although these upper limits are currently less restrictive than those obtained using other techniques, they can be improved in a future measuring the rate of change of the period of massive white dwarfs.

  11. An independent constraint on the secular rate of variation of the gravitational constant from pulsating white dwarfs

    Energy Technology Data Exchange (ETDEWEB)

    Córsico, Alejandro H.; Althaus, Leandro G. [Facultad de Ciencias Astronómicas y Geofísicas, Universidad Nacional de La Plata, Paseo del Bosque s/n, (1900) La Plata (Argentina); García-Berro, Enrique [Departament de Física Aplicada, Universitat Politècnica de Catalunya, c/Esteve Terrades, 5, 08860 Castelldefels (Spain); Romero, Alejandra D., E-mail: acorsico@fcaglp.unlp.edu.ar, E-mail: althaus@fcaglp.unlp.edu.ar, E-mail: enrique.garcia-berro@upc.edu, E-mail: alejandra.romero@ufrgs.br [Departamento de Astronomia, Universidade Federal do Rio Grande do Sul, Av. Bento Goncalves 9500, Porto Alegre 91501-970, RS (Brazil)

    2013-06-01

    A secular variation of the gravitational constant modifies the structure and evolutionary time scales of white dwarfs. Using an state-of-the-art stellar evolutionary code and an up-to-date pulsational code we compute the effects of a secularly varying G on the pulsational properties of variable white dwarfs. Comparing the the theoretical results obtained taking into account the effects of a running G with the observed periods and measured rates of change of the periods of two well studied pulsating white dwarfs, G117-B15A and R548, we place constraints on the rate of variation of Newton's constant. We derive an upper bound Ġ/G ∼ −1.8 × 10{sup −10} yr{sup −1} using the variable white dwarf G117-B15A, and Ġ/G ∼ −1.3 × 10{sup −10} yr{sup −1} using R548. Although these upper limits are currently less restrictive than those obtained using other techniques, they can be improved in a future measuring the rate of change of the period of massive white dwarfs.

  12. Automated Method for Estimating Nutation Time Constant Model Parameters for Spacecraft Spinning on Axis

    Science.gov (United States)

    2008-01-01

    Calculating an accurate nutation time constant (NTC), or nutation rate of growth, for a spinning upper stage is important for ensuring mission success. Spacecraft nutation, or wobble, is caused by energy dissipation anywhere in the system. Propellant slosh in the spacecraft fuel tanks is the primary source for this dissipation and, if it is in a state of resonance, the NTC can become short enough to violate mission constraints. The Spinning Slosh Test Rig (SSTR) is a forced-motion spin table where fluid dynamic effects in full-scale fuel tanks can be tested in order to obtain key parameters used to calculate the NTC. We accomplish this by independently varying nutation frequency versus the spin rate and measuring force and torque responses on the tank. This method was used to predict parameters for the Genesis, Contour, and Stereo missions, whose tanks were mounted outboard from the spin axis. These parameters are incorporated into a mathematical model that uses mechanical analogs, such as pendulums and rotors, to simulate the force and torque resonances associated with fluid slosh.

  13. Spectral model selection in the electronic measurement of the Boltzmann constant by Johnson noise thermometry

    Science.gov (United States)

    Coakley, Kevin J.; Qu, Jifeng

    2017-04-01

    In the electronic measurement of the Boltzmann constant based on Johnson noise thermometry, the ratio of the power spectral densities of thermal noise across a resistor at the triple point of water, and pseudo-random noise synthetically generated by a quantum-accurate voltage-noise source is constant to within 1 part in a billion for frequencies up to 1 GHz. Given knowledge of this ratio, and the values of other parameters that are known or measured, one can determine the Boltzmann constant. Due, in part, to mismatch between transmission lines, the experimental ratio spectrum varies with frequency. We model this spectrum as an even polynomial function of frequency where the constant term in the polynomial determines the Boltzmann constant. When determining this constant (offset) from experimental data, the assumed complexity of the ratio spectrum model and the maximum frequency analyzed (fitting bandwidth) dramatically affects results. Here, we select the complexity of the model by cross-validation—a data-driven statistical learning method. For each of many fitting bandwidths, we determine the component of uncertainty of the offset term that accounts for random and systematic effects associated with imperfect knowledge of model complexity. We select the fitting bandwidth that minimizes this uncertainty. In the most recent measurement of the Boltzmann constant, results were determined, in part, by application of an earlier version of the method described here. Here, we extend the earlier analysis by considering a broader range of fitting bandwidths and quantify an additional component of uncertainty that accounts for imperfect performance of our fitting bandwidth selection method. For idealized simulated data with additive noise similar to experimental data, our method correctly selects the true complexity of the ratio spectrum model for all cases considered. A new analysis of data from the recent experiment yields evidence for a temporal trend in the offset

  14. Rate constants and isotope effects for the reaction of H-atom abstraction from RH substrates by PINO radicals

    Science.gov (United States)

    Opeida, I. A.; Litvinov, Yu. E.; Kushch, O. V.; Kompanets, M. A.; Shendrik, A. N.; Matvienko, A. G.; Novokhatko, A. A.

    2016-11-01

    The kinetics of the reactions of hydrogen atom abstraction from the C-H bonds of substrates of different structures by phthalimide- N-oxyl radicals is studied. The rate constants of this reaction are measured and the kinetic isotope effects are determined. It is shown that in addition to the thermodynamic factor, Coulomb forces and donor-acceptor interactions affect the reaction between phthalimide- N-oxyl radicals and substrate molecules, altering the shape of the transition state. This favors the tunneling of hydrogen atoms and leads to a substantial reduction in the activation energy of the process.

  15. Measurement of rate constant for gas-phase reaction of DDVP with OH radical by using LP-FTIR

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Pollution caused by organic pesticides has received increasing attention. Until now, studies on organic pesticides pollution are mainly focused on soil and water. For reactions of organic pesticides in gas-phase, there are very little research results reported. Using a long path quartz reactor to simulate the atmospheric reaction of dimethyl_dichloro_vinyl_phosphate(DDVP) with OH radicals, the rate constant for the reaction at room temperature is measured at (3.06±0.46)×10-11 cm3 s-1 with Fourier transform infrared spectrograph.The result indicates that DDVP degrades relatively fast in the atmosphere and is unlikely to cause persistent pollution.

  16. The hillslope-storage Boussinesq model for non-constant bedrock slope

    NARCIS (Netherlands)

    Hilberts, A.G.J.; Loon, van E.E.; Troch, P.A.A.; Paniconi, C.

    2004-01-01

    In this study the recently introduced hill slope-storage Boussinesq (hsB) model is cast in a generalized formulation enabling the model to handle non-constant bedrock slopes (i.e. bedrock profile curvature). This generalization extends the analysis of hydrological behavior to hillslopes of arbitrary

  17. A Lagrange Multiplier Test for Testing the Adequacy of the Constant Conditional Correlation GARCH Model

    DEFF Research Database (Denmark)

    Catani, Paul; Teräsvirta, Timo; Yin, Meiqun

    A Lagrange multiplier test for testing the parametric structure of a constant conditional correlation generalized autoregressive conditional heteroskedasticity (CCC-GARCH) model is proposed. The test is based on decomposing the CCC-GARCH model multiplicatively into two components, one of which...

  18. Dark Energy Model with Non-Minimal Coupling and Cosmological Constant Boundary

    Institute of Scientific and Technical Information of China (English)

    张晓菲

    2011-01-01

    In this paper, we study a kind of dark energy models in the framework of the non-minimal coupling. With this kind of models, dark energy could cross the cosmological constant boundary, and at early time, dark energy could have "tracking" behavior.

  19. Dynamics of a stochastic tuberculosis model with constant recruitment and varying total population size

    Science.gov (United States)

    Liu, Qun; Jiang, Daqing; Shi, Ningzhong; Hayat, Tasawar; Alsaedi, Ahmed

    2017-03-01

    In this paper, we develop a mathematical model for a tuberculosis model with constant recruitment and varying total population size by incorporating stochastic perturbations. By constructing suitable stochastic Lyapunov functions, we establish sufficient conditions for the existence of an ergodic stationary distribution as well as extinction of the disease to the stochastic system.

  20. Charge of the Electron, and the Constants of Radiation According to J. A. Wheeler's Geometrodynamic Model

    Directory of Open Access Journals (Sweden)

    Belyakov A. V.

    2010-10-01

    Full Text Available This study suggests a mechanical interpretation of Wheeler's model of the charge. According to the suggested interpretation, the oppositely charged particles are connected through the vortical lines of the current thus create a close contour "input-output" whose parameters determine the properties of the charge and spin. Depending on the energetic state of the system, the contour can be structurized into the units of the second and third order (photons. It is found that, in the framework of this interpretation, the charge is equivalent to the momentum. The numerical value of the unit charge has also been calculated proceeding from this basis. A system of the relations, connecting the charge to the constants of radiation (the Boltzmann, Wien, and Stefan-Boltzmann constants, and the fine structure constant has been obtained: this give a possibility for calculating all these constants through the unit charge.

  1. Charge of the Electron, and the Constants of Radiation According to J. A. Wheeler's Geometrodynamic Model

    Directory of Open Access Journals (Sweden)

    Belyakov A. V.

    2010-10-01

    Full Text Available This study suggests a mechanical interpretation of Wheller’s model of the charge. Ac- cording to the suggested interpretation, the oppositely charged particles are connected through the vortical lines of the current thus create a close contour “input-output” whose parameters determine the properties of the charge and spin. Depending on the energetic state of the system, the contour can be structurized into the units of the second and thirs order (photons. It is found that, in the framework of this interpretation, the charge is equivalent to the momentum. The numerical value of the unit charge has also been cal- culated proceeding from this basis. A system of the relations, connecting the charge to the constants of radiation (the Boltzmann, Wien, and Stefan-Boltzmann constants, and the fine structure constant has been obtained: this give a possibility for calculating all these constants through the unit charge.

  2. The Effect of Trailing Vortices on the Production of Lift on an Airfoil Undergoing a Constant Rate of Change of Angle of Attack.

    Science.gov (United States)

    1983-12-01

    The purpose of this study was to investigate the effect a trailing vortex wake has on an airfoil undergoing a constant rate of change of angle of...When applied to the constant rate - of - change of angle-of-attack problem, the results showed that a trailing vortex wake has a measurable and

  3. Rate Constants and Deuterium Kinetic Isotope Effects for Methoxy Radical Reacting with NO_2 and O_2

    Science.gov (United States)

    Chai, J.; Hu, H.; Dibble, T. S.; Tyndall, G. S.; Orlando, J. J.

    2013-06-01

    Alkoxy radicals (RO) are important intermediates in the photooxidation of volatile organic compounds due to their great impacts on ozone formation and gas-particle partitioning of stable oxidation products. Methoxy radical (CH_3O) is the prototype for all alkoxy radicals. The absolute rate constants k_N_O_2(T) for reaction of CH_3O and CD_3O with NO_2 have been measured using laser flash photolysis to generate radicals and laser-induced fluorescence for time-resolved detection. The pressure and temperature dependence for k_N_O_2 have been observed over the range 30-700 Torr and 250-335 K. This will be the first direct measurement of k_N_O_2 for CH_3O near ambient pressure and the first ever for CD_3O.The relative rate constants k_N_O_2/k_O_2(T) have been measured in an environmental chamber with FTIR detection. This combination enables the first determination of k_O_2 (T) for CH_3O and CD_3O for T < 298 K. The results will also help validate theoretical methods for studying alkoxy + O_2 reactions, which are challenging for quantum chemistry.

  4. Optical factors determined by the T-matrix method in turbidity measurement of absolute coagulation rate constants.

    Science.gov (United States)

    Xu, Shenghua; Liu, Jie; Sun, Zhiwei

    2006-12-01

    Turbidity measurement for the absolute coagulation rate constants of suspensions has been extensively adopted because of its simplicity and easy implementation. A key factor in deriving the rate constant from experimental data is how to theoretically evaluate the so-called optical factor involved in calculating the extinction cross section of doublets formed during aggregation. In a previous paper, we have shown that compared with other theoretical approaches, the T-matrix method provides a robust solution to this problem and is effective in extending the applicability range of the turbidity methodology, as well as increasing measurement accuracy. This paper will provide a more comprehensive discussion of the physical insight for using the T-matrix method in turbidity measurement and associated technical details. In particular, the importance of ensuring the correct value for the refractive indices for colloidal particles and the surrounding medium used in the calculation is addressed, because the indices generally vary with the wavelength of the incident light. The comparison of calculated results with experiments shows that the T-matrix method can correctly calculate optical factors even for large particles, whereas other existing theories cannot. In addition, the data of the optical factor calculated by the T-matrix method for a range of particle radii and incident light wavelengths are listed.

  5. Hydroxyl-radical-induced degradative oxidation of beta-lactam antibiotics in water: absolute rate constant measurements.

    Science.gov (United States)

    Dail, Michelle K; Mezyk, Stephen P

    2010-08-19

    The beta-lactam antibiotics are some of the most prevalent pharmaceutical contaminants currently being detected in aquatic environments. Because the presence of any trace level of antibiotic in water may adversely affect aquatic ecosystems and contribute to the production of antibiotic-resistant bacteria, active removal by additional water treatments, such as using advanced oxidation and reduction processes (AO/RPs), may be required. However, to ensure that any AOP treatment process occurs efficiently and quantitatively, a full understanding of the kinetics and mechanisms of all of the chemical reactions involved under the conditions of use is necessary. In this study, we report on our kinetic measurements for the hydroxyl-radical-induced oxidation of 11 beta-lactam antibiotics obtained using electron pulse radiolysis techniques. For the 5-member ring species, an average reaction rate constant of (7.9 +/- 0.8) x 10(9) M(-1) s(-1) was obtained, slightly faster than for the analogous 6-member ring containing antibiotics, (6.6 +/- 1.2) x 10(9) M(-1) s(-1). The consistency of these rate constants for each group infers a common reaction mechanism, consisting of the partitioning of the hydroxyl radical between addition to peripheral aromatic rings and reaction with the central double-ring core of these antibiotics.

  6. Tissue vitamin concentrations are maintained constant by changing the urinary excretion rate of vitamins in rats' restricted food intake.

    Science.gov (United States)

    Shibata, Katsumi; Fukuwatari, Tsutomu

    2014-01-01

    We previously reported that mild food restriction induces a reduction in tryptophan-nicotinamide conversion, which helps to explain why death secondary to pellagra is pandemic during the hungry season. In this study, we investigated the levels of B-group vitamins in the liver, kidney, blood, and urine in rats that underwent gradual restriction of food intake (80, 60, 40, and 20% restriction vs. ad libitum food intake). No significant differences in the B-group vitamin concentrations (mol/g tissue) in the liver and kidney were observed at any level of food restriction. However, the urine excretion rates exhibited some characteristic phenomena that differed by vitamin. These results show that the tissue concentrations of B-group vitamins were kept constant by changing the urinary elimination rates of vitamins under various levels of food restriction. Only vitamin B12 was the only (exception).

  7. Apparent activation energy for densification of -Al2O3 powder at constant heating-rate sintering

    Indian Academy of Sciences (India)

    W Q Shao; S O Chen; D Li; H S Cao; Y C Zhang; S S Zhang

    2008-11-01

    The apparent activation energy for densification is a characteristic quantity that elucidates the fundamental diffusion mechanisms during the sintering process. Based on the Arrhenius theory, the activation energy for densification of -Al2O3 at constant heating-rates sintering has been estimated. Sintering of -Al2O3 powder has been executed by the way of a push rod type dilatometer. It is shown that the apparent activation energy does not have a single value but depends directly on the relative density. The apparent activation energy corresponding to lower relative density was higher than that corresponding to higher relative density. In addition, the value of the evaluated activation energy is different at the same density level when the Arrhenius plot involves different heating rates.

  8. Slow Crack Growth of Brittle Materials With Exponential Crack-Velocity Formulation. Part 2; Constant Stress Rate Experiments

    Science.gov (United States)

    Choi, Sung R.; Nemeth, Noel N.; Gyekenyesi, John P.

    2002-01-01

    The previously determined life prediction analysis based on an exponential crack-velocity formulation was examined using a variety of experimental data on glass and advanced structural ceramics in constant stress rate and preload testing at ambient and elevated temperatures. The data fit to the relation of strength versus the log of the stress rate was very reasonable for most of the materials. Also, the preloading technique was determined equally applicable to the case of slow-crack-growth (SCG) parameter n greater than 30 for both the power-law and exponential formulations. The major limitation in the exponential crack-velocity formulation, however, was that the inert strength of a material must be known a priori to evaluate the important SCG parameter n, a significant drawback as compared with the conventional power-law crack-velocity formulation.

  9. Estimating Energy Conversion Efficiency of Thermoelectric Materials: Constant Property Versus Average Property Models

    Science.gov (United States)

    Armstrong, Hannah; Boese, Matthew; Carmichael, Cody; Dimich, Hannah; Seay, Dylan; Sheppard, Nathan; Beekman, Matt

    2017-01-01

    Maximum thermoelectric energy conversion efficiencies are calculated using the conventional "constant property" model and the recently proposed "cumulative/average property" model (Kim et al. in Proc Natl Acad Sci USA 112:8205, 2015) for 18 high-performance thermoelectric materials. We find that the constant property model generally predicts higher energy conversion efficiency for nearly all materials and temperature differences studied. Although significant deviations are observed in some cases, on average the constant property model predicts an efficiency that is a factor of 1.16 larger than that predicted by the average property model, with even lower deviations for temperature differences typical of energy harvesting applications. Based on our analysis, we conclude that the conventional dimensionless figure of merit ZT obtained from the constant property model, while not applicable for some materials with strongly temperature-dependent thermoelectric properties, remains a simple yet useful metric for initial evaluation and/or comparison of thermoelectric materials, provided the ZT at the average temperature of projected operation, not the peak ZT, is used.

  10. Decay rates of the magnetohydrodynamic model for quantum plasmas

    Science.gov (United States)

    Pu, Xueke; Xu, Xiuli

    2017-02-01

    In this paper, we consider the quantum magnetohydrodynamic model for quantum plasmas. We prove the optimal decay rates for the solution to the constant state in the whole space in the Lp-norm with 2≤ p≤ 6 and its first derivatives in L2-norm. The proof is based on the optimal decay of the linearized equation and nonlinear energy estimates.

  11. Varying Constants

    CERN Document Server

    Damour, Thibault Marie Alban Guillaume

    2003-01-01

    We review some string-inspired theoretical models which incorporate a correlated spacetime variation of coupling constants while remaining naturally compatible both with phenomenological constraints coming from geochemical data (Oklo; Rhenium decay) and with present equivalence principle tests. Barring unnatural fine-tunings of parameters, a variation of the fine-structure constant as large as that recently ``observed'' by Webb et al. in quasar absorption spectra appears to be incompatible with these phenomenological constraints. Independently of any model, it is emphasized that the best experimental probe of varying constants are high-precision tests of the universality of free fall, such as MICROSCOPE and STEP. Recent claims by Bekenstein that fine-structure-constant variability does not imply detectable violations of the equivalence principle are shown to be untenable.

  12. Role of the constant deceleration parameter in cosmological models with perfect fluid and dark energy

    CERN Document Server

    Pawar, D D; Mapari, R V

    2016-01-01

    The main purpose of the present paper is to investigate LRS Bianchi type I metric in the presence of perfect fluid and dark energy. In order to obtain a deterministic solution of the field equations we have assumed that, the two sources of the perfect fluid and dark energy interact minimally with separate conservation of their energy momentum tensors. The EoS parameter of the perfect fluid is also assumed to be constant. In addition to these we have used a special law of variation of Hubble parameter proposed by Berman that yields constant deceleration parameter. For two different values of the constant deceleration parameters we have obtained two different cosmological models. The physical behaviors of both the models have been discussed by using some physical parameters.

  13. Modeling Nonlinear Adsorption with a Single Chemical Parameter: Predicting Chemical Median Langmuir Binding Constants.

    Science.gov (United States)

    Davis, Craig Warren; Di Toro, Dominic M

    2015-07-07

    Procedures for accurately predicting linear partition coefficients onto various sorbents (e.g., organic carbon, soils, clay) are reliable and well established. However, similar procedures for the prediction of sorption parameters of nonlinear isotherm models are not. The purpose of this paper is to present a procedure for predicting nonlinear isotherm parameters, specifically the median Langmuir binding constants, K̃L, obtained utilizing the single-chemical parameter log-normal Langmuir isotherm developed in the accompanying work. A reduced poly parameter linear free energy relationship (pp-LFER) is able to predict median Langmuir binding constants for graphite, charcoal, and Darco granular activated carbon (GAC) adsorption data. For the larger F400 GAC data set, a single pp-LFER model was insufficient, as a plateau is observed for the median Langmuir binding constants of larger molecular volume sorbates. This volumetric cutoff occurs in proximity to the median pore diameter for F400 GAC. A log-linear relationship exists between the aqueous solubility of these large compounds and their median Langmuir binding constants. Using this relationship for the chemicals above the volumetric cutoff and the pp-LFER below the cutoff, the median Langmuir binding constants can be predicted with a root-mean square error for graphite (n = 13), charcoal (n = 11), Darco GAC (n = 14), and F400 GAC (n = 44) of 0.129, 0.307, 0.407, and 0.424, respectively.

  14. Random forest models of the retention constants in the thin layer chromatography

    CERN Document Server

    Kursa, Miron B; Rudnicki, Witold R

    2011-01-01

    In the current study we examine an application of the machine learning methods to model the retention constants in the thin layer chromatography (TLC). This problem can be described with hundreds or even thousands of descriptors relevant to various molecular properties, most of them redundant and not relevant for the retention constant prediction. Hence we employed feature selection to significantly reduce the number of attributes. Additionally we have tested application of the bagging procedure to the feature selection. The random forest regression models were built using selected variables. The resulting models have better correlation with the experimental data than the reference models obtained with linear regression. The cross-validation confirms robustness of the models.

  15. Two-level renegotiated constant bit rate algorithm (2RCBR) for scalable MPEG2 video over QoS networks

    Science.gov (United States)

    Pegueroles, Josep R.; Alins, Juan J.; de la Cruz, Luis J.; Mata, Jorge

    2001-07-01

    MPEG family codecs generate variable-bit-rate (VBR) compressed video with significant multiple-time-scale bit rate variability. Smoothing techniques remove the periodic fluctuations generated by the codification modes. However, global efficiency concerning network resource allocation remains low due to scene-time-scale variability. RCBR techniques provide suitable means to achieving higher efficiency. Among all RCBR techniques described in literature, 2RCBR mechanism seems to be especially suitable for video-on demand. The method takes advantage of the knowledge of the stored video to calculate the renegotiation intervals and of the client buffer memory to perform work-ahead buffering techniques. 2RCBR achieves 100% bandwidth global efficiency with only two renegotiation levels. The algorithm is based on the study of the second derivative of the cumulative video sequence to find out sharp-sloped inflection points that point out changes in the scene complexity. Due to its nature, 2RCBR becomes very adequate to deliver MPEG2 scalable sequences into the network cause it can assure a constant bit rate to the base MPEG2 layer and use the higher rate intervals to deliver the enhanced MPEG2 layer. However, slight changes in the algorithm parameters must be introduced to attain an optimal behavior. This is verified by means of simulations on MPEG2 video patterns.

  16. Creatine kinase rate constant in the human heart measured with 3D-localization at 7 tesla.

    Science.gov (United States)

    Clarke, William T; Robson, Matthew D; Neubauer, Stefan; Rodgers, Christopher T

    2017-07-01

    We present a new Bloch-Siegert four Angle Saturation Transfer (BOAST) method for measuring the creatine kinase (CK) first-order effective rate constant kf in human myocardium at 7 tesla (T). BOAST combines a variant of the four-angle saturation transfer (FAST) method using amplitude-modulated radiofrequency pulses, phosphorus Bloch-Siegert B1+-mapping to determine the per-voxel flip angles, and nonlinear fitting to Bloch simulations for postprocessing. Optimal flip angles and repetition time parameters were determined from Monte Carlo simulations. BOAST was validated in the calf muscle of two volunteers at 3T and 7T. The myocardial CK forward rate constant was then measured in 10 volunteers at 7T in 82 min (after (1) H localization). BOAST kfCK values were 0.281 ± 0.002 s(-1) in the calf and 0.35 ± 0.05 s(-1) in myocardium. These are consistent with literature values from lower fields. Using a literature values for adenosine triphosphate concentration, we computed CK flux values of 4.55 ± 1.52 mmol kg(-1) s(-1) . The sensitive volume for BOAST depends on the B1 inhomogeneity of the transmit coil. BOAST enables measurement of the CK rate constant in the human heart at 7T, with spatial localization in three dimensions to 5.6 mL voxels, using a 10-cm loop coil. Magn Reson Med 78:20-32, 2017. © 2016 The Authors Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. © 2016 The Authors Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine.

  17. Influence of pH and ionic strength on electrostatic properties of ferredoxin, FNR, and hydrogenase and the rate constants of their interaction

    Science.gov (United States)

    Diakonova, A. N.; Khrushchev, S. S.; Kovalenko, I. B.; Riznichenko, G. Yu; Rubin, A. B.

    2016-10-01

    Ferredoxin (Fd) protein transfers electrons from photosystem I (PSI) to ferredoxin:NADP+-reductase (FNR) in the photosynthetic electron transport chain, as well as other metabolic pathways. In some photosynthetic organisms including cyanobacteria and green unicellular algae under anaerobic conditions Fd transfers electrons not only to FNR but also to hydrogenase—an enzyme which catalyzes reduction of atomic hydrogen to H2. One of the questions posed by this competitive relationship between proteins is which characteristics of thylakoid stroma media allow switching of the electron flow between the linear path PSI-Fd-FNR-NADP+ and the path PSI-Fd-hydrogenase-H2. The study was conducted using direct multiparticle simulation approach. In this method protein molecules are considered as individual objects that experience Brownian motion and electrostatic interaction with the surrounding media and each other. Using the model we studied the effects of pH and ionic strength (I) upon complex formation between ferredoxin and FNR and ferredoxin and hydrogenase. We showed that the rate constant of Fd-FNR complex formation is constant in a wide range of physiologically significant pH values. Therefore it can be argued that regulation of FNR activity doesn’t involve pH changes in stroma. On the other hand, in the model rate constant of Fd-hydrogenase interaction dramatically depends upon pH: in the range 7-9 it increases threefold. It may seem that because hydrogenase reduces protons it should be more active when pH is acidic. Apparently, regulation of hydrogenase’s affinity to both her reaction partners (H+ and Fd) is carried out by changes in its electrostatic properties. In the dark, the protein is inactive and in the light it is activated and starts to interact with both Fd and H+. Therefore, we can conclude that in chloroplasts the rate of hydrogen production is regulated by pH through the changes in the affinity between hydrogenase and ferredoxin.

  18. Analytical model for relativistic corrections to the nuclear magnetic shielding constant in atoms

    Energy Technology Data Exchange (ETDEWEB)

    Romero, Rodolfo H. [Facultad de Ciencias Exactas, Universidad Nacional del Nordeste, Avenida Libertad 5500 (3400), Corrientes (Argentina)]. E-mail: rhromero@exa.unne.edu.ar; Gomez, Sergio S. [Facultad de Ciencias Exactas, Universidad Nacional del Nordeste, Avenida Libertad 5500 (3400), Corrientes (Argentina)

    2006-04-24

    We present a simple analytical model for calculating and rationalizing the main relativistic corrections to the nuclear magnetic shielding constant in atoms. It provides good estimates for those corrections and their trends, in reasonable agreement with accurate four-component calculations and perturbation methods. The origin of the effects in deep core atomic orbitals is manifestly shown.

  19. Decay constants in the heavy quark limit in models à la Bakamjian and Thomas

    CERN Document Server

    Morénas, V; Oliver, L; Pène, O; Raynal, J C

    1998-01-01

    In quark models à la Bakamjian and Thomas, that yield covariance and Isgur-Wise scaling of form factors in the heavy quark limit, we compute the decay constants $f^{(n)}$ and $f^{(n)}_{1/2}$ of S-wave and P-wave mesons composed of heavy and light quarks. Heavy quark limit scaling $\\sqrt{M} f = Cst$ is obtained, and it is shown that this class of models satisfies the sum rules involving decay constants and Isgur-Wise functions recently formulated by us in the heavy quark limit of QCD. Moreover, the model also satisfies the selection rules of the type $f^{(n)}_{3/2} = 0$ that must hold in this limit. We discuss different Ansätze for the dynamics of the mass operator at rest. For non-relativistic kinetic energies ${p^2 \\over 2m}$ the decay constants are finite even if the potential $V(r)$ has a Coulomb part. For the relativistic form $\\sqrt{p^2 + m^2}$, the S-wave decay constants diverge if there is a Coulomb singularity. Using phenomenological models of the spectrum with relativistic kinetic energy and regula...

  20. The Weierstrass Criterion and the Lemaitre-Tolman-Bondi Models with Cosmological Constant \\lambda

    CERN Document Server

    Bochicchio, Ivana; Laserra, Ettore

    2011-01-01

    We analyze Lemaitre-Tolman-Bondi models in presence of the cosmological constant \\Lambda through the classical Weierstrass criterion. Precisely, we show that the Weierstrass approach allows us to classify the dynamics of these inhomogeneous spherically symmetric Universes taking into account their relationship with the sign of \\Lambda.

  1. A Note on "Stability of the Constant Cost Dynamic Lot Size Model" by K. Richter

    NARCIS (Netherlands)

    S. van Hoesel (Stan); A.P.M. Wagelmans (Albert)

    1991-01-01

    textabstractIn a paper by K. Richter the stability regions of the dynamic lot size model with constant cost parameters are analyzed. In particular, an algorithm is suggested to compute the stability region of a so-called generalized solution. In general this region is only a subregion of the stabili

  2. Pricing Volatility Derivatives Under the Modified Constant Elasticity of Variance Model

    OpenAIRE

    Leunglung Chan; Eckhard Platen

    2015-01-01

    This paper studies volatility derivatives such as variance and volatility swaps, options on variance in the modified constant elasticity of variance model using the benchmark approach. The analytical expressions of pricing formulas for variance swaps are presented. In addition, the numerical solutions for variance swaps, volatility swaps and options on variance are demonstrated.

  3. Estimation of the plasma effect site equilibration rate constant of sufentanil in children using the time to peak effect of heart rate and blood pressure.

    Science.gov (United States)

    Song, In-Kyung; Lee, Ji-Hyun; Jung, SungAe; Kim, Jin-Tae; Kim, Hee-Soo

    2015-01-01

    Although targeting the effect site concentration may offer advantages over the traditional forms of administering intravenous anesthetics, it is not applicable for sufentanil in children because its plasma effect site equilibration rate constant (ke0) is not known yet. We estimated ke0 of sufentanil in children using the time to peak effect (t peak) method. Under general anesthesia, sufentanil t peak was measured after administration of a submaximal bolus dose by means of the decrease in heart rate, blood pressure and calculated approximate entropy (ApEn) of electroencephalogram in 105 children (age range: 3-11 years). ke0 was estimated using t peak and known sufentanil pharmacokinetic parameters in normal children. The mean t peaks were measured as 44 ± 22 s and 227 ± 91 s by heart rate and by mean blood pressure respectively. The estimated ke0 were 5.16/min and 0.49/min by heart rate and blood pressure respectively. t peak could not be measured using the ApEn, thus ke0 could not be calculated by ApEn in children. Shorter measured sufentanil t peak by heart rate compared to blood pressure indicate that the heart rate decrease faster than decreasing of blood pressure. Moreover, the calculated sufentanil ke0 in children depends on the pharmacodynamics parameters.

  4. Calculated Third Order Rate Constants for Interpreting the Mechanisms of Hydrolyses of Chloroformates, Carboxylic Acid Halides, Sulfonyl Chlorides and Phosphorochloridates

    Directory of Open Access Journals (Sweden)

    T. William Bentley

    2015-05-01

    Full Text Available Hydrolyses of acid derivatives (e.g., carboxylic acid chlorides and fluorides, fluoro- and chloroformates, sulfonyl chlorides, phosphorochloridates, anhydrides exhibit pseudo-first order kinetics. Reaction mechanisms vary from those involving a cationic intermediate (SN1 to concerted SN2 processes, and further to third order reactions, in which one solvent molecule acts as the attacking nucleophile and a second molecule acts as a general base catalyst. A unified framework is discussed, in which there are two reaction channels—an SN1-SN2 spectrum and an SN2-SN3 spectrum. Third order rate constants (k3 are calculated for solvolytic reactions in a wide range of compositions of acetone-water mixtures, and are shown to be either approximately constant or correlated with the Grunwald-Winstein Y parameter. These data and kinetic solvent isotope effects, provide the experimental evidence for the SN2-SN3 spectrum (e.g., for chloro- and fluoroformates, chloroacetyl chloride, p-nitrobenzoyl p-toluenesulfonate, sulfonyl chlorides. Deviations from linearity lead to U- or V-shaped plots, which assist in the identification of the point at which the reaction channel changes from SN2-SN3 to SN1-SN2 (e.g., for benzoyl chloride.

  5. Model of constant probability event and its application in information fusion

    Institute of Scientific and Technical Information of China (English)

    邓勇; 施文康

    2004-01-01

    A model of constant probability event is constructed rigorously in event space of PSCEA. It is showed that the numerical-based fusion and the algebraic-based fusion have a consistent result when the weight is regarded as a constant probability event. From the point of view of algebra, we present a novel similarity measure in product space. Based on the similarity degree, we use a similarity aggregation method to fusion experts' evaluation. We also give a numerical example to illustrate the method.

  6. Bekenstein model and the time variation of the strong coupling constant

    CERN Document Server

    Chamoun, N; Vucetich, H

    2001-01-01

    We propose to generalize Bekenstein model for the time variation of the fine structure "constant" $\\alpha_{em}$ to QCD strong coupling constant $\\alpha_S$. We find that, except for a ``fine tuned'' choice of the free parameters, the extension can not be performed trivially without being in conflict with experimental constraints and this rules out $\\alpha_S$ variability. This is due largely to the huge numerical value of the QCD vacuum gluon condensate when compared to the mass density of the universe.

  7. Prediction of Henry's law constants of triazine derived herbicides from quantum chemical continuum solvation models.

    Science.gov (United States)

    Delgado, Eduardo J; Alderete, Joel B

    2003-01-01

    The Henry's law constants (H) for triazine derived herbicides are calculated using quantum chemical solvation models, SM2, SM3, PCM-DFT, and CPCM-DFT, and their performances are discussed. The results show considerable differences in performance among the different levels of theory. The values of H calculated by the semiempirical methods agree much better with the experimental values than those obtained at the DFT level. The differences are discussed in terms of the different contributions, electrostatic and no-electrostatic, to Gibbs free energy of solvation. In addition, the Henry's law constants of some triazine derived herbicides whose values have not been reported earlier are predicted as well.

  8. Exact diffusion constant for the one-dimensional partially asymmetric exclusion model

    Science.gov (United States)

    Derrida, B.; Mallick, K.

    1997-02-01

    We calculate exactly the diffusion constant associated with the fluctuations of the current for the partial asymmetric exclusion model on a ring with an arbitrary number of particles and holes. We also give the diffusion constant of a tagged particle on that ring. Our approach extends, using the deformed harmonic oscillator algebra, a result already known for the fully asymmetric case. In the limit of weak asymmetry, we extract from our exact expression the crossover between the Edwards - Wilkinson and the Kardar - Parisi - Zhang equations in (1 + 1) dimensions.

  9. Global behaviour of a predator-prey like model with piecewise constant arguments.

    Science.gov (United States)

    Kartal, Senol; Gurcan, Fuat

    2015-01-01

    The present study deals with the analysis of a predator-prey like model consisting of system of differential equations with piecewise constant arguments. A solution of the system with piecewise constant arguments leads to a system of difference equations which is examined to study boundedness, local and global asymptotic behaviour of the positive solutions. Using Schur-Cohn criterion and a Lyapunov function, we derive sufficient conditions under which the positive equilibrium point is local and global asymptotically stable. Moreover, we show numerically that periodic solutions arise as a consequence of Neimark-Sacker bifurcation of a limit cycle.

  10. RESEARCH NOTE Static dielectric constant of the polarizable NCC water model

    Science.gov (United States)

    Millot, Jean-Christophe Soetens Marilia T. C. Martins Costa Claude

    The static dielectric constant epsilon0 of the ab initio water model NCC including polarizability (Niesar, U., Corongiu, G., Clementi, E., Kneller, G. R., and Bhattacharya, D. K., 1990, J. phys. Chem., 94, 7949) has been computed by molecular dynamics simulation at 25oC and a density of 1gcm-3. The long range electrostatic interactions are taken into account by the reaction field method. Values of 100 8 and 8ps are found for the static dielectric constant and dielectric relaxation time, respectively.

  11. Elastic Constants of Superconducting MgB2 from Molecular Dynamics Simulations with Shell Model

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    The elastic constants of superconducting MgB2 are calculated using a molecular dynamics method (MD)with shell model. The lattice parameters, five independent elastic constants, equations of state (EOS), Debye temperature, and bulk modulus of MgB2 are obtained. Meanwhile, the dependence of the bulk modulus B, the lattice parameters a and c, and the unit cell volume V on the applied pressure are presented. It is demonstrated that the method introduced here can well reproduce the experimental results with a reasonable accuracy.

  12. Constraints on field theoretical models for variation of the fine structure constant

    Science.gov (United States)

    Steinhardt, Charles L.

    2005-02-01

    Recent theoretical ideas and observational claims suggest that the fine structure constant α may be variable. We examine a spectrum of models in which α is a function of a scalar field. Specifically, we consider three scenarios: oscillating α, monotonic time variation of α, and time-independent α that is spatially varying. We examine the constraints imposed upon these theories by cosmological observations, particle detector experiments, and “fifth force” experiments. These constraints are very strong on models involving oscillation but cannot compete with bounds from the Oklo subnuclear reactor on models with monotonic timelike variation of α. One particular model with spatial variation is consistent with all current experimental and observational measurements, including those from two seemingly conflicting measurements of the fine structure constant using the many multiplet method on absorption lines.

  13. A molecular copper catalyst for electrochemical water reduction with a large hydrogen-generation rate constant in aqueous solution.

    Science.gov (United States)

    Zhang, Peili; Wang, Mei; Yang, Yong; Yao, Tianyi; Sun, Licheng

    2014-12-08

    The copper complex [(bztpen)Cu](BF4)2 (bztpen=N-benzyl-N,N',N'-tris(pyridin-2-ylmethyl)ethylenediamine) displays high catalytic activity for electrochemical proton reduction in acidic aqueous solutions, with a calculated hydrogen-generation rate constant (k(obs)) of over 10000 s(-1). A turnover frequency (TOF) of 7000 h(-1) cm(-2) and a Faradaic efficiency of 96% were obtained from a controlled potential electrolysis (CPE) experiment with [(bztpen)Cu](2+) in pH 2.5 buffer solution at -0.90 V versus the standard hydrogen electrode (SHE) over two hours using a glassy carbon electrode. A mechanism involving two proton-coupled reduction steps was proposed for the dihydrogen generation reaction catalyzed by [(bztpen)Cu](2+).

  14. Calculated rate constants of the chemical reactions involving the main byproducts SO2F, SOF2, SO2F2 of SF6 decomposition in power equipment

    Science.gov (United States)

    Fu, Yuwei; Rong, Mingzhe; Yang, Kang; Yang, Aijun; Wang, Xiaohua; Gao, Qingqing; Liu, Dingxin; Murphy, Anthony B.

    2016-04-01

    SF6 is widely used in electrical equipment as an insulating gas. In the presence of an electric arc, partial discharge (PD) or spark, SF6 dissociation products (such as SF2, SF3 and SF4) react with the unavoidable gas impurities (such as water vapor and oxygen), electrodes and surrounding solid insulation materials, forming several toxic and corrosive byproducts. The main stable decomposition products are SO2F, SO2F2 and SOF2, which have been confirmed experimentally to have a direct relationship with discharge faults, and are thus expected to be useful in the fault diagnosis of power equipment. Various studies have been performed of the main SF6 decomposition species and their concentrations under different types of faults. However, most of the experiments focused on the qualitative analysis of the relationship between the stable products and discharge faults. Although some theoretical research on the formation of main SF6 derivatives have been carried out using chemical kinetics models, the basic data (chemical reactions and their rate constants) adopted in the model are inaccurate and incomplete. The complex chemical reactions of SF6 with the impurities are ignored in most cases. The rate constants of some reactions obtained at ambient temperature or in a narrow temperature range are adopted in the models over a far greater range, for example up to 12 000 K, due to the difficulty in the experimental measurement and theoretical estimation of rate coefficients, particularly at high temperatures. Therefore, improved theoretical models require not only the consideration of additional SF6 decomposition reactions in the presence of impurities but also on improved values of rate constants. This paper is devoted to determining the rate constants of the chemical reactions relating to the main byproducts of SF6 decomposition in SF6 gas-insulated power equipment: SO2F, SOF2 and SO2F2. Quantum chemistry calculations with density functional theory, conventional

  15. The variation of the fine structure constant: testing the dipole model with thermonuclear supernovae

    CERN Document Server

    Kraiselburd, Lucila; Negrelli, Carolina; Berro, Enrique García

    2014-01-01

    The large-number hypothesis conjectures that fundamental constants may vary. Accordingly, the spacetime variation of fundamental constants has been an active subject of research for decades. Recently, using data obtained with large telescopes a phenomenological model in which the fine structure constant might vary spatially has been proposed. We test whether this hypothetical spatial variation of {\\alpha}, which follows a dipole law, is compatible with the data of distant thermonuclear supernovae. Unlike previous works, in our calculations we consider not only the variation of the luminosity distance when a varying {\\alpha} is adopted, but we also take into account the variation of the peak luminosity of Type Ia supernovae resulting from a variation of {\\alpha}. This is done using an empirical relation for the peak bolometric magnitude of thermonuclear supernovae that correctly reproduces the results of detailed numerical simulations. We find that there is no significant difference between the several phenome...

  16. Time variation of the fine structure constant in the early universe and the Bekenstein model

    CERN Document Server

    Mosquera, Mercedes E; Landau, Susana J; Vucetich, Hector

    2007-01-01

    We use observational primordial abundances of $\\De$, $\\Het$, $\\He$ and $\\Li$, recent data from the Cosmic Microwave Background and the 2dFGRS power spectrum, to put limits on the variation of the fine structure constant in the early universe. Furthermore, we use these constraints together with other astronomical and geophysical bounds from the late universe to test Bekenstein's model for the variation of $\\alpha$. The model is not able to fit all observational and experimental data.

  17. An analytic model for accurate spring constant calibration of rectangular atomic force microscope cantilevers.

    Science.gov (United States)

    Li, Rui; Ye, Hongfei; Zhang, Weisheng; Ma, Guojun; Su, Yewang

    2015-10-29

    Spring constant calibration of the atomic force microscope (AFM) cantilever is of fundamental importance for quantifying the force between the AFM cantilever tip and the sample. The calibration within the framework of thin plate theory undoubtedly has a higher accuracy and broader scope than that within the well-established beam theory. However, thin plate theory-based accurate analytic determination of the constant has been perceived as an extremely difficult issue. In this paper, we implement the thin plate theory-based analytic modeling for the static behavior of rectangular AFM cantilevers, which reveals that the three-dimensional effect and Poisson effect play important roles in accurate determination of the spring constants. A quantitative scaling law is found that the normalized spring constant depends only on the Poisson's ratio, normalized dimension and normalized load coordinate. Both the literature and our refined finite element model validate the present results. The developed model is expected to serve as the benchmark for accurate calibration of rectangular AFM cantilevers.

  18. Effects of a constant rate infusion of detomidine on cardiovascular function, isoflurane requirements and recovery quality in horses.

    Science.gov (United States)

    Schauvliege, Stijn; Marcilla, Miguel Gozalo; Verryken, Kirsten; Duchateau, Luc; Devisscher, Lindsey; Gasthuys, Frank

    2011-11-01

    To examine the influence of a detomidine constant rate infusion (CRI) on cardiovascular function, isoflurane requirements and recovery quality in horses undergoing elective surgery. Prospective, randomized, blinded, clinical trial. Twenty adult healthy horses. After sedation (detomidine, 10 μg kg(-1) intravenously [IV]) and induction of anaesthesia (midazolam 0.06 mg kg(-1) , ketamine 2.2 mg kg(-1) IV), anaesthesia was maintained with isoflurane in oxygen/air (inspiratory oxygen fraction 55%). When indicated, the lungs were mechanically ventilated. Dobutamine was administered when MAPquality and duration were recorded in each horse. For statistical analysis, anova, Pearson chi-square and Wilcoxon rank sum tests were used as relevant. Heart rate (p=0.0176) and ḊO(2) I (p= 0.0084) were lower and SVR higher (p=0.0126) in group D, compared to group S. Heart rate (p=0.0011) and pH (p=0.0187) increased over time. Significant differences in isoflurane requirements were not detected. Recovery quality and duration were comparable between treatments. A detomidine CRI produced cardiovascular effects typical for α(2) -agonists, without affecting isoflurane requirements, recovery duration or recovery quality. © 2011 The Authors. Veterinary Anaesthesia and Analgesia. © 2011 Association of Veterinary Anaesthetists and the American College of Veterinary Anesthesiologists.

  19. Energy landscape analysis of native folding of the prion protein yields the diffusion constant, transition path time, and rates.

    Science.gov (United States)

    Yu, Hao; Gupta, Amar Nath; Liu, Xia; Neupane, Krishna; Brigley, Angela M; Sosova, Iveta; Woodside, Michael T

    2012-09-04

    Protein folding is described conceptually in terms of diffusion over a configurational free-energy landscape, typically reduced to a one-dimensional profile along a reaction coordinate. In principle, kinetic properties can be predicted directly from the landscape profile using Kramers theory for diffusive barrier crossing, including the folding rates and the transition time for crossing the barrier. Landscape theory has been widely applied to interpret the time scales for protein conformational dynamics, but protein folding rates and transition times have not been calculated directly from experimentally measured free-energy profiles. We characterized the energy landscape for native folding of the prion protein using force spectroscopy, measuring the change in extension of a single protein molecule at high resolution as it unfolded/refolded under tension. Key parameters describing the landscape profile were first recovered from the distributions of unfolding and refolding forces, allowing the diffusion constant for barrier crossing and the transition path time across the barrier to be calculated. The full landscape profile was then reconstructed from force-extension curves, revealing a double-well potential with an extended, partially unfolded transition state. The barrier height and position were consistent with the previous results. Finally, Kramers theory was used to predict the folding rates from the landscape profile, recovering the values observed experimentally both under tension and at zero force in ensemble experiments. These results demonstrate how advances in single-molecule theory and experiment are harnessing the power of landscape formalisms to describe quantitatively the mechanics of folding.

  20. Observational constraints on models of the Universe with time variable Gravitational and Cosmological constants along MOG

    CERN Document Server

    Khurshudyan, M; Momeni, D; Myrzakulov, R; Raza, M

    2014-01-01

    The subject of this paper is to investigate the weak regime covariant scalar-tensor-vector gravity (STVG) theory, known as the MOdified gravity (MOG) theory of gravity. First, we show that the MOG in the absence of scalar fields is converted into $\\Lambda(t),G(t)$ models. Time evolution of the cosmological parameters for a family of viable models have been investigated. Numerical results with the cosmological data have been adjusted. We've introduced a model for dark energy (DE) density and cosmological constant which involves first order derivatives of Hubble parameter. To extend this model, correction terms including the gravitational constant are added. In our scenario, the cosmological constant is a function of time. To complete the model,interaction terms between dark energy and dark matter (DM) manually entered in phenomenological form. Instead of using the dust model for DM, we have proposed DM equivalent to a barotropic fluid. Time evolution of DM is a function of other cosmological parameters. Using ...

  1. Modelling the Central Constant Emission X-ray component of η Carinae

    Science.gov (United States)

    Russell, Christopher M. P.; Corcoran, Michael F.; Hamaguchi, Kenji; Madura, Thomas I.; Owocki, Stanley P.; Hillier, D. John

    2016-05-01

    The X-ray emission of η Carinae shows multiple features at various spatial and temporal scales. The central constant emission (CCE) component is centred on the binary and arises from spatial scales much smaller than the bipolar Homunculus nebula, but likely larger than the central wind-wind collision region between the stars as it does not vary over the ˜2-3 month X-ray minimum when it can be observed. Using large-scale 3D smoothed particle hydrodynamics (SPH) simulations, we model both the colliding-wind region between the stars, and the region where the secondary wind collides with primary wind ejected from the previous periastron passage. The simulations extend out to one hundred semimajor axes and make two limiting assumptions (strong coupling and no coupling) about the influence of the primary radiation field on the secondary wind. We perform 3D radiative transfer calculations on the SPH output to synthesize the X-ray emission, with the aim of reproducing the CCE spectrum. For the preferred primary mass-loss rate dot{M}_A≈ 8.5× 10^{-4} M_{⊙} yr-1, the model spectra well reproduce the observation as the strong- and no-coupling spectra bound the CCE observation for longitude of periastron ω ≈ 252°, and bound/converge on the observation for ω ≈ 90°. This suggests that η Carinae has moderate coupling between the primary radiation and secondary wind, that both the region between the stars and the comoving collision on the backside of the secondary generate the CCE, and that the CCE cannot place constraints on the binary's line of sight. We also discuss comparisons with common X-ray fitting parameters.

  2. On reevaluation rate in discrete time Hogg-Huberman model

    Science.gov (United States)

    Tanaka, Toshijiro; Shibata, Junko; Inoue, Masayoshi

    2002-06-01

    The discrete time Hogg-Huberman model is extended to a case with time-dependent reevaluation rate at which agents using one resource decide to evaluate their resource choice. In this paper the time dependence of the reevaluation rate is determined by states of the system. The dynamical behavior of the extended Hogg-Huberman model is discussed. It is found that the change of fraction of agents using resource 1 is suppressed to be smaller than that in the case of constant reevaluation rate.

  3. Constraining spatial variations of the fine-structure constant in symmetron models

    Science.gov (United States)

    Pinho, A. M. M.; Martinelli, M.; Martins, C. J. A. P.

    2017-06-01

    We introduce a methodology to test models with spatial variations of the fine-structure constant α, based on the calculation of the angular power spectrum of these measurements. This methodology enables comparisons of observations and theoretical models through their predictions on the statistics of the α variation. Here we apply it to the case of symmetron models. We find no indications of deviations from the standard behavior, with current data providing an upper limit to the strength of the symmetron coupling to gravity (log ⁡β2 constrain the model when also the symmetry breaking scale factor aSSB is free to vary.

  4. Testing anthropic reasoning for the cosmological constant with a realistic galaxy formation model

    CERN Document Server

    Sudoh, Takahiro; Makiya, Ryu; Nagashima, Masahiro

    2016-01-01

    The anthropic principle is one of the possible explanations for the cosmological constant ($\\Lambda$) problem. In previous studies, a dark halo mass threshold comparable with our Galaxy must be assumed in galaxy formation to get a reasonably large probability of finding the observed small value, $P(<$$\\Lambda_{\\rm obs})$, though stars are found in much smaller galaxies as well. Here we examine the anthropic argument by using a semi-analytic model of cosmological galaxy formation, which can reproduce many observations such as galaxy luminosity functions. We calculate the probability distribution of $\\Lambda$ by running the model code for a wide range of $\\Lambda$, while other cosmological parameters and model parameters for baryonic processes of galaxy formation are kept constant. Assuming that the prior probability distribution is flat per unit $\\Lambda$, and that the number of observers is proportional to stellar mass, we find $P(<$$\\Lambda_{\\rm obs}) = 6.7 \\%$ without introducing any galaxy mass thres...

  5. Spherically symmetric solutions of a (4 + n)-dimensional Einstein Yang Mills model with cosmological constant

    Science.gov (United States)

    Brihaye, Yves; Hartmann, Betti

    2005-01-01

    We construct solutions of an Einstein Yang Mills system including a cosmological constant in 4 + n spacetime dimensions, where the n-dimensional manifold associated with the extra dimensions is taken to be Ricci flat. Assuming the matter and metric fields to be independent of the n extra coordinates, a spherical symmetric ansatz for the fields leads to a set of coupled ordinary differential equations. We find that for n > 1 only solutions with either one non-zero Higgs field or with all Higgs fields constant and zero gauge field function (corresponding to a Wu Yang-type ansatz) exist. We give the analytic solutions available in this model. These are 'embedded' Abelian solutions with a diverging size of the manifold associated with the extra n dimensions. Depending on the choice of parameters, these latter solutions either represent naked singularities or they possess a single horizon. We also present solutions of the effective four-dimensional Einstein Yang Mills Higgs-dilaton model, where the higher-dimensional cosmological constant induces a Liouville-type potential. The solutions are non-Abelian solutions with diverging Higgs fields, which exist only up to a maximal value of the cosmological constant.

  6. Discrete fragment model for apparent formation constants of actinide ions with humic substances

    Energy Technology Data Exchange (ETDEWEB)

    Sasaki, Takayuki; Yoshida, Hatsumi; Aoyama, Shunsuke; Kobayashi, Taishi; Takagi, Ikuji [Kyoto Univ. (Japan). Dept. of Nuclear Engineering; Moriyama, Hirotake [Kyoto Univ., Osaka (Japan). Research Reactor Inst.

    2015-09-01

    A semi-empirical thermodynamic model was applied to estimate the apparent formation constants of actinide ions, i.e., Th(IV), Pu(IV) and Np(V), with humic substances (HSs), including humic and fulvic acids, over a wide range of solution conditions, i.e., pH, ionic strength, and HS and metal concentrations. The hypothetical HSs consist of humic and fulvic acids with nine types of simple organic ligands, which include aromatic and aliphatic carboxyl groups and phenol groups, as binding sites. The abundance of each binding site in the hypothetical HSs was determined via a fitting analysis using an acid-dissociation dataset for several HSs. To determine the apparent formation constant of a given metal ion with HSs, 54 specific binding sites were considered, including nine monodentate sites (1:1 metal/ligand complexes) and 45 bidentate sites (1:2 metal/ligand complexes). The formation constant of each monodentate binding was determined from the experimental data, while those of the bidentate bindings were determined by considering two monodentate bindings and the chelating effect, for which one of the adjustable parameters was introduced in the model. Introduction of the other parameter, which is related to the fraction of monodentate to bidentate sites (i.e., the heterogeneity), afforded the parameter values with good correlation with the apparent formation constant data. The present model with adjusted parameter values well reproduced the experimental apparent complex formation constants for actinide ion interaction with HSs in a wide range of solution conditions except for those obtained at trace concentrations.

  7. Rate Constants of PSII Photoinhibition and its Repair, and PSII Fluorescence Parameters in Field Plants in Relation to their Growth Light Environments.

    Science.gov (United States)

    Miyata, Kazunori; Ikeda, Hiroshi; Nakaji, Masayoshi; Kanel, Dhana Raj; Terashima, Ichiro

    2015-09-01

    The extent of photoinhibition of PSII is determined by a balance between the rate of photodamage to PSII and that of repair of the damaged PSII. It has already been indicated that the rate constants of photodamage (kpi) and repair (krec) of the leaves differ depending on their growth light environment. However, there are no studies using plants in the field. We examined these rate constants and fluorescence parameters of several field-grown plants to determine inter-relationships between these values and the growth environment. The kpi values were strongly related to the excess energy, EY, of the puddle model and non-regulated energy dissipation, Y(NO), of the lake model, both multiplied by the photosynthetically active photon flux density (PPFD) level during the photoinhibitory treatment. In contrast, the krec values corrected against in situ air temperature were very strongly related to the daily PPFD level. The plants from the fields showed higher NPQ than the chamber-grown plants, probably because these field plants acclimated to stronger lightflecks than the averaged growth PPFD. Comparing chamber-grown plants and the field plants, we showed that kpi is determined by the incident light level and the photosynthetic capacities such as in situ rate of PSII electron transport and non-photochemical quenching (NPQ) [e.g. Y(NO)×PPFD] and that krec is mostly determined by the growth light and temperature levels. © The Author 2015. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

  8. Oxygen consumption and heart rate responses during and after constant load and alternating intensity exercise at 105% of lactate threshold.

    Science.gov (United States)

    Spanoudaki, S; Karatzanos, E; Baltopoulos, P; Maridaki, M

    2015-12-01

    The purpose of this study was a secondary-analysis of previously published data, in order to compare the acute VO2 responses, the time spent at high percentage of VO2max and total VO2 consumed (TVO2) between constant and alternating intensity exercise of the same intensity and duration. This study also aimed to examine VO2 and heart rate (HR) responses one hour after both exercises. Ten recreationally trained men (24.7±4.7 years) completed the following two exercise tests lasting an hour each and having the same mean intensity at 105% of lactate threshold (70% VO2max): 1) constant load cycling (CON), and 2) alternating intensity exercise (ALT), during which 40 seconds of light exercise (47% VO2max) were alternated with 20 seconds of supramaximal intensity at 120% of VO2max. TVO2 (69.89±7.02 vs. 58.22±9.13 mL/kg/min, P=0.03) and HR (142±16, 128±12, P=0.04) was higher in CON exercise compared to ALT. All participants reached 70% and 80% of VO2max irrespective of the exercise protocol. In ALT exercise the time spent at 90% was higher compared to CON exercise (70.81±21.37 vs. 36.88±11.88 seconds). Also, TVO2 recovery values after ALT exercise was higher compared to CON (11.1 ±2.93 vs. 9.94±3.54 mL/kg/min). ALT exercise allowed participants to spend longer time at 90% of VO2max, even if TVO2 in CON exercise was higher, suggesting that in ALT exercise greater aerobic stress (as based on exercise intensity) is imposed on the athletes. While VO2 recovery values were higher in ALT compared to CON, indicating different substrate utilization during and after exercise.

  9. Optimal Homotopy Asymptotic Solution for Exothermic Reactions Model with Constant Heat Source in a Porous Medium

    Directory of Open Access Journals (Sweden)

    Fazle Mabood

    2015-01-01

    Full Text Available The heat flow patterns profiles are required for heat transfer simulation in each type of the thermal insulation. The exothermic reaction models in porous medium can prescribe the problems in the form of nonlinear ordinary differential equations. In this research, the driving force model due to the temperature gradients is considered. A governing equation of the model is restricted into an energy balance equation that provides the temperature profile in conduction state with constant heat source on the steady state. The proposed optimal homotopy asymptotic method (OHAM is used to compute the solutions of the exothermic reactions equation.

  10. Evolution of the fine-structure constant in runaway dilaton models

    Energy Technology Data Exchange (ETDEWEB)

    Martins, C.J.A.P., E-mail: Carlos.Martins@astro.up.pt [Centro de Astrofísica, Universidade do Porto, Rua das Estrelas, 4150-762 Porto (Portugal); Instituto de Astrofísica e Ciências do Espaço, CAUP, Rua das Estrelas, 4150-762 Porto (Portugal); Vielzeuf, P.E., E-mail: pvielzeuf@ifae.es [Institut de Física d' Altes Energies, Universitat Autònoma de Barcelona, E-08193 Bellaterra (Barcelona) (Spain); Martinelli, M., E-mail: martinelli@thphys.uni-heidelberg.de [Institute for Theoretical Physics, University of Heidelberg, Philosophenweg 16, 69120, Heidelberg (Germany); Calabrese, E., E-mail: erminia.calabrese@astro.ox.ac.uk [Sub-department of Astrophysics, University of Oxford, Keble Road, Oxford OX1 3RH (United Kingdom); Pandolfi, S., E-mail: stefania@dark-cosmology.dk [Dark Cosmology Centre, Niels Bohr Institute, University of Copenhagen, Juliane Maries Vej 30, DK-2100 Copenhagen (Denmark)

    2015-04-09

    We study the detailed evolution of the fine-structure constant α in the string-inspired runaway dilaton class of models of Damour, Piazza and Veneziano. We provide constraints on this scenario using the most recent α measurements and discuss ways to distinguish it from alternative models for varying α. For model parameters which saturate bounds from current observations, the redshift drift signal can differ considerably from that of the canonical ΛCDM paradigm at high redshifts. Measurements of this signal by the forthcoming European Extremely Large Telescope (E-ELT), together with more sensitive α measurements, will thus dramatically constrain these scenarios.

  11. a Unified Dark Energy Model from a Vanishing Speed of Sound with Emergent Cosmological Constant

    Science.gov (United States)

    Luongo, Orlando; Quevedo, Hernando

    2014-11-01

    The problem of the cosmic acceleration is here revisited by using the fact that the adiabatic speed of sound can be assumed to be negligible small. Within the context of general relativity, the total energy budget is recovered under the hypothesis of a vanishing speed of sound by assuming the existence of one fluid only. We find a cosmological model which reproduces the main results of the ΛCDM paradigm at late-times, showing an emergent cosmological constant, which is not at all related with the vacuum energy term. As a consequence, the model presented here behaves as a unified dark energy (DE) model.

  12. Evolution of the fine-structure constant in runaway dilaton models

    CERN Document Server

    Martins, C J A P; Martinelli, M; Calabrese, E; Pandolfi, S

    2015-01-01

    We study the detailed evolution of the fine-structure constant $\\alpha$ in the string-inspired runaway dilaton class of models of Damour, Piazza and Veneziano. We provide constraints on this scenario using the most recent $\\alpha$ measurements and discuss ways to distinguish it from alternative models for varying $\\alpha$. For model parameters which saturate bounds from current observations, the redshift drift signal can differ considerably from that of the canonical $\\Lambda$CDM paradigm at high redshifts. Measurements of this signal by the forthcoming European Extremely Large Telescope (E-ELT), together with more sensitive $\\alpha$ measurements, will thus dramatically constrain these scenarios.

  13. Evolution of the fine-structure constant in runaway dilaton models

    Directory of Open Access Journals (Sweden)

    C.J.A.P. Martins

    2015-04-01

    Full Text Available We study the detailed evolution of the fine-structure constant α in the string-inspired runaway dilaton class of models of Damour, Piazza and Veneziano. We provide constraints on this scenario using the most recent α measurements and discuss ways to distinguish it from alternative models for varying α. For model parameters which saturate bounds from current observations, the redshift drift signal can differ considerably from that of the canonical ΛCDM paradigm at high redshifts. Measurements of this signal by the forthcoming European Extremely Large Telescope (E-ELT, together with more sensitive α measurements, will thus dramatically constrain these scenarios.

  14. Determination of a dielectric waveguide propagation constant using a multifilament-current model.

    Science.gov (United States)

    Cory, H; Altman, Z; Leviatan, Y

    1989-09-15

    A moment method using a multifilament-current model is presented to analyze the modes propagating in a cylindrical dielectric waveguide. In this model, analytically derivable fields of filamentary electric and magnetic currents (of yet unknown propagation constant and amplitude) are used to simulate the field of each mode inside and outside the guiding core. A simple point-matching procedure is subsequently used to enforce the boundary conditions at the core periphery and results in a homogeneous matrix equation. The longitudinal propagation constant of each mode and the currents that yield the field distribution of this mode are then found by solving this equation. As an example, a circular dielectric waveguide is analyzed and the results are presented.

  15. Analysis of a Periodic Single Species Population Model Involving Constant Impulsive Perturbation

    Directory of Open Access Journals (Sweden)

    Ronghua Tan

    2014-01-01

    Full Text Available This is a continuation of the work of Tan et al. (2012. In this paper a periodic single species model controlled by constant impulsive perturbation is investigated. The constant impulse is realized at fixed moments of time. With the help of the comparison theorem of impulsive differential equations and Lyapunov functions, sufficient conditions for the permanence and global attractivity are established, respectively. Also, by comparing the above results with corresponding known results of Tan et al. (2012 (i.e., the above model with linear impulsive perturbations, we find that the two different types of impulsive perturbations have influence on the above dynamics. Numerical simulations are presented to substantiate our analytical results.

  16. Testing anthropic reasoning for the cosmological constant with a realistic galaxy formation model

    Science.gov (United States)

    Sudoh, Takahiro; Totani, Tomonori; Makiya, Ryu; Nagashima, Masahiro

    2017-01-01

    The anthropic principle is one of the possible explanations for the cosmological constant (Λ) problem. In previous studies, a dark halo mass threshold comparable with our Galaxy must be assumed in galaxy formation to get a reasonably large probability of finding the observed small value, P(running the model code for a wide range of Λ, while other cosmological parameters and model parameters for baryonic processes of galaxy formation are kept constant. Assuming that the prior probability distribution is flat per unit Λ, and that the number of observers is proportional to stellar mass, we find P(extremely small, we conclude that the anthropic argument is a viable explanation, if the value of Λ observed in our Universe is determined by a probability distribution.

  17. SU-E-T-421: Feasibility Study of Volumetric Modulated Arc Therapy with Constant Dose Rate for Endometrial Cancer

    Energy Technology Data Exchange (ETDEWEB)

    Yang, R; Wang, J [Peking University Third Hospital, Beijing, Beijing (China)

    2014-06-01

    Purpose: To investigate the feasibility, efficiency, and delivery accuracy of volumetric modulated arc therapy with constant dose rate (VMAT-CDR) for whole-pelvic radiotherapy (WPRT) of endometrial cancer. Methods: The nine-Field intensity-modulated radiotherapy (IMRT), VMAT with variable dose-rate (VMAT-VDR), and VMAT-CDR plans were created for 9 patients with endometrial cancer undergoing WPRT. The dose distribution of planning target volume (PTV), organs at risk (OARs), and normal tissue (NT) were compared. The monitor units (MUs) and treatment delivery time were also evaluated. For each VMAT-CDR plan, a dry Run was performed to assess the dosimetric accuracy with MatriXX from IBA. Results: Compared with IMRT, the VMAT-CDR plans delivered a slightly greater V20 of the bowel, bladder, pelvis bone, and NT, but significantly decreased the dose to the high-dose region of the rectum and pelvis bone. The MUs Decreased from 1105 with IMRT to 628 with VMAT-CDR. The delivery time also decreased from 9.5 to 3.2 minutes. The average gamma pass rate was 95.6% at the 3%/3 mm criteria with MatriXX pretreatment verification for 9 patients. Conclusion: VMAT-CDR can achieve comparable plan quality with significant shorter delivery time and smaller number of MUs compared with IMRT for patients with endometrial cancer undergoing WPRT. It can be accurately delivered and be an alternative to IMRT on the linear accelerator without VDR capability. This work is supported by the grant project, National Natural; Science Foundation of China (No. 81071237)

  18. Dynamics of chest wall volume regulation during constant work rate exercise in patients with chronic obstructive pulmonary disease

    Energy Technology Data Exchange (ETDEWEB)

    Takara, L.S.; Cunha, T.M.; Barbosa, P.; Rodrigues, M.K.; Oliveira, M.F.; Nery, L.E. [Setor de Função Pulmonar e Fisiologia Clínica do Exercício, Disciplina de Pneumologia, Departamento de Medicina, Universidade Federal de São Paulo, São Paulo, SP (Brazil); Neder, J.A. [Setor de Função Pulmonar e Fisiologia Clínica do Exercício, Disciplina de Pneumologia, Departamento de Medicina, Universidade Federal de São Paulo, São Paulo, SP (Brazil); Division of Respiratory and Critical Care Medicine, Department of Medicine, Queen' s University, Kingston, ON (Canada)

    2012-10-15

    This study evaluated the dynamic behavior of total and compartmental chest wall volumes [(V{sub CW}) = rib cage (V{sub RC}) + abdomen (V{sub AB})] as measured breath-by-breath by optoelectronic plethysmography during constant-load exercise in patients with stable chronic obstructive pulmonary disease. Thirty males (GOLD stages II-III) underwent a cardiopulmonary exercise test to the limit of tolerance (Tlim) at 75% of peak work rate on an electronically braked cycle ergometer. Exercise-induced dynamic hyperinflation was considered to be present when end-expiratory (EE) V{sub CW} increased in relation to resting values. There was a noticeable heterogeneity in the patterns of V{sub CW} regulation as EEV{sub CW} increased non-linearly in 17/30 “hyperinflators” and decreased in 13/30 “non-hyperinflators” (P < 0.05). EEV{sub AB} decreased slightly in 8 of the “hyperinflators”, thereby reducing and slowing the rate of increase in end-inspiratory (EI) V{sub CW} (P < 0.05). In contrast, decreases in EEV{sub CW} in the “non-hyperinflators” were due to the combination of stable EEV{sub RC} with marked reductions in EEV{sub AB}. These patients showed lower EIV{sub CW} and end-exercise dyspnea scores but longer Tlim than their counterparts (P < 0.05). Dyspnea increased and Tlim decreased non-linearly with a faster rate of increase in EIV{sub CW} regardless of the presence or absence of dynamic hyperinflation (P < 0.001). However, no significant between-group differences were observed in metabolic, pulmonary gas exchange and cardiovascular responses to exercise. Chest wall volumes are continuously regulated during exercise in order to postpone (or even avoid) their migration to higher operating volumes in patients with COPD, a dynamic process that is strongly dependent on the behavior of the abdominal compartment.

  19. Dynamics of chest wall volume regulation during constant work rate exercise in patients with chronic obstructive pulmonary disease

    Directory of Open Access Journals (Sweden)

    L.S. Takara

    2012-12-01

    Full Text Available This study evaluated the dynamic behavior of total and compartmental chest wall volumes [(V CW = rib cage (V RC + abdomen (V AB] as measured breath-by-breath by optoelectronic plethysmography during constant-load exercise in patients with stable chronic obstructive pulmonary disease. Thirty males (GOLD stages II-III underwent a cardiopulmonary exercise test to the limit of tolerance (Tlim at 75% of peak work rate on an electronically braked cycle ergometer. Exercise-induced dynamic hyperinflation was considered to be present when end-expiratory (EE V CW increased in relation to resting values. There was a noticeable heterogeneity in the patterns of V CW regulation as EEV CW increased non-linearly in 17/30 "hyperinflators" and decreased in 13/30 "non-hyperinflators" (P < 0.05. EEV AB decreased slightly in 8 of the "hyperinflators", thereby reducing and slowing the rate of increase in end-inspiratory (EI V CW (P < 0.05. In contrast, decreases in EEV CW in the "non-hyperinflators" were due to the combination of stable EEV RC with marked reductions in EEV AB. These patients showed lower EIV CW and end-exercise dyspnea scores but longer Tlim than their counterparts (P < 0.05. Dyspnea increased and Tlim decreased non-linearly with a faster rate of increase in EIV CW regardless of the presence or absence of dynamic hyperinflation (P < 0.001. However, no significant between-group differences were observed in metabolic, pulmonary gas exchange and cardiovascular responses to exercise. Chest wall volumes are continuously regulated during exercise in order to postpone (or even avoid their migration to higher operating volumes in patients with COPD, a dynamic process that is strongly dependent on the behavior of the abdominal compartment.

  20. Ion-neutral gas reactions in a collision/reaction cell in inductively coupled plasma mass spectrometry: Correlation of ion signal decrease to kinetic rate constants

    Energy Technology Data Exchange (ETDEWEB)

    Gray, Patrick J. [Trace Element Research Laboratory, School of Earth Sciences, The Ohio State University, 125 S. Oval Mall, Columbus, OH 43210 (United States); Department of Chemistry, The Ohio State University, 120 18th Avenue, Columbus, OH 43210 (United States); Olesik, John W., E-mail: olesik.2@osu.edu [Trace Element Research Laboratory, School of Earth Sciences, The Ohio State University, 125 S. Oval Mall, Columbus, OH 43210 (United States)

    2015-03-01

    Reaction gas flow rate dependent Ar{sub 2}{sup +} and Ar{sup +} signals are correlated to fundamental kinetic rate coefficients. A simple calculation, assuming that gas exits the reaction cell due only to effusion, is described to estimate the gas pressure in the reaction cell. The value of the product of the kinetic rate constant and the ion residence time in the reaction cell can be determined from experimental measurement of the decrease in an ion signal as a function of reaction gas flow rate. New kinetic rate constants are determined for the reaction of CH{sub 3}F with Ar{sup +} and Ar{sub 2}{sup +}. - Highlights: • How to determine pressure and the product of the kinetic rate constant times the ion residence time in reaction cell • Relate measured ICP-DRC-MS signals versus gas flow rate to kinetic rate constants measured previously using SIFT-MS • Describe how to determine previously unmeasured kinetic rate constants using ICP-DRC-MS.

  1. A Time Varying Strong Coupling Constant as a Model of Inflationary Universe

    CERN Document Server

    Chamoun, N; Vucetich, H

    2000-01-01

    We consider a scenario where the strong coupling constant was changing in the early universe. We attribute this change to a variation in the colour charge within a Bekenstein-like model. Allowing for a large value for the vacuum gluon condensate $\\sim 10^{22}GeV^4$, we could generate inflation with the required properties to solve the fluctuation and other standard cosmology problems. A possible approach to end the inflation is suggested.

  2. Self-tuning Solution of Cosmological Constant in RS-II Model and Goldstone Boson

    CERN Document Server

    Kim, J E

    2001-01-01

    I give a review on the self-tuning solution of the cosmological constant in a 5D RS-II model using a three index antisymmetric tensor field $A_{MNP}$. The three index antisymmetric tensor field can be the fundamental one appearing in 11D supergravity. Also, the dual of its field strength $H_{MNPQ}$, being a massless scalar, may be interpreted as a Goldstone boson of some spontaneously broken global symmetry.

  3. CONSTANT ELASTICITY OF VARIANCE MODEL AND ANALYTICAL STRATEGIES FOR ANNUITY CONTRACTS

    Institute of Scientific and Technical Information of China (English)

    XIAO Jian-wu; YIN Shao-hua; QIN Cheng-lin

    2006-01-01

    The constant elasticity of variance(CEV) model was constructed to study a defined contribution pension plan where benefits were paid by annuity. It also presents the process that the Legendre transform and dual theory can be applied to find an optimal investment policy during a participant's whole life in the pension plan. Finally, two explicit solutions to exponential utility function in the two different periods (before and after retirement) are revealed. Hence, the optimal investment strategies in the two periods are obtained.

  4. Lemaître Class Dark Energy Model for Relaxing Cosmological Constant

    Directory of Open Access Journals (Sweden)

    Irina Dymnikova

    2017-05-01

    Full Text Available Cosmological constant corresponds to the maximally symmetric cosmological term with the equation of state p = − ρ . Introducing a cosmological term with the reduced symmetry, p r = − ρ in the spherically symmetric case, makes cosmological constant intrinsically variable component of a variable cosmological term which describes time-dependent and spatially inhomogeneous vacuum dark energy. Relaxation of the cosmological constant from the big initial value to the presently observed value can be then described in general setting by the spherically symmetric cosmology of the Lemaître class. We outline in detail the cosmological model with the global structure of the de Sitter spacetime distinguished by the holographic principle as the only stable product of quantum evaporation of the cosmological horizon entirely determined by its quantum dynamics. Density of the vacuum dark energy is presented by semiclassical description of vacuum polarization in the spherically symmetric gravitational field, and its initial value is chosen at the GUT scale. The final non-zero value of the cosmological constant is tightly fixed by the quantum dynamics of evaporation and appears in the reasonable agreement with its observational value.

  5. Predicted Chemical Activation Rate Constants for HO2 + CH2NH: The Dominant Role of a Hydrogen-Bonded Pre-reactive Complex.

    Science.gov (United States)

    Ali, Mohamad Akbar; Sonk, Jason A; Barker, John R

    2016-09-15

    The reaction of methanimine (CH2NH) with the hydroperoxy (HO2) radical has been investigated by using a combination of ab initio and density functional theory (CCSD(T)/CBSB7//B3LYP+Dispersion/CBSB7) and master equation calculations based on transition state theory (TST). Variational TST was used to compute both canonical (CVTST) and microcanonical (μVTST) rate constants for barrierless reactions. The title reaction starts with the reversible formation of a cyclic prereactive complex (PRC) that is bound by ∼11 kcal/mol and contains hydrogen bonds to both nitrogen and oxygen. The reaction path for the entrance channel was investigated by a series of constrained optimizations, which showed that the reaction is barrierless (i.e., no intrinsic energy barrier along the path). However, the variations in the potential energy, vibrational frequencies, and rotational constants reveal that the two hydrogen bonds are formed sequentially, producing two reaction flux bottlenecks (i.e., two transition states) along the reaction path, which were modeled using W. H. Miller's unified TST approach. The rate constant computed for the formation of the PRC is pressure-dependent and increases at lower temperatures. Under atmospheric conditions, the PRC dissociates rapidly and its lifetime is too short for it to undergo significant bimolecular reaction with other species. A small fraction isomerizes via a cyclic transition state and subsequent reactions lead to products normally expected from hydrogen abstraction reactions. The kinetics of the HO2 + CH2NH reaction system differs substantially from the analogous isoelectronic reaction systems involving C2H4 and CH2O, which have been the subjects of previous experimental and theoretical studies.

  6. Realizations of interest rate models

    NARCIS (Netherlands)

    Nieuwenhuis, J.W.

    2000-01-01

    In this paper we comment on a recent paper by Bj¨ork and Gombani. In contrast to this paper our starting point is not the Musiela equation but the forward rate dynamics. In our approach we do not need to talk about infinitesimal generators.

  7. Realizations of interest rate models

    NARCIS (Netherlands)

    Nieuwenhuis, J.W.

    2000-01-01

    In this paper we comment on a recent paper by Bj¨ork and Gombani. In contrast to this paper our starting point is not the Musiela equation but the forward rate dynamics. In our approach we do not need to talk about infinitesimal generators.

  8. Multiplicative earthquake likelihood models incorporating strain rates

    Science.gov (United States)

    Rhoades, D. A.; Christophersen, A.; Gerstenberger, M. C.

    2017-01-01

    SUMMARYWe examine the potential for strain-rate variables to improve long-term earthquake likelihood models. We derive a set of multiplicative hybrid earthquake likelihood models in which cell rates in a spatially uniform baseline model are scaled using combinations of covariates derived from earthquake catalogue data, fault data, and strain-rates for the New Zealand region. Three components of the strain rate estimated from GPS data over the period 1991-2011 are considered: the shear, rotational and dilatational strain rates. The hybrid model parameters are optimised for earthquakes of M 5 and greater over the period 1987-2006 and tested on earthquakes from the period 2012-2015, which is independent of the strain rate estimates. The shear strain rate is overall the most informative individual covariate, as indicated by Molchan error diagrams as well as multiplicative modelling. Most models including strain rates are significantly more informative than the best models excluding strain rates in both the fitting and testing period. A hybrid that combines the shear and dilatational strain rates with a smoothed seismicity covariate is the most informative model in the fitting period, and a simpler model without the dilatational strain rate is the most informative in the testing period. These results have implications for probabilistic seismic hazard analysis and can be used to improve the background model component of medium-term and short-term earthquake forecasting models.

  9. Dose rate constants for the quantity H{sub p}(3) for frequently used radionuclides in nuclear medicine

    Energy Technology Data Exchange (ETDEWEB)

    Szermerski, Bastian; Bruchmann, Iris; Geworski, Lilli [Medical School Hannover (Germany). Dept. for Radiation Protection and Medical Physics; Behrens, Rolf [Physikalisch-Technische Bundesanstalt (PTB), Braunschweig (Germany)

    2016-07-01

    According to recent studies, the human eye lens is more sensitive to ionising radiation than previously assumed. Therefore, the dose limit for personnel occupationally exposed to ionising radiation will be lowered from currently 150 mSv to 20 mSv per year. Currently, no data base for a reliable estimation of the dose to the lens of the eye is available for nuclear medicine. Furthermore, the dose is usually not monitored. The aim of this work was to determine dose rate constants for the quantity H{sub p}(3), which is supposed to estimate the dose to the lens of the eye. For this, H{sub p}(3)-dosemeters were fixed to an Alderson Phantom at different positions. The dosemeters were exposed to radiation from nuclides typically used in nuclear medicine in their geometries analog to their application in nuclear medicine, e.g. syringe or vial. The results show that the handling of high-energy beta (i.e. electron or positron) emitters may lead to a relevant dose to the lens of the eye. For low-energy beta emitters and gamma emitters, an exceeding of the lowered dose limit seems to be unlikely.

  10. Pressure dependence of the absolute rate constant for the reaction Cl + C2H2 from 210-361 K

    Science.gov (United States)

    Brunning, J.; Stief, L. J.

    1985-01-01

    In recent years, considerable attention has been given to the role of chlorine compounds in the catalytic destruction of stratospheric ozone. However, while some reactions have been studied extensively, the kinetic data for the reaction of Cl with C2H2 is sparse with only three known determinations of the rate constant k3. The reactions involved are Cl + C2H2 yields reversibly ClC2H2(asterisk) (3a) and ClC2H2(asterisk) + M yields ClC2H2 + M (3b). In the present study, flash photolysis coupled with chlorine atomic resonance fluorescence have been employed to determine the pressure and temperature dependence of k3 with the third body M = Ar. Room temperature values are also reported for M = N2. The pressure dependence observed in the experiments confirms the expectation that the reaction involves addition of Cl to the unsaturated C2H2 molecule followed by collisional stabilization of the resulting adduct radical.

  11. Using a Family of Dividing Surfaces Normal to the Minimum EnergyPath for Quantum Instanton Rate Constants

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yimin; Miller, Wlliam H.

    2006-02-22

    One of the outstanding issues in the quantum instanton (QI) theory (or any transition state-type theory) for thermal rate constants of chemical reactions is the choice of an appropriate ''dividing surface'' (DS) that separates reactants and products. (In the general version of the QI theory, there are actually two dividing surfaces involved.) This paper shows one simple and general way for choosing DS's for use in QI Theory, namely using the family of (hyper) planes normal to the minimum energy path (MEP) on the potential energy surface at various distances s along it. Here the reaction coordinate is not one of the dynamical coordinates of the system (which will in general be the Cartesian coordinates of the atoms), but rather simply a parameter which specifies the DS. It is also shown how this idea can be implemented for an N-atom system in 3d space in a way that preserves overall translational and rotational invariance. Numerical application to a simple system (the colliner H + H{sub 2} reaction) is presented to illustrate the procedure.

  12. Absolute rate constants for hydrogen atom transfer from tertiary amides to the cumyloxyl radical: evaluating the role of stereoelectronic effects.

    Science.gov (United States)

    Salamone, Michela; Milan, Michela; DiLabio, Gino A; Bietti, Massimo

    2014-08-01

    A time-resolved kinetic study of the hydrogen atom transfer (HAT) reactions from a series of alkanamides to the cumyloxyl radical (CumO(•)) was carried out. With N,N-dialkylformamides HAT preferentially occurs from the formyl C-H bond, while in N-formylpyrrolidine HAT mostly occurs from the ring α-C-H bonds. With the acetamides and the alkanamides almost exclusive HAT from the C-H bonds that are α to nitrogen was observed. The results obtained show that alignment between the C-H bond being broken and the amide π-system can lead to significant increases in the HAT rate constant (kH). This finding points toward the important role of stereoelectronic effects on the HAT reactivity and selectivity. The highest kH values were measured for the reactions of CumO(•) with N-acylpyrrolidines. These substrates have ring α-C-H bonds that are held in a conformation that is optimally aligned with the amide π-system, thus allowing for the relatively facile HAT reaction. The lowest kH value was measured for the reaction of N,N-diisobutylacetamide, wherein the steric bulk associated with the N-isobutyl groups increases the energy barrier required to reach the most suitable conformation for HAT. The experimental results are well supported by the computed BDEs for the C-H bonds of the most representative substrates.

  13. Low-pressure effective fluorescence lifetimes and photo-physical rate constants of one- and two-ring aromatics

    Science.gov (United States)

    Benzler, Thorsten; Faust, Stephan; Dreier, Thomas; Schulz, Christof

    2015-12-01

    One- and two-ring aromatics such as toluene and naphthalene are frequently used molecular tracer species in laser-induced fluorescence (LIF) imaging diagnostics. Quantifying LIF signal intensities requires knowledge of the photo-physical processes that determine the fluorescence quantum yield. Collision-induced and intramolecular energy transfer processes in the excited electronic state closely interact under practical conditions. They can be separated through experiments at variable low pressures. Effective fluorescence lifetimes of gaseous toluene, 1,2,4-trimethylbenzene, anisole, naphthalene, and 1-methylnaphthalene diluted in CO2 were measured after picosecond laser excitation at 266 nm and time-resolved detection of fluorescence intensities. Measurements in an optically accessible externally heated cell between 296 and 475 K and 0.010-1 bar showed that effective fluorescence lifetimes generally decrease with temperature, while the influence of the bath-gas pressure depends on the respective target species and temperature. The results provide non-radiative and fluorescence rate constants and experimentally validate the effect of photo-induced cooling.

  14. Modeling selenium (IV and VI) adsorption envelopes in selected tropical soils using the constant capacitance model

    Science.gov (United States)

    The adsorption of selenium (Se) on soil is important due to the relevance of Se to environmental and health issues. The adsorption of Se(IV) and Se(VI) was evaluated on soil samples from São Paulo state, Brazil, as a function of varying pH, and the experimental data were fitted to the constant capac...

  15. Structure constants of the OSP(1 vertical stroke 2) WZNW model

    Energy Technology Data Exchange (ETDEWEB)

    Hikida, Y.; Schomerus, V.

    2007-11-15

    We propose exact formulas for the 2- and 3-point functions of the WZNW model on the non-compact supergroup OSP(1 vertical stroke 2). Using the path integral approach that was recently developed in arXiv:0706.1030 we show how local correlation functions in the OSP(p vertical stroke 2) WZNW models can be obtained from those of N=p supersymmetric Liouville field theory for p=1,2. We then employ known results on correlators in N=1 Liouville theory to determine the structure constants of the OSP(1 vertical stroke 2) theory. (orig.)

  16. Nuclear magnetic shielding constants of liquid water: Insights from hybrid quantum mechanics/molecular mechanics models

    Science.gov (United States)

    Kongsted, Jacob; Nielsen, Christian B.; Mikkelsen, Kurt V.; Christiansen, Ove; Ruud, Kenneth

    2007-01-01

    We present a gauge-origin independent method for the calculation of nuclear magnetic shielding tensors of molecules in a structured and polarizable environment. The method is based on a combination of density functional theory (DFT) or Hartree-Fock wave functions with molecular mechanics. The method is unique in the sense that it includes three important properties that need to be fulfilled in accurate calculations of nuclear magnetic shielding constants: (i) the model includes electron correlation effects, (ii) the model uses gauge-including atomic orbitals to give gauge-origin independent results, and (iii) the effect of the environment is treated self-consistently using a discrete reaction-field methodology. The authors present sample calculations of the isotropic nuclear magnetic shielding constants of liquid water based on a large number of solute-solvent configurations derived from molecular dynamics simulations employing potentials which treat solvent polarization either explicitly or implicitly. For both the O17 and H1 isotropic shielding constants the best predicted results compare fairly well with the experimental data, i.e., they reproduce the experimental solvent shifts to within 4ppm for the O17 shielding and 1ppm for the H1 shielding.

  17. New contractivity condition in a population model with piecewise constant arguments

    Science.gov (United States)

    Muroya, Yoshiaki

    2008-10-01

    In this paper, we improve contractivity conditions of solutions for the positive equilibrium of the following differential equation with piecewise constant arguments: where r(t) is a nonnegative continuous function on [0,+[infinity]), r(t)[not identical with]0, , bi[greater-or-equal, slanted]0, i=0,1,2,...,m, and . In particular, for the case a=0 and m[greater-or-equal, slanted]1, we really improve the known three type conditions of the contractivity for solutions of this model (see for example, [Y. Muroya, A sufficient condition on global stability in a logistic equation with piecewise constant arguments, Hokkaido Math. J. 32 (2003) 75-83]). For the other case a[not equal to]0 and m[greater-or-equal, slanted]1, under the condition , the obtained result partially improves the known results on the contractivity of solutions for the positive equilibrium of this model given by the author [Y. Muroya, Persistence, contractivity and global stability in logistic equations with piecewise constant delays, J. Math. Anal. Appl. 270 (2002) 602-635] and others.

  18. Nuclear magnetic shielding constants of liquid water: insights from hybrid quantum mechanics/molecular mechanics models.

    Science.gov (United States)

    Kongsted, Jacob; Nielsen, Christian B; Mikkelsen, Kurt V; Christiansen, Ove; Ruud, Kenneth

    2007-01-21

    We present a gauge-origin independent method for the calculation of nuclear magnetic shielding tensors of molecules in a structured and polarizable environment. The method is based on a combination of density functional theory (DFT) or Hartree-Fock wave functions with molecular mechanics. The method is unique in the sense that it includes three important properties that need to be fulfilled in accurate calculations of nuclear magnetic shielding constants: (i) the model includes electron correlation effects, (ii) the model uses gauge-including atomic orbitals to give gauge-origin independent results, and (iii) the effect of the environment is treated self-consistently using a discrete reaction-field methodology. The authors present sample calculations of the isotropic nuclear magnetic shielding constants of liquid water based on a large number of solute-solvent configurations derived from molecular dynamics simulations employing potentials which treat solvent polarization either explicitly or implicitly. For both the (17)O and (1)H isotropic shielding constants the best predicted results compare fairly well with the experimental data, i.e., they reproduce the experimental solvent shifts to within 4 ppm for the (17)O shielding and 1 ppm for the (1)H shielding.

  19. Simplified Burn-Rate Model for CMDB Propellants

    Directory of Open Access Journals (Sweden)

    A. R. Kulkarni

    1990-07-01

    Full Text Available A single model has been proposed to predict the burning rates of bimodal AP,RDX and aluminum containing CMDB propellants. This is done in terms of the respective physical constants on the basis of a recently developed model of combustion of CMDB propellants. The study has been carried out to examine the effects of changes in propellants composition, AP particle size and pressures on burning rate. Computer programs were developed for this purpose and the results obtained for typical sets of input data have been presented and compared with the actual results.

  20. Modelling and simulation of multi-phase effects on X-ray elasticity constants

    Energy Technology Data Exchange (ETDEWEB)

    Freour, S.; Gloaguen, D.; Guillen, R. [Laboratoire d' Applications des Materiaux a la Mecanique (L.A.M.M.), L.A.M.M.-C.R.T.T., Boulevard de L' Universite, BP 406, 44602 Saint Nazaire Cedex (France); Francois, M. [Laboratoire des Systemes Mecaniques et d' Ingenierie Simultanee (L.A.S.M.I.S.), Universite de Technologie de Troyes, 12 Rue Marie Curie, BP 2060, 10010 Troyes (France)

    2003-10-01

    This paper deals with the calculation of X-ray Elasticity Constants (XEC) of phases embedded in multi-phase polycrystals. A three scales (macroscopic, pseudo-macroscopic, mesoscopic) model based on the classical self-consistent formalism is developed in order to analyse multi-phase effects on XEC values. Simulations are performed for cubic or hexagonal crystallographic structure phases embedded in several two-phases materials. In fact, it is demonstrated that XEC vary with the macroscopic stiffness of the whole polycrystal. In consequence, the constants of one particular phase depend on the elastic behaviour and the volume fraction of all the phases constituting the material. Now, XEC play a leading role in pseudo-macroscopic stresses determination by X-Ray Diffraction (XRD) methods. In this work, a quantitative analysis of the multi-phase effects on stresses determination by XRD methods was performed. Numerical results will be compared and discussed. (Abstract Copyright [2003], Wiley Periodicals, Inc.)

  1. A review of shear strength models for rock joints subjected to constant normal stiffness

    Directory of Open Access Journals (Sweden)

    Sivanathan Thirukumaran

    2016-06-01

    Full Text Available The typical shear behaviour of rough joints has been studied under constant normal load/stress (CNL boundary conditions, but recent studies have shown that this boundary condition may not replicate true practical situations. Constant normal stiffness (CNS is more appropriate to describe the stress–strain response of field joints since the CNS boundary condition is more realistic than CNL. The practical implications of CNS are movements of unstable blocks in the roof or walls of an underground excavation, reinforced rock wedges sliding in a rock slope or foundation, and the vertical movement of rock-socketed concrete piles. In this paper, the highlights and limitations of the existing models used to predict the shear strength/behaviour of joints under CNS conditions are discussed in depth.

  2. Absolute Determination of Optical Constants by a Direct Physical Modeling of Reflection Electron Energy Loss Spectra

    CERN Document Server

    Xu, H; Toth, J; Tokesi, K; Ding, Z J

    2016-01-01

    We present an absolute extraction method of optical constants of metal from the measured reflection electron energy loss (REELS) spectra by using the recently developed reverse Monte Carlo (RMC) technique. The method is based on a direct physical modeling of electron elastic and electron inelastic scattering near the surface region where the surface excitation becomes important to fully describe the spectrum loss feature intensity in relative to the elastic peak intensity. An optimization procedure of oscillator parameters appeared in the energy loss function (ELF) for describing electron inelastic scattering due to the bulk- and surface-excitations was performed with the simulated annealing method by a successive comparison between the measured and Monte Carlo simulated REELS spectra. The ELF and corresponding optical constants of Fe were obtained from the REELS spectra measured at incident energies of 1000, 2000 and 3000 eV. The validity of the present optical data has been verified with the f- and ps-sum r...

  3. Surface-enhanced Raman scattering: effective optical constants for electric field modelling of nanostructured Ag films

    Science.gov (United States)

    Perera, M. Nilusha M. N.; Schmidt, Daniel; Gibbs, W. E. Keith; Juodkazis, Saulius; Stoddart, Paul R.

    2016-09-01

    Surface-enhanced Raman scattering (SERS) is drawing increasing interest in fields such as chemical and biomolecular sensing, nanoscale plasmonic engineering and surface science. In addition to the electromagnetic and chemical enhancements in SERS, several studies have reported a "back-side" enhancement when nanostructures are excited through a transparent base rather than directly through air. This additional enhancement has been attributed to a local increase in the electric field for propagation from high to low refractive index media. In this study, Mueller matrix ellipsometry was used to derive the effective optical constants of Ag nanostructures fabricated by thermal evaporation at oblique angles. The results confirm that the effective optical constants of the nanostructured Ag film depart substantially from the bulk properties. Detailed analysis suggests that the optical constants of the nano-island Ag structures exhibit uniaxial optical properties with the optical axis inclined from the substrate normal towards the deposition direction of the vapour flux. The substrates were functionalized with thiophenol and used to measure the wavelength dependence of the additional SERS signal. Further, a model based on the Fresnel equations was developed, using the Ag film optical constants and thickness as determined by ellipsometry. Both experimental data and the model show a significant additional enhancement in the back-side SERS, blue shifted from the plasmon resonance of the nanostructures. This information will be useful for a range of applications where it is necessary to understand the effective optical behaviour of thin films and in designing miniaturized optical fibre sensors for remote sensing applications.

  4. Biological evolution model with conditional mutation rates

    Science.gov (United States)

    Saakian, David B.; Ghazaryan, Makar; Bratus, Alexander; Hu, Chin-Kun

    2017-05-01

    We consider an evolution model, in which the mutation rates depend on the structure of population: the mutation rates from lower populated sequences to higher populated sequences are reduced. We have applied the Hamilton-Jacobi equation method to solve the model and calculate the mean fitness. We have found that the modulated mutation rates, directed to increase the mean fitness.

  5. An "Emergent Model" for Rate of Change

    Science.gov (United States)

    Herbert, Sandra; Pierce, Robyn

    2008-01-01

    Does speed provide a "model for" rate of change in other contexts? Does JavaMathWorlds (JMW), animated simulation software, assist in the development of the "model for" rate of change? This project investigates the transference of understandings of rate gained in a motion context to a non-motion context. Students were 27 14-15 year old students at…

  6. Selection of noise power ratio spectrum models for electronic measurement of the Boltzmann constant

    CERN Document Server

    Coakley, Kevin J

    2016-01-01

    In the electronic measurement of the Boltzmann constant based on Johnson noise thermometry, the ratio of the power spectral densities of thermal noise across a resistor and pseudo-random noise synthetically generated by a quantum-accurate voltage-noise source varies with frequency due to mismatch between transmission lines. We model this ratio spectrum as an even polynomial function of frequency. For any given frequency range, defined by the maximum frequency $f_{max}$, we select the optimal polynomial ratio spectrum model with a cross-validation method and estimate the conditional uncertainty of the constant term in the ratio spectrum model in a way that accounts for both random and systematic effects associated with imperfect knowledge of the model with a resampling method. We select $f_{max}$ by minimizing this conditional uncertainty. Since many values of $f_{max}$ yield conditional uncertainties close to the observed minimum value on a frequency grid, we quantify an additional component of uncertainty as...

  7. Thermal time constant: optimising the skin temperature predictive modelling in lower limb prostheses using Gaussian processes

    Science.gov (United States)

    Buis, Arjan

    2016-01-01

    Elevated skin temperature at the body/device interface of lower-limb prostheses is one of the major factors that affect tissue health. The heat dissipation in prosthetic sockets is greatly influenced by the thermal conductive properties of the hard socket and liner material employed. However, monitoring of the interface temperature at skin level in lower-limb prosthesis is notoriously complicated. This is due to the flexible nature of the interface liners used which requires consistent positioning of sensors during donning and doffing. Predicting the residual limb temperature by monitoring the temperature between socket and liner rather than skin and liner could be an important step in alleviating complaints on increased temperature and perspiration in prosthetic sockets. To predict the residual limb temperature, a machine learning algorithm – Gaussian processes is employed, which utilizes the thermal time constant values of commonly used socket and liner materials. This Letter highlights the relevance of thermal time constant of prosthetic materials in Gaussian processes technique which would be useful in addressing the challenge of non-invasively monitoring the residual limb skin temperature. With the introduction of thermal time constant, the model can be optimised and generalised for a given prosthetic setup, thereby making the predictions more reliable. PMID:27695626

  8. Time since death and decay rate constants of Norway spruce and European larch deadwood in subalpine forests determined using dendrochronology and radiocarbon dating

    Directory of Open Access Journals (Sweden)

    M. Petrillo

    2015-09-01

    Full Text Available Due to the large size and highly heterogeneous spatial distribution of deadwood, the time scales involved in the coarse woody debris (CWD decay of Picea abies (L. Karst. and Larix decidua Mill. in Alpine forests have been poorly investigated and are largely unknown. We investigated the CWD decay dynamics in an Alpine valley in Italy using the five-decay class system commonly employed for forest surveys, based on a macromorphological and visual assessment. For the decay classes 1 to 3, most of the dendrochronological samples were cross-dated to assess the time that had elapsed since tree death, but for decay classes 4 and 5 (poorly preserved tree rings and some others not having enough tree rings, radiocarbon dating was used. In addition, density, cellulose and lignin data were measured for the dated CWD. The decay rate constants for spruce and larch were estimated on the basis of the density loss using a single negative exponential model. In the decay classes 1 to 3, the ages of the CWD were similar varying between 1 and 54 years for spruce and 3 and 40 years for larch with no significant differences between the classes; classes 1–3 are therefore not indicative for deadwood age. We found, however, distinct tree species-specific differences in decay classes 4 and 5, with larch CWD reaching an average age of 210 years in class 5 and spruce only 77 years. The mean CWD rate constants were 0.012 to 0.018 yr−1 for spruce and 0.005 to 0.012 yr−1 for larch. Cellulose and lignin time trends half-lives (using a multiple-exponential model could be derived on the basis of the ages of the CWD. The half-lives for cellulose were 21 yr for spruce and 50 yr for larch. The half-life of lignin is considerably higher and may be more than 100 years in larch CWD.

  9. Kinematic equivalence between models driven by DBI field with constant $\\gamma$ and exotic holographic quintessence cosmological models

    CERN Document Server

    Forte, Mónica

    2016-01-01

    We show the kinematic equivalence between cosmological models driven by Dirac-Born-Infeld fields $\\phi$ with constant proper velocity of the brane and exponential potential $V=V_0e^{-B\\phi}$ and interactive cosmological systems with Modified Holographic Ricci type fluids as dark energy in flat Friedmann-Robertson-Walker cosmologies.

  10. Static Potential in the SU(2)-Higgs Model and Coupling Constant Definitions in Lattice and Continuum Models

    CERN Document Server

    Csikor, Ferenc; Hegedüs, P; Piróth, A

    1999-01-01

    We present a one-loop calculation of the static potential in the SU(2)-Higgs model. The connection to the coupling constant definition used in lattice simulations is clarified. The consequences in comparing lattice simulations and perturbative results for finite temperature applications are explored.

  11. Decay Constants and Distribution Amplitudes of B Meson in the Relativistic Potential Model

    CERN Document Server

    Sun, Hao-Kai

    2016-01-01

    In this work we study the decay constants of $B$ and $B_s$ mesons based on the wave function obtained in the relativistic potential model. Our results are in good agreement with experiment data which enables us to apply this method to the investigation of $B$-meson distribution amplitudes. A very compact form of the distribution amplitudes is obtained. We also investigate the one-loop QCD corrections to the purely leptonic decays of $B$ mesons. We find that, after subtracting the infrared divergence in the one-loop corrections using the factorization method, the QCD one-loop corrections to the leptonic decay amplitude will be zero.

  12. Time Evolution of the Fine Structure Constant in a Two-Field Quintessence Model

    CERN Document Server

    Bento, M C; Santos, N M C

    2004-01-01

    We examine the variation of the fine structure constant in the context of a two-field quintessence model. We find that, for solutions that lead to a transient late period of accelerated expansion, it is possible to fit the data arising from quasar spectra and comply with the bounds on the variation of $\\alpha$ from the Oklo reactor, meteorite analysis, atomic clock measurements, Cosmic Microwave Background Radiation and Big Bang Nucleosynthesis. That is more difficult if we consider solutions corresponding to a late period of permanent accelerated expansion.

  13. Time evolution of the fine structure constant in a two-field quintessence model

    Science.gov (United States)

    Bento, M. C.; Bertolami, O.; Santos, N. M.

    2004-11-01

    We examine the variation of the fine structure constant in the context of a two-field quintessence model. We find that, for solutions that lead to a transient late period of accelerated expansion, it is possible to fit the data arising from quasar spectra and comply with the bounds on the variation of α from the Oklo reactor, meteorite analysis, atomic clock measurements, cosmic microwave background radiation, and big bang nucleosynthesis. That is more difficult if we consider solutions corresponding to a late period of permanent accelerated expansion.

  14. Time variation of the fine structure constant α from realistic models of Oklo reactors.

    Science.gov (United States)

    Gould, C. R.; Sharapov, E. I.; Lamoreaux, S. K.

    2006-11-01

    The topic of whether the fundamental constants of nature vary with time has been a subject of great interest since Dirac originally proposed the possibility that GN˜1/tuniverse. Recent observations of absorption spectra lines from distant quasars appeared to indicate a possible increase in the fine structure constant α over ten billion years. Contrarily, analyses of the time evolution of α from Oklo natural nuclear reactor data have yielded inconsistent results, some indicating a decrease over two billion years while others indicated no change. We have used known Oklo reactor epithermal spectral indices as criteria for selecting realistic reactor models. Reactors RZ2 and RZ10 were modeled with MCNP and the resulting neutron spectra were used to calculate the change in the ^149Sm capture cross section as a function of a possible shift in the energy of the 97.3-meV resonance. Our study resolves the contradictory situation with previous Oklo α-results. Our suggested 2 σ bound on a possible time variation of α over two billion years is stringent: -0.11 <=δαα <=0.24, in units of 10-7, but model dependent in that it assumes only α has varied over time.

  15. Non-Extensive Entropy Econometrics: New Statistical Features of Constant Elasticity of Substitution-Related Models

    Directory of Open Access Journals (Sweden)

    Second Bwanakare

    2014-05-01

    Full Text Available Power-law (PL formalism is known to provide an appropriate framework for canonical modeling of nonlinear systems. We estimated three stochastically distinct models of constant elasticity of substitution (CES class functions as non-linear inverse problem and showed that these PL related functions should have a closed form. The first model is related to an aggregator production function, the second to an aggregator utility function (the Armington and the third to an aggregator technical transformation function. A q-generalization of K-L information divergence criterion function with a priori consistency constraints is proposed. Related inferential statistical indices are computed. The approach leads to robust estimation and to new findings about the true stochastic nature of this class of nonlinear—up until now—analytically intractable functions. Outputs from traditional econometric techniques (Shannon entropy, NLLS, GMM, ML are also presented.

  16. Optimal Investment and Consumption Decisions under the Constant Elasticity of Variance Model

    Directory of Open Access Journals (Sweden)

    Hao Chang

    2013-01-01

    Full Text Available We consider an investment and consumption problem under the constant elasticity of variance (CEV model, which is an extension of the original Merton’s problem. In the proposed model, stock price dynamics is assumed to follow a CEV model and our goal is to maximize the expected discounted utility of consumption and terminal wealth. Firstly, we apply dynamic programming principle to obtain the Hamilton-Jacobi-Bellman (HJB equation for the value function. Secondly, we choose power utility and logarithm utility for our analysis and apply variable change technique to obtain the closed-form solutions to the optimal investment and consumption strategies. Finally, we provide a numerical example to illustrate the effect of market parameters on the optimal investment and consumption strategies.

  17. Estimation of autotrophic maximum specific growth rate constant--experience from the long-term operation of a laboratory-scale sequencing batch reactor system.

    Science.gov (United States)

    Su, Yu-min; Makinia, Jacek; Pagilla, Krishna R

    2008-04-01

    The autotrophic maximum specific growth rate constant, muA,max, is the critical parameter for design and performance of nitrifying activated sludge systems. In literature reviews (i.e., Henze et al., 1987; Metcalf and Eddy, 1991), a wide range of muA,max values have been reported (0.25 to 3.0 days(-1)); however, recent data from several wastewater treatment plants across North America revealed that the estimated muA,max values remained in the narrow range 0.85 to 1.05 days(-1). In this study, long-term operation of a laboratory-scale sequencing batch reactor system was investigated for estimating this coefficient according to the low food-to-microorganism ratio bioassay and simulation methods, as recommended in the Water Environment Research Foundation (Alexandria, Virginia) report (Melcer et al., 2003). The estimated muA,max values using steady-state model calculations for four operating periods ranged from 0.83 to 0.99 day(-1). The International Water Association (London, United Kingdom) Activated Sludge Model No. 1 (ASM1) dynamic model simulations revealed that a single value of muA,max (1.2 days(-1)) could be used, despite variations in the measured specific nitrification rates. However, the average muA,max was gradually decreasing during the activated sludge chlorination tests, until it reached the value of 0.48 day(-1) at the dose of 5 mg chlorine/(g mixed liquor suspended solids x d). Significant discrepancies between the predicted XA/YA ratios were observed. In some cases, the ASM1 predictions were approximately two times higher than the steady-state model predictions. This implies that estimating this ratio from a complex activated sludge model and using it in simple steady-state model calculations should be accepted with great caution and requires further investigation.

  18. Toward Improving Atmospheric Models and Ozone Projections: Laboratory UV Absorption Cross Sections and Equilibrium Constant of ClOOCl

    Science.gov (United States)

    Wilmouth, D. M.; Klobas, J. E.; Anderson, J. G.

    2015-12-01

    Thirty years have now passed since the discovery of the Antarctic ozone hole, and despite comprehensive international agreements being in place to phase out CFCs and halons, polar ozone losses generally remain severe. The relevant halogen compounds have very long atmospheric lifetimes, which ensures that seasonal polar ozone depletion will likely continue for decades to come. Changes in the climate system can further impact stratospheric ozone abundance through changes in the temperature and water vapor structure of the atmosphere and through the potential initiation of solar radiation management efforts. In many ways, the rate at which climate is changing must now be considered fast relative to the slow removal of halogens from the atmosphere. Photochemical models of Earth's atmosphere play a critical role in understanding and projecting ozone levels, but in order for these models to be accurate, they must be built on a foundation of accurate laboratory data. ClOOCl is the centerpiece of the catalytic cycle that accounts for more than 50% of the chlorine-catalyzed ozone loss in the Arctic and Antarctic stratosphere every spring, and so uncertainties in the ultraviolet cross sections of ClOOCl are particularly important. Additionally, the equilibrium constant of the dimerization reaction of ClO merits further study, as there are important discrepancies between in situ measurements and lab-based models, and the JPL-11 recommended equilibrium constant includes high error bars at atmospherically relevant temperatures (~75% at 200 K). Here we analyze available data for the ClOOCl ultraviolet cross sections and equilibrium constant and present new laboratory spectroscopic results.

  19. Model-independent determination of the carrier multiplication time constant in CdSe nanocrystals.

    Science.gov (United States)

    Califano, Marco

    2009-11-21

    The experimental determination of the carrier multiplication (CM) time constant is complicated by the fact that this process occurs within the initial few hundreds of femtoseconds after excitation and, in transient-absorption experiments, cannot be separated from the buildup time of the 1p-state population. This work provides an accurate theoretical determination of the electron relaxation lifetime during the last stage of the p-state buildup, in CdSe nanocrystals, in the presence of a single photogenerated hole (no CM) and of a hole plus an additional electron-hole pair (following CM). From the invariance of the 1p buildup time observed experimentally for excitations above and below the CM threshold producing hot carriers with the same average per-exciton excess energy, and the calculated corresponding variations in the electron decay time in the two cases, an estimate is obtained for the carrier multiplication time constant. Unlike previous estimates reported in the literature so far, this result is model-independent, i.e., is obtained without making any assumption on the nature of the mechanism governing carrier multiplication. It is then compared with the time constant calculated, as a function of the excitation energy, assuming an impact-ionization-like process for carrier multiplication (DCM). The two results are in good agreement and show that carrier multiplication can occur on timescales of the order of tens of femtoseconds at energies close to the observed onset. These findings, which are compatible with the fastest lifetime estimated experimentally, confirm the suitability of the impact-ionization model to explain carrier multiplication in CdSe nanocrystals.

  20. The modelling of carbon-based supercapacitors: Distributions of time constants and Pascal Equivalent Circuits

    Science.gov (United States)

    Fletcher, Stephen; Kirkpatrick, Iain; Dring, Roderick; Puttock, Robert; Thring, Rob; Howroyd, Simon

    2017-03-01

    Supercapacitors are an emerging technology with applications in pulse power, motive power, and energy storage. However, their carbon electrodes show a variety of non-ideal behaviours that have so far eluded explanation. These include Voltage Decay after charging, Voltage Rebound after discharging, and Dispersed Kinetics at long times. In the present work, we establish that a vertical ladder network of RC components can reproduce all these puzzling phenomena. Both software and hardware realizations of the network are described. In general, porous carbon electrodes contain random distributions of resistance R and capacitance C, with a wider spread of log R values than log C values. To understand what this implies, a simplified model is developed in which log R is treated as a Gaussian random variable while log C is treated as a constant. From this model, a new family of equivalent circuits is developed in which the continuous distribution of log R values is replaced by a discrete set of log R values drawn from a geometric series. We call these Pascal Equivalent Circuits. Their behaviour is shown to resemble closely that of real supercapacitors. The results confirm that distributions of RC time constants dominate the behaviour of real supercapacitors.

  1. Compensation technique for Q-limit enforcements in a constant complex Jacobian power flow model

    Energy Technology Data Exchange (ETDEWEB)

    Raju, V.B.; Bijwe, P.R.; Nanda, J. (Dept. of Electrical Engineering, Indian Inst. of Technology, Delhi, New Delhi 110 016 (IN))

    1990-01-01

    This paper presents a simple and efficient compensation technique to deal with but-type switchings associated with Q-limit enforcement at voltage controlled (PV) buses in a constant Jacobian power flow model. The Jacobian is expressed in the complex variable form resulting in reduced storage requirements as compared to real form of representation of the Jacobian. The structure of the Jacobian is preserved irrespective of bus-type switchings while Q-limit enforcements are performed at the PV buses. This feature permits implementation of optimal ordering of buses in an efficient way while factorizing the Jacobian matrix. The Jacobian is held constant throughout the load flow solution process. Incremental secondary injections (ISIs) are provided at the respective PV buses to maintain the specified voltages. The required injections are computed from the proposed compensation model. Results indicate that the proposed technique is quite efficient as the number of iterations for solution to converge, irrespective of bus-type switchings remains same as that in unadjusted solution case.

  2. Effective Henry's Law constant measurements for glyoxal in model aerosols containing sulfate

    Science.gov (United States)

    Kampf, C.; Waxman, E.; Slowik, J.; Dommen, J.; Prevot, A.; Baltensperger, U.; Noziere, B.; Hoffmann, T.; Volkamer, R.

    2012-04-01

    Traditional models represent secondary organic aerosol (SOA) formation based on the gas-phase oxidation of a limited set of precursor molecules. However, these models tend to under-estimate the amounts and degree of oxygenation of actual SOA, indicating missing processes. One such source that has become increasingly important in recent years is glyoxal (CHOCHO, the smallest alpha-dicarbonyl). Unlike traditional SOA precursors, glyoxal forms SOA by partitioning to the aqueous phase according to Henry's Law. This work presents an analysis of Henry's Law constants for glyoxal uptake to laboratory-generated aerosols in a dynamically coupled gas-aerosol system. We combine CU LED-CE-DOAS measurements of gas-phase glyoxal with online HR-Tof-AMS and time-resolved HPLC ESI MS/MS particle-phase measurements to characterize the time resolved evolution of glyoxal partitioning, and relate molecular-specific measurements to AMS mass spectra. The experiments were performed in the simulation chamber facility at PSI, Switzerland, and investigate ammonium sulfate (AS), and mixed AS / fulvic acid seed aerosols under relative humidity conditions ranging from 50 to 85% RH. The Henry's Law and effective Henry's Law constants are compared with other values reported in the literature.

  3. Modeling helicity dissipation-rate equation

    CERN Document Server

    Yokoi, Nobumitsu

    2016-01-01

    Transport equation of the dissipation rate of turbulent helicity is derived with the aid of a statistical analytical closure theory of inhomogeneous turbulence. It is shown that an assumption on the helicity scaling with an algebraic relationship between the helicity and its dissipation rate leads to the transport equation of the turbulent helicity dissipation rate without resorting to a heuristic modeling.

  4. Time since death and decay rate constants of Norway spruce and European larch deadwood in subalpine forests determined using dendrochronology and radiocarbon dating

    Science.gov (United States)

    Petrillo, Marta; Cherubini, Paolo; Fravolini, Giulia; Marchetti, Marco; Ascher-Jenull, Judith; Schärer, Michael; Synal, Hans-Arno; Bertoldi, Daniela; Camin, Federica; Larcher, Roberto; Egli, Markus

    2016-03-01

    Due to the large size (e.g. sections of tree trunks) and highly heterogeneous spatial distribution of deadwood, the timescales involved in the coarse woody debris (CWD) decay of Picea abies (L.) Karst. and Larix decidua Mill. in Alpine forests are largely unknown. We investigated the CWD decay dynamics in an Alpine valley in Italy using the chronosequence approach and the five-decay class system that is based on a macromorphological assessment. For the decay classes 1-3, most of the dendrochronological samples were cross-dated to assess the time that had elapsed since tree death, but for decay classes 4 and 5 (poorly preserved tree rings) radiocarbon dating was used. In addition, density, cellulose, and lignin data were measured for the dated CWD. The decay rate constants for spruce and larch were estimated on the basis of the density loss using a single negative exponential model, a regression approach, and the stage-based matrix model. In the decay classes 1-3, the ages of the CWD were similar and varied between 1 and 54 years for spruce and 3 and 40 years for larch, with no significant differences between the classes; classes 1-3 are therefore not indicative of deadwood age. This seems to be due to a time lag between the death of a standing tree and its contact with the soil. We found distinct tree-species-specific differences in decay classes 4 and 5, with larch CWD reaching an average age of 210 years in class 5 and spruce only 77 years. The mean CWD rate constants were estimated to be in the range 0.018 to 0.022 y-1 for spruce and to about 0.012 y-1 for larch. Snapshot sampling (chronosequences) may overestimate the age and mean residence time of CWD. No sampling bias was, however, detectable using the stage-based matrix model. Cellulose and lignin time trends could be derived on the basis of the ages of the CWD. The half-lives for cellulose were 21 years for spruce and 50 years for larch. The half-life of lignin is considerably higher and may be more than

  5. Cosmological constant in SUGRA models with Planck scale SUSY breaking and degenerate vacua

    CERN Document Server

    Froggatt, C D; Nielsen, H B; Thomas, A W

    2014-01-01

    We argue that the measured value of the cosmological constant, as well as the small values of quartic Higgs self--coupling and the corresponding beta function at the Planck scale, which can be obtained by extrapolating the Standard Model (SM) couplings to high energies, can originate from supergravity (SUGRA) models with degenerate vacua. This scenario is realised if there are at least three exactly degenerate vacua. In the first vacuum, associated with the physical one, local supersymmetry (SUSY) is broken near the Planck scale while the breakdown of the SU(2)_W\\times U(1)_Y symmetry takes place at the electroweak (EW) scale. In the second vacuum local SUSY breaking is induced by gaugino condensation at a scale which is just slightly lower than \\Lambda_{QCD} in the physical vacuum. Finally, in the third vacuum local SUSY and EW symmetry are broken near the Planck scale.

  6. PENENTUAN KONSTANTA LAJU PENURUNAN KADAR IODAT DALAM GARAM BERIODIUM [Determination of the Rate Constant on the Decrease of Iodate Content in Iodized Salt

    Directory of Open Access Journals (Sweden)

    Wisnu Cahyadi

    2006-04-01

    Full Text Available Potassium iodate used as the source of iodine can be decomposed to become the other species i.e. iodide and iodine during processing and storage. The objective of this research was determination of the rate constant on the decrease of iodate content in iodized salt. The method was used to determine the temperature and the length of storage effects on iodate stability in iodized salt. The research was obtained the rate constant on the decrease of iodate content in iodized salt (K 2.55 x 10-8 ppm day-1 and energy of activation (Ea 12.002 kcal mol-1 K-1.

  7. PENENTUAN KONSTANTA LAJU PENURUNAN KADAR IODAT DALAM GARAM BERIODIUM [Determination of the Rate Constant on the Decrease of Iodate Content in Iodized Salt

    OpenAIRE

    Wisnu Cahyadi

    2006-01-01

    Potassium iodate used as the source of iodine can be decomposed to become the other species i.e. iodide and iodine during processing and storage. The objective of this research was determination of the rate constant on the decrease of iodate content in iodized salt. The method was used to determine the temperature and the length of storage effects on iodate stability in iodized salt. The research was obtained the rate constant on the decrease of iodate content in iodized salt (K) 2.55 x 10-8 ...

  8. Absolute rate constant determinations for the deactivation of O/1D/ by time resolved decay of O/1D/ yields O/3P/ emission

    Science.gov (United States)

    Davidson, J. A.; Sadowski, C. M.; Schiff, H. I.; Howard, C. J.; Schmeltekopf, A. L.; Jennings, D. A.; Streit, G. E.

    1976-01-01

    Absolute rate constants for the deactivation of O(1D) atoms by some atmospheric gases have been determined by observing the time-resolved emission of O(1D) at 630 nm. O(1D) atoms were produced by the dissociation of ozone via repetitive laser pulses at 266 nm. Absolute rate constants for the relaxation of O(1D) at 298 K are reported for N2, O2, CO2, O3, H2, D2, CH4, HCl, NH3, H2O, N2O, and Ne. The results obtained are compared with previous relative and absolute measurements reported in the literature.

  9. The Constant-Sound-Speed parameterization for NJL models of quark matter in hybrid stars

    CERN Document Server

    Ranea-Sandoval, Ignacio F; Orsaria, Milva G; Contrera, Gustavo A; Weber, Fridolin; Alford, Mark G

    2016-01-01

    The discovery of pulsars as heavy as 2 solar masses has led astrophysicists to rethink the core compositions of neutron stars, ruling out many models for the nuclear equations of state (EoS). We explore the hybrid stars that occur when hadronic matter is treated in a relativistic mean-field approximation and quark matter is modeled by three-flavor local and non-local Nambu Jona-Lasinio (NJL) models with repulsive vector interactions. The NJL models typically yield equations of state that feature a first order transition to quark matter. Assuming that the quark-hadron surface tension is high enough to disfavour mixed phases, and restricting to EoSes that allow stars to reach 2 solar masses, we find that the appearance of the quark matter core either destabilizes the star immediately (this is typical for non-local NJL models) or leads to a very short hybrid star branch in the mass-radius relation (this is typical for local NJL models). Using the Constant-Sound-Speed parametrization we can see that the reason fo...

  10. Testing for constant nonparametric effects in general semiparametric regression models with interactions

    KAUST Repository

    Wei, Jiawei

    2011-07-01

    We consider the problem of testing for a constant nonparametric effect in a general semi-parametric regression model when there is the potential for interaction between the parametrically and nonparametrically modeled variables. The work was originally motivated by a unique testing problem in genetic epidemiology (Chatterjee, et al., 2006) that involved a typical generalized linear model but with an additional term reminiscent of the Tukey one-degree-of-freedom formulation, and their interest was in testing for main effects of the genetic variables, while gaining statistical power by allowing for a possible interaction between genes and the environment. Later work (Maity, et al., 2009) involved the possibility of modeling the environmental variable nonparametrically, but they focused on whether there was a parametric main effect for the genetic variables. In this paper, we consider the complementary problem, where the interest is in testing for the main effect of the nonparametrically modeled environmental variable. We derive a generalized likelihood ratio test for this hypothesis, show how to implement it, and provide evidence that our method can improve statistical power when compared to standard partially linear models with main effects only. We use the method for the primary purpose of analyzing data from a case-control study of colorectal adenoma.

  11. Testing for Constant Nonparametric Effects in General Semiparametric Regression Models with Interactions.

    Science.gov (United States)

    Wei, Jiawei; Carroll, Raymond J; Maity, Arnab

    2011-07-01

    We consider the problem of testing for a constant nonparametric effect in a general semi-parametric regression model when there is the potential for interaction between the parametrically and nonparametrically modeled variables. The work was originally motivated by a unique testing problem in genetic epidemiology (Chatterjee, et al., 2006) that involved a typical generalized linear model but with an additional term reminiscent of the Tukey one-degree-of-freedom formulation, and their interest was in testing for main effects of the genetic variables, while gaining statistical power by allowing for a possible interaction between genes and the environment. Later work (Maity, et al., 2009) involved the possibility of modeling the environmental variable nonparametrically, but they focused on whether there was a parametric main effect for the genetic variables. In this paper, we consider the complementary problem, where the interest is in testing for the main effect of the nonparametrically modeled environmental variable. We derive a generalized likelihood ratio test for this hypothesis, show how to implement it, and provide evidence that our method can improve statistical power when compared to standard partially linear models with main effects only. We use the method for the primary purpose of analyzing data from a case-control study of colorectal adenoma.

  12. Estimating a continuous p-wave velocity profile with constant squared-slowness gradient models from seismic field data

    NARCIS (Netherlands)

    Ponomarenko, A.V.; Kashtan, B.M.; Troyan, V.N.; Mulder, W.A.

    2015-01-01

    We inverted seismic field data for a continuous, laterally invariant P-wave velocity profile. Instead of the usual approach that involves horizontal layers with piecewise constant densities and velocities, we consider models of one or two layers with a constant gradient of the squared slowness above

  13. Procedures for Static and Constant-Rate Tests on a Single-Degree-of-Freedom (SDF) Strapdown Gyroscope.

    Science.gov (United States)

    1983-10-01

    permettant de tester des gyroscopes auto correcteurs A centrale lige et . 1° de libert6. Les tests sont limitgs aux modes statistiques et A taux constants...conventionnels utilisEs sont aussi presentfs, de Seme que les considfrations concernant la r6gulation thermique . iii 5 TABLE OF CONTENTS Page Abstract

  14. Modeling inflation rates and exchange rates in Ghana: application of multivariate GARCH models.

    Science.gov (United States)

    Nortey, Ezekiel Nn; Ngoh, Delali D; Doku-Amponsah, Kwabena; Ofori-Boateng, Kenneth

    2015-01-01

    This paper was aimed at investigating the volatility and conditional relationship among inflation rates, exchange rates and interest rates as well as to construct a model using multivariate GARCH DCC and BEKK models using Ghana data from January 1990 to December 2013. The study revealed that the cumulative depreciation of the cedi to the US dollar from 1990 to 2013 is 7,010.2% and the yearly weighted depreciation of the cedi to the US dollar for the period is 20.4%. There was evidence that, the fact that inflation rate was stable, does not mean that exchange rates and interest rates are expected to be stable. Rather, when the cedi performs well on the forex, inflation rates and interest rates react positively and become stable in the long run. The BEKK model is robust to modelling and forecasting volatility of inflation rates, exchange rates and interest rates. The DCC model is robust to model the conditional and unconditional correlation among inflation rates, exchange rates and interest rates. The BEKK model, which forecasted high exchange rate volatility for the year 2014, is very robust for modelling the exchange rates in Ghana. The mean equation of the DCC model is also robust to forecast inflation rates in Ghana.

  15. Transfer Rate Models for Gnutella Signaling Traffic

    OpenAIRE

    2006-01-01

    This paper reports on transfer rate models for the Gnutella signaling protocol. New results on message-level and IP-level rates are presented. The models are based on traffic captured at the Blekinge Institute of Technology (BTH) campus in Sweden and offer several levels of granularity: message type, application layer and network layer. The aim is to obtain parsimonous models suitable for analysis and simulation of P2P workload. IEEE Explorer

  16. EOS simulation and GRNN modeling of the constant volume depletion behavior of gas condensate reservoirs

    Energy Technology Data Exchange (ETDEWEB)

    Elsharkawy, A.M.; Foda, S.G. [Kuwait University, Safat (Kuwait). Petroleum Engineering Dept.

    1998-03-01

    Currently, two approaches are being used to predict the changes in retrograde gas condensate composition and estimate the pressure depletion behavior of gas condensate reservoirs. The first approach uses the equation of states whereas the second uses empirical correlations. Equations of states (EOS) are poor predictive tools for complex hydrocarbon systems. The EOS needs adjustment against phase behavior data of reservoir fluid of known composition. The empirical correlation does not involve numerous numerical computations but their accuracy is limited. This study presents two general regression neural network (GRNN) models. The first model, GRNNM1, is developed to predict dew point pressure and gas compressibility at dew point using initial composition of numerous samples while the second model, GRNNM2, is developed to predict the changes in well stream effluent composition at any stages of pressure depletion. GRNNM2 can also be used to determine the initial reservoir fluid composition using dew point pressure, gas compressibility at dew point, and reservoir temperature. These models are based on analysis of 142 sample of laboratory studies of constant volume depletion (CVD) for gas condensate systems forming a total of 1082 depletion stages. The database represents a wide range of gas condensate systems obtained worldwide. The performance of the GRNN models has been compared to simulation results of the equation of state. The study shows that the proposed general regression neural network models are accurate, valid, and reliable. These models can be used to forecast CVD data needed for many reservoir engineering calculations in case laboratory data is unavailable. The GRNN models save computer time involved in EOS calculations. The study also show that once these models are properly trained they can be used to cut expenses of frequent sampling and laborious experimental CVD tests required for gas condensate reservoirs. 55 refs., 13 figs., 6 tabs.

  17. The fine tuning of the cosmological constant in a conformal model

    Science.gov (United States)

    Jain, Pankaj; Kashyap, Gopal; Mitra, Subhadip

    2015-10-01

    We consider a conformal model involving two real scalar fields in which the conformal symmetry is broken by a soft mechanism and is not anomalous. One of these scalar fields is representative of the standard model Higgs. The model predicts exactly zero cosmological constant. In the simplest version of the model, some of the couplings need to be fine-tuned to very small values. We formulate the problem of fine tuning of these couplings. We argue that the problem arises since we require a soft mechanism to break conformal symmetry. The symmetry breaking is possible only if the scalar fields do not evolve significantly over the time scale of the Universe. Ignoring contributions due to quantum gravity, we present two solutions to this fine tuning problem. We argue that the problem is solved if the classical value of one of the scalar fields is super-Planckian, i.e. takes a value much larger than the Planck mass. The second solution involves introduction of a strongly coupled hidden sector that we call hypercolor. In this case, the conformal invariance is broken dynamically and triggers the breakdown of the electroweak symmetry. We argue that our analysis applies also to the case of the standard model Higgs multiplet.

  18. Physiological Flow of Jeffrey Six Constant Fluid Model due to Ciliary Motion

    Science.gov (United States)

    Shaheen, A.; Hussain, S.; Nadeem, S.

    2016-12-01

    The main purpose of this article is to present a mathematical model of ciliary motion in an annulus. In this analysis, the peristaltic motion of non-Newtonian Jeffrey six constant fluid is observed in an annulus with ciliated tips in the presence of heat and mass transfer. The effects of viscous dissipation are also considered. The flow equations of non-Newtonian fluid for the two-dimensional tube in cylindrical coordinates are simplified using the low Reynolds number and long wave-length approximations. The main equations for Jeffrey six constant fluid are considered in cylindrical coordinates system. The resulting nonlinear problem is solved using the regular perturbation technique in terms of a variant of small dimensionless parameter α. The results of the solutions for velocity, temperature and concentration field are presented graphically. Bk is Brinkman number, ST is soret number, and SH is the Schmidth number. Outcome for the longitudinal velocity, pressure rise, pressure gradient and stream lines are represented through graphs. in the history, the viscous-dissipation effect is usually represented by the Brinkman number.

  19. Vector and tensor meson decay constants in light-front quark model

    CERN Document Server

    Geng, Chao-Qiang; Xia, Chuanhui

    2016-01-01

    We study the decay constants ($f_M$) of the vector ($D^{*}$, $D^{*}_{s}$, $B^{*}$, $B^{*}_{s}$, $B^{*}_{c}$) and tensor ($D_{2}^{*}$, $D_{s2}^{*}$, $B^{*}_{2}$, $B^{*}_{s2}$) mesons in the light front quark model. With the known pseudoscalar meson decay constants of $f_D$, $f_{D_s}$, $f_B$, $f_{B_s}$, and $f_{B_c}$ as the input parameters to determine the light-front meson wave functions, we obtain that $f_{D^{*}, D^{*}_{s}, B^{*},B^{*}_s,B^{*}_c} = (252.0^{+13.8}_{-11.6}$, $318.3^{+15.3}_{-12.6}$ , $201.9^{+43.2}_{-41.4}$, $244.2\\pm7.0$, $473.4\\pm18.2$) and $(264.9^{+10.2}_{-9.5}$, $330.9^{+9.9}_{-9.0}$, $220.2^{+49.1}_{-46.2}$, $265.7\\pm8.0$, $487.6\\pm19.2$) MeV with Gaussian and power-law wave functions, respectively, while $f_{D_{2}^{*},D_{s2}^{*},B^{*}_{2},B^{*}_{s2}}$=($143.6^{+24.9}_{-21.8}$, $209.5^{+29.1}_{-24.2}$, $80.9^{+33.8}_{-27.7}$, $109.7^{+15.7}_{-15.0}$) MeV with only Gaussian wave functions.

  20. Modeling and Analysis of Transitional Tube with Constant Sectional Area along Derivative Central Route

    Institute of Scientific and Technical Information of China (English)

    MENG Xiang-bao; TONG Bao-guo; PAN Zi-jian; LI Hai-xing

    2011-01-01

    Firstly, sample square-circular transition tube along straight central route was modeled on CATIA software. The parameters are as follows: let the tube length is L, and the constant cross section area is S, and S = πR^2 = a2, in which R stands for the circle radius on one end, and a the square side length on the other end; set up the coordinate system with OX axis on the central route in which the origin O is on centroid of the square end and assume the cross section size at x as the square shaped with all four comers filleted in radius r which is proportional to x, that is, the linear slope of r is R/L, thus, both values r and square side length ax can be attained on the constant cross section area assumption. Secondly, some sample polygonal-circular transition tubes along straight, circular and helical central route were implemented similarly. Thirdly, numerical analysis of stress and displacement of these tubes were carried out on MSC/PATRAN software which are important to the distribution of turbulent flow and the layout of these transitional tube structures.

  1. Properties of potential modelling three benchmarks: the cosmological constant, inflation and three generations

    CERN Document Server

    Kiselev, V V

    2010-01-01

    We argue for a model of low-energy correction to the inflationary potential as caused by the gauge-mediated breaking down the supersymmetry at the scale of $\\mu_\\textsc{x}\\sim 10^4$ GeV, that provides us with the seesaw mechanism of thin domain wall fluctuations in the flat vacuum. The fluctuations are responsible for the vacuum with the cosmological constant at the scale of $\\mu_\\Lambda\\sim 10^{-2}$ eV suppressed by the Planckian mass $m_\\mathtt{Pl}$ via $\\mu_\\Lambda\\sim\\mu_\\textsc{x}^2/m_\\mathtt{Pl}$. The appropriate vacuum state is occupied after the inflation with quartic coupling constant $\\lambda\\sim\\mu_\\textsc{x}/m_\\mathtt{Pl}\\sim 10^{-14}$ inherently related with the bare mass scale of $\\widetilde m\\sim\\sqrt{\\mu_\\textsc{x}m_\\mathtt{Pl}}\\sim 10^{12}$ GeV determining the thickness of domain walls $\\delta r\\sim1/\\widetilde m$. Such the parameters of potential are still marginally consistent with the observed inhomogeneity of matter density in the Universe. The inflationary evolution suggests the vacuum s...

  2. Modelling and operation of sub-miniature constant temperature hot-wire anemometry

    Science.gov (United States)

    Samie, M.; Watmuff, J. H.; Van Buren, T.; Hutchins, N.; Marusic, I.; Hultmark, M.; Smits, A. J.

    2016-12-01

    High-Reynolds number flows are very common in technological applications and in nature, and hot-wire anemometry is the preferred method for measuring the time-series of fluctuating velocity in such flows. However, measurement of very high-Reynolds number flows requires hot-wires with higher temporal and spatial resolution than is available with conventional probes. Much effort has therefore been devoted to decreasing the size of the hot-wire probes and this has led to associated challenges with operation. It is this latter operation problem which is the focus of this paper. To this end, an existing theoretical model of constant-temperature hot-wire anemometers (Perry 1982 Hot-Wire Anemometry (New York: Oxford University Press), Watmuff 1995 Exp. Therm. Fluid Sci. 11 117-34) is applied, and its accuracy is tested for the first time by comparison to measurements using an in-house constant temperature anemometer (CTA) for both conventional 5~μ m-diameter wires and sub-miniature hot-wires. With the aid of this model, we propose modifications to the CTA design and demonstrate successful operation of the CTA with the Princeton nano-scale thermal anemometry probe (NSTAP) (Bailey et al 2010 J. Fluid Mech. 663 160-79). It is also shown that the transfer function obtained from the model can be utilized to estimate the true frequency response and cut-off frequency of a hot-wire-CTA system to the velocity fluctuations, which is essential in accurate measurements of energy spectrum and higher order statistics of turbulent flows.

  3. Resolution of a Challenge for Solvation Modeling: Calculation of Dicarboxylic Acid Dissociation Constants Using Mixed Discrete-Continuum Solvation Models

    Energy Technology Data Exchange (ETDEWEB)

    Marenich, Aleksandr; Ding, Wendu; Cramer, Christopher J.; Truhlar, Donald G.

    2012-06-07

    First and second dissociation constants (pKa values) of oxalic acid, malonic acid, and adipic acid were computed by using a number of theoretical protocols based on density functional theory and using both continuum solvation models and mixed discrete-continuum solvation models. We show that fully implicit solvation models (in which the entire solvent is represented by a dielectric continuum) fail badly for dicarboxylic acids with mean unsigned errors averaged over six pKa values) of 2.4-9.0 log units, depending on the particular implicit model used. The use of water-solute clusters and accounting for multiple conformations in solution significantly improve the performance of both generalized Born solvation models and models that solve the nonhomogeneous dielectric Poisson equation for bulk electrostatics. The four most successful models have mean unsigned errors of only 0.6-0.8 log units.

  4. Overnight Index Rate: Model, calibration and simulation

    OpenAIRE

    Olga Yashkir; Yuri Yashkir

    2014-01-01

    In this study, the extended Overnight Index Rate (OIR) model is presented. The fitting function for the probability distribution of the OIR daily returns is based on three different Gaussian distributions which provide modelling of the narrow central peak and the wide fat-tailed component. The calibration algorithm for the model is developed and investigated using the historical OIR data.

  5. Overnight Index Rate: Model, calibration and simulation

    Directory of Open Access Journals (Sweden)

    Olga Yashkir

    2014-12-01

    Full Text Available In this study, the extended Overnight Index Rate (OIR model is presented. The fitting function for the probability distribution of the OIR daily returns is based on three different Gaussian distributions which provide modelling of the narrow central peak and the wide fat-tailed component. The calibration algorithm for the model is developed and investigated using the historical OIR data.

  6. Overnight Index Rate: Model, Calibration, and Simulation

    OpenAIRE

    Olga Yashkir; Yuri Yashkir

    2013-01-01

    In this study, the extended Overnight Index Rate (OIR) model is presented. The fitting function for the probability distribution of the OIR daily returns is based on three different Gaussian distributions which provide modelling of the narrow central peak and the wide fat-tailed component. The calibration algorithm for the model is developed and investigated using the historical OIR data.

  7. Time constants for temperature elevation in human models exposed to dipole antennas and beams in the frequency range from 1 to 30 GHz

    Science.gov (United States)

    Morimoto, Ryota; Hirata, Akimasa; Laakso, Ilkka; Ziskin, Marvin C.; Foster, Kenneth R.

    2017-03-01

    This study computes the time constants of the temperature elevations in human head and body models exposed to simulated radiation from dipole antennas, electromagnetic beams, and plane waves. The frequency range considered is from 1 to 30 GHz. The specific absorption rate distributions in the human models are first computed using the finite-difference time-domain method for the electromagnetics. The temperature elevation is then calculated by solving the bioheat transfer equation. The computational results show that the thermal time constants (defined as the time required to reach 63% of the steady state temperature elevation) decrease with the elevation in radiation frequency. For frequencies higher than 4 GHz, the computed thermal time constants are smaller than the averaging time prescribed in the ICNIRP guidelines, but larger than the averaging time in the IEEE standard. Significant differences between the different head models are observed at frequencies higher than 10 GHz, which is attributable to the heat diffusion from the power absorbed in the pinna. The time constants for beam exposures become large with the increase in beam diameter. The thermal time constant in the brain is larger than that in the superficial tissues at high frequencies, because the brain temperature elevation is caused by the heat conduction of energy absorbed in the superficial tissue. The thermal time constant is minimized with an ideal beam with a minimum investigated diameter of 10 mm this minimal time constant is approximately 30 s and is almost independent of the radiation frequency, which is supported by analytic methods. In addition, the relation between the time constant, as defined in this paper, and ‘averaging time’ as it appears in the exposure limits is discussed, especially for short intense pulses. Similar to the laser guidelines, provisions should be included in the limits to limit the fluence for such pulses.

  8. An analytical model for the evolution of starless cores I: The constant-mass case

    CERN Document Server

    Pattle, Kate

    2016-01-01

    We propose an analytical model for the quasistatic evolution of starless cores confined by a constant external pressure, assuming that cores are isothermal and obey a spherically-symmetric density distribution. We model core evolution for Plummer-like and Gaussian density distributions in the adiabatic and isothermal limits, assuming Larson-like dissipation of turbulence. We model the variation in the terms in the virial equation as a function of core characteristic radius, and determine whether cores are evolving toward virial equilibrium or gravitational collapse. We ignore accretion onto cores in the current study. We discuss the different behaviours predicted by the isothermal and adiabatic cases, and by our choice of index for the size-linewidth relation, and suggest a means of parameterising the magnetic energy term in the virial equation. We model the evolution of the set of cores observed by Pattle et al. (2015) in the L1688 region of Ophiuchus in the 'virial plane'. We find that not all virially-boun...

  9. A simple model for hydromagnetic instabilities in the presence of a constant magnetic field

    CERN Document Server

    Sandoval-Villalbazo, A; Arrieta, A

    2005-01-01

    In this paper we study a simple model consisting of a dilute fully ionized plasma in the presence of the gravitational and a constant magnetic field to analyze the propagation of hydromagnetic instabilities. In particular we show that the so called Jeans instability is in principle affected by the presence of the magnetic field. A brief discussion is made attempting to assess this influence in the stage of the evolution of the Universe where structures were formed. The most logical conclusion is that if magnetic fields existed in those times their magnitudes were too small to modify Jeans' mass. Our results places limits of the possible values of seed magnetic fields consistent with the formation structures in the Universe. These values are within the range of the results obtained by other authors.

  10. Hyperon puzzle and the RMF model with scaled hadron masses and coupling constants

    Science.gov (United States)

    Kolomeitsev, E. E.; Maslov, K. A.; Voskresensky, D. N.

    2016-01-01

    The equation of state of cold baryonic matter is studied within a relativistic mean-field model with hadron masses and coupling constants depending on a scalar field. We demonstrate that if the effective nucleon mass stops to decrease with a density increase at densities n > n*> n0, where n0 is the nuclear saturation density, the equation of state stiffens for these densities and the limiting neutron star mass increases. The stabilization of the nucleon mass can be realised if in the equation of motion for the scalar mean-field there appear a term sharply varying in a narrow vicinity of the field value corresponding to the density n*. We show several possible realizations of this mechanism getting sufficiently stiff equations of state. The appearance of hyperons in dense neutron star interiors is accounted for. The obtained equations of state remain sufficiently stiff if the reduction of the ϕ meson mass is incorporated. Thereby, the hyperon puzzle can be resolved.

  11. Thermal Modelling Analysis of Spiral Wound Supercapacitor under Constant-Current Cycling.

    Directory of Open Access Journals (Sweden)

    Kai Wang

    Full Text Available A three-dimensional modelling approach is used to study the effects of operating and ambient conditions on the thermal behaviour of the spiral wound supercapacitor. The transient temperature distribution during cycling is obtained by using the finite element method with an implicit predictor-multicorrector algorithm. At the constant current of 2A, the results show that the maximum temperature appears in core area. After 5 cycles, the maximum temperature is 34.5°C, while in steady state, it's up to 42.5°C. This paper further studies the relationship between the maximum temperature and charge-discharge current. The maximum temperature will be more than 60°C after 5 cycles at the current of 4A, and cooling measurements should be taken at that time. It can provide thoughts on inner temperature field distribution and structure design of the spiral wound supercapacitor in working process.

  12. Exact diffusion constant of a one-dimensional asymmetric exclusion model with open boundaries

    Science.gov (United States)

    Derrida, B.; Evans, M. R.; Mallick, K.

    1995-06-01

    For the 1D fully asymmetric exclusion model with open boundary conditions, we calculate exactly the fluctuations of the current of particles. The method used is an extension of a matrix technique developed recently to describe the equatime steady-state properties for open boundary conditions and the diffusion constant for particles on a ring. We show how the fluctuations of the current are related to non-equal-time correlations. In the thermodynamic limit, our results agree with recent results of Ferrari and Fontes obtained by working directly in the infinite system. We also show that the fluctuations of the current become singular when the system undergoes a phase transition with discontinuities along the first-order transition line.

  13. Improved Shock Tube Measurement of the CH4 + Ar = CH3 + H + Ar Rate Constant using UV Cavity-Enhanced Absorption Spectroscopy of CH3.

    Science.gov (United States)

    Wang, Shengkai; Davidson, David F; Hanson, Ronald K

    2016-07-21

    We report an improved measurement for the rate constant of methane dissociation in argon (CH4 + Ar = CH3 + H + Ar) behind reflected shock waves. The experiment was conducted using a sub-parts per million sensitivity CH3 diagnostic recently developed in our laboratory based on ultraviolet cavity-enhanced absorption spectroscopy. The high sensitivity of this diagnostic allowed for measurements of quantitatively resolved CH3 time histories during the initial stage of CH4 pyrolysis, where the reaction system is clean and free from influences of secondary reactions and temperature change. This high sensitivity also allowed extension of our measurement range to much lower temperatures (shock measurements were performed at temperatures between 1487 and 1866 K and pressures near 1.7 atm, resulting in the following Arrhenius rate constant expression for the title reaction: k(1.7 atm) = 3.7 × 10(16) exp(-42 200 K/T) cm(3)/mol·s, with a 2σ uncertainty factor of 1.25. The current data are in good consensus with various theoretical and review studies, but at the low temperature end they suggest a slightly higher (up to 35%) rate constant compared to these previous results. A re-evaluation of previous and current experimental data in the falloff region was also performed, yielding updated expressions for both the low-pressure limit and the high-pressure limit rate constants and improved agreement with all existing data.

  14. Determination of first order rate constants by natural logarithm of the slope plot exemplified by analysis of Aspergillus niger in batch culture

    NARCIS (Netherlands)

    Poulsen, B.R.; Ruiter, G.; Visser, J.; Iversen, J.J.L.

    2003-01-01

    Finding rate constants from experimental data is often difficult because of offset and noise. A computer program was developed to average experimental data points, reducing the effect of noise, and to produce a loge of slope plot - a plot of the natural logarithm of the slope of a curve -

  15. Adsorption Rate Models for Multicomponent Adsorption Systems

    Institute of Scientific and Technical Information of China (English)

    姚春才

    2004-01-01

    Three adsorption rate models are derived for multicomponent adsorption systems under either pore diffusion or surface diffusion control. The linear driving force (LDF) model is obtained by assuming a parabolic intraparticle concentration profile. Models I and Ⅱ are obtained from the parabolic concentration layer approximation. Examples are presented to demonstrate the usage and accuracy of these models. It is shown that Model I is suitable for batch adsorption calculations and Model Ⅱ provides a good approximation in fixed-bed adsorption processes while the LDF model should not be used in batch adsorption and may be considered acceptable in fixed-bed adsorption where the parameter Ti is relatively large.

  16. Study of Antigravity in an F(R) Model and in Brans-Dicke Theory with Cosmological Constant

    OpenAIRE

    2014-01-01

    We study antigravity, that is having an effective gravitational constant with a negative sign, in scalar-tensor theories originating from $F(R)$-theory and in a Brans-Dicke model with cosmological constant. For the $F(R)$ theory case, we obtain the antigravity scalar-tensor theory in the Jordan frame by using a variant of the Lagrange multipliers method and we numerically study the time dependent effective gravitational constant. As we shall demonstrate by using a specific $F(R)$ model, altho...

  17. Fitting the elementary rate constants of the P-gp transporter network in the hMDR1-MDCK confluent cell monolayer using a particle swarm algorithm.

    Directory of Open Access Journals (Sweden)

    Deep Agnani

    Full Text Available P-glycoprotein, a human multidrug resistance transporter, has been extensively studied due to its importance to human health and disease. In order to understand transport kinetics via P-gp, confluent cell monolayers overexpressing P-gp are widely used. The purpose of this study is to obtain the mass action elementary rate constants for P-gp's transport and to functionally characterize members of P-gp's network, i.e., other transporters that transport P-gp substrates in hMDR1-MDCKII confluent cell monolayers and are essential to the net substrate flux. Transport of a range of concentrations of amprenavir, loperamide, quinidine and digoxin across the confluent monolayer of cells was measured in both directions, apical to basolateral and basolateral to apical. We developed a global optimization algorithm using the Particle Swarm method that can simultaneously fit all datasets to yield accurate and exhaustive fits of these elementary rate constants. The statistical sensitivity of the fitted values was determined by using 24 identical replicate fits, yielding simple averages and standard deviations for all of the kinetic parameters, including the efflux active P-gp surface density. Digoxin required additional basolateral and apical transporters, while loperamide required just a basolateral tranporter. The data were better fit by assuming bidirectional transporters, rather than active importers, suggesting that they are not MRP or active OATP transporters. The P-gp efflux rate constants for quinidine and digoxin were about 3-fold smaller than reported ATP hydrolysis rate constants from P-gp proteoliposomes. This suggests a roughly 3∶1 stoichiometry between ATP hydrolysis and P-gp transport for these two drugs. The fitted values of the elementary rate constants for these P-gp substrates support the hypotheses that the selective pressures on P-gp are to maintain a broad substrate range and to keep xenobiotics out of the cytosol, but not out of the

  18. Electrochemical modelling of Li-ion battery pack with constant voltage cycling

    Science.gov (United States)

    Ashwin, T. R.; McGordon, A.; Jennings, P. A.

    2017-02-01

    In a battery pack, cell-to-cell chemical variation, or the variation in operating conditions, can possibly lead to current imbalance which can accelerate pack ageing. In this paper, the Pseudo-Two-Dimensional(P2D) porous electrode model is extended to a battery pack layout, to predict the overall behaviour and the cell-to-cell variation under constant voltage charging and discharging. The algorithm used in this model offers the flexibility in extending the layout to any number of cells in a pack, which can be of different capacities, chemical characteristics and physical dimensions. The coupled electro-thermal effects such as differential cell ageing, temperature variation, porosity change and their effects on the performance of the pack, can be predicted using this modelling algorithm. The pack charging voltage is found to have an impact on the performance as well as the SEI layer growth. Numerical studies are conducted by keeping the cells at different thermal conditions and the results show the necessity to increase the heat transfer coefficient to cool the pack, compared to single cell. The results show that the thermal imbalance has more impact than the change in inter-connecting resistance on the split current distribution, which accelerates the irreversible porous filling and ageing.

  19. Use of SAMC for Bayesian analysis of statistical models with intractable normalizing constants

    KAUST Repository

    Jin, Ick Hoon

    2014-03-01

    Statistical inference for the models with intractable normalizing constants has attracted much attention. During the past two decades, various approximation- or simulation-based methods have been proposed for the problem, such as the Monte Carlo maximum likelihood method and the auxiliary variable Markov chain Monte Carlo methods. The Bayesian stochastic approximation Monte Carlo algorithm specifically addresses this problem: It works by sampling from a sequence of approximate distributions with their average converging to the target posterior distribution, where the approximate distributions can be achieved using the stochastic approximation Monte Carlo algorithm. A strong law of large numbers is established for the Bayesian stochastic approximation Monte Carlo estimator under mild conditions. Compared to the Monte Carlo maximum likelihood method, the Bayesian stochastic approximation Monte Carlo algorithm is more robust to the initial guess of model parameters. Compared to the auxiliary variable MCMC methods, the Bayesian stochastic approximation Monte Carlo algorithm avoids the requirement for perfect samples, and thus can be applied to many models for which perfect sampling is not available or very expensive. The Bayesian stochastic approximation Monte Carlo algorithm also provides a general framework for approximate Bayesian analysis. © 2012 Elsevier B.V. All rights reserved.

  20. Term structure modeling and asymptotic long rate

    NARCIS (Netherlands)

    Yao, Y.

    1999-01-01

    This paper examines the dynamics of the asymptotic long rate in three classes of term structure models. It shows that, in a frictionless and arbitrage-free market, the asymptotic long rate is a non-decreasing process. This gives an alternative proof of the same result of Dybvig et al. (Dybvig, P.H.,

  1. Methods of modelling relative growth rate

    Institute of Scientific and Technical Information of China (English)

    Arne Pommerening; Anders Muszta

    2015-01-01

    Background:Analysing and modelling plant growth is an important interdisciplinary field of plant science. The use of relative growth rates, involving the analysis of plant growth relative to plant size, has more or less independently emerged in different research groups and at different times and has provided powerful tools for assessing the growth performance and growth efficiency of plants and plant populations. In this paper, we explore how these isolated methods can be combined to form a consistent methodology for modelling relative growth rates. Methods:We review and combine existing methods of analysing and modelling relative growth rates and apply a combination of methods to Sitka spruce (Picea sitchensis (Bong.) Carr.) stem-analysis data from North Wales (UK) and British Douglas fir (Pseudotsuga menziesi (Mirb.) Franco) yield table data. Results:The results indicate that, by combining the approaches of different plant-growth analysis laboratories and using them simultaneously, we can advance and standardise the concept of relative plant growth. Particularly the growth multiplier plays an important role in modelling relative growth rates. Another useful technique has been the recent introduction of size-standardised relative growth rates. Conclusions:Modelling relative growth rates mainly serves two purposes, 1) an improved analysis of growth performance and efficiency and 2) the prediction of future or past growth rates. This makes the concept of relative growth ideally suited to growth reconstruction as required in dendrochronology, climate change and forest decline research and for interdisciplinary research projects beyond the realm of plant science.

  2. Methods of modelling relative growth rate

    Directory of Open Access Journals (Sweden)

    Arne Pommerening

    2015-03-01

    Full Text Available Background Analysing and modelling plant growth is an important interdisciplinary field of plant science. The use of relative growth rates, involving the analysis of plant growth relative to plant size, has more or less independently emerged in different research groups and at different times and has provided powerful tools for assessing the growth performance and growth efficiency of plants and plant populations. In this paper, we explore how these isolated methods can be combined to form a consistent methodology for modelling relative growth rates. Methods We review and combine existing methods of analysing and modelling relative growth rates and apply a combination of methods to Sitka spruce (Picea sitchensis (Bong. Carr. stem-analysis data from North Wales (UK and British Douglas fir (Pseudotsuga menziesii (Mirb. Franco yield table data. Results The results indicate that, by combining the approaches of different plant-growth analysis laboratories and using them simultaneously, we can advance and standardise the concept of relative plant growth. Particularly the growth multiplier plays an important role in modelling relative growth rates. Another useful technique has been the recent introduction of size-standardised relative growth rates. Conclusions Modelling relative growth rates mainly serves two purposes, 1 an improved analysis of growth performance and efficiency and 2 the prediction of future or past growth rates. This makes the concept of relative growth ideally suited to growth reconstruction as required in dendrochronology, climate change and forest decline research and for interdisciplinary research projects beyond the realm of plant science.

  3. Roll paper pilot. [mathematical model for predicting pilot rating of aircraft in roll task

    Science.gov (United States)

    Naylor, F. R.; Dillow, J. D.; Hannen, R. A.

    1973-01-01

    A mathematical model for predicting the pilot rating of an aircraft in a roll task is described. The model includes: (1) the lateral-directional aircraft equations of motion; (2) a stochastic gust model; (3) a pilot model with two free parameters; and (4) a pilot rating expression that is a function of rms roll angle and the pilot lead time constant. The pilot gain and lead time constant are selected to minimize the pilot rating expression. The pilot parameters are then adjusted to provide a 20% stability margin and the adjusted pilot parameters are used to compute a roll paper pilot rating of the aircraft/gust configuration. The roll paper pilot rating was computed for 25 aircraft/gust configurations. A range of actual ratings from 2 to 9 were encountered and the roll paper pilot ratings agree quite well with the actual ratings. In addition there is good correlation between predicted and measured rms roll angle.

  4. A generalized Prandtl-Ishlinskii model for characterizing the rate-independent and rate-dependent hysteresis of piezoelectric actuators.

    Science.gov (United States)

    Gan, Jinqiang; Zhang, Xianmin; Wu, Heng

    2016-03-01

    In this paper, a generalized hysteresis model is developed to describe both rate-independent and rate-dependent hysteresis in piezoelectric actuators. Based on the classical Prandtl-Ishlinskii (P-I) model, the developed model adds a quadratic polynomial and makes other small changes. When it is used to describe rate-independent hysteresis, the parameters of the model are constants, which can be identified by self-adaptive particle swarm optimization. The effectiveness of this rate-independent modified P-I model is demonstrated by comparing simulation results of the developed model and the classic Prandtl-Ishlinskii model. Simulation results suggest that the rate-independent modified P-I model can describe hysteresis more precisely. Compared with the classical P-I model, the rate-independent modified P-I model reduces modeling error by more than 50%. When it is used to describe rate-independent hysteresis, a one-side operator is adopted and the parameters are functions with input frequency. The results of the experiments and simulations have shown that the proposed models can accurately describe both rate-independent and rate-dependent hysteresis in piezoelectric actuators.

  5. The Hubble constant from galaxy lenses: impacts of triaxiality and model degeneracies

    OpenAIRE

    2008-01-01

    The Hubble constant can be constrained using the time delays between multiple images of gravitationally lensed sources. In some notable cases, typical lensing analyses assuming isothermal galaxy density profiles produce low values for the Hubble constant, inconsistent with the result of the HST Key Project (72 +- 8 km/s/Mpc). Possible systematics in the values of the Hubble constant derived from galaxy lensing systems can result from a number of factors, e.g. neglect of environmental effects,...

  6. Bianchi type-I transit cosmological models with time dependent gravitational and cosmological constants

    CERN Document Server

    Pradhan, Anirudh; Rikhvitsky, Victor

    2013-01-01

    The present study deals with the exact solutions of the Einstein's field equations with variable gravitational and cosmological "constants" for a spatially homogeneous and anisotropic Bianchi type-I space-time. To study the transit behaviour of Universe, we consider a law of variation of scale factor $a(t) = \\left(t^{k} e^{t}\\right)^{\\frac{1}{n}}$ which yields a time dependent deceleration parameter (DP) $q = - 1 + \\frac{nk}{(k + t)^{2}}$, comprising a class of models that depicts a transition of the universe from the early decelerated phase to the recent accelerating phase. We find that the time dependent DP is reasonable for the present day Universe and give an appropriate description of the evolution of the universe. For $n = 0.27k$, we obtain $q_{0} = -0.73$ which is similar to observed value of DP at present epoch. It is also observed that for $n \\geq 2$ and $k = 1$, we obtain a class of transit models of the universe from early decelerating to present accelerating phase. For $k = 0$, the universe has no...

  7. Cosmological constant problem in a scenario with compactifications (RS-I model)

    CERN Document Server

    Martinez-Robles, C

    2016-01-01

    In this letter, we apply the Randall-Sundrum (RS) model, a scenario based on compactifications, to control the UV divergence of the zero-point energy density equation for the vacuum fluctuations, which has been unsuccessfully addressed to the cosmological constant (CC) due to a heavy discrepancy between theory and observation. Historically, the problem of CC has been shelved in the RS point of view, having few or non literature on the subject. In this sense and as done with the hierarchy problem, we apply the RS model to solve this difference via extra dimensions; we also describe how brane effects could be the solution to this substantial difference. It should be noticed that this problem is studied assuming first Minkoswki type branes, and then followed by cosmologically more realistic FLRW type branes. We finally find some remarkably interesting consequences in the RS scenario: The CC problem can be solved via compactification of the extra dimension and the compactification radius turns out to be approxima...

  8. Convective organization in the super-parameterized community atmosphere model with constant surface temperature

    Science.gov (United States)

    Kuang, Z.

    2015-12-01

    Organization in a moist convecting atmosphere is investigated using the super-parameterized community atmosphere model (SPCAM) in aquaplanet setting with constant surface temperature, with and without planetary rotation. Without radiative and surface feedbacks, convective organization is dominated by convectively coupled gravity waves without planetary rotation and convectively coupled equatorial waves when there is planetary rotation. This behavior is well captured when the cloud resolving model (CRM) in SPCAM is replaced by its linear response function, computed following Kuang (2010), for the state of radiative convective equilibrium (RCE). With radiative feedback, however, convection self-aggregates, and with planetary rotation, the tropical zonal wavenumber-frequency spectrum features a red noise background. These behaviors in the presence of the radiative feedback are not captured when the CRM is replaced by its linear response function around the RCE state with radiative feedback included in the construction. Implications to organization in a moist convecting atmosphere will be discussed. Kuang, Z., Linear response functions of a cumulus ensemble to temperature and moisture perturbations and implication to the dynamics of convectively coupled waves, J. Atmos. Sci., 67, 941-962, (2010)

  9. An analytical model for the evolution of starless cores - I. The constant-mass case

    Science.gov (United States)

    Pattle, K.

    2016-07-01

    We propose an analytical model for the quasi-static evolution of starless cores confined by a constant external pressure, assuming that cores are isothermal and obey a spherically symmetric density distribution. We model core evolution for Plummer-like and Gaussian density distributions in the adiabatic and isothermal limits, assuming Larson-like dissipation of turbulence. We model the variation in the terms in the virial equation as a function of core characteristic radius, and determine whether cores are evolving towards virial equilibrium or gravitational collapse. We ignore accretion on to cores in the current study. We discuss the different behaviours predicted by the isothermal and adiabatic cases, and by our choice of index for the size-linewidth relation, and suggest a means of parametrizing the magnetic energy term in the virial equation. We model the evolution of the set of cores observed by Pattle et al. in the L1688 region of Ophiuchus in the `virial plane'. We find that not all virially bound and pressure-confined cores will evolve to become gravitationally bound, with many instead contracting to virial equilibrium with their surroundings, and find an absence of gravitationally dominated and virially unbound cores. We hypothesize a `starless core desert' in this quadrant of the virial plane, which may result from cores initially forming as pressure-confined objects. We conclude that a virially bound and pressure-confined core will not necessarily evolve to become gravitationally bound, and thus cannot be considered pre-stellar. A core can only be definitively considered pre-stellar (collapsing to form an individual stellar system) if it is gravitationally unstable.

  10. An ETAS model with varying productivity rates

    Science.gov (United States)

    Harte, D. S.

    2014-07-01

    We present an epidemic type aftershock sequenc (ETAS) model where the offspring rates vary both spatially and temporally. This is achieved by distinguishing between those space-time volumes where the interpoint space and time distances are small, and those where they are considerably larger. We also question the nature of the background component in the ETAS model. Is it simply a temporal boundary correction (t = 0) or does it represent an additional tectonic process not described by the aftershock component? The form of these stochastic models should not be considered to be fixed. As we accumulate larger and better earthquake catalogues, GPS data, strain rates, etc., we have the ability to ask more complex questions about the nature of the process. By fitting modified models consistent with such questions, we should gain a better insight into the earthquake process. Hence, we consider a sequence of incrementally modified ETAS type models rather than `the' ETAS model.

  11. High-accuracy measurements of OH(•) reaction rate constants and IR and UV absorption spectra: ethanol and partially fluorinated ethyl alcohols.

    Science.gov (United States)

    Orkin, Vladimir L; Khamaganov, Victor G; Martynova, Larissa E; Kurylo, Michael J

    2011-08-11

    Rate constants for the gas phase reactions of OH(•) radicals with ethanol and three fluorinated ethyl alcohols, CH(3)CH(2)OH (k(0)), CH(2)FCH(2)OH (k(1)), CHF(2)CH(2)OH (k(2)), and CF(3)CH(2)OH (k(3)) were measured using a flash photolysis resonance-fluorescence technique over the temperature range 220 to 370 K. The Arrhenius plots were found to exhibit noticeable curvature for all four reactions. The temperature dependences of the rate constants can be represented by the following expressions over the indicated temperature intervals: k(0)(220-370 K) = 5.98 × 10(-13)(T/298)(1.99) exp(+515/T) cm(3) molecule(-1) s(-1), k(0)(220-298 K) = (3.35 ± 0.06) × 10(-12) cm(3) molecule(-1) s(-1) [for atmospheric modeling purposes, k(0)(T) is essentially temperature-independent below room temperature, k(0)(220-298 K) = (3.35 ± 0.06) × 10(-12) cm(3) molecule(-1) s(-1)], k(1)(230-370 K) = 3.47 × 10(-14)(T/298)(4.49) exp(+977/T) cm(3) molecule(-1) s(-1), k(2)(220-370 K) = 3.87 × 10(-14)(T/298)(4.25) exp(+578/T) cm(3) molecule(-1) s(-1), and k(3)(220-370 K) = 2.48 × 10(-14)(T/298)(4.03) exp(+418/T) cm(3) molecule(-1) s(-1). The atmospheric lifetimes due to reactions with tropospheric OH(•) were estimated to be 4, 16, 62, and 171 days, respectively, under the assumption of a well-mixed atmosphere. UV absorption cross sections of all four ethanols were measured between 160 and 215 nm. The IR absorption cross sections of the three fluorinated ethanols were measured between 400 and 1900 cm(-1), and their global warming potentials were estimated.

  12. Photochemical properties of trans-1-chloro-3,3,3-trifluoropropene (trans-CHCl═CHCF3): OH reaction rate constant, UV and IR absorption spectra, global warming potential, and ozone depletion potential.

    Science.gov (United States)

    Orkin, Vladimir L; Martynova, Larissa E; Kurylo, Michael J

    2014-07-17

    Measurements of the rate constant for the gas-phase reactions of OH radicals with trans-1-chloro-3,3,3-trifluoropropene (trans-CHCl═CHCF3) were performed using a flash photolysis resonance-fluorescence technique over the temperature range 220-370 K. The reaction rate constant exhibits a noticeable curvature of the temperature dependence in the Arrhenius plot, which can be represented by the following expression: kt-CFP (220-370 K) = 1.025 × 10(-13) × (T/298)(2.29) exp(+384/T) cm(3 )molecule(-1) s(-1). The room-temperature rate constant was determined to be kt-CFP (298 K) = (3.29 ± 0.10) × 10(-13) cm(3) molecule(-1) s(-1), where the uncertainty includes both two standard errors (statistical) and the estimated systematic error. For atmospheric modeling purposes, the rate constant below room temperature can be represented by the following expression: kt-CFP (220-298 K) = (7.20 ± 0.46) × 10(-13) exp[-(237 ± 16)/T] cm(3) molecule(-1) s(-1). There was no difference observed between the rate constants determined at 4 kPa (30 Torr) and 40 kPa (300 Torr) at both 298 and 370 K. The UV and IR absorption cross sections of this compound were measured at room temperature. The atmospheric lifetime, global warming potential, and ozone depletion potential of trans-CHCl═CHCF3 were estimated.

  13. Model predictive control of servo motor driven constant pump hydraulic system in injection molding process based on neurodynamic optimization

    Institute of Scientific and Technical Information of China (English)

    Yong-gang PENG; Jun WANG; Wei WEI

    2014-01-01

    In view of the high energy consumption and low response speed of the traditional hydraulic system for an injection molding machine, a servo motor driven constant pump hydraulic system is designed for a precision injection molding process, which uses a servo motor, a constant pump, and a pressure sensor, instead of a common motor, a constant pump, a pressure pro-portion valve, and a flow proportion valve. A model predictive control strategy based on neurodynamic optimization is proposed to control this new hydraulic system in the injection molding process. Simulation results showed that this control method has good control precision and quick response.

  14. ECONOMETRIC MODELS FOR DETERMING THE EXCHANGE RATE

    Directory of Open Access Journals (Sweden)

    Mihaela BRATU

    2012-05-01

    Full Text Available The simple econometric models for the exchange rate, according to recent researches, generates the forecasts with the highest degree of accuracy. This type of models (Simultaneous Equations Model, MA(1 Procedure, Model with lagged variables is used to describe the evolution of the average exchange rate in Romanian in January 1991-March 2012 and to predict it on short run. The best forecasts, in terms of accuracy, on the forecasting horizon April-May 2012 were those based on a Simultaneous Equations Model that takes into account the Granger causality. An almost high degree of accuracy was gotten by combining the predictions based on MA(1 model with those based on the simultaneous equations model, when INV weighting scheme was applied (the forecasts are inversely weighted to their relative mean squared forecast error. The lagged variables Model provided the highest prediction errors. The importance of knowing the best exchange rate forecasts is related to the improvement of decision-making and the building of the monetary policy.

  15. Predicting pressure-dependent unimolecular rate constants using variational transition state theory with multidimensional tunneling combined with system-specific quantum RRK theory: a definitive test for fluoroform dissociation.

    Science.gov (United States)

    Bao, Junwei Lucas; Zhang, Xin; Truhlar, Donald G

    2016-06-22

    Understanding the falloff in rate constants of gas-phase unimolecular reaction rate constants as the pressure is lowered is a fundamental problem in chemical kinetics, with practical importance for combustion, atmospheric chemistry, and essentially all gas-phase reaction mechanisms. In the present work, we use our recently developed system-specific quantum RRK theory, calibrated by canonical variational transition state theory with small-curvature tunneling, combined with the Lindemann-Hinshelwood mechanism, to model the dissociation reaction of fluoroform (CHF3), which provides a definitive test for falloff modeling. Our predicted pressure-dependent thermal rate constants are in excellent agreement with experimental values over a wide range of pressures and temperatures. The present validation of our methodology, which is able to include variational transition state effects, multidimensional tunneling based on the directly calculated potential energy surface along the tunneling path, and torsional and other vibrational anharmonicity, together with state-of-the-art reaction-path-based direct dynamics calculations, is important because the method is less empirical than models routinely used for generating full mechanisms, while also being simpler in key respects than full master equation treatments and the full reduced falloff curve and modified strong collision methods of Troe.

  16. Direct estimation of the rate constant of the reaction ClO + HO2 → HOCl + O2 from SMILES atmospheric observations

    Directory of Open Access Journals (Sweden)

    K. Kuribayashi

    2013-05-01

    Full Text Available Diurnal variations of ClO, HO2, and HOCl were simultaneously observed by the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES between 12 October 2009 and 21 April 2010. These were the first global observations of the diurnal variation of HOCl in the upper atmosphere. A major reaction to produce HOCl is ClO + HO2 → HOCl + O2 (R1 in extra polar region. A model study suggested that in the mesosphere during night this is the only reaction influencing the amount of HOCl and ClO. The evaluation of the pure reaction period, where only reaction (R1 occurred in Cly chemical system, was performed by the consistency between two reaction rates, HOCl production and ClO loss, from SMILES observation data. It turned out that the SMILES data at the pressure level of 0.28 hPa (about 58 km during night (between local time 18:30 and 04:00 in the autumn mid-latitude region (20–40° February–April 2010 were suitable for the estimation of k1. The rate constant was obtained to be k1(245 K = 7.73 ± 0.26 (1σ [× 10–12 cm3/molecule s] from SMILES atmospheric observations. This result was consistent with that from both the laboratory experiment and the ab initio calculations for similar low-pressure conditions. The 1σ precision of k1 obtained was 2–10 times better than those of previous laboratory measurements.

  17. Modelling the Central Constant Emission X-ray component of eta Carinae

    CERN Document Server

    Russell, Christopher M P; Hamaguchi, Kenji; Madura, Thomas I; Owocki, Stanley P; Hillier, D John

    2016-01-01

    The X-ray emission of $\\eta$ Carinae shows multiple features at various spatial and temporal scales. The central constant emission (CCE) component is centred on the binary and arises from spatial scales much smaller than the bipolar Homunculus nebula, but likely larger than the central wind--wind collision region between the stars as it does not vary over the $\\sim$2-3 month X-ray minimum when it can be observed. Using large-scale 3D smoothed particle hydrodynamics (SPH) simulations, we model both the colliding-wind region between the stars, and the region where the secondary wind collides with primary wind ejected from the previous periastron passage. The simulations extend out to one hundred semimajor axes and make two limiting assumptions (strong coupling and no coupling) about the influence of the primary radiation field on the secondary wind. We perform 3D radiative transfer calculations on the SPH output to synthesize the X-ray emission, with the aim of reproducing the CCE spectrum. For the preferred pr...

  18. Successive Generations in a Rat Model Respond Differently to a Constant Obesogenic Environment.

    Science.gov (United States)

    Tait, Alice H; Raubenheimer, David; Green, Mark P; Cupido, Cinda L; Gluckman, Peter D; Vickers, Mark H

    2015-01-01

    Research has shown that if a mother experiences a transitory perturbation to her environment during pregnancy or lactation, there are transgenerational consequences often involving a disordered metabolic phenotype in first generation offspring with recovery across subsequent generations. In contrast, little is known about the nature of the transgenerational response of offspring when a mother experiences a perturbation that is not transitory but instead persists across generations. Our study, using a rat model, subjected the parental generation to a change in environment and concomitant shift from a grain-based to obesogenic diets to generate an adipose phenotype in first generation offspring emulating a common scenario in human urbanisation and migration. We then investigated whether the obese phenotype was stable across generations when maintained in the transitioned environment, and whether dietary macronutrient balance affected the response. We found that second and third generation offspring had a reduced body fat to lean mass ratio and a reduced appetite relative to first generation offspring, irrespective of dietary macronutrient balance. The trajectory of this response is suggestive of a reduction in chronic disease risk across generations. This is one of the first studies, to our knowledge, to investigate the transgenerational response following parental transition to a persistent obesogenic environment, and to demonstrate that successive generations respond differently to this constant environment.

  19. A new analysis of fine-structure constant measurements and modelling errors from quasar absorption lines

    CERN Document Server

    Wilczynska, Michael R; King, Julian A; Murphy, Michael T; Bainbridge, Matthew B; Flambaum, Victor V

    2015-01-01

    We present an analysis of 23 absorption systems along the lines of sight towards 18 quasars in the redshift range of $0.4 \\leq z_{abs} \\leq 2.3$ observed on the Very Large Telescope (VLT) using the Ultraviolet and Visual Echelle Spectrograph (UVES). Considering both statistical and systematic error contributions we find a robust estimate of the weighted mean deviation of the fine-structure constant from its current, laboratory value of $\\Delta\\alpha/\\alpha=\\left(0.22\\pm0.23\\right)\\times10^{-5}$, consistent with the dipole variation reported in Webb et al. and King et al. This paper also examines modelling methodologies and systematic effects. In particular we focus on the consequences of fitting quasar absorption systems with too few absorbing components and of selectively fitting only the stronger components in an absorption complex. We show that using insufficient continuum regions around an absorption complex causes a significant increase in the scatter of a sample of $\\Delta\\alpha/\\alpha$ measurements, th...

  20. Successive Generations in a Rat Model Respond Differently to a Constant Obesogenic Environment.

    Directory of Open Access Journals (Sweden)

    Alice H Tait

    Full Text Available Research has shown that if a mother experiences a transitory perturbation to her environment during pregnancy or lactation, there are transgenerational consequences often involving a disordered metabolic phenotype in first generation offspring with recovery across subsequent generations. In contrast, little is known about the nature of the transgenerational response of offspring when a mother experiences a perturbation that is not transitory but instead persists across generations. Our study, using a rat model, subjected the parental generation to a change in environment and concomitant shift from a grain-based to obesogenic diets to generate an adipose phenotype in first generation offspring emulating a common scenario in human urbanisation and migration. We then investigated whether the obese phenotype was stable across generations when maintained in the transitioned environment, and whether dietary macronutrient balance affected the response. We found that second and third generation offspring had a reduced body fat to lean mass ratio and a reduced appetite relative to first generation offspring, irrespective of dietary macronutrient balance. The trajectory of this response is suggestive of a reduction in chronic disease risk across generations. This is one of the first studies, to our knowledge, to investigate the transgenerational response following parental transition to a persistent obesogenic environment, and to demonstrate that successive generations respond differently to this constant environment.

  1. Hyperon puzzle and the RMF model with scaled hadron masses and coupling constants

    CERN Document Server

    Kolomeitsev, E E; Voskresensky, D N

    2015-01-01

    The equation of state of cold baryonic matter is studied within a relativistic mean-field model with hadron masses and coupling constants depending on a scalar field. We demonstrate that if the effective nucleon mass stops to decrease with a density increase at densities $n>n_*>n_0$, where $n_0$ is the nuclear saturation density, the equation of state stiffens for these densities and the limiting neutron star mass increases. The stabilization of the nucleon mass can be realised if in the equation of motion for the scalar mean-field there appear a term sharply varying in a narrow vicinity of the field value corresponding to the density $n_*$. We show several possible realizations of this mechanism getting sufficiently stiff equations of state. The appearance of hyperons in dense neutron star interiors is accounted for. The obtained equations of state remain sufficiently stiff if the reduction of the $\\phi$ meson mass is incorporated. Thereby, the hyperon puzzle can be resolved.

  2. Dielectronic recombination rate in statistical model

    OpenAIRE

    Demura A.V.; Leontyev D.S.; Lisitsa V.S.; Shurigyn V.A.

    2017-01-01

    The dielectronic recombination rate of multielectron ions was calculated by means of the statistical approach. It is based on an idea of collective excitations of atomic electrons with the local plasma frequencies. These frequencies are expressed via the Thomas-Fermi model electron density distribution. The statistical approach provides fast computation of DR rates that are compared with the modern quantum mechanical calculations. The results are important for current studies of thermonuclear...

  3. Dielectronic recombination rate in statistical model

    Directory of Open Access Journals (Sweden)

    Demura A.V.

    2017-01-01

    Full Text Available The dielectronic recombination rate of multielectron ions was calculated by means of the statistical approach. It is based on an idea of collective excitations of atomic electrons with the local plasma frequencies. These frequencies are expressed via the Thomas-Fermi model electron density distribution. The statistical approach provides fast computation of DR rates that are compared with the modern quantum mechanical calculations. The results are important for current studies of thermonuclear plasmas with the tungsten impurities.

  4. Dielectronic recombination rate in statistical model

    Science.gov (United States)

    Demura, A. V.; Leontyev, D. S.; Lisitsa, V. S.; Shurigyn, V. A.

    2016-12-01

    The dielectronic recombination rate of multielectron ions was calculated by means of the statistical approach. It is based on an idea of collective excitations of atomic electrons with the local plasma frequencies. These frequencies are expressed via the Thomas-Fermi model electron density distribution. The statistical approach provides fast computation of DR rates that are compared with the modern quantum mechanical calculations. The results are important for current studies of thermonuclear plasmas with the tungsten impurities.

  5. On the evolution of accretion disc flow in cataclysmic variables. III - Outburst properties of constant and uniform-alpha model discs

    Science.gov (United States)

    Lin, D. N. C.; Faulkner, J.; Papaloizou, J.

    1985-01-01

    Attention is given to the stability and evolution of some simple accretion disk models in which the viscosity is prescribed by an ad hoc, uniform-alpha model. Emphasis is placed on systems in which the mass input rate from the secondary to the disk around the primary is assumed to be constant, although initial calculations with variable mass input rates are also performed. Time-dependent visual magnitude light curves constructed for cataclysmic binaries with a range of disk size, primary mass and mass input rate, and viscosity magnitude, are compared with the observed properties of various cataclysmic variable subclasses. The results obtained indicate that the observational differences between novae and dwarf novae may be due to mass input rate differences. The present models can reproduce the gross observational features of U-Gem-type dwarf nova outbursts.

  6. Upper limits for the rate constants of the reactions of CF3O2 and CF3O radicals with ozone at 295 K

    DEFF Research Database (Denmark)

    Nielsen, O.J.; Sehested, J.

    1993-01-01

    Using the pulse radiolysis UV absorption technique and subsequent simulations of experimental absorption transients at 254 and 276 nm, upper limits of the rate constants for the reactions of CF3O2 and CF3O radicals with ozone were determined at 295 K, CF3O2+O3-->CF3O+2O2 (4), CF3O+O3-->CF3O2+O2 (......). The upper limits were derived as k4 ozone depletion by hydrofluorocarbons.......Using the pulse radiolysis UV absorption technique and subsequent simulations of experimental absorption transients at 254 and 276 nm, upper limits of the rate constants for the reactions of CF3O2 and CF3O radicals with ozone were determined at 295 K, CF3O2+O3-->CF3O+2O2 (4), CF3O+O3-->CF3O2+O2 (5...

  7. Study of Antigravity in an F(R Model and in Brans-Dicke Theory with Cosmological Constant

    Directory of Open Access Journals (Sweden)

    V. K. Oikonomou

    2014-01-01

    Full Text Available We study antigravity, that is, having an effective gravitational constant with a negative sign, in scalar-tensor theories originating from F(R theory and in a Brans-Dicke model with cosmological constant. For the F(R theory case, we obtain the antigravity scalar-tensor theory in the Jordan frame by using a variant of the Lagrange multipliers method and we numerically study the time dependent effective gravitational constant. As we will demonstrate by using a specific F(R model, although there is no antigravity in the initial model, it might occur or not in the scalar-tensor counterpart, mainly depending on the parameter that characterizes antigravity. Similar results hold true in the Brans-Dicke model.

  8. Study of Antigravity in an F(R) Model and in Brans-Dicke Theory with Cosmological Constant

    CERN Document Server

    Oikonomou, V K

    2014-01-01

    We study antigravity, that is having an effective gravitational constant with a negative sign, in scalar-tensor theories originating from $F(R)$-theory and in a Brans-Dicke model with cosmological constant. For the $F(R)$ theory case, we obtain the antigravity scalar-tensor theory in the Jordan frame by using a variant of the Lagrange multipliers method and we numerically study the time dependent effective gravitational constant. As we shall demonstrate by using a specific $F(R)$ model, although there is no antigravity in the initial model, it might occur or not in the scalar-tensor counterpart, mainly depending on the parameter that characterizes antigravity. Similar results hold true in the Brans-Dicke model.

  9. Modeling the variability of firing rate of retinal ganglion cells.

    Science.gov (United States)

    Levine, M W

    1992-12-01

    Impulse trains simulating the maintained discharges of retinal ganglion cells were generated by digital realizations of the integrate-and-fire model. If the mean rate were set by a "bias" level added to "noise," the variability of firing would be related to the mean firing rate as an inverse square root law; the maintained discharges of retinal ganglion cells deviate systematically from such a relationship. A more realistic relationship can be obtained if the integrate-and-fire mechanism is "leaky"; with this refinement, the integrate-and-fire model captures the essential features of the data. However, the model shows that the distribution of intervals is insensitive to that of the underlying variability. The leakage time constant, threshold, and distribution of the noise are confounded, rendering the model unspecifiable. Another aspect of variability is presented by the variance of responses to repeated discrete stimuli. The variance of response rate increases with the mean response amplitude; the nature of that relationship depends on the duration of the periods in which the response is sampled. These results have defied explanation. But if it is assumed that variability depends on mean rate in the way observed for maintained discharges, the variability of responses to abrupt changes in lighting can be predicted from the observed mean responses. The parameters that provide the best fits for the variability of responses also provide a reasonable fit to the variability of maintained discharges.

  10. Parametric Regression Models Using Reversed Hazard Rates

    Directory of Open Access Journals (Sweden)

    Asokan Mulayath Variyath

    2014-01-01

    Full Text Available Proportional hazard regression models are widely used in survival analysis to understand and exploit the relationship between survival time and covariates. For left censored survival times, reversed hazard rate functions are more appropriate. In this paper, we develop a parametric proportional hazard rates model using an inverted Weibull distribution. The estimation and construction of confidence intervals for the parameters are discussed. We assess the performance of the proposed procedure based on a large number of Monte Carlo simulations. We illustrate the proposed method using a real case example.

  11. Upper limit on the rate constant for isotope exchange between molecular oxygen and ozone at 298 K

    Science.gov (United States)

    Anderson, S. M.; Morton, J.; Mauersberger, K.

    1987-01-01

    The gas phase bimolecular isotope exchange reaction between molecular oxygen and ozone has been investigated directly for the first time. Its rate coefficient is found to be less than 2 x 10 to the -25th cu cm/sec at 298 K, over six orders of magnitude below recent estimates. Much faster exchange was observed over condensed ozone at 77 K, suggesting isotopic scrambling is catalyzed under these conditions. The low rate coefficient implies that homogeneous exchange between ground state oxygen and ozone molecules cannot play a significant role in heavy ozone chemistry.

  12. Learning Rates and Known-to-Unknown Flash-Card Ratios: Comparing Effectiveness While Holding Instructional Time Constant

    Science.gov (United States)

    Forbes, Bethany E.; Skinner, Christopher H.; Black, Michelle P.; Yaw, Jared; Booher, Joshua; Delisle, Jean

    2013-01-01

    Using alternating treatments designs, we compared learning rates across 2 computer-based flash-card interventions (3?min each): a traditional drill intervention with 15 unknown words and an interspersal intervention with 12 known words and 3 unknown words. Each student acquired more words under the traditional drill intervention. Discussion…

  13. Model of the universe including dark energy accounted for by both a quintessence field and a (negative) cosmological constant

    Science.gov (United States)

    Cardenas, Rolando; Gonzalez, Tame; Leiva, Yoelsy; Martin, Osmel; Quiros, Israel

    2003-04-01

    In this work we present a model of the universe in which dark energy is modeled explicitly with both a dynamical quintessence field and a cosmological constant. Our results confirm the possibility of a future collapsing universe (for a given region of the parameter space), which is necessary for a consistent formulation of both string and quantum field theories. The predictions of this model for distance modulus of supernovae are similar to those of the standard ΛCDM model.

  14. Modelling growth of Penicillium expansum and Aspergillus niger at constant and fluctuating temperature conditions.

    Science.gov (United States)

    Gougouli, Maria; Koutsoumanis, Konstantinos P

    2010-06-15

    The growth of Penicillium expansum and Aspergillus niger, isolated from yogurt production environment, was investigated on malt extract agar with pH=4.2 and a(w)=0.997, simulating yogurt, at isothermal conditions ranging from -1.3 to 35 degrees C and from 5 to 42.3 degrees C, respectively. The growth rate (mu) and (apparent) lag time (lambda) of the mycelium growth were modelled as a function of temperature using a Cardinal Model with Inflection (CMI). The results showed that the CMI can describe successfully the effect of temperature on fungal growth within the entire biokinetic range for both isolates. The estimated values of the CMI for mu were T(min)=-5.74 degrees C, T(max)=30.97 degrees C, T(opt)=22.08 degrees C and mu(opt)=0.221 mm/h for P. expansum and T(min)=10.13 degrees C, T(max)=43.13 degrees C, T(opt)=31.44 degrees C, and mu(opt)=0.840 mm/h for A. niger. The cardinal values for lambda were very close to the respective values for mu indicating similar temperature dependence of the growth rate and the lag time of the mycelium growth. The developed models were further validated under fluctuating temperature conditions using various dynamic temperature scenarios. The time-temperature conditions studied included single temperature shifts before or after the end of the lag time and continuous periodic temperature fluctuations. The prediction of growth at changing temperature was based on the assumption that after a temperature shift the growth rate is adopted instantaneously to the new temperature, while the lag time was predicted using a cumulative lag approach. The results showed that when the temperature shifts occurred before the end of the lag, they did not cause any significant additional lag and the observed total lag was very close to the cumulative lag predicted by the model. In experiments with temperature shifts after the end of the lag time, accurate predictions were obtained when the temperature profile included temperatures which were inside the

  15. Absolute rate constants for the reaction of NO3 radicals with a series of dienes at 295 K

    DEFF Research Database (Denmark)

    Ellermann, T.; Nielsen, O.J.; Skov, H.

    1992-01-01

    The rate constants for the reaction of NO3 radicals with a series of 7 dienes, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, trans-1,3-pentadiene, cis-1,3-pentadiene, trans,trans-2,4-hexadiene, and 1,3-cyclohexadiene, were measured at 295 K and at a total pressure of 1 atm. The rate consta...... were obtained using the absolute technique of pulse radiolysis combined with kinetic UV-VIS spectroscopy. The results are discussed in terms of reactivity trends and previous literature data....

  16. Direct determination of rate constants for coupling between aromatic radical anions and alkyl and benzyl radicals by laser-flash photolysis

    DEFF Research Database (Denmark)

    Lund, T.; Christensen, P.; Wilbrandt, Robert Walter

    2003-01-01

    Coupling rates between the radicals methyl, n-, sec-, tert-butyl and benzyl (R-.) and the aromatic radical anions of 1,4-dicyanonaphthalene, 9,10-dicyanoanthracene and fluorenone (A(-.)) have been obtained using a new laser-flash photolysis method. The radicals R-. and the radical anions A(-.) were...... generated by a photoinduced electron transfer reaction between the aromatic compound A and the alkyl or benzyl triphenylborate anion RB(Ph)(3)(-). For the first time the rate constants of the coupling reaction between methyl and benzyl radicals with aromatic radical anions have been obtained. For all...... of the radicals and the structure and standard potentials of the aromatic radical anions....

  17. The Transfer of Atoms, Ions and Molecular Groups in Solution. Part 3. Monte Carlo Methods for the Evaluation of Rate Constants.

    Science.gov (United States)

    1983-10-31

    tranal. Sykes and Bell) pp. 342-51 12. J. M. McKinley and P. P. Schmidt, Che. Phys. Letters, submitted. and ref. (4) 13. G. Arfken . Mathematical Methods ...Transfer of Atoms, Ions and Molecular Groups Nf in Solution.III. Monte Carlo methods for the evaluation of rate constants I by P. P. Schmidt Prepared...technical Groups in Solution.poilI. Monte Carlo methods for the evaluation of rate a. PERFORMING ORG. REPORT NUMBER congtant 7, AUTHOR(e) B. CONTRACT Oft

  18. Structural effects on the beta-scission reaction of alkoxyl radicals. Direct measurement of the absolute rate constants for ring opening of benzocycloalken-1-oxyl radicals.

    Science.gov (United States)

    Bietti, Massimo; Lanzalunga, Osvaldo; Salamone, Michela

    2005-02-18

    [reaction: see text] The absolute rate constants for beta-scission of a series of benzocycloalken-1-oxyl radicals and of the 2-(4-methylphenyl)-2-butoxyl radical have been measured directly by laser flash photolysis. The benzocycloalken-1-oxyl radicals undergo ring opening with rates which parallel the ring strain of the corresponding cycloalkanes. In the 1-X-indan-1-oxyl radical series, ring opening is observed when X = H, Me, whereas exclusive C-X bond cleavage occurs when X = Et. The factors governing the fragmentation regioselectivity are discussed.

  19. Investigation of the Flow Rate Effect Upstream of the Constant-Geometry Throttle on the Gas Mass Flow

    Directory of Open Access Journals (Sweden)

    Yu. M. Timofeev

    2016-01-01

    Full Text Available The turbulent-flow throttles are used in pneumatic systems and gas-supply ones to restrict or measure gas mass flow. It is customary to install the throttles in joints of pipelines (in teejoints and cross tees or in joints of pipelines with pneumatic automation devices Presently, in designing the pneumatic systems and gas-supply ones a gas mass flow through a throttle is calculated by a known equation derived from the Saint-Venant-Vantсel formula for the adiabatic flow of ideal gas through a nozzle from an unrestrictedly high capacity tank. Neglect of gas velocity at the throttle inlet is one of the assumptions taken in the development of the above equation. As may be seen in practice, in actual systems the diameters of the throttle and the pipe wherein it is mounted can be commensurable. Neglect of the inlet velocity therewith can result in an error when determining the required throttle diameter in design calculation and a flow rate in checking calculation, as well as when measuring a flow rate in the course of the test. The theoretical study has revealed that the flow velocity at the throttle inlet is responsible for two parameter values: the outlet flow velocity and the critical pressure ratio, which in turn determine the gas mass flow value. To calculate the gas mass flow, the dependencies are given in the paper, which allow taking into account the flow rate at the throttle inlet. The analysis of obtained dependencies has revealed that the degree of influence of inlet flow rate upon the mass flow is defined by two parameters: pressure ratio at the throttle and open area ratio of the throttle and the pipe wherein it is mounted. An analytical investigation has been pursued to evaluate the extent to which the gas mass flow through the throttle is affected by the inlet flow rate. The findings of the investigation and the indications for using the present dependencies are given in this paper. By and large the investigation allowed the

  20. Fracture in Westerly granite under AE feedback and constant strain rate loading: Nucleation, quasi-static propagation, and the transition to unstable fracture propagation

    Science.gov (United States)

    Thompson, B.D.; Young, R.P.; Lockner, D.A.

    2006-01-01

    New observations of fracture nucleation are presented from three triaxial compression experiments on intact samples of Westerly granite, using Acoustic Emission (AE) monitoring. By conducting the tests under different loading conditions, the fracture process is demonstrated for quasi-static fracture (under AE Feedback load), a slowly developing unstable fracture (loaded at a 'slow' constant strain rate of 2.5 ?? 10-6/s) and an unstable fracture that develops near instantaneously (loaded at a 'fast' constant strain rate of 5 ?? 10-5/s). By recording a continuous ultrasonic waveform during the critical period of fracture, the entire AE catalogue can be captured and the exact time of fracture defined. Under constant strain loading, three stages are observed: (1) An initial nucleation or stable growth phase at a rate of ??? 1.3 mm/s, (2) a sudden increase to a constant or slowly accelerating propagation speed of ??? 18 mm/s, and (3) unstable, accelerating propagation. In the ??? 100 ms before rupture, the high level of AE activity (as seen on the continuous record) prevented the location of discrete AE events. A lower bound estimate of the average propagation velocity (using the time-to-rupture and the existing fracture length) suggests values of a few m/s. However from a low gain acoustic record, we infer that in the final few ms, the fracture propagation speed increased to 175 m/s. These results demonstrate similarities between fracture nucleation in intact rock and the nucleation of dynamic instabilities in stick slip experiments. It is suggested that the ability to constrain the size of an evolving fracture provides a crucial tool in further understanding the controls on fracture nucleation. ?? Birkha??user Verlag, Basel, 2006.