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.
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.
2010-01-01
Pacific Northwest National Laboratory (PNNL) has been tasked by Bechtel National Inc. (BNI) on the River Protection Project-Hanford Tank Waste Treatment and Immobilization Plant (RPP-WTP) project to perform research and development activities to resolve technical issues identified for the Pretreatment Facility (PTF). The Pretreatment Engineering Platform (PEP) was designed, constructed and operated as part of a plan to respond to issue M12, “Undemonstrated Leaching Processes” of the External Flowsheet Review Team (EFRT) issue response plan.( ) The PEP is a 1/4.5-scale test platform designed to simulate the WTP pretreatment caustic leaching, oxidative leaching, ultrafiltration solids concentration, and slurry washing processes. The PEP replicates the WTP leaching processes using prototypic equipment and control strategies. The PEP also includes non-prototypic ancillary equipment to support the core processing. The work described in this report addresses caustic leaching under WTP conditions, based on tests performed with a Hanford waste simulant. Because gibbsite leaching kinetics are rapid (gibbsite is expected to be dissolved by the time the final leach temperature is reached), boehmite leach kinetics are the main focus of the caustic-leach tests. The tests were completed at the laboratory-scale and in the PEP, which is a 1/4.5-scale mock-up of key PTF process equipment. Two laboratory-scale caustic-leach tests were performed for each of the PEP runs. For each PEP run, unleached slurry was taken from the PEP caustic-leach vessel for one batch and used as feed for both of the corresponding laboratory-scale tests.
Caustic Leaching of Hanford Tank S-110 Sludge
Energy Technology Data Exchange (ETDEWEB)
Lumetta, Gregg J.; Carson, Katharine J.; Darnell, Lori P.; Greenwood, Lawrence R.; Hoopes, Francis V.; Sell, Richard L.; Sinkov, Sergey I.; Soderquist, Chuck Z.; Urie, Michael W.; Wagner, John J.
2001-10-31
This report describes the Hanford Tank S-110 sludge caustic leaching test conducted in FY 2001 at the Pacific Northwest National Laboratory. The data presented here can be used to develop the baseline and alternative flowsheets for pretreating Hanford tank sludge. The U.S. Department of Energy funded the work through the Efficient Separations and Processing Crosscutting Program (ESP; EM50).
Washing and Caustic Leaching of Hanford Tank Sludge: Results of FY 1998 Studies
Energy Technology Data Exchange (ETDEWEB)
GJ Lumetta; BM Rapko; J Liu; DJ Temer; RD Hunt
1998-12-11
Sludge washing and parametric caustic leaching tests were performed on sludge samples tiom five Hanford tanks: B-101, BX-1 10, BX-112, C-102, and S-101. These studies examined the effects of both dilute hydroxide washing and caustic leaching on the composition of the residual sludge solids. ` Dilute hydroxide washing removed from <1 to 25% of the Al, -20 to 45% of the Cr, -25 to 97% of the P, and 63 to 99% of the Na from the Hdord tank sludge samples examined. The partial removal of these elements was likely due to the presence of water-soluble sodium salts of aluminate, chromate, hydroxide, nitrate, nitrite, and phosphate, either in the interstitial liquid or as dried salts.
Mechanism of Phosphorus Removal from Hanford Tank Sludge by Caustic Leaching
Energy Technology Data Exchange (ETDEWEB)
Lumetta, Gregg J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
2008-03-05
Two experiments were conducted to explore the mechanism by which phosphorus is removed from Hanford tank sludge by caustic leaching. In the first experiment, a series of phosphate salts were treated with 3 M NaOH under conditions prototypic of the actual leaching process to be performed in the Waste Treatment and Immobilization Plant (WTP). The phosphates used were aluminum phosphate, bismuth phosphate, chromium(III) phosphate, and β-tri-calcium phosphate; all of these phases have previously been determined to exist in Hanford tank sludge. The leachate solution was sampled at selected time intervals and analyzed for the specific metal ion involved (Al, Bi, Ca, or Cr) and for P (total and as phosphate). The solids remaining after completion of the caustic leaching step were analyzed to determine the reaction product. In the second experiment, the dependence of P removal from bismuth phosphate was examined as a function of the hydroxide ion concentration. It was anticipated that a plot of log[phosphate] versus log[hydroxide] would provide insight into the phosphorus-removal mechanism. This report describes the test activities outlined in Section 6.3.2.1, Preliminary Investigation of Phosphate Dissolution, in Test Plan TP-RPP-WTP-467, Rev.1. The objectives, success criteria, and test conditions of Section 6.3.2.1 are summarized here.
Washing and caustic leaching of Hanford tank sludges: results of FY 1996 studies. Revision
International Nuclear Information System (INIS)
During the past few years, the primary mission at the US Department of Energy's Hanford Site has changed from producing plutonium to restoring the environment. Large volumes of high-level radioactive wastes (HLW), generated during past Pu production and other operations, are stored in underground tanks on site. The current plan for remediating the Hanford tank farms consists of waste retrieval, pretreatment, treatment (immobilization), and disposal. The HLW will be immobilized in a borosilicate glass matrix and then disposed of in a geologic repository. Because of the expected high cost of HLW vitrification and geologic disposal, pretreatment processes will be implemented to reduce the volume of borosilicate glass produced in disposing of the tank wastes. On this basis, a pretreatment plan is being developed. This report describes the sludge washing and caustic leaching test conducted to create a Hanford tank sludge pretreatment flowsheet
Washing and caustic leaching of Hanford tank sludges: Results of FY 1995 studies
International Nuclear Information System (INIS)
During the past few years, the primary mission at the US Department of Energy's Hanford Site has changed from producing plutonium to environmental restoration. Large volumes of high-level radioactive wastes (HLW), generated during past Pu production and other operations, are stored in underground tanks on site. The current plan for remediating the Hanford tank farms consists of waste retrieval, pretreatment, treatment (immobilization), and disposal. The HLW will be immobilized in a borosilicate glass matrix; the resulting glass canisters will then be disposed of in a geologic repository. Because of the expected high cost of HLW immobilization and disposal, pretreatment processes will be implemented to reduce the volume of borosilicate glass produced in processing the tank wastes. This document describes sludge washing and caustic leaching tests conducted in FY 1995 at the Pacific Northwest Laboratory (PNL) at the request of Westinghouse Hanford Company. These tests were performed using sludges from seven Hanford waste tanks -- B-111, BX-107, C-103, S-104, SY-103, T-104, and T-111. The primary and secondary types of waste stored in each of these tanks are given in Table 1. 1. The data collected in this effort will be used to support the March 1998 Tri-Party Agreement decision on the extent of pretreatment to be performed on the Hanford tank sludges (Ecology, EPA, and DOE 1994)
International Nuclear Information System (INIS)
In 1993, the Department of Energy (DOE) selected the enhanced sludge washing (ESW) process as the baseline for pretreatment of Hanford tank sludges. The ESW process uses a series of water washes and caustic leaches to separate nonradioactive components such as aluminum, chromium, and phosphate from the high-level waste sludges. If the ESW process is successful, the volume of immobilized high-level waste will be significantly reduced. The tests on the sludge from Hanford Tank S-101 focused on the effects of process variables such as sodium hydroxide concentration (1 and 3 M), temperature (70 and 95 C), and leaching time (5, 24, 72, and 168 h) on the efficacy of the ESW process with realistic liquid-to-solid ratios. Another goal of this study was to evaluate the effectiveness of water washes on a sludge sample from hanford Tank C-103. The final objective of this study was to test potential process control monitors during the water washes and caustic leaches with actual sludge. Both 137Cs activity and conductance were measured for each of the water washes and caustic leaches. Experimental procedures, a discussion of results, conclusions and recommendations are included in this report
Energy Technology Data Exchange (ETDEWEB)
Hunt, R.D.; Collins, J.L.; Chase, C.W.
1998-07-01
In 1993, the Department of Energy (DOE) selected the enhanced sludge washing (ESW) process as the baseline for pretreatment of Hanford tank sludges. The ESW process uses a series of water washes and caustic leaches to separate nonradioactive components such as aluminum, chromium, and phosphate from the high-level waste sludges. If the ESW process is successful, the volume of immobilized high-level waste will be significantly reduced. The tests on the sludge from Hanford Tank S-101 focused on the effects of process variables such as sodium hydroxide concentration (1 and 3 M), temperature (70 and 95 C), and leaching time (5, 24, 72, and 168 h) on the efficacy of the ESW process with realistic liquid-to-solid ratios. Another goal of this study was to evaluate the effectiveness of water washes on a sludge sample from hanford Tank C-103. The final objective of this study was to test potential process control monitors during the water washes and caustic leaches with actual sludge. Both {sup 137}Cs activity and conductance were measured for each of the water washes and caustic leaches. Experimental procedures, a discussion of results, conclusions and recommendations are included in this report.
FLOTATION RATE CONSTANT MODEL FOR FINE COAL
Institute of Scientific and Technical Information of China (English)
LuMaixi; CaiZhang; TaoYoujun; KuangYali
1996-01-01
The density of fine coal has a major effect on the value of its floxation rate constant. The collector dose can increase the flotation rate of fine coal, especially for low ash coal, but the effect for gangue is not notable. The flotation rate of gangue is mainly governed by the water entrainment. A coal flotation rate constant model has been developed.
Energy Technology Data Exchange (ETDEWEB)
Guzman-Leong, Consuelo E.; Bredt, Ofelia P.; Burns, Carolyn A.; Daniel, Richard C.; Su, Yin-Fong; Geeting, John GH; Golovich, Elizabeth C.; Josephson, Gary B.; Kurath, Dean E.; Sevigny, Gary J.; Smith, Dennese M.; Valdez, Patrick LJ; Yokuda, Satoru T.; Young, Joan K.
2009-12-04
Pacific Northwest National Laboratory (PNNL) was tasked by Bechtel National Inc. (BNI) on the River Protection Project-Hanford Tank Waste Treatment and Immobilization Plant (RPP-WTP) project to perform research and development activities to resolve technical issues identified for the Pretreatment Facility (PTF). The Pretreatment Engineering Platform (PEP) was designed and constructed and operated as part of a plan to respond to issue M12, “Undemonstrated Leaching Processes.”(a) The PEP, located in the Process Engineering Laboratory-West (PDLW) located in Richland, Washington, is a 1/4.5-scale test platform designed to simulate the WTP pretreatment caustic leaching, oxidative leaching, ultrafiltration solids concentration, and slurry washing processes. The PEP replicates the WTP leaching processes using prototypic equipment and control strategies. The PEP also includes non-prototypic ancillary equipment to support the core processing.
Theophylline: constant-rate infusion predictions.
Mesquita, C A; Sahebjami, H; Imhoff, T; Thomas, J P; Myre, S A
1984-01-01
This study was undertaken to evaluate a method of prospectively estimating appropriate aminophylline infusion rates in acutely ill, hospitalized patients with bronchospasm. Steady-state serum theophylline concentrations (Css), clearances (Cl), and half-lives (t1/2) were estimated by the Chiou method using serum concetrantions obtained 1 and 6 h after the start of a constant-rate intravenous aminophylline infusion in 10 male patients averaging 57 years of age. Using an enzyme-multiplied immunoassay (EMIT) system for theophylline analysis, pharmacokinetic estimations were excellent for Css (r = 0.9103, p less than 0.01) and Cl (r = 0.9750, p less than 0.01). The mean estimation errors were 9.4% (range 0.8-21.5) for Css and 12.3% (range 1.3-28.0) for Cl. There was no correlation between patient age and Cl. This method is useful for rapidly individualizing aminophylline therapy in patients with acute bronchospasm. PMID:6740734
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.
Phototransformation Rate Constants of PAHs Associated with Soot Particles
Kim, Daekyun; Young, Thomas M.; Anastasio, Cort
2012-01-01
Photodegradation is a key process governing the residence time and fate of polycyclic aromatic hydrocarbons (PAHs) in particles, both in the atmosphere and after deposition. We have measured photodegradation rate constants of PAHs in bulk deposits of soot particles illuminated with simulated sunlight. The photodegradation rate constants at the surface (k0p), the effective diffusion coefficients (Deff), and the light penetration depths (z0.5) for PAHs on soot layers of variable thickness were ...
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.
Li, Xiaogai; von Holst, Hans; Kleiven, Svein
2013-01-01
A 3D finite element (FE) model has been developed to study the mean intracranial pressure (ICP) response during constant-rate infusion using linear poroelasticity. Due to the uncertainties in the poroelastic constants for brain tissue, the influence of each of the main parameters on the transient ICP infusion curve was studied. As a prerequisite for transient analysis, steady-state simulations were performed first. The simulated steady-state pressure distribution in the brain tissue for a normal cerebrospinal fluid (CSF) circulation system showed good correlation with experiments from the literature. Furthermore, steady-state ICP closely followed the infusion experiments at different infusion rates. The verified steady-state models then served as a baseline for the subsequent transient models. For transient analysis, the simulated ICP shows a similar tendency to that found in the experiments, however, different values of the poroelastic constants have a significant effect on the infusion curve. The influence of the main poroelastic parameters including the Biot coefficient α, Skempton coefficient B, drained Young's modulus E, Poisson's ratio ν, permeability κ, CSF absorption conductance C(b) and external venous pressure p(b) was studied to investigate the influence on the pressure response. It was found that the value of the specific storage term S(ε) is the dominant factor that influences the infusion curve, and the drained Young's modulus E was identified as the dominant parameter second to S(ε). Based on the simulated infusion curves from the FE model, artificial neural network (ANN) was used to find an optimised parameter set that best fit the experimental curve. The infusion curves from both the FE simulation and using ANN confirmed the limitation of linear poroelasticity in modelling the transient constant-rate infusion. PMID:22452461
High-temperature rate constant measurements for OH+xylenes
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.
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.
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.
Recent developments in semiclassical mechanics: eigenvalues and reaction rate constants
Energy Technology Data Exchange (ETDEWEB)
Miller, W.H.
1976-04-01
A semiclassical treatment of eigenvalues for a multidimensional non-separable potential function and of the rate constant for a chemical reaction with an activation barrier is presented. Both phenomena are seen to be described by essentially the same semiclassical formalism, which is based on a construction of the total Hamiltonian in terms of the complete set of ''good'' action variables (or adiabatic invariants) associated with the minimum in the potential energy surface for the eigenvalue case, or the saddle point in the potential energy surface for the case of chemical reaction.
Balanced anesthesia and constant-rate infusions in horses.
Valverde, Alexander
2013-04-01
Balanced anesthetic techniques are commonly used in equine patients, and include the combination of a volatile anesthetic with at least one injectable anesthetic throughout the maintenance period. Injectable anesthetics used in balanced anesthesia include the α2-agonists, lidocaine, ketamine, and opioids, and those with muscle-relaxant properties such as benzodiazepines and guaifenesin. Administration of these injectable anesthetics is best using constant-rate infusions based on the pharmacokinetics of the drug, which allows steady-state concentrations and predictable pharmacodynamic actions. This review summarizes the different drug combinations used in horses, and provides calculated recommended doses based on the pharmacokinetics of individual drugs. PMID:23498047
Rate Constant Calculation for Thermal Reactions Methods and Applications
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
Interpretation of the temperature dependence of equilibrium and rate constants.
Winzor, Donald J; Jackson, Craig M
2006-01-01
The objective of this review is to draw attention to potential pitfalls in attempts to glean mechanistic information from the magnitudes of standard enthalpies and entropies derived from the temperature dependence of equilibrium and rate constants for protein interactions. Problems arise because the minimalist model that suffices to describe the energy differences between initial and final states usually comprises a set of linked equilibria, each of which is characterized by its own energetics. For example, because the overall standard enthalpy is a composite of those individual values, a positive magnitude for DeltaH(o) can still arise despite all reactions within the subset being characterized by negative enthalpy changes: designation of the reaction as being entropy driven is thus equivocal. An experimenter must always bear in mind the fact that any mechanistic interpretation of the magnitudes of thermodynamic parameters refers to the reaction model rather than the experimental system. For the same reason there is little point in subjecting the temperature dependence of rate constants for protein interactions to transition-state analysis. If comparisons with reported values of standard enthalpy and entropy of activation are needed, they are readily calculated from the empirical Arrhenius parameters. PMID:16897812
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.
The air-kerma rate constant of 192Ir.
Ninković, M M; Raiĉevìć, J J
1993-01-01
The air-kerma rate constant gamma delta (and its precursors), as one of the basic radiation characteristics of 192Ir, was determined by many authors. Analysis of accessible data on this quantity led us to the conclusion that published data strongly disagree. That is the reason we calculated this quantity on the basis of our and many other authors' gamma-ray spectral data and the latest data for mass energy-transfer coefficients for air. In this way, a value was obtained for gamma delta of 30.0 +/- 0.9 a Gy m2 s-1 Bq-1 for an unshielded 192Ir source and 27.8 +/- 0.9 a Gy m2s -1Bq-1 for a standard packaged radioactive source taking into account attenuation of gamma rays in the platinum source wall. PMID:8416220
DeMore, W.; Wilson, E., Jr.
1998-01-01
Relative rate experiments were used to measure the rate constant and temperature dependence of the reaction of OH radicals with 2-fluoropropane (HFC-281ea), using ethane, propane, ethyl chloride as reference standards.
Rotzoll, K.; El-Kadi, A. I.; Gingerich, S.B.
2007-01-01
In recent years the ground-water demand of the population of the island of Maui, Hawaii, has significantly increased. To ensure prudent management of the ground-water resources, an improved understanding of ground-water flow systems is needed. At present, large-scale estimations of aquifer properties are lacking for Maui. Seven analytical methods using constant-rate and variable-rate withdrawals for single wells provide an estimate of hydraulic conductivity and transmissivity for 103 wells in central Maui. Methods based on constant-rate tests, although not widely used on Maui, offer reasonable estimates. Step-drawdown tests, which are more abundantly used than other tests, provide similar estimates as constant-rate tests. A numerical model validates the suitability of analytical solutions for step-drawdown tests and additionally provides an estimate of storage parameters. The results show that hydraulic conductivity is log-normally distributed and that for dike-free volcanic rocks it ranges over several orders of magnitude from 1 to 2,500 m/d. The arithmetic mean, geometric mean, and median values of hydraulic conductivity are respectively 520, 280, and 370 m/d for basalt and 80, 50, and 30 m/d for sediment. A geostatistical approach using ordinary kriging yields a prediction of hydraulic conductivity on a larger scale. Overall, the results are in agreement with values published for other Hawaiian islands. ?? 2007 American Water Resources Association.
Kurylo, M. J.; Cornett, K. D.; Murphy, J. L.
1982-01-01
The rate constant for the reaction of hydroxyl radicals with nitric acid in the 225-443 K temperature range has been measured by means of the flash photolysis resonance fluorescence technique. Above 300 K, the rate constant levels off in a way that can only be explained by the occurrence of two reaction channels, of which one, operative at low temperatures, proceeds through the formation of an adduct intermediate. The implications of these rate constant values for stratospheric reaction constants is discussed.
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
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)
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.
DeMore, W.; Bayes, K.
1998-01-01
Relative rate experiements were used to measure rate constants and temperature denpendencies of the reactions of OH with propane, n-butane, n-pentane, n-hexane, cyclopropane, cyclobutane, cyclopentane, and dimethyl ether.
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...
International Nuclear Information System (INIS)
The complex formation and redox decomposition of several hydroxo complexes that form in the Ce4+ - SO42- - R(OH)m systems, where R(OH)m (m = 3, 5, 6) is glycerol, xylitol, and sorbitol, respectively, were studied spectrophotometrically, pH metrically, and kinetically at the ionic strength I = 2 with the pH of the sulfate background in the range of 1.7-3.4 and temperatures of 20.0-23.0 deg C. The stability constants of the [CeOHHxL]3-x (L = R(OH)m) complexes, the ligand speciation, and the rate constants of the intramolecular redox decomposition of the complexes were determined in the sulfate background. The apparent stabilization of the +4 oxidation state of cerium in the specified complexes is demonstrated
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
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.
DeMore, W.B.
1996-01-01
Relative rate experiments are used to measure rate constants and temperature dependencies of the reactions of OH with CH3F (41), CH2FCl (31), CH2BrCl (30B1), CH2Br2 (3OB2), CHBr3 (2OB3), CF2BrCHFCl (123aBl(alpha)), and CF2ClCHCl2 (122). Rate constants for additional compounds of these types are estimated using an empirical rate constant estimation method which is based on measured rate constants for a wide range of halocarbons. The experimental data are combined with the estimated and previously reported rate constants to illustrate the effects of F, Cl, and Br substitution on OH rate constants for a series of 19 halomethanes and 25 haloethanes. Application of the estimation technique is further illustrated for some higher hydrofluorocarbons (HFCs), including CHF2CF2CF2CF2H (338pcc), CF3CHFCHFCF2CF3 (43-10mee), CF3CH2CH2CF3 (356ffa), CF3CH2CF2CH2CF3 (458mfcf), CF3CH2CHF2 (245fa), and CF3CH2CF2CH3 (365mfc). The predictions are compared with literature data for these compounds.
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...
Ion-quadrupole effects in thermal energy ion-molecule collision rate constants
Kosmas, A.M.
1985-01-01
A simplified version of the Averaged Quadrupole Orientation (AQO) theory is attempted, by taking into account the adiabatic invariance approximation, to investigate the effect of the ionquadrupolar molecule interaction on thermal energy reaction rate constant. The theory is formulated in terms of an orientation averaged potential energy function and predicts a significant increase in the capture rate constant over the Langevin value for molecules with large quadrupole moments and small polari...
Rate constants for the reactions of hydroxyl and hydroperoxyl radicals with ozone.
Demore, W. B.
1973-01-01
Chain decomposition of ozone by hydroxyl and hydroperoxyl radicals has been observed. The rate constant at 300 K for OH + O3 yielding HO2 + O2 is eight times ten to the -14th power cubic centimeters per second. The rate constant for HO2 + O3 yielding OH + 2O2 is three times ten to the -15th power cubic centimeters per second. These results have implications concerning stratospheric ozone.
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.
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.
DEFF Research Database (Denmark)
Harrod, Steven; Kelton, W. David
2006-01-01
with piecewise-constant instantaneous rate functions, a capability that has been implemented in commercial simulation software. They test these algorithms in C programs and make comparisons of accuracy, speed, and variability across disparate rate functions and microprocessor architectures. Choice of optimal...... algorithm could not be predicted without knowledge of microprocessor architecture....
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.
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
K. Föller; B. Stelbrink; Hauffe, T.; Albrecht, C.; Wilke, T.
2015-01-01
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 modes are conceivable. Diversification rates may be constant over time, they may fluctuate, rates may be higher ...
K. Föller; B. Stelbrink; Hauffe, T.; Albrecht, C.; Wilke, T.
2015-01-01
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 ph...
A study on the jet characteristic by using of Coanda effect in constant expansion rate nozzle
Energy Technology Data Exchange (ETDEWEB)
Lee, Sak; Lee, Dong Won; Kwon, Soon Bum [Kyungpook National Univ., Daegu (Korea, Republic of); Kim, Byung Ji [Catholic Sangji College, Andong (Korea, Republic of)
2005-07-01
Jets issuing from a conventional nozzle and convergent nozzles of a constant expansion rates and a certain normal using an annular slit are compared to investigate the characteristics of the 3 jets. In experiments, to compare the characteristics between jets, the nozzle exit mean velocity is fixed as 90m/s. The pressures along the jet axis and radial directions is measured by scanning valve system moving with 3-axis auto-traverse unit, and the velocity distribution can be obtained by calculation from the measured static and total pressures. To obtain the highly stable and convergency jets, a nozzle has to be designed with an annular slit connected to an conical cylinder, furthermore, the flow through a constant expansion rate nozzle using annular slit is the most probable. And the pressure drop along the nozzle for the constant expansion rate nozzle is small.
Accurate quantum thermal rate constants for the three-dimensional H+H2 reaction
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.
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.
Ion-quadrupole effects in thermal energy ion-molecule collision rate constants
International Nuclear Information System (INIS)
A simplified version of the Average Quadrupole Orientation (AQO) theory is attempted, by taking into account the adiabatic invariance approximation, to investigate the effect of the ion-quadrupolar molecule interaction on thermal energy reaction rate constant. The theory is formulated in terms of an orientation averaged potential energy function and predicts a significant increase in the capture rate constant over the Langevin value for molecules with large quadrupole moments and small polarizabilities. The results of the theory are compared to various experimental data and predictions of other theories
An Empirical Rate Constant Based Model to Study Capacity Fading in Lithium Ion Batteries
Directory of Open Access Journals (Sweden)
Srivatsan Ramesh
2015-01-01
Full Text Available A one-dimensional model based on solvent diffusion and kinetics to study the formation of the SEI (solid electrolyte interphase layer and its impact on the capacity of a lithium ion battery is developed. The model uses the earlier work on silicon oxidation but studies the kinetic limitations of the SEI growth process. The rate constant of the SEI formation reaction at the anode is seen to play a major role in film formation. The kinetics of the reactions for capacity fading for various battery systems are studied and the rate constants are evaluated. The model is used to fit the capacity fade in different battery systems.
Estimation of the reaction rate constant of HOCl by SMILES observation
Kuribayashi, Kouta; Kasai, Yasuko; Sato, Tomohiro; Sagawa, Hideo
2012-07-01
Hypochlorous acid, HOCl plays an important role to link the odd ClOx and the odd HOx in the atmospheric chemistry with the reaction: {ClO} + {HO_{2}} \\longrightarrow {HOCl} + {O_{2}} Quantitative understanding of the rate constant of the reaction (1.1) is essential for understanding the ozone loss in the mid-latitude region because of a view point of its rate controlling role in the ozone depletion chemistry. Reassessment of the reaction rate constant was pointed out from MIPAS/Envisat observations (von Clarmann et al., 2011) and balloon-borne observations (Kovalenko et al., 2007). Several laboratory studies had been reported, although the reaction rate constants have large uncertainties, as k{_{HOCl}} = (1.75 ± 0.52) × 10^{-12} exp[(368 ± 78)/T] (Hickson et al., 2007), and large discrepancies (Hickson et al., 2007;Stimpfle et al., 1979). Moreover, theoretical ab initio studies pointed out the pressure dependence of the reaction (1.1) (Xu et al., 2003). A new high-sensitive remote sensing technology named Superconducting SubMillimeter-wave Limb-Emission Sounder (SMILES) on the International Space Station (ISS) had observed diurnal variations of HOCl in the upper stratosphere/lower mesosphere (US/LM) region for the first time. ClO and HO_{2} were slso observed simultaneously with HOCl. SMILES performed the observations between 12^{{th}} October 2009 and 21^{{th}} April 2010. The latitude coverage of SMILES observation is normally 38°S-65°N. The altitude region of HOCl observation is about 28-70 km. We estimated the time period in which the reaction (1.1) becomes dominant in the ClO_{y} diurnal chemistry in US/LM. The reaction rate constant was directly estimated by decay of [ClO] and [HO_{2}] amounts in that period. The derived reaction rate constant represented well the increase of [HOCl] amount.
Wang, P-H; De Sancho, D; Best, R B; Blumberger, J
2016-01-01
The diffusion of ligands to actives sites of proteins is essential to enzyme catalysis and many cellular signaling processes. In this contribution we review our recently developed methodology for calculation of rate constants for diffusion and binding of small molecules to buried protein active sites. The diffusive dynamics of the ligand obtained from molecular dynamics simulation is coarse grained and described by a Markov state model. Diffusion and binding rate constants are then obtained either from the reactive flux formalism or by fitting the time-dependent population of the Markov state model to a phenomenological rate law. The method is illustrated by applications to diffusion of substrate and inhibitors in [NiFe] hydrogenase, CO-dehydrogenase, and myoglobin. We also discuss a recently developed sensitivity analysis that allows one to identify hot spots in proteins, where mutations are expected to have the strongest effects on ligand diffusion rates. PMID:27497172
Apparent rate constant mapping using hyperpolarized [1-(13) C]pyruvate
DEFF Research Database (Denmark)
Khegai, O.; Schulte, R. F.; Janich, M. A.;
2014-01-01
-up of downstream metabolites from the pyruvate substrate) and (ii) an effective decay rate (summarizing signal depletion due to repetitive excitation, T1-relaxation and backward conversion). The presented spectral and kinetic quantification were experimentally verified in vitro and in vivo using hyperpolarized [1......) and suppression of high perfusion regions with low conversion (e.g. blood vessels). Apparent build-up rate constant mapping provides a novel quantitative image contrast for the characterization of metabolic activity. Its possible implementation as a quantitative standard will be subject to further studies...... frequencies are automatically estimated using a matching pursuit algorithm. Second, a time-discretized formulation of the two-site exchange kinetic model is used to quantify metabolite signal dynamics by two characteristic rate constants in the form of (i) an apparent build-up rate (quantifying the build...
Jongberg, Sisse; Lund, Marianne N; Pattison, David I; Skibsted, Leif H; Davies, Michael J
2016-05-15
Competitive kinetics were applied as a tool to determine apparent rate constants for the reduction of hypervalent haem pigment ferrylmyoglobin (MbFe(IV)O) by proteins and phenols in aqueous solution of pH 7.4 and I=1.0 at 25°C. Reduction of MbFe(IV)O by a myofibrillar protein isolate (MPI) from pork resulted in kMPI=2.2 ± 0.1 × 10(4)M(-1)s(-1). Blocking of the protein thiol groups on the MPI by N-ethylmaleimide (NEM) markedly reduced this rate constant to kMPI-NEM=1.3 ± 0.4 × 10(3)M(-1)s(-1) consistent with a key role for the Cys residues on MPI as targets for haem protein-mediated oxidation. 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 extracts, though possible confounding reactions need to be considered. These kinetic data suggest that small molar excesses of some plant extracts relative to the MPI thiol concentration should afford significant protection against MbFe(IV)O-mediated oxidation. PMID:26775941
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...
DEFF Research Database (Denmark)
Jongberg, Sisse; Lund, Marianne Nissen; Pattison, David I.;
2016-01-01
Competitive kinetics were applied as a tool to determine apparent rate constants for the reduction of hypervalent haem pigment ferrylmyoglobin (MbFe(IV)=O) by proteins and phenols in aqueous solution of pH 7.4 and I = 1.0 at 25 °C. Reduction of MbFe(IV)=O by a myofibrillar protein isolate (MPI...
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.
Mechanism and thermal rate constant for the gas-phase ozonolysis of acenaphthylene in the atmosphere
International Nuclear Information System (INIS)
Due to its prevalent presence, it is critical to clarify the atmospheric fate of acenaphthylene (Ary). In this paper, the reaction mechanism of the gas-phase ozonolysis of Ary was investigated by using quantum chemistry methods. Possible reaction pathways were discussed, and the theoretical results were compared with the available experimental data. The rate constants of the crucial elementary reactions were determined by the Rice–Ramsperger–Kassel–Marcus (RRKM) theory. The main products include secondary ozonide, naphthalene-1,8-dicarbaldehyde, 1,8-naphthalic anhydride, oxaacenaphthylene-2-one, 1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, and α-hydroxyhydroperoxide. The reaction of the unsaturated cyclo-pentafused ring with O3 is the dominant pathway. The overall rate constant of the O3 addition reaction is 5.31 × 10−16 cm3 molecule−1 s−1 at 298 K and 1 atm. The atmospheric lifetime of Ary determined by O3 is about 0.75 h. This work provides a comprehensive investigation of the ozonolysis of Ary and should help to understand its atmospheric fate. - Highlights: • We studied a comprehensive mechanism of O3-initiated oxidation of Ary. • The overall rate constant of O3 addition reactions is 5.31 × 10−16 cm3 molecule−1 s−1. • The atmospheric lifetime of Ary determined by O3 is about 0.75 h. • The rate constants of the crucial elementary steps were evaluated
Institute of Scientific and Technical Information of China (English)
Hai-tao Wang; Chang-jiang Hu; Yu-jing Mu; Yu-jie Zhang
2008-01-01
The rate constants of the reaction between hydroxyl radical (OH.) and dimethyl sulfide (DMS) were investigated by using the relative methods in air, N2, and O2. Strong influences of ground state oxygen O(3p) on DMS consumption were found by the photolysis of HONO and CH3ONO as OH- sources, and the rate constants obtained in these systems varied significantly. The rate constants of the reaction between DMS and OH- (generated by photolysis of H2O2) at room temperature were 8.56x 10-12, 11.31 x 10-12, and 4.50x10-12 cm3/(molecule·s), in air, O2, and N2, respectively. The temperature dependence of the rate constants for OH·with DMS over the temperature range of 287-338 K was also investigated in nitrogen and air, and the Arrhenius expression was obtained as follows: kair=(7.244-O.28)x10-13exp[(770.7±97.2)/T],kN2 =(3.40-4-0.15) X 10-11 exp[- (590.34-165.9)/T].
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 (eaq. 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 eaq 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.
Structural model for the dynamic buckling of a column under constant rate compression
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...
DEFF Research Database (Denmark)
Menné, Charlotte; Møller Sørensen, Tine; Siersma, Volkert;
2002-01-01
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...
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
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
Ab-Initio Based Computation of Rate Constants for Spin Forbidden Metalloprotein-Substrate Reactions
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.
Properties of human motor units after prolonged activity at a constant firing rate.
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.
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.
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 ...
Rate constant and mechanism for the reaction of hydroxyl radical with formic acid
Energy Technology Data Exchange (ETDEWEB)
Jolly, G.S.; McKenney, D.J.; Singleton, D.L.; Paraskevopoulos, G.; Bossard, A.R.
1986-11-20
The rate constants for the reaction of OH with the monomer and dimer of formic acid have been determined at 296 K by a laser photolysis-resonance absorption technique. The OH radicals were generated by photolysis of formic acid at 222 nm with a KrCl excimer laser and were monitored by time-resolved absorption at several resonance lines of the (0,0) band of the A/sup 2/..sigma../sup +/-X/sup 2/II transition. The rate constant for the monomer was found to be 2.95 x 10/sup 11/ cm/sup 3/ mol/sup -1/ s/sup -1/. The dimer is much less reactive. Experiments with small amounts of oxygen added indicate that H atoms are formed during the reaction. The results can be interpreted as indicating significantly more abstraction of hydrogen by OH from the -OH bond than from the -CH bond of formic acid.
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...
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(...
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.
Andreas Gansäuer; Meriam Seddiqzai; Tobias Dahmen; Rebecca Sure; Stefan Grimme
2013-01-01
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 furthe...
Mechanism and thermal rate constant for the gas-phase ozonolysis of acenaphthylene in the atmosphere
Energy Technology Data Exchange (ETDEWEB)
Dang, Juan; Shi, Xiangli; Zhang, Qingzhu, E-mail: zqz@sdu.edu.cn; Hu, Jingtian; Wang, Wenxing
2015-05-01
Due to its prevalent presence, it is critical to clarify the atmospheric fate of acenaphthylene (Ary). In this paper, the reaction mechanism of the gas-phase ozonolysis of Ary was investigated by using quantum chemistry methods. Possible reaction pathways were discussed, and the theoretical results were compared with the available experimental data. The rate constants of the crucial elementary reactions were determined by the Rice–Ramsperger–Kassel–Marcus (RRKM) theory. The main products include secondary ozonide, naphthalene-1,8-dicarbaldehyde, 1,8-naphthalic anhydride, oxaacenaphthylene-2-one, 1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, and α-hydroxyhydroperoxide. The reaction of the unsaturated cyclo-pentafused ring with O3 is the dominant pathway. The overall rate constant of the O{sub 3} addition reaction is 5.31 × 10{sup −16} cm{sup 3} molecule{sup −1} s{sup −1} at 298 K and 1 atm. The atmospheric lifetime of Ary determined by O{sub 3} is about 0.75 h. This work provides a comprehensive investigation of the ozonolysis of Ary and should help to understand its atmospheric fate. - Highlights: • We studied a comprehensive mechanism of O{sub 3}-initiated oxidation of Ary. • The overall rate constant of O{sub 3} addition reactions is 5.31 × 10{sup −16} cm{sup 3} molecule{sup −1} s{sup −1}. • The atmospheric lifetime of Ary determined by O{sub 3} is about 0.75 h. • The rate constants of the crucial elementary steps were evaluated.
Study on improving the turbidity measurement of the absolute coagulation rate constant.
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.
Wang, Shengkai; Davidson, David F; Hanson, Ronald K
2016-09-01
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. PMID:27523494
QSPR prediction of the hydroxyl radical rate constant of water contaminants.
Borhani, Tohid Nejad Ghaffar; Saniedanesh, Mohammadhossein; Bagheri, Mehdi; Lim, Jeng Shiun
2016-07-01
In advanced oxidation processes (AOPs), the aqueous hydroxyl radical (HO) acts as a strong oxidant to react with organic contaminants. The hydroxyl radical rate constant (kHO) is important for evaluating and modelling of the AOPs. In this study, quantitative structure-property relationship (QSPR) method is applied to model the hydroxyl radical rate constant for a diverse dataset of 457 water contaminants from 27 various chemical classes. The constricted binary particle swarm optimization and multiple-linear regression (BPSO-MLR) are used to obtain the best model with eight theoretical descriptors. An optimized feed forward neural network (FFNN) is developed to investigate the complex performance of the selected molecular parameters with kHO. Although the FFNN prediction results are more accurate than those obtained using BPSO-MLR, the application of the latter is much more convenient. Various internal and external validation techniques indicate that the obtained models could predict the logarithmic hydroxyl radical rate constants of a large number of water contaminants with less than 4% absolute relative error. Finally, the above-mentioned proposed models are compared to those reported earlier and the structural factors contributing to the AOP degradation efficiency are discussed. PMID:27124124
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
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...
Shock tube measurements of the rate constants for seven large alkanes+OH
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 R
Constant-quality constrained-rate allocation for FGS video coded bitstreams
Zhang, Xi Min; Vetro, Anthony; Shi, Yun-Qing; Sun, Huifang
2002-01-01
This paper proposes an optimal rate allocation scheme for Fine-Granular Scalability (FGS) coded bitstreams that can achieve constant quality reconstruction of frames under a dynamic rate budget constraint. In doing so, we also aim to minimize the overall distortion at the same time. To achieve this, we propose a novel R-D labeling scheme to characterize the R-D relationship of the source coding process. Specifically, sets of R-D points are extracted during the encoding process and linear interpolation is used to estimate the actual R-D curve of the enhancement layer signal. The extracted R-D information is then used by an enhancement layer transcoder to determine the bits that should be allocated per frame. A sliding window based rate allocation method is proposed to realize constant quality among frames. This scheme is first considered for a single FGS coded source, then extended to operate on multiple sources. With the proposed scheme, the rate allocation can be performed in a single pass, hence the complexity is quite low. Experimental results confirm the effectiveness of the proposed scheme under static and dynamic bandwidth conditions.
A constant-g_m and high-slew-rate operational amplifier for an LCD driver
Institute of Scientific and Technical Information of China (English)
Lai Xinquan; Li Xinlin; Ye Qiang; Yuan Bing; Li Xianrui
2009-01-01
To drive the backplane of a liquid crystal display device and achieve different kinds of grey levels, a high-slew-rate operational amplifier with constant-gin input stage is presented. A Zener-diode structure is inserted between the tails of the complementary input pairs to keep the gm of the input stage constant. A novel slew rate enhancement circuit is implemented to achieve a very high slew rate. The chip has been implemented in a 0.5μm CMOS process and the chip area of the operational amplifier circuit is 0.11 mm~2. The testing results indicate that in the 5-8 V input range, the maximum gm fluctuation is only 4.2%. The result exhibits a high slew rate of 111 V/μsand 102 V/μs for the rising and falling edges under a 20 pF capacitance load, and the low frequency gain is up to109 dB with a phase margin of 70 ℃.
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
Method for estimating S(N)1 rate constants: solvolytic reactivity of benzoates.
Matić, Mirela; Denegri, Bernard; Kronja, Olga
2012-10-19
Nucleofugalities of pentafluorobenzoate (PFB) and 2,4,6-trifluorobenzoate (TFB) leaving groups have been derived from the solvolysis rate constants of X,Y-substituted benzhydryl PFBs and TFBs measured in a series of aqueous solvents, by applying the LFER equation: log k = s(f)(E(f) + N(f)). The heterolysis rate constants of dianisylmethyl PFB and TFB, and those determined for 10 more dianisylmethyl benzoates in aqueous ethanol, constitute a set of reference benzoates whose experimental ΔG(‡) have been correlated with the ΔH(‡) (calculated by PCM quantum-chemical method) of the model epoxy ring formation. Because of the excellent correlation (r = 0.997), the method for calculating the nucleofugalities of substituted benzoate LGs have been established, ultimately providing a method for determination of the S(N)1 reactivity for any benzoate in a given solvent. Using the ΔG(‡) vs ΔH(‡) correlation, and taking s(f) based on similarity, the nucleofugality parameters for about 70 benzoates have been determined in 90%, 80%, and 70% aqueous ethanol. The calculated intrinsic barriers for substituted benzoate leaving groups show that substrates producing more stabilized LGs proceed over lower intrinsic barriers. Substituents on the phenyl ring affect the solvolysis rate of benzhydryl benzoates by both field and inductive effects. PMID:22973993
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...... range of data reported for this temperature range. The reactions on the NH2 + NO2 potential energy surface were studied using high level ab initio transition state theory (TST) based master equation methods, yielding a rate constant of k1,theory(T) = 7.5 × 10–12(T/K)−0.172 exp(687 K/T) cm3 molecule–1 s...... 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...
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.
Rate constants for chemical reactions in high-temperature nonequilibrium air
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.
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 of...... the radio link power consumption. Based on these description and analysis, we propose power consumption model. The power model was evaluated on the smartphone Nokia N900, which follows a 3GPP Release 5 and 6 supporting HSDPA/HSPA data bearers. Further we propose method of parameters selection for 3GPP...
DEFF Research Database (Denmark)
Rasmussen, Christian Lund; Skjøth-Rasmussen, Martin Skov; Jensen, Anker;
2005-01-01
3 at temperatures below 1000 K, while data at high temperature and low pressure only can be obtained from flames. In the present work, an estimate of the rate constant for the reaction at 1400 +/- 50 K and 20 Torr is obtained from analysis of the fuel-rich acetylene flame of Westmoreland, Howard......)/mol-s, with C6H5 + H as the dominating product channel. The estimated uncertainty in this value, a factor of 5, mainly originates from the uncertainty in the measured propargyl radical profile, although other experimental and kinetic uncertainties also contribute. (c) 2004 The Combustion Institute....... Published by Elsevier Inc. All rights reserved....
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.
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.
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.
Basic study on relationship between estimated rate constants and noise in FDG kinetic analysis
Energy Technology Data Exchange (ETDEWEB)
Kimura, Yuichi [Tokyo Medical and Dental Univ. (Japan). Inst. for Medical and Dental Engineering; Toyama, Hinako; Senda, Michio
1996-02-01
For accurate estimation of the rate constants in {sup 18}F-FDG dynamic study, the shape of the estimation function ({Phi}) is crucial. In this investigation, the relationship between the noise level in tissue time activity curve and the shape of the least squared estimation function which is the sum of squared error between a function of model parameters and a measured data is calculated in 3 parameter model of {sup 18}F-FDG. In the first simulation, by using actual plasma time activity curve, the true tissue curve was generated from known sets of rate constants ranging 0.05{<=}k{sub 1}{<=}0.15, 0.1{<=}k{sub 2}{<=}0.2 and 0.01{<=}k{sub 3}{<=}0.1 in 0.01 step. This procedure was repeated under various noise levels in the tissue time activity curve from 1 to 8% of the maximum value in the tissue activity. In the second simulation, plasma and tissue time activity curves from clinical {sup 18}F-FDG dynamic study were used to calculate the {Phi}. In the noise-free case, because the global minima is separated from neighboring local minimums, it was easy to find out the optimum point. However, with increasing noise level, the optimum point was buried in many neighboring local minima. Making it difficult to find out the optimum point. The optimum point was found within 20% of the convergence point by standard non-linear optimization method. The shape of {Phi} for the clinical data was similar to that with the noise level of 3 or 5% in the first simulation. Therefore direct search within the area extending 20% from the result of usual non-linear curve fitting procedure is recommended for accurate estimation of the constants. (author).
Development of a piezoelectric pump for a highly-precise constant flow rate
International Nuclear Information System (INIS)
Recently, piezoelectric-driven small and micro-sized pumps have been developed for applications in microfluidics, bio-chemistry diagnostics, fuel cell systems, drug delivery, and high-power electronics cooling, etc. This paper describes a piezoelectric pump using a multilayered piezoelectric actuator for highly-precise constant flow rate. The design, fabrication, and basic characteristics of the developed piezoelectric pump are summarized. The proposed pump consists of a pump housing, a multilayered piezoelectric actuator, a valve sheet and a single check valve for an inlet port. The overall dimensions of the fabricated piezoelectric pump are 25 mm x 25 mm x 53 mm. Pumping characteristics were experimentally investigated. The fabricated pump achieved a no-load flow rate of 110 ml/min and a maximum output power of 130 mW at an applied voltage of 150 Vpp and a driving frequency of 700 Hz.
Greene, Samuel M.; Shan, Xiao; Clary, David C.
2016-06-01
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.
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. PMID:27369506
Determination of Interfacial Charge-Transfer Rate Constants in Perovskite Solar Cells.
Pydzińska, Katarzyna; Karolczak, Jerzy; Kosta, Ivet; Tena-Zaera, Ramon; Todinova, Anna; Idígoras, Jesus; Anta, Juan A; Ziółek, Marcin
2016-07-01
A simple protocol to study the dynamics of charge transfer to selective contacts in perovskite solar cells, based on time-resolved laser spectroscopy studies, in which the effect of bimolecular electron-hole recombination has been eliminated, is proposed. Through the proposed procedure, the interfacial charge-transfer rate constants from methylammonium lead iodide perovskite to different contact materials can be determined. Hole transfer is faster for CuSCN (rate constant 0.20 ns(-1) ) than that for 2,2',7,7'-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene (spiro-OMeTAD; 0.06 ns(-1) ), and electron transfer is faster for mesoporous (0.11 ns(-1) ) than that for compact (0.02 ns(-1) ) TiO2 layers. Despite more rapid charge separation, the photovoltaic performance of CuSCN cells is worse than that of spiro-OMeTAD cells; this is explained by faster charge recombination in CuSCN cells, as revealed by impedance spectroscopy. The proposed direction of studies should be one of the key strategies to explore efficient hole-selective contacts as an alternative to spiro-OMeTAD. PMID:27253726
Voltage affects the dissociation rate constant of the m2 muscarinic receptor.
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Yair Ben Chaim
Full Text Available G-protein coupled receptors (GPCRs comprise the largest protein family and mediate the vast majority of signal transduction processes in the body. Until recently GPCRs were not considered to be voltage dependent. Newly it was shown for several GPCRs that the first step in GPCR activation, the binding of agonist to the receptor, is voltage sensitive: Voltage shifts the receptor between two states that differ in their binding affinity. Here we show that this shift involves the rate constant of dissociation. We used the m2 muscarinic receptor (m2R a prototypical GPCR and measured directly the dissociation of [(3H]ACh from m2R expressed Xenopus oocytes. We show, for the first time, that the voltage dependent change in affinity is implemented by voltage shifting the receptor between two states that differ in their rate constant of dissociation. Furthermore, we provide evidence that suggest that the above shift is achieved by voltage regulating the coupling of the GPCR to its G protein.
Gansäuer, Andreas; Seddiqzai, Meriam; Dahmen, Tobias; Sure, Rebecca; Grimme, Stefan
2013-01-01
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
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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.
Dang, Juan; Shi, Xiangli; Zhang, Qingzhu; Hu, Jingtian; Wang, Wenxing
2015-05-01
Due to its prevalent presence, it is critical to clarify the atmospheric fate of acenaphthylene (Ary). In this paper, the reaction mechanism of the gas-phase ozonolysis of Ary was investigated by using quantum chemistry methods. Possible reaction pathways were discussed, and the theoretical results were compared with the available experimental data. The rate constants of the crucial elementary reactions were determined by the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The main products include secondary ozonide, naphthalene-1,8-dicarbaldehyde, 1,8-naphthalic anhydride, oxaacenaphthylene-2-one, 1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, and α-hydroxyhydroperoxide. The reaction of the unsaturated cyclo-pentafused ring with O₃ is the dominant pathway. The overall rate constant of the O₃ addition reaction is 5.31×10(-16)cm(3)molecule(-1)s(-1) at 298 K and 1 atm. The atmospheric lifetime of Ary determined by O₃ is about 0.75 h. This work provides a comprehensive investigation of the ozonolysis of Ary and should help to understand its atmospheric fate. PMID:25679814
Protein balance and evaluation of velocity constant k (drained rate on syneresis of milk
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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%.
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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.
The Influence of Photolysis Rate Constants in Ozone Production for the Paso del Norte Region
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.
International Nuclear Information System (INIS)
The stress corrosion cracking behaviors in 22Cr5Ni2Mo duplex stainless steel have been investigated. The SCC has been examined by means of constant strain rate and constant load methods in terms of relevant electrochemical parameters in boiling 40% MgCl2 solution. The SCC susceptibility of the steel increased reversely proportional to strain rate and the critical strain rate was about 2.4 x 10-7/sec at open circuit. The steel had threshold stress of 29kg/mm2 and the critical cracking potential(ECC) of -410mV w.r.t. Ag/AgCl electrode immune to the SCC, and possessed superior SCC resistance compared to the austenite stainless steel. Cracks were initiated and propagated transgranularly without retarding effect by the austenite phase in high stress region
The Constant Growth Rate of the Bound-Zone Peculiar Velocity Profile
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...
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.
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
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...... and measurements of the radio link power consumption. Based on this description and analysis, we propose our power consumption model. The power model was evaluated on a smartphone Nokia N900, which follows 3GPP Release 5 and 6 supporting HSDPA/HSUPA data bearers. We also propose a method for parameter selection...... 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...
Table 5.1. Exchange current densities and rate constants in aqueous systems
Holze, R.
This document is part of Volume 9 `Electrochemistry', Subvolume A, of Landolt-Börnstein - Group IV `Physical Chemistry'. This document lists the exchange current densities and the electrode reaction rate constants of the following metallic electrodes in aqueous systems for various electrolyte reactions: silver (Ag), aluminium (Al), gold (Au), bismuth (Bi), carbon (C), cadmium (Cd), cobalt (Co), chromium (Cr), cesium (Cs), copper (Cu), iron (Fe), gallium (Ga), mercury (Hg), indium (In), iridium (Ir), potassium (K), lithium (Li), molybdenum (Mo), natrium (Na), niobium (Nb), nickel (Ni), lead (Pb), palladium (Pd), platinum (Pt), rubidium (Rb), rhodium (Rh), ruthenium (Ru), antimony (Sb), tin (Sn), tantalum (Ta), titanium (Ti), thallium (Tl), vanadium (V), tungsten (W), zinc (Zn). For each electrolyte reaction the electrolyte solution, the educt, product and concentration are specified along with the temperature of determination of the given values.
Energy Technology Data Exchange (ETDEWEB)
Jain, Amber; Subotnik, Joseph E., E-mail: subotnik@sas.upenn.edu [Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104 (United States)
2015-10-07
We investigate a simple approach to compute a non-adiabatic thermal rate constant using the fewest switches surface hopping (FSSH) dynamics. We study the effects of both decoherence (using our augmented-FSSH (A-FSSH) algorithm) and forbidden hops over a large range of parameters, including high and low friction regimes, and weak and strong electronic coupling regimes. Furthermore, when possible, we benchmark our results against exact hierarchy equations of motion results, where we usually find a maximum error of roughly a factor of two (at reasonably large temperatures). In agreement with Hammes-Schiffer and Tully, we find that a merger of transition state theory and surface hopping can be both accurate and efficient when performed correctly. We further show that detailed balance is followed approximately by A-FSSH dynamics.
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.
Determination of ultimate carbonaceous BOD and the specific rate constant (K1)
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.
Malavasi, Lais M; Greene, Stephen A; Gay, John M; Grubb, Tammy L
2016-01-01
Lidocaine is commonly used in ruminants but has an anecdotal history of being toxic to goats. To evaluate lidocaine's effects on selected cardiopulmonary parameters. Isoflurane-anesthetized adult goats (n = 24) undergoing abdominal surgery received a loading dose of lidocaine (2.5 mg/kg) over 20 min followed by constant-rate infusion of lidocaine (100 μg/kg/min); control animals received saline instead of lidocaine. Data collected at predetermined time points during the 60-min surgery included heart rate, mean arterial blood pressure, pO2, and pCO2. According to Welch 2-sample t tests, cardiopulmonary variables did not differ between groups. For example, after administration of the loading dose, goats in the lidocaine group had a mean heart rate of 88 ± 28 bpm, mean arterial blood pressure of 70 ± 19 mm Hg, pCO2 of 65 ± 13 mm Hg, and pO2 of 212 ± 99 mm Hg; in the saline group, these values were 90 ± 16 bpm, 76 ± 12 mm Hg, 61 ± 9 mm Hg, and 209 ± 83 mm Hg, respectively. One goat in the saline group required an additional dose of butorphanol. Overall our findings indicate that, at the dose provided, intravenous lidocaine did not cause adverse cardiopulmonary effects in adult goats undergoing abdominal surgery. Adding lidocaine infusion during general anesthesia is an option for enhancing transoperative analgesia in goats. PMID:27423150
Schroeder, T J; Myre, S A; Melvin, D B; Van der Bel-Kahn, J; Stephens, G W; Collins, J A; Wolf, R K; Brown, L L; Pesce, A J; First, M R
1989-01-01
Oral cyclosporine therapy immediately after heart transplantation is erratic and difficult to predict. The purpose of this study was to evaluate the relative efficacy and safety of cyclosporine when administered by constant-rate infusion immediately after transplantation. Nineteen patients (17 men and two women) aged 50 years (range 25 to 61 years) who weighed 71 +/- 9 kg, participated in the study and received cyclosporine, 7 to 10 mg/hr (117 +/- 15 micrograms/kg/hr). The infusions were initially maintained for 26 +/- 5 hours (range 18 to 42 hours) without adjustments in dosage. Whole blood samples were obtained at hourly intervals for the first 8 to 12 hours and then daily throughout the 7-day study period and were analyzed by high-performance liquid chromatography. Constant-rate cyclosporine infusion resulted in therapeutic blood levels (350 to 450 ng/ml) at 6 hours. These levels remained relatively steady throughout the 7-day infusion, requiring only minimal dosage adjustments. Kidney function was not altered significantly after 7 days of intravenous cyclosporine therapy as evidenced by a mean serum creatinine level of 1.3 mg/dl before therapy and 1.4 mg/dl after therapy. There, however, was a transient rise in serum creatinine level in most patients on the second or third day after transplantation that resolved without a reduction in cyclosporine dosage. The mean endomyocardial biopsy score at 1 week after transplantation was 0.1, and only four of the patients required additional immunosuppressive therapy to treat rejection during the first 6 weeks after transplantation.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:2647932
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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.
Sattar, Simeen
2011-01-01
Tris(1,10-phenanthroline)iron(II) is the basis of a suite of four experiments spanning 5 weeks. Students determine the rate law, activation energy, and equilibrium constant for the dissociation of the complex ion in acid solution and base dissociation constant for phenanthroline. The focus on one chemical system simplifies a daunting set of…
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.
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.
Effects of strain rate and identification of material constants for three automotive steels
Energy Technology Data Exchange (ETDEWEB)
Larour, P.; Bleck, W. [Technische Hochschule Aachen (Germany). Lehrstuhl und Inst. fuer Eisenhuettenkunde; Rusinek, A.; Klepaczko, J.R. [Metz Univ., 57 (France). Lab. de Physique et Technologie des Materiaux
2007-04-15
The main topic of this paper is an analysis of experimental results for three kinds of sheet steel: DP600, TRIP700 and H340LAD, which are used in the automotive industry. Such results were partly reported earlier. For comparison purposes the experimental results obtained at LPMM for an ES (DC05) mild steel have also been integrated in this paper. The tension tests were performed at room temperature in a relatively wide range of strain rates, that is from {proportional_to}3.0.10{sup -4}s{sup -1} up to {proportional_to}10{sup 3}s{sup -1}. Since at low and high strain rates two different specimen geometries were applied, detailed numerical analyses have been performed in order to estimate the geometry effects on the final true stress versus true strain characteristics at different strain rates. A relatively new constitutive relation of the form (anti {sigma}, anti {epsilon}{sup {rho}}, anti {epsilon}{sup {rho}},T) = O is applied. This constitutive relation in the form of the Mechanical Equation of State (MES), called also the RK relation, has been developed by Rusinek and Klepaczko. The main advantage introduced in the RK approach is the rate and temperature sensitivity of the strain hardening exponent, {eta}(anti {epsilon}{sup {rho}},T), a very important improvement in comparison to other constitutive formulations. It appears that introduction of the rate and temperature sensitivity of strain hardening is very important in all BCC and FCC micro-structures. In BCC structures the tangent modulus of anti {sigma}(anti {epsilon}{sup {rho}}) {sub anti} {sub {epsilon}}{sub ,T} may substantially decrease when strain rate increases. A special procedure was applied, according to Rusinek and Klepaczko, to determine the material constants for those three steels. An excellent fit to experimental data was obtained. Some FE calculations performed earlier on the energy absorbing profiles under impact with the RK constitutive relation have shown very good confirmation of experiment
Ren, Hongjiang; Li, Xiaojun
2015-12-01
The mechanism of H abstraction reactions for Isoflurane with the OH radical was investigated using density functional theory and G3(MP2) duel theory methods. The geometrical structures of all the species were fully optimised at B3LYP/6-311++G** level of theory. Thermochemistry data were obtained by utilising the high accurate model chemistry method G3(MP2) combined with the standard statistical thermodynamic calculations. Gibbs free energies were used for the reaction channels analysis. All the reaction channels were confirmed throughout the intrinsic reaction coordinate analysis. The results show that two channels were obtained, which correspond to P(1) and P(2) with the respective activation barriers of 63.03 and 54.82 kJ/mol. The rate constants for the two channels over a wide temperature range of 298.15-2000 K were predicted and the calculated data are in agreement with the experimental one. The results show that P(2) is the dominant reaction channel under 800 K and above 800 K, it can be found that P(1) will be more preferable reaction channel.
Measuring OH Reaction Rate Constants and Estimating the Atmospheric Lifetimes of Trace Gases.
Orkin, Vladimir; Kurylo, Michael
2015-04-01
Reactions with hydroxyl radicals and photolysis are the main processes dictating a compound's residence time in the atmosphere for a majority of trace gases. In case of very short-lived halocarbons their reaction with OH dictates both the atmospheric lifetime and active halogen release. Therefore, the accuracy of OH kinetic data is of primary importance for the comprehensive modeling of a compound's impact on the atmosphere, such as in ozone depletion (i.e., the Ozone Depletion Potential, ODP) and climate change (i.e., the Global Warming Potential, GWP), each of which are dependent on the atmospheric lifetime of the compound. We have demonstrated the ability to conduct very high accuracy determinations of OH reaction rate constants over the temperature range of atmospheric interest, thereby decreasing the uncertainty of kinetic data to 2-3%. The atmospheric lifetime of a well-mixed compound due to its reaction with tropospheric hydroxyl radicals can be estimated by using a simple scaling procedure that is based on the results of field observations of methyl chloroform concentrations and detailed modeling of the OH distribution in the atmosphere. The currently available modeling results of the atmospheric fate of various trace gases allow for an improved understanding of the ability and accuracy of simplified semi-empirical estimations of atmospheric lifetimes. These aspects will be illustrated in this presentation for a variety of atmospheric trace gases.
Jin, Xiaohui; Peldszus, Sigrid; Huck, Peter M
2015-11-01
Quantitative structure-property relationship (QSPR) models which predict hydroxyl radical rate constants (kOH) for a wide range of emerging micropollutants are a cost effective approach to assess the susceptibility of these contaminants to advanced oxidation processes (AOPs). A QSPR model for the prediction of kOH of emerging micropollutants from their physico-chemical properties was developed with special attention to model validation, applicability domain and mechanistic interpretation. In this study, 118 emerging micropollutants including those experimentally determined by the author and data collected from the literature, were randomly divided into the training set (n=89) and validation set (n=29). 951 DRAGON molecular descriptors were calculated for model development. The QSPR model was calibrated by applying forward multiple linear regression to the training set. As a result, 7 DRAGON descriptors were found to be important in predicting the kOH values which related to the electronegativity, polarizability, and double bonds, etc. of the compounds. With outliers identified and removed, the final model fits the training set very well and shows good robustness and internal predictivity. The model was then externally validated with the validation set showing good predictive power. The applicability domain of the model was also assessed using the Williams plot approach. Overall, the developed QSPR model provides a valuable tool for an initial assessment of the susceptibility of micropollutants to AOPs. PMID:26005810
Hsu, K.-J.; DeMore, W. B.
1995-01-01
Rate constants and temperature dependencies for the reactions of OH with CF3OCH3 (HFOC-143a), CF2HOCF2H (HFOC-134), and CF3OCF2H (HFOC-125) were studied using a relative rate technique in the temperature range 298-393 K. The following absolute rate constants were derived: HFOC-143a, 1.9E-12 exp(-1555/T); HFOC-134, 1.9E-12 exp(-2006/T); HFOC-125, 4.7E-13 exp(-2095/T). Units are cm(exp 3)molecule(exp -1) s(exp -1). Substituent effects on OH abstraction rate constants are discussed, and it is shown that the CF3O group has an effect on the OH rate constants similar to that of a fluorine atom. The effects are related to changes in the C-H bond energies of the reactants (and thereby the activation energies) rather than changes in the preexponential factors. On the basis of a correlation of rate constants with bond energies, the respective D(C-H) bond strengths in the three ethers are found to be 102, 104, and 106 kcal/mol, with an uncertainty of about 1 kcal/mol.
100 kV/2A three-phase constant-current repetitive-rate charging equipment
International Nuclear Information System (INIS)
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 1μF capacitor
100 kV/2A three-phase constant-current repetitive-rate charging equipment
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
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
Sun, Xiang; Geva, Eitan
2016-06-01
In this paper, we test the accuracy of the linearized semiclassical (LSC) expression for the equilibrium Fermi's golden rule rate constant for electronic transitions in the presence of non-Condon effects. We do so by performing a comparison with the exact quantum-mechanical result for a model where the donor and acceptor potential energy surfaces are parabolic and identical except for shifts in the equilibrium energy and geometry, and the coupling between them is linear in the nuclear coordinates. Since non-Condon effects may or may not give rise to conical intersections, both possibilities are examined by considering: (1) A modified Garg-Onuchic-Ambegaokar model for charge transfer in the condensed phase, where the donor-acceptor coupling is linear in the primary mode coordinate, and for which non-Condon effects do not give rise to a conical intersection; (2) the linear vibronic coupling model for electronic transitions in gas phase molecules, where non-Condon effects give rise to conical intersections. We also present a comprehensive comparison between the linearized semiclassical expression and a progression of more approximate expressions. The comparison is performed over a wide range of frictions and temperatures for model (1) and over a wide range of temperatures for model (2). The linearized semiclassical method is found to reproduce the exact quantum-mechanical result remarkably well for both models over the entire range of parameters under consideration. In contrast, more approximate expressions are observed to deviate considerably from the exact result in some regions of parameter space.
Sun, Xiang; Geva, Eitan
2016-06-28
In this paper, we test the accuracy of the linearized semiclassical (LSC) expression for the equilibrium Fermi's golden rule rate constant for electronic transitions in the presence of non-Condon effects. We do so by performing a comparison with the exact quantum-mechanical result for a model where the donor and acceptor potential energy surfaces are parabolic and identical except for shifts in the equilibrium energy and geometry, and the coupling between them is linear in the nuclear coordinates. Since non-Condon effects may or may not give rise to conical intersections, both possibilities are examined by considering: (1) A modified Garg-Onuchic-Ambegaokar model for charge transfer in the condensed phase, where the donor-acceptor coupling is linear in the primary mode coordinate, and for which non-Condon effects do not give rise to a conical intersection; (2) the linear vibronic coupling model for electronic transitions in gas phase molecules, where non-Condon effects give rise to conical intersections. We also present a comprehensive comparison between the linearized semiclassical expression and a progression of more approximate expressions. The comparison is performed over a wide range of frictions and temperatures for model (1) and over a wide range of temperatures for model (2). The linearized semiclassical method is found to reproduce the exact quantum-mechanical result remarkably well for both models over the entire range of parameters under consideration. In contrast, more approximate expressions are observed to deviate considerably from the exact result in some regions of parameter space. PMID:27369495
Seasonally constant field metabolic rates in free-ranging sugar gliders (Petaurus breviceps).
Quin, Darren G; Riek, Alexander; Green, Stuart; Smith, Andrew P; Geiser, Fritz
2010-03-01
Sugar gliders, Petaurus breviceps (average body mass: 120 g) like other small wild mammals must cope with seasonal changes in food availability and weather and therefore thermoregulatory and energetic challenges. To determine whether free-ranging sugar gliders, an arboreal marsupial, seasonally adjust their energy expenditure and water use, we quantified field metabolic rates (FMR) and water flux at a seasonal cool-temperate site in eastern Australia. Thirty six male and female sugar gliders were labelled with doubly labelled water for this purpose in spring, summer and autumn. The mean FMR was 159+/-6 kJ d(-1) (spring), 155+/-8 kJ d(-1) (summer), and 152+/-20 kJ d(-1) (autumn) and the mean FMR for the three seasons combined was 158+/-5 kJ d(-1) (equivalent to 1.33 kJ g(-)(1)d(-1) or 780 kJ kg(-0.)(75)d(-1)). The mean total body water was 83+/-2 g, equal to 68.5% of body weight. Mean water flux was 29+/-1 mL day(-1). Season, ambient temperature or sex did not affect any of the measured and estimated physiological variables, but body mass and total body water differed significantly between sexes and among seasons. Our study is the first to provide evidence for a constant FMR in a small mammal in three different seasons and despite different thermal conditions. This suggests that seasonal changes in climate are compensated for by behavioural and physiological adjustments such as huddling and torpor known to be employed extensively by sugar gliders in the wild.
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.
Minakata, Daisuke; Crittenden, John
2011-04-15
The hydroxyl radical (HO(•)) is a strong oxidant that reacts with electron-rich sites on organic compounds and initiates complex radical chain reactions in aqueous phase advanced oxidation processes (AOPs). Computer based kinetic modeling requires a reaction pathway generator and predictions of associated reaction rate constants. Previously, we reported a reaction pathway generator that can enumerate the most important elementary reactions for aliphatic compounds. For the reaction rate constant predictor, we develop linear free energy relationships (LFERs) between aqueous phase literature-reported HO(•) reaction rate constants and theoretically calculated free energies of activation for H-atom abstraction from a C-H bond and HO(•) addition to alkenes. The theoretical method uses ab initio quantum mechanical calculations, Gaussian 1-3, for gas phase reactions and a solvation method, COSMO-RS theory, to estimate the impact of water. Theoretically calculated free energies of activation are found to be within approximately ±3 kcal/mol of experimental values. Considering errors that arise from quantum mechanical calculations and experiments, this should be within the acceptable errors. The established LFERs are used to predict the HO(•) reaction rate constants within a factor of 5 from the experimental values. This approach may be applied to other reaction mechanisms to establish a library of rate constant predictions for kinetic modeling of AOPs. PMID:21410278
Transfer and quenching rate constants for XeF(B) and XeF(C) state in low vibrational levels
Brashears, H. C., Jr.; Setser, D. W.
1982-05-01
The relative XeF(B-X) and XeF(C-A) emission intensities from the steady-state vacuum ultraviolet photolysis of XeF2 have been used to measure the B-C transfer and quenching rate constants of XeF molecules in low vibrational levels. The rare gases N2, CF4, SF6, F2, NF3, CF3H, CF3Cl, HF, CO2, and XeF2 were investigated as buffer gases at room temperature. The transfer rate constants are much larger than the quenching rate constants for He, Ne, Ar, Kr, N2, CF4, and SF6. For Xe, NF3, CHF3, and CClF3 transfer is only 2-4 times faster than quenching and for F2, HF, and CO2 quenching is faster than B-C state transfer. Quenching for XeF(D) was studied for rare gases and for N2. No convincing evidence was found for three-body quenching by the rare gases and their quenching of the XeF(B, C) and XeF(D) states are reported as two-body processes for pressures below ˜5 atm. The XeF(D) quenching rate constants are of the same magnitude as the B-C state transfer rate constants. The photochemical and collisional (metastable rare gas atom) dissociative excitation of XeF2 and KrF2 are summarized in the Appendix.
Lurquin, Paul F.
2012-01-01
Electroporation parameters can be optimized by coupling RC constant values with the amount of electrical power dissipation in the electroporation medium. Electroporation efficiency increases more steeply with power at low power values.
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
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.
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...... particle concentration gradients inside -25 mu m droplets with a primary particle size of 0.2 mu m were observed. Unfortunately, the boundary condition at the droplet surface for the parabolic second-order PDE did not conserve the solid mass in the droplet, and the plots for the primary particle...
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...... particle concentration gradients inside -25 mu m droplets with a primary particle size of 0.2 mu m were observed. Unfortunately, the boundary condition at the droplet surface for the parabolic second-order PDE did not conserve the solid mass in the droplet, and the plots for the primary particle...
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.
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.
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...
Dissociation and rate constants of some human liver alcohol dehydrogenase isoenzymes.
Pietruszko, R; de Zalenski, C; Theorell, H
1976-01-01
ADH from human liver forms binary complexes with NADH, associated with a blue shift of the peak of the fluorescence emission of NADH. The wavelength shift is the same for all isoenzymes but the accompanying intensification of the fluorescence is different. The fluorescence is further increased by the formation of the very tight ternary enzyme-NADH-isobutyramide complexes. These properties are similar to those for the horse liver ADH, as well as the molecular weight of E=40 000 per active site of the dimer molecule (EE). "Stopped-flow" determined velocity constants (ER in equilibrium E+R) were found to be in good agreement with ethanol activity constants previously determined by activity measurement, confirming the validity of the ordered ternary complex mechanism also for the human ADH. No single isoenzyme activity as high as that reported by Mourad and Woronick or Drum has been found. PMID:184631
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.
Simmonds, Boris; Wang, Chun-Wei; Kapoor, Rakesh
2010-02-01
This document reports a novel method of measuring association rate constant (ka) for antibody-antigen interaction using evanescent wave-based combination tapered fiber-optic biosensor (CTFOB) dip-probes. The method was demonstrated by measuring association rate constant for bovine serum albumin (BSA) and anti-BSA antibody interaction. "Direct method" was used for detection; goat anti-BSA "capture" antibodies were immobilized on the probe surfaces while the antigen (BSA) was directly labeled with Alexa 488 dye. The probes were subsequently submerged in 3nM Labeled BSA in egg albumin (1 mg/ml). The fluorescence signal recorded was proportional to BSA anti-BSA conjugates and continuous signal was acquired suing a fiber optic spectrometer (Ocean Optics, Inc.). A 476 nm diode laser was use as an excitation source. Association constant was estimated from a plot of signal as a function of time. Measured association rate constant ka for the binding of BSA with anti-BSA at room temperature is (8.33 +/- 0.01) x 104 M-1s-1.
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
The muscle force component in pedaling retains constant direction across pedaling rates.
Loras, Havardn; Ettema, Gertjan; Leirdal, Stig
2009-02-01
Changes in pedaling rate during cycling have been found to alter the pedal forces. Especially, the force effectiveness is reduced when pedaling rate is elevated. However, previous findings related to the muscular force component indicate strong preferences for certain force directions. Furthermore, inertial forces (due to limb inertia) generated at the pedal increase with elevated pedaling rate. It is not known how pedaling rate alters the inertia component and subsequently force effectiveness. With this in mind, we studied the effect of pedal rate on the direction of the muscle component, quantified with force effectiveness. Cycle kinetics were recorded for ten male competitive cyclists at five cadences (60-100 rpm) during unloaded cycling (to measure inertia) and at a submaximal load (~260 W). The force effectiveness decreased as a response to increased pedaling rate, but subtracting inertia eliminated this effect. This indicates consistent direction of the muscle component of the foot force. PMID:19299833
PEP Support: Laboratory Scale Leaching and Permeate Stability Tests
Energy Technology Data Exchange (ETDEWEB)
Russell, Renee L.; Peterson, Reid A.; Rinehart, Donald E.; Buchmiller, William C.
2010-05-21
This report documents results from a variety of activities requested by the Hanford Tank Waste Treatment and Immobilization Plant (WTP). The activities related to caustic leaching, oxidative leaching, permeate precipitation behavior of waste as well as chromium (Cr) leaching are: • Model Input Boehmite Leaching Tests • Pretreatment Engineering Platform (PEP) Support Leaching Tests • PEP Parallel Leaching Tests • Precipitation Study Results • Cr Caustic and Oxidative Leaching Tests. Leaching test activities using the PEP simulant provided input to a boehmite dissolution model and determined the effect of temperature on mass loss during caustic leaching, the reaction rate constant for the boehmite dissolution, and the effect of aeration in enhancing the chromium dissolution during caustic leaching. Other tests were performed in parallel with the PEP tests to support the development of scaling factors for caustic and oxidative leaching. Another study determined if precipitate formed in the wash solution after the caustic leach in the PEP. Finally, the leaching characteristics of different chromium compounds under different conditions were examined to determine the best one to use in further testing.
The saddle-node-transcritical bifurcation in a population model with constant rate harvesting
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.
DYNAMIC RESPONSE OF METALS TO SINGLE AND MULTISTAGE, CONSTANT STRAIN RATE COMPRESSION
Lenard, J
1985-01-01
Single and multistage, uniaxial compression tests are conducted on Al-Mg-Si and 0.02% Nb HSLA steel alloys. Rate sensitivity, activation energy and the effect of interruption on the flow strength of the metals are determined.
Constant growth rate can be supported by decreasing energy flux and increasing aerobic glycolysis
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
Energy Technology Data Exchange (ETDEWEB)
Debreczeny, M.P.; Sauer, K. [Lawrence Berkeley Lab., CA (United States); Zhou, J.; Bryant, D.A. [Pennsylvania State Univ., University Park, PA (United States)
1995-05-18
Rate constants for excitation energy transfer in light-harvesting protein, C-phycocyanin (PC), in the monomeric aggregation state, isolated from the cyanobacterium cynechococcus sp. PCC 7002, are calculated, using Foerster theory and compared with the results of time-resolved fluorescence measurements. The assignments of the energy-transfer rate constants in PC monomers are confirmed here by time-resolved fluorescence anisotropy measurements of the PC monomers isolated from both the wild-type and a mutant strain (cpcB/C155S) whose PC is missing the {beta}{sub 155} chromophore. It is concluded that the Foerster model of resonant energy transfer in the weak coupling limit successfully describes the dominant energy-transfer processes in this protein in the monomeric state. 31 refs., 3 figs., 4 tabs.
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Debreczeny, M.F.; Sauer, K. [Lawrence Berkeley Lab., CA (United States); Zhou, J.; Bryant, D.A. [Pennsylvania State Univ., University Park, PA (United States)
1995-05-18
Resolution of the absorption spectrum of the {beta}{sub 155} chromophore in C-phycocyanin (PC) trimers is achieved by comparison of the steady state absorption spectra of ({alpha}{sup PC}{beta}{sup PC}){sub 3} and ({alpha}{sup PC}{beta}{sup *}){sub 3}. Comparison of the anisotropy decays of ({alpha}{sup PC}{beta}{sup PC}){sub 3} and ({alpha}{sup PC}{beta}{sup *}){sub 3} also greatly aids in the assignment of the dominant kinetic processes in PC trimers. A comparison is made of calculated Foerster rate constants for energy transfer with those rate constants resolved experimentally in the PC trimers. 35 refs.., 10 figs., 2 tabs.
Niland, Courtney N; Jankowsky, Eckhard; Harris, Michael E
2016-10-01
Quantification of the specificity of RNA binding proteins and RNA processing enzymes is essential to understanding their fundamental roles in biological processes. High-throughput sequencing kinetics (HTS-Kin) uses high-throughput sequencing and internal competition kinetics to simultaneously monitor the processing rate constants of thousands of substrates by RNA processing enzymes. This technique has provided unprecedented insight into the substrate specificity of the tRNA processing endonuclease ribonuclease P. Here, we investigated the accuracy and robustness of measurements associated with each step of the HTS-Kin procedure. We examine the effect of substrate concentration on the observed rate constant, determine the optimal kinetic parameters, and provide guidelines for reducing error in amplification of the substrate population. Importantly, we found that high-throughput sequencing and experimental reproducibility contribute to error, and these are the main sources of imprecision in the quantified results when otherwise optimized guidelines are followed. PMID:27296633
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.
Stief, L. J.; Nava, D. F.; Payne, W. A.; Michael, J. V.
1980-01-01
Absolute rate constants for the reaction OH + H2CO have been measured over the temperature range 228-362 K using the flash photolysis-resonance fluorescence technique. The results were independent of variations in forbidden H2CO, total pressure of forbidden Ar and flash intensity (i.e., initial forbidden OH). The rate constant was found to be invariant with temperature in this range, the best representation being k1 = (1.05 + or - 0.11) x 10 to the -11th cu cm/molecule sec where the error is two standard deviations. This result is compared with previous absolute and relative determinations of k1. The reaction is also discussed from a theoretical point of view.
International Nuclear Information System (INIS)
Transient kinetic data for partial reactions of alcohol dehydrogenase and simulations of progress curves have led to estimates of rate constants for the following mechanism, at pH 8.0 and 25 degrees C: E in equilibrium E-NAD+ in equilibrium *E-NAD+ in equilibrium E-NAD(+)-RCH2OH in equilibrium E-NAD+-RCH2O- in equilibrium *E-NADH-RCHO in equilibrium E-NADH-RCHO in equilibrium E-NADH in equilibrium E. Previous results show that the E-NAD+ complex isomerizes with a forward rate constant of 620 s-1. The enzyme-NAD(+)-alcohol complex has a pK value of 7.2 and loses a proton rapidly (greater than 1000 s-1). The transient oxidation of ethanol is 2-fold faster in D2O, and proton inventory results suggest that the transition state has a charge of -0.3 on the substrate oxygen. Rate constants for hydride ion transfer in the forward or reverse reactions were similar for short-chain aliphatic substrates (400-600 s-1). A small deuterium isotope effect for transient oxidation of longer chain alcohols is apparently due to the isomerization of the E-NAD+ complex. The transient reduction of aliphatic aldehydes showed no primary deuterium isotope effect; thus, an isomerization of the E-NADH-aldehyde complex is postulated, as isomerization of the E-NADH complex was too fast to be detected. The estimated microscopic rate constants show that the observed transient reactions are controlled by multiple steps
International Nuclear Information System (INIS)
The reaction rate constants and transient spectra of 11 flavonoids and 4 phenolic acids reacting with eaq- at neutral pH were measured. The results suggest that C4 keto group is the active site for eaq- to attack on flavonoids and phenolic acids, while the o-dihydroxy structure in B-ring, the C2,3 double bond, the C3-OH group and glycosylation have little effects on the eaq- scavenging activities. (author)
Mangia, Silvia; Liimatainen, Timo; Garwood, Michael; Tkac, Ivan; Henry, Pierre-Gilles; Deelchand, Dinesh; Michaeli, Shalom
2011-01-01
In this work, we investigated the frequency-offset dependence of the rotating frame longitudinal (R1ρ) and transverse (R2ρ) relaxation rate constants when using hyperbolic-secant adiabatic full passage pulses or continuous-wave spin-lock irradiation. Phantom and in vivo measurements were performed to validate theoretical predictions of the dominant relaxation mechanisms existing during adiabatic full passage pulses when using different settings of the frequency offset relative to the carrier....
Modi, Stephanie; Stanton, Anthony W. B.; MELLOR, RUSSELL H.; MICHAEL PETERS, A.; RODNEY LEVICK, J.; Mortimer, Peter S.
2005-01-01
Background: The view that breast cancer-related lymphedema (BCRL) is a simple, direct mechanical result of axillary lymphatic obstruction (‘stopcock’ mechanism) appears incomplete, because parts of the swollen limb (e.g., hand) can remain nonswollen. The lymph drainage rate constant (k) falls in the swollen forearm but not in the spared hand, indicating regional differences in lymphatic function. Here the generality of the hypothesis that regional epifascial lymphatic failure underlies region...
Hsu, K.-J.; DeMore, W. B.
1995-01-01
Rate constants of 15 OH reactions with halogen-substituted alkanes, C1 to C3, were studied using a relative rate technique in the temperature range 283-403 K. Compounds studied were CHF2Cl (22), CHF2Br (22B), CH3F (41), CH2F2 (32), CHF3 (23), CHClFCCl2F (122a), CHCl2CF3 (123), CHClFCF3 (124), CH3CF3 (143a), CH3CH2F (161), CF3CHFCF3 (227ea), CF3CH2CF3 (236fa), CF3CHFCHF2 (236ea), and CHF2CF2CH2F (245ca). Using CH4, CH3CCl3, CF3CF2H, and C2H6 as primary reference standards (JPL 92-20 rate constants), absolute rate constants are derived. Results are in good agreement with previous experimental results for six of the compounds studied, including CHF2Cl, CHF2Br, CH2F2, CH3CF3, CHFClCFCl2, and CF3CHFCF3. For the remainder the relative rate constants are lower than those derived from experiments in which OH loss was used to measure the reaction rate. Comparisons of the derived Arrhenius A factors with previous literature transition-state calculations show order of magnitude agreement in most cases. However, the experimental A factors show a much closer proportionality to the number of H atoms in the molecule than is evident from the transition state calculations. For most of the compounds studied, an A factor of (8 +/- 3)E-13 cm(exp 3)/(molecule s) per C-H bond is observed. A new measurement of the ratio k(CH3CCl3)/k(CH4) is reported that is in good agreement with previous data.
The H2 + CO ↔ H2CO Reaction: Rate Constants and Relevance to Hot and Dense Astrophysical Media
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.
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.
Energy Technology Data Exchange (ETDEWEB)
Bahnemann, D.; Hart, E.J.
1982-01-21
Absolute rate constants for the reaction of the hydrated electron and hydroxyl radical with ozone in aqueous solution have been determined by using pulse radiolysis techniques. The rate constant, k(e/sub aq//sup -/ + O/sub 3/) = (3.60 +- 0.14) x 10/sup 10/ dm/sup 3/ mol/sup -1/ s/sup -1/, was measured in the pH range 4.1 to 6.05 by following the decay of e/sub aq//sup -/ at 600 nm. The rate constant k(OH. + O/sub 3/) = (3.02 +- 0.25) x 10/sup 9/ dm/sup 3/ mol/sup -1/ s/sup -1/, was obtained by a competition method at pH 6.7 with acetate ions as the OH. radical scavengers. The ozone concentration for both studies varied from 0.05 x 10/sup -3/ to 0.50 x 10/sup -3/ mol dm/sup -3/.
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Williams, J.A.; Cooper, William J.; Mezyk, Stephen P. E-mail: smezyk@csulb.edu; Bartels, David M
2002-11-01
Bimolecular rate constants for chloroacetone (CAce), 1,1-dichloroacetone (1,1-DCAce) and 1,1,1-trichloroacetone (1,1,1-TCAce) reaction with the aqueous electron (e{sup -}{sub aq}), the hydroxyl radical ({sup {center_dot}}OH), and the hydrogen atom ({sup {center_dot}}H) have been measured using electron pulse radiolysis in combination with transient absorption spectroscopy (e{sup -}{sub aq}, {sup {center_dot}}OH), and electron paramagnetic resonance detection ({sup {center_dot}}H). The measured rate constants with each substrate, in M{sup -1} s{sup -1} for e{sup -}{sub aq}, {sup {center_dot}}OH and {sup {center_dot}}H reaction, are: CAce: (1.34{+-}0.15) x10{sup 10}, (1.69{+-}0.05) x10{sup 8}, (2.63{+-}0.07) x10{sup 7}; 1,1-DCAce: (1.22{+-}0.12) x10{sup 10}, (8.8{+-}0.4) x10{sup 7}, (2.9{+-}0.3) x10{sup 7}; and 1,1,1-TCAce: (1.56{+-}0.17) x10{sup 10}, (3.3{+-}0.1) x10{sup 7}, (2.8{+-}0.2) x10{sup 7}, respectively. The trends observed in these rate constants are discussed in terms of the initial reaction mechanisms of the three reactive species with these chloroacetones.
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...
Rate Constant Change of Photo Reaction of Bacteriorhodopsin Observed in Trimeric Molecular System.
Tsujiuchi, Yutaka; Masumoto, Hiroshi; Goto, Takashi
2016-04-01
To elucidate the time evolution of photo reaction of bacteriorhodopsin in glycerol mixed purple membrane at around 196 K under irradiation by red light, a kinetic model was constructed. The change of absorption with irradiation at times of 560 nm and 412 nm was analyzed for the purpose of determining reaction rates of photo reaction of bacteriorhodopsin and its product M intermediate. In this study it is shown that reaction rates of conversion from bacteriorhodopsin to the M intermediate can be explained by a set of linear differential equations. This model analysis concludes that bacteriorhodopsin in which constitutes a trimer unit with other two bacteriorhodopsin molecules changes into M intermediates in the 1.73 of reaction rate, in the initial step, and according to the number of M intermediate in a trimer unit, from three to one, the reaction rate of bacteriorhodopsin into M intermediates smaller as 1.73, 0.80, 0.19 which caused by influence of inter-molecular interaction between bacteriorhodopsin. PMID:27451646
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.
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Pitts, J.N.; Winer, A.M.; Aschmann, S.M.; Carter, W.P.L.; Atkinson, R.
1985-07-01
An experimental protocol for the determination at room temperature of rate constants for the reactions of hydroxyl radicals with organic chemicals in the gas phase is described in detail. This protocol provides a basis for evaluating the reactivity of organic substances which are emitted into the environment and which are consumed primarily by reaction with hydroxyl radicals. The experimental technique is based upon monitoring the disappearance rates of the test compound and of a reference organic in irradiated methyl nitrite-NO-organic-air mixtures.
Directory of Open Access Journals (Sweden)
Cenxi Yuan
2016-01-01
Full Text Available A simple and analytical formula is suggested to solve the problems of the local burnup and the isotope distributions. The present method considers two extreme conditions of neutrons penetrating the fuel rod. Based on these considerations, the formula is obtained to calculate the reaction rates of 235U, 238U, and 239Pu and straightforward the local burnup and the isotope distributions. Starting from an initial burnup level, the parameters of the formula are fitted to the reaction rates given by a Monte Carlo (MC calculation. Then the present formula independently gives very similar results to the MC calculation from the starting to high burnup level but takes just a few minutes. The relative reaction rates are found to be almost independent of the radius (except (n,γ of 238U and the burnup, providing a solid background for the present formula. A more realistic examination is also performed when the fuel rods locate in an assembly. A combination of the present formula and the MC calculation is expected to have a nice balance between the numerical accuracy and time consumption.
A simple formula for local burnup based on constant relative reaction rate per nuclei
Yuan, Cenxi
2015-01-01
A simple and analytical formula is suggested to solve the problems on the local burnup and the isotope distributions. Present method considers that the slowing down neutrons going into the fuel rod is similar to the light going into the medium. Based on the assumption, the formula are obtained to calculate the reaction rates of $^{235}$U, $^{238}$U, and $^{239}$Pu and straightforward the local burnup and the isotope distributions. From a starting burnup point, the parameters of the formula are fitted to the reaction rates given by a Monte Carlo (MC) calculation. Then the present formula independently gives almost the same results as the MC calculation from the starting burnup point to high burnup, but takes just a few minutes. The relative reaction rate per nuclei are found to be almost independent on the radius (except $(n,\\gamma)$ of $^{238}$U) and burnup, providing a solid background for present formula. A combination of present formula and MC calculation is expected to have a nice balance on the accuracy ...
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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.
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
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.
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.
Gioannis, G De; Muntoni, A; Cappai, G; Milia, S
2009-03-01
Mechanical biological treatment (MBT) of residual municipal solid waste (RMSW) was investigated with respect to landfill gas generation. Mechanically treated RMSW was sampled at a full-scale plant and aerobically stabilized for 8 and 15 weeks. Anaerobic tests were performed on the aerobically treated waste (MBTW) in order to estimate the gas generation rate constants (k,y(-1)), the potential gas generation capacity (L(o), Nl/kg) and the amount of gasifiable organic carbon. Experimental results show how MBT allowed for a reduction of the non-methanogenic phase and of the landfill gas generation potential by, respectively, 67% and 83% (8 weeks treatment), 82% and 91% (15 weeks treatment), compared to the raw waste. The amount of gasified organic carbon after 8 weeks and 15 weeks of treatment was equal to 11.01+/-1.25kgC/t(MBTW) and 4.54+/-0.87kgC/t(MBTW), respectively, that is 81% and 93% less than the amount gasified from the raw waste. The values of gas generation rate constants obtained for MBTW anaerobic degradation (0.0347-0.0803y(-1)) resemble those usually reported for the slowly and moderately degradable fractions of raw MSW. Simulations performed using a prediction model support the hypothesis that due to the low production rate, gas production from MBTW landfills is well-suited to a passive management strategy. PMID:18954969
[Determination of rate constants of gas-phase reactions of alpha-pinene and beta-pinene with ozone].
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.
González-Lezana, Tomás; Scribano, Yohann; Honvault, Pascal
2014-08-21
The D(+) + H2 reaction is investigated by means of a time independent quantum mechanical (TIQM) and statistical quantum mechanical (SQM) methods. Differential cross sections and product rotational distributions obtained with these two theoretical approaches for collision energies between 1 meV and 0.1 eV are compared to analyze the dynamics of the process. The agreement observed between the TIQM differential cross sections and the SQM predictions as the energy increases revealed the role played by the complex-forming mechanism. The importance of a good description of the asymptotic regions is also investigated by calculating rate constants for the title reaction at low temperature. PMID:24802076
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)
无
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.
Energy Technology Data Exchange (ETDEWEB)
Cai, Zhongli; Li, Xifeng; Katsumura, Yosuke [Tokyo Univ., Tokai, Ibaraki (Japan). Nuclear Engineering Research Lab
2000-03-01
The reaction rate constants and transient spectra of 11 flavonoids and 4 phenolic acids reacting with e{sub aq}{sup -} at neutral pH were measured. The results suggest that C{sub 4} keto group is the active site for e{sub aq}{sup -} to attack on flavonoids and phenolic acids, while the o-dihydroxy structure in B-ring, the C{sub 2,3} double bond, the C{sub 3}-OH group and glycosylation have little effects on the e{sub aq}{sup -} scavenging activities. (author)
Olid, Carolina; Diego, David; Garcia-Orellana, Jordi; Cortizas, Antonio Martínez; Klaminder, Jonatan
2016-01-15
The vertical distribution of (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 (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 210Pb profiles that are altered by an initial migration of the radionuclide. This new, two-phased, model describes the distribution of atmospheric-derived (210)Pb ((210)Pbxs) in peat taking into account both incorporation of (210)Pb into the accumulating peat matrix as well as an initial flushing of (210)Pb through the uppermost peat layers. The validity of the IP-CRS model is tested in four anomalous (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 (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. (241)Am and (137)Cs). Our results showed that the IP-CRS can provide chronologies from peat records where (210)Pb mobility is evident, being a valuable tool for studies reconstructing past environmental changes using peat archives during the Anthropocene. PMID:26476062
International Nuclear Information System (INIS)
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 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, Geff, 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 G double-doteff(t0) = −1.19 ± 0.95·10−20 h2 yr−2, where h is defined via H0 = 100 h km s−1 Mpc−1, while using both the WiggleZ and the Sloan Digital Sky Survey Luminous Red Galaxy (SDSS LRG) data is G double-doteff(t0) = −3.6 ± 6.8·10−21 h2 yr−2, both being consistent with General Relativity. Finally, our constraint for the rms mass fluctuation σ8 using the WiggleZ data is σ8 = 0.75 ± 0.08, while using both the WiggleZ and the SDSS LRG data σ8 = 0.77 ± 0.07, both in good agreement with the latest measurements from the Cosmic Microwave Background radiation
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).
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.
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.
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.
van der Vaart, Hester; Murgatroyd, Scott R; Rossiter, Harry B; Chen, Carey; Casaburi, Richard; Porszasz, Janos
2014-06-01
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 (tlim) is 6 minutes (WR6) may provide a useful interventional study baseline. WR6 can be extracted from the power-duration relationship, but requires 4 CWR tests. We sought to develop prediction algorithms for easier WR6 identification using backward stepwise linear regression, one in 69 COPD patients (FEV1 45 ± 15% pred) and another in 30 healthy subjects (HLTH), in whom cycle ergometer ramp incremental (RI) and CWR tests with tlim of ∼6 minutes had been performed. Demographics, pulmonary function, and RI responses were used as predictors. We validated these algorithms against power-duration measurements in 27 COPD and 30 HLTH (critical power 43 ± 18W and 231 ± 43W; curvature constant 5.1 ± 2.7 kJ and 18.5 ± 3.1 kJ, respectively). This analysis revealed that, on average, only corrected peak work rate ( = WRpeak-1 min × WRslope) in RI was required to predict WR6 (COPD SEE = 5.0W; HLTH SEE = 5.6W; R(2) > 0.96; p COPD R(2) = 0.937; HLTH 0.978; p COPD, unlike in HLTH, there was a wide range of tlim values at predicted WR6: COPD 8.3 ± 4.1 min (range 3.6 to 22.2 min), and HLTH 5.5 ± 0.7 min (range 3.9 to 7.0 min). This analysis indicates that corrected WRpeak in an incremental test can yield an acceptable basis for calculating endurance testing work rate in HLTH, but not in COPD patients. PMID:24182350
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.
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.
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.
International Nuclear Information System (INIS)
Previous work has shown the ability of a chemical kinetic model, applied using the FACSIMILE computer code, to predict the thermal decomposition of ethane in a silica flow reactor. To optimise the performance of the model, the present report reviews the literature data on the twenty reactions which it incorporates. Critical assessment has shown some discrepancies in the previously used rate constants, especially those leading to ethyne formation. Table 2 of the report gives the kinetic data which, as a result of the present evaluation, are recommended for future work. Use of these data gives significantly improved agreement between the model and the experimental results, particularly for ethyne formation, which had previously been underestimated. (author)
International Nuclear Information System (INIS)
At Chalk River Laboratories, a computer code is being developed to model the radiolysis of the heavy water in the moderator and the heat-transport system in CANDU reactors. This report collects together, for heavy water, the current knowledge regarding the rate constants, pKa's, yields and diffusion coefficients based on measurements in this laboratory and reports in the literature. The latest data available for the radiolysis of light water are generally included for comparison, which forms a partial update to the report on the radiolysis of light water (Elliot, AECL- 11073, COG-94-167, 1994). There are some reactions where little or no data are available at ambient or elevated temperatures; in these cases, an indication is given of the approach that will be taken to measure or estimate the required parameters. (author)
Energy Technology Data Exchange (ETDEWEB)
Soudackov, Alexander V.; Hammes-Schiffer, Sharon [Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Ave., Urbana, Illinois 61801 (United States)
2015-11-21
Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency proton donor-acceptor vibrational modes. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term in the framework of the cumulant expansion framework may significantly impact the rate constants at high temperatures for proton transfer interfaces with soft proton donor-acceptor modes that are associated with small force constants and weak hydrogen bonds. The effects of the quadratic term may also become significant in these regimes when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant. In this case, however, the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances sampled. The effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances. Additionally, the rigorous relation between the cumulant expansion and thermal averaging approaches is clarified. In particular, the cumulant expansion rate constant includes effects from dynamical interference between the proton donor-acceptor and solvent motions and becomes equivalent to the thermally averaged rate constant when these dynamical effects are neglected. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton
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.
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.
International Nuclear Information System (INIS)
This study evaluated the dynamic behavior of total and compartmental chest wall volumes [(VCW) = rib cage (VRC) + abdomen (VAB)] 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) VCW increased in relation to resting values. There was a noticeable heterogeneity in the patterns of VCW regulation as EEVCW increased non-linearly in 17/30 “hyperinflators” and decreased in 13/30 “non-hyperinflators” (P < 0.05). EEVAB decreased slightly in 8 of the “hyperinflators”, thereby reducing and slowing the rate of increase in end-inspiratory (EI) VCW (P < 0.05). In contrast, decreases in EEVCW in the “non-hyperinflators” were due to the combination of stable EEVRC with marked reductions in EEVAB. These patients showed lower EIVCW 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 EIVCW 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
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.
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 ...
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.
Mangia, Silvia; Liimatainen, Timo; Garwood, Michael; Tkac, Ivan; Henry, Pierre-Gilles; Deelchand, Dinesh; Michaeli, Shalom
2011-08-01
In this work, we investigated the frequency-offset dependence of the rotating frame longitudinal (R(1ρ)) and transverse (R(2ρ)) relaxation rate constants when using hyperbolic-secant adiabatic full passage pulses or continuous-wave spin-lock irradiation. Phantom and in vivo measurements were performed to validate theoretical predictions of the dominant relaxation mechanisms existing during adiabatic full passage pulses when using different settings of the frequency offset relative to the carrier. In addition, adiabatic R(1ρ) and R(2ρ) values of total creatine and N-acetylaspartate were measured in vivo from the human brain at 4 T. When the continuous-wave pulse power was limited to safe specific absorption rates for humans, simulations revealed a strong dependence of R(1ρ) and R(2ρ) values on the frequency offset for both dipolar interactions and anisochronous exchange mechanisms. By contrast, theoretical and experimental results showed adiabatic R(1ρ) and R(2ρ) values to be practically invariant within the large subregion of the bandwidth of the hyperbolic-secant pulse where complete inversion was achieved. However, adiabatic R(1ρ) and R(2ρ) values of the methyl protons of total creatine (at 3.03 ppm) were almost doubled when compared with those of the methyl protons of N-acetylaspartate (at 2.01 ppm) in spite of the fact that these resonances were in the flat region of the inversion band of the adiabatic full passage pulses. We conclude that differences in adiabatic R(1ρ) and R(2ρ) values of human brain metabolites are not a result of their chemical shifts, but instead reflect differences in dynamics. PMID:21264976
International Nuclear Information System (INIS)
A geochronological study of the Guanabara Bay (Rio de Janeiro, Brazil) based on 210Pb dating technique to determine sedimentation rates and using the Constant Rate of Supply model (CRS) is presented in this work. Sediment samples were collected from river-head of Estrela, Sao Joao de Meriti, Guapimirim, Guaxindiba e Imbuacu. A low energy gamma spectrometry (210Pb, samples taken from the Estrela and Sao Joao de Meriti rivers. Radiochemical method was applied to determine the amount of 210Pb in samples collected near Guapimirim, Guaxindiba and Imbuacu Rivers. Atomic absorption spectrometry with air-acetylene flame technique was used to determine the amount of copper in all these samples. Experimental data shown the following variation in the concentration levels of copper and 210Pb: (i) copper; from 2.5 μg/g to 37.1 μg/g (Imbuacu River); from 3.6 to 228.1 μg/g (Estrela River); from 11.6 to 73.4 μg/g (Guapimirim River); from 12.0 to 52.9 μg/g (Guaxindiba River) and from 90.8 to to 237.7 μg/g (Sao Joao de Meriti River), (ti) 210Pb; from 2.0 Bq/kg to 27.0 Bq/kg (Imbuacu River); from 25.2 to 136.6 Bq/kg (Estrela River); from 40.0 to 90.0 Bq/kg (Sao Joao de Meriti River); from 7.0 to 70.0 Bq/kg (Guapimirim River); from 10.0 to 48.0 Bq/kg (Guaxindiba River). The sedimentation rates ranged from 0.30 cm/y in the Imbuacu River for a depth below of 35 cm to 1.3 cm/y for 0-30 cm depth in Guaxindiba River. It was concluded that the experimental data found in this work are consistent with those published in the scientific literature and that they can be predicted by the CRS model. (author)
International Nuclear Information System (INIS)
Removal rate constants for CH3O by CH4, Ar, N2, Xe, and CF4 were measured over a 400K temperature range using a laser photolysis/laser-induced fluorescence technique. Rapid methoxy removal rates are observed for the non-reactive collision partners (Ar, N2, Xe, and CF4) at elevated temperatures showing that the dissociation and isomerization channels for CH3O are indeed important. The total removal rate constant (reaction /plus/ dissociation and/or isomerization) for CH4 exhibits a linear dependence on temperature and has a removal rate constant, k/sub r/ /equals/ (1.2 +- 0.6) /times/ 10/sup /minus/8/exp[(/minus/101070 +- 350)/T]cm3molecule/sup /minus/1/s/sup /minus/1/. Assuming that the removal rate constant due to dissociation and/or isomerization are similar for CH4 and CF4, the reaction rate constant for CH3O /plus/ CH4 is equal to (1.7 +- 1.0) /times/ 10/sup /minus/10/exp[(/minus/7480 +- 1100)/T]cm3molecule/sup /minus/1/s/sup /minus/1/. 7 refs., 4 figs
Kim, S.; Hosseini, S. A.
2015-12-01
Operations such as CO2 geologic storage, enhanced geothermal systems, and wastewater injection are rendering fluid injection as important as fluid extraction. In particular, injecting fluid colder than the original fluid causes thermal contraction and ensuing decreases in stresses, which yield an effect opposite of what volume expansion driven by the fluid injection imposes. In this study, we conduct numerical simulations to investigate pore-pressure buildup, thermal diffusion, and stress changes for two conditions: (1) constant rate, and (2) stepwise injection of cold fluid. The numerical-simulation method—which combines fluid flow, poroelasticity, thermal diffusion, and thermal stress—is based on the single-phase flow condition to simplify a computation model and thus facilitate a focus on mechanical responses. We also examine temporal evolutions of stress states and mobilized friction angles across base, injection-zone, and caprock layers for two different stress regimes: normal-faulting and reverse-faulting. Under the normal-faulting stress regime, the maximum mobilized friction angle occurs inside of the injection zone, which may act to improve the stability of the caprock. Special attention is required, however, because the location of the maximum mobilized friction angle is close to interfaces with the caprock and base layers. The hypothetical stepwise injection of cold fluid is shown to improve the stability of the injection zone to some extent. Under the reverse-faulting stress regime, the maximum mobilized friction angle occurs near the middle of the injection zone; stability in the injection zone is enhanced while that in the caprock/base is aggravated with time. The hypothetical stepwise injection not only helps improve the stability of the injection zone but also delays the moment when the maximum friction angle is mobilized. Finally, we suggest using dimensionless parameters to determine a prevalence of the thermal-stress effect in the injection
Energy Technology Data Exchange (ETDEWEB)
Soudackov, Alexander; Hammes-Schiffer, Sharon
2015-11-17
Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency regimes for the proton donor-acceptor vibrational mode. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term does not significantly impact the rate constants derived using the cumulant expansion approach in any of the regimes studied. The effects of the quadratic term may become significant when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant, however, particularly at high temperatures and for proton transfer interfaces with extremely soft proton donor-acceptor modes that are associated with extraordinarily weak hydrogen bonds. Even with the thermal averaging procedure, the effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances, and the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton transfer and proton-coupled electron transfer in chemical and biological processes. We are grateful for support from National Institutes of Health Grant GM056207 (applications to enzymes) and the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy
Energy Technology Data Exchange (ETDEWEB)
Krajnovich, D.J.; Giardini-Guidoni, A.; Sudboe, A.S.; Schulz, P.A.; Shen, Y.R.; Lee, Y.T.
1978-09-01
Rate constants for the photodissociation of C/sub 2/F/sub 5/Cl as well as the yield of C/sub 2/F/sub 4//sup +/ were measured. The dynamics of the two dissociation channels was studied by measuring the angular and velocity distributions of the products. 2 references. (JFP)
Directory of Open Access Journals (Sweden)
S. A. Carl
2008-10-01
Full Text Available The absolute rate constant for the reaction that is the major source of stratospheric NOx, O(1D+N2O → products, has been determined in the temperature range 227 K to 719 K, and, in the temperature range 248 K to 600 K, the fraction of the reaction that yields O(3P. Both the rate constants and product yields were determined using a recently-developed chemiluminescence technique for monitoring O(1D that allows for higher precision determinations for both rate constants, and, particularly, O(3P yields, than do other methods. We found the rate constant, kR1, to be essentially independent of temperature between 400 K and 227 K, having a value of (1.37±0.11×10−10 cm3 s−1, and for temperatures greater than 450 K a marked decrease in rate constant was observed, with a rate constant of only (0.94±0.11×10−10 cm3 s−1 at 719 K. The rate constants determined over the 227 K–400 K range show very low scatter and are significantly greater, by 20% at room temperature and 15% at 227 K, than the current recommended values. The fraction of O(3P produced in this reaction was determined to be 0.002±0.002 at 250 K rising steadily to 0.010±0.004 at 600 K, thus the channel producing O(3P can be entirely neglected in atmospheric kinetic modeling calculations. A further result of this study is an expression of the relative quantum yields as a function of temperature for the chemiluminescence reactions (kCL1C2H + O(1D → CH(A + CO and (kCL2C2H + O(3P → CH(A + CO, both followed by CH(A → CH(X + hν, as kCL1(T/kCL2(T=(32.8T−3050/(6.29T+398.
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
Caustic leaching of high-level radioactive tank sludge: A critical literature review
Energy Technology Data Exchange (ETDEWEB)
McGinnis, C.P.; Welch, T.D.; Hunt, R.D.
1998-08-01
The Department of Energy (DOE) must treat and safely dispose of its radioactive tank contents, which can be separated into high-level waste (HLW) and low-level waste (LLW) fractions. Since the unit costs of treatment and disposal are much higher for HLW than for LLW, technologies to reduce the amount of HLW are being developed. A key process currently being studied to reduce the volume of HLW sludges is called enhanced sludge washing (ESW). This process removes, by water washes, soluble constituents such as sodium salts, and the washed sludge is then leached with 2--3 M NaOH at 60--100 C to remove nonradioactive metals such as aluminum. The remaining solids are considered to be HLW while the solutions are LLW after radionuclides such as {sup 137}Cs have been removed. Results of bench-scale tests have shown that the ESW will probably remove the required amounts of inert constituents. While both experimental and theoretical results have shown that leaching efficiency increases as the time and temperature of the leach are increased, increases in the caustic concentration above 2--3 M will only marginally improve the leach factors. However, these tests were not designed to validate the assumption that the caustic used in the ESW process will generate only a small increase (10 Mkg) in the amount of LLW; instead the test conditions were selected to maximize leaching in a short period and used more water and caustic than is planned during full-scale operations. Even though calculations indicate that the estimate for the amount of LLW generated by the ESW process appears to be reasonable, a detailed study of the amount of LLW from the ESW process is still required. If the LLW analysis indicates that sodium management is critical, then a more comprehensive evaluation of the clean salt process or caustic recycle would be needed. Finally, experimental and theoretical studies have clearly demonstrated the need for the control of solids formation during and after leaching.
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.
Temelkov, K. A.; Vuchkov, N. K.; Sabotinov, N. V.
2007-04-01
Cross-sections and rate constants for thermal energy charge transfer into some Ag+, I+, and Cu+ excited states are theoretically and experimentally obtained for a gas discharge in the He-CuBr, Ne-CuBr, He-AgI, and Ne-AgI mixtures. Besides the pumping process the formation of the inversion population is determined by the radiative transitions, which populate or depopulate the upper and lower laser levels.
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.
International Nuclear Information System (INIS)
This report collects together all the rate constants, pK's and g-values required for the simulation of the radiolysis of light water, at near-neutral pH, over the temperature range of room temperature to 300 deg C. As very few of the rate constants have been measured over this whole temperature range, the experimental data have been extrapolated using both the Arrhenius equation and the Noyes model. In general, each rate constant is given as a function of temperature using the Arrhenius equation. In some cases a polynomial function was used. The g-values for the radiolysis with low linear energy transfer radiation are given as linear functions of temperature. A preliminary estimate of the g-values for fast-neutron radiolysis at room temperature and at 300 deg C has been made, based on the results of the published ion-beam data and on unpublished high-temperature ion-beam studies at Chalk River Laboratories. (author). 91 refs., 14 tabs., 24 figs
McDonagh, Louis; Wallenstein, Richard; Knappe, Ralf
2006-11-15
We report on a cavity-dumped Q-switched TEM(00) Nd:YVO(4) oscillator offering a unique combination of high power, constant short pulse duration, and high repetition rate, suppressing the gain dependence of pulse duration in classical Q-switched oscillators. Its performance is compared with that of the same oscillator operated in a classical Q-switched regime, demonstrating the much higher peak powers achievable with this technique, especially at high repetition rates. Up to 31 W of 532 nm green light was generated by frequency doubling in a noncritical phase matched LBO crystal, corresponding to 70% conversion efficiency. PMID:17072404
Wang, Wenji; Zhao, Yi
2012-12-01
Thermal rate constants for the title reaction are calculated by using the quantum instanton approximation within the full dimensional Cartesian coordinates. The results reveal that the quantum effect is remarkable for the reaction at both low and high temperatures, and the obtained rates are in good agreement with experimental measurements at high temperatures. Compared to the harmonic approximation, the torsional anharmonic effect of the internal rotation has a little influence on the rates at low temperatures, however, it enhances the rate by about 20% at 1000 K. In addition, the free energy barriers for the isotopic reactions and the temperature dependence of kinetic isotope effects are also investigated. Generally speaking, for the title reaction, the replacement of OH with OD will reduce the free energy barrier, while substituting D for H (connected to C) will increase the free energy barrier.
Damos, Petros; Soulopoulou, Polyxeni
2015-01-01
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 rate 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
Energy Technology Data Exchange (ETDEWEB)
Poutsma, Marvin L [ORNL
2012-01-01
Rate constants for the reaction (R 3C + X2 R 3CX + X ; X = F, Cl, Br, and I) are reviewed. Because of curved Arrhenius plots and negative EX values, empirical structure-reactivity correlations are sought for log kX,298 rather than EX. The well-known poor correlation with measures of reaction enthalpy is demonstrated. The best quantitative predictor for R 3C is p, the sum of the Hammett p constants for the three substituents, R . Electronegative substituents with lone pairs, such as halogen or oxygen, thus appear to destabilize the formation of a polarized pre-reaction complex and/or TS ( +R---X---X -) by -inductive/field electron withdrawal while simultaneously stabilizing them by -resonance electron donation. The best quantitative predictor of the reactivity order of the halogens, I2 > Br2 >> Cl2 F2, is the polarizability of the halogen, (X-X). For the data set of 60 rate constants which span 6.5 orders of magnitude, a modestly successful correlation of log kX,298 is achieved with only two parameters, p and (X-X), with a mean unsigned deviation of 0.59 log units. How much of this residual variance is the result of inaccuracies in the data compared with over-simplification of the correlation approach remains to be seen.
Energy Technology Data Exchange (ETDEWEB)
Guerrero, C. [Centro de Investigaciones Medioambientales, Energéticas y Tecnológicas (CIEMAT), Madrid (Spain); Departamento de Física Atómica, Molecular y Nuclear, Universidad de Sevilla (Spain); Cano-Ott, D.; Mendoza, E. [Centro de Investigaciones Medioambientales, Energéticas y Tecnológicas (CIEMAT), Madrid (Spain); Wright, T. [University of Manchester, Manchester (United Kingdom)
2015-03-21
The effect of dead-time and pile-up in counting experiments may become a significant source of uncertainty if not properly taken into account. Although analytical solutions to this problem have been proposed for simple set-ups with one or two detectors, these are limited when it comes to arrays where time correlation between the detector modules is used, and also in situations of variable counting rates. In this paper we describe the dead-time and pile-up corrections applied to the n-TOF Total Absorption Calorimeter (TAC), a 4π γ-ray detector made of 40 BaF{sub 2} modules operating at the CERN n-TOF facility. Our method is based on the simulation of the complete signal detection and event reconstruction processes and can be applied as well in the case of rapidly varying counting rates. The method is discussed in detail and then we present its successful application to the particular case of the measurement of {sup 238}U(n, γ) reactions with the TAC detector.
Guerrero, C.; Cano-Ott, D.; Mendoza, E.; Wright, T.
2015-03-01
The effect of dead-time and pile-up in counting experiments may become a significant source of uncertainty if not properly taken into account. Although analytical solutions to this problem have been proposed for simple set-ups with one or two detectors, these are limited when it comes to arrays where time correlation between the detector modules is used, and also in situations of variable counting rates. In this paper we describe the dead-time and pile-up corrections applied to the n_TOF Total Absorption Calorimeter (TAC), a 4π γ-ray detector made of 40 BaF2 modules operating at the CERN n_TOF facility. Our method is based on the simulation of the complete signal detection and event reconstruction processes and can be applied as well in the case of rapidly varying counting rates. The method is discussed in detail and then we present its successful application to the particular case of the measurement of 238U(n, γ) reactions with the TAC detector.
International Nuclear Information System (INIS)
The recombination reaction H + O2 + M → HO2 + M is studied by laser flash photolysis in the bath gases M = Ar, N2, and CH4 at pressures between 1 and 200 bar. By extrapolation of the falloff curves, a limiting high-pressure rate coefficient k/sub infinity/ = 7.5 x 10-11 cm3 molecule-1 s-1 is derived at 298 K. An analysis of this result in terms of the statistical adiabatic channel model leads to a looseness parameter of a similarly ordered 0.94 A-1. The corresponding specific rate constants k(E,J) for dissociation of HO2 are constructed and compared with trajectory calculations. The results are also compared with data on the reaction HO + O → H + O2 for which a nearly temperature-independent rate constant of 2.8 x 10-11 cm3 molecule-1 s-1 is predicted. An analysis of the limiting low-pressure rate coefficients with respect to energy-transfer properties is made. The results are compared with trajectory calculations of energy transfer of excited HO2. 77 references, 8 figures, 5 tables
Lauraguais, Amélie; Coeur-Tourneur, Cécile; Cassez, Andy; Seydi, Abdoulaie
2012-08-01
Syringol (2,6-dimethoxyphenol) is a potential marker compound for wood smoke emissions in the atmosphere. To investigate the atmospheric reactivity of this compound, the rate constant for its reaction with hydroxyl radicals (OH) has been determined in a simulation chamber (8 m3) at 294 ± 2 K, atmospheric pressure and low relative humidity (2-4%) using the relative rate method. The syringol and reference compound concentrations were followed by GC/FID (Gas chromatography/Flame Ionization Detection). The determined rate constant (in units of cm3 molecule-1 s-1) is ksyringol = (9.66 ± 1.11) × 10-11. The calculated atmospheric lifetime for syringol is 1.8 h, indicating that it is too reactive to be used as a tracer for wood smoke emissions. Secondary Organic Aerosol (SOA) formation from the OH reaction with syringol was also investigated. The initial mixing ratios for syringol were in the range 495-3557 μg m-3. The aerosol production was monitored using a SMPS (Scanning Mobility Particle Sizer). The SOA yields (Y) were determined as the ratio of the suspended aerosol mass corrected for wall losses (M0) to the total reacted syringol concentration assuming a particle density of 1.4 g cm-3. The aerosol formation yield increases as the initial syringol concentration increases, and leads to aerosol yields ranging from 0.10 to 0.36. Y is a strong function of M0 and the organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. To our knowledge, this work represents the first investigation of the rate constant and SOA formation for the reaction of syringol with OH radicals. The atmospheric implications of this reaction are also discussed.
Energy Technology Data Exchange (ETDEWEB)
Partridge, G.P. Jr.
1987-01-01
In the spray dryer, flue gas from a coal-fired boiler is contacted with an atomized lime slurry; during this contact SO/sub 2/ absorbs and reacts with dissolved Ca(OH)/sub 2/. The mathematical model developed in this activity superimposes SO/sub 2/ absorption and reaction phenomena on existing mathematical descriptions of spray dryer operation. The SO/sub 2/ removal appears to occur primarily in the constant rate period where a continuous liquid phase exists in the atomized slurry droplet. The constant rate period proceeds until evaporation has reduced the liquid phase volume to the point where the Ca(OH)/sub 2/ sorbent particles touch and the diffusion paths for reactants are restricted. The SO/sub 2/ absorption flux involves liquid phase as well as gas phase resistances. The liquid phase resistance includes mass transfer and chemical reaction phenomena associated with the absorption and reaction of SO/sub 2/ and Ca(OH)/sub 2/ and the dissolution of Ca(OH)/sub 2/. Instantaneous reaction occurs between SO/sub 2/ and Ca(OH)/sub 2/ in the liquid phase. Solid dissolution in the liquid film is unimportant and solid dissolution and reaction occur in series. A comprehensive model was developed for the constant rate period. The model is based on film theory and treats the atomized slurry droplet as a sphere of discrete sorbent particles with the fluid phase uniformly distributed around the individual sorbent particles. This concept allows prediction of the mass transfer coefficients and the enhancement due to increasing solids concentration as evaporation proceeds. Efficiency predicts using the model were compared with pilot plant data taken at different inlet flue gas temperatures, stoichiometric ratios and slurry flow rates.
Mosher, Nathaniel; Perkins-Harbin, Emily; Aho, Brandon; Wang, Lihua; Kumon, Ronald; Rablau, Corneliu; Vaishnava, Prem; Tackett, Ronald; Therapeutic Biomaterials Group Team
2015-03-01
Colloidal suspensions of superparamagnetic nanoparticles, known as ferrofluids, are promising candidates for the mediation of magnetic fluid hyperthermia (MFH). In such materials, the dissipation of heat occurs as a result of the relaxation of the particles in an applied ac magnetic field via the Brownian and Neel mechanisms. In order to isolate and study the role of the Neel mechanism in this process, the sample can be frozen, using liquid nitrogen, in order to suppress the Brownian relaxation. In this experiment, dextran-coated Fe3O4 nanoparticles synthesized via co-precipitation and characterized via transmission electron microscopy and dc magnetization are used as MFH mediators over the temperature range between -70 °C to -10 °C (Brownian-suppressed state). Heating the nanoparticles using ac magnetic field (amplitude ~300 Oe), the frequency dependence of the specific absorption rate (SAR) is calculated between 150 kHz and 350 kHz and used to determine the magnetocrystalline anisotropy of the sample. We would like to thank Fluxtrol, Inc. for their help with this project
Nachman, G; Gotoh, T
2015-06-01
We present a general and flexible mathematical model (called SANDY) that can be used to describe many biological phenomena, including the phenology of arthropods. In this paper, we demonstrate how the model can be fitted to vital rates (i.e., rates associated with development, survival, hatching, and oviposition) of the two-spotted spider mite (Tetranychus urticae (Koch)) exposed to different constant temperatures ranging from 15°C to 37.5°C. SANDY was incorporated into an age-, stage- and sex-structured dynamic model, which was fitted to cohort life-tables of T. urticae conducted at five constant temperatures (15, 20, 25, 30, and 35°C). Age- and temperature-dependent vital rates for the three main stages (eggs, immatures, and adults) constituting the life-cycle of mites were adequately described by the SANDY model. The modeling approach allows for simulating the growth of a population in a variable environment. We compared the predicted net reproductive rate (R0) and intrinsic rate of natural increase (rm) at fluctuating temperatures with empirical values obtained from life-table experiments conducted at temperatures that changed with a daily amplitude (±0, ±3, ±6, ±9, and ±12°C) around an average of 22°C. Results show that R0 decreases with increasing amplitude, while rm is more robust to variable temperatures. An advantage of SANDY is that the same simple mathematical expression can be applied to describe all the vital rates. Besides, the approach is not confined to modeling the influence of a single factor on population growth but allows for incorporating the combined effect of several limiting factors, provided that the combined effect of the factors is multiplicative. PMID:26313989
DEFF Research Database (Denmark)
Klaning, U. K.; Sehested, Knud; Holcman, J.
1985-01-01
Eoa,(OH/OH-) were determined by means of kf and k,, the equilibrium constant of 03- + O2 + 0-, the pK of the hydroxyl radical, A&Oa, of 030, 2a,n d OH-i n aqueous solution, and E0,,(C1O2/C1O2-) = 0.934 V determined in the present work. Apoa,(OH) = 26.8 * 1 kJ mol-' and Eoao(OH/OH-) = 1.91 * 0.01 V......The rate constants of the following reactions were determined by pulse radiolysis and stopped-flow experiments: C102- + O3 + C102 + 03-(k f= (4 f 1) X lo6 dm3 mol-' s-', k, = (1.8 f 0.2) X lo5 dm3 mol-' s-]); C102 + OH - C103- + H+ (k = (4.0 * 0.4) X lo9 dm3 mol-' s-l); C102 + 0- - C103- (k = (2.......7 * 0.4) X lo9 dm3 mol-' s-l); and O3 + C102 - C103 + O2 (k = (1.05 f 0.10) X lo3 dm3 mol-l s-'), where kf is the forward rate of reaction and k, is the reverse rate of reaction. The standard Gibbs energy of formation of OH in aqueous solution A&O,,(OH) and the corresponding standard oxidation potential...
Meagher, Daniel T; Latimer, Federico G; Sutter, W Wes; Saville, William J A
2006-06-15
OBJECTIVE-To determine clinical findings and outcome in horses treated by means of a balloon constant rate infusion system. DESIGN-Retrospective case series. ANIMALS-23 horses. PROCEDURES-Medical records of horses examined at The Ohio State University veterinary teaching hospital from 2002 to 2005 that had septic arthritis, septic tenosynovitis, or penetration of a synovial structure and in which treatment involved a balloon constant rate infusion system were searched. Information pertaining to signalment, history, physical examination findings, clinicopathologic data, treatment, and duration of hospitalization was recorded. RESULTS-Mean+/- SD duration of hospitalization was 11.5+/-5.26 days. No correlation between duration of clinical signs and duration of hospitalization or duration of infusion pump use was detected, but correlations between WBC count and duration of hospitalization and WBC and duration of infusion-pump use were observed. All horses survived to discharge. Follow-up information was obtained on 17 horses, 16 of which were alive at the time of follow-up. Twelve of 13 horses for which followup information was available for at least 5 months were alive 5 months or longer after discharge. Thirteen of the 16 horses alive at follow-up were reported by owners as not lame, whereas the remaining 3 were mildly lame or intermittently moderately lame or had developed angular limb deformity in the contralateral limb. CONCLUSIONS AND CLINICAL RELEVANCE-Balloon constant rate infusion systems may be used effectively in treatment of septic arthritis, septic tenosynovitis, and contaminated synovial wounds. Clinical response and long-term outcome appeared to be comparable to results obtained with other techniques.
Fassheber, Nancy; Dammeier, Johannes; Friedrichs, Gernot
2014-06-21
The overall rate constant of the reaction (2), NCN + H, which plays a key role in prompt-NO formation in flames, has been directly measured at temperatures 962 K enthalpy of formation of NCN, ΔfH = 450 kJ mol(-1). The analysis verifies the expected strong temperature dependence of the branching fraction ϕ = k2b/k2 with reaction channel (2b) dominating at the experimental high-temperature limit. In contrast, reaction (2a) dominates at the low-temperature limit with a possible minor contribution of the HNCN forming recombination channel (2d) at T < 1150 K.
Badra, Jihad
2014-07-03
Site-specific rate constants for hydrogen (H) and deuterium (D) abstraction by hydroxyl (OH) radicals were determined experimentally by monitoring the reaction of OH with two normal and six deuterated alkanes. The studied alkanes include propane (C3H8), propane 2,2 D2 (CH 3CD2CH3), propane 1,1,1-3,3,3 D6 (CD 3CH2CD3), propane D8 (C3D 8), n-butane (n-C4H10), butane 2,2-3,3 D4 (CH3CD2CD2CH3), butane 1,1,1-4,4,4 D6 (CD3CH2CH2CD3), and butane D10 (C4D10). Rate constant measurements were carried out over 840-1470 K and 1.2-2.1 atm using a shock tube and OH laser absorption. Previous low-temperature data were combined with the current high-temperature measurements to generate three-parameter fits which were then used to determine the site-specific rate constants. Two primary (P1,H and P 1,D) and four secondary (S00,H, S00,D, S 01,H, and S01,D) H- and D-abstraction rate constants, in which the subscripts refer to the number of C atoms connected to the next-nearest-neighbor C atom, are obtained. The modified Arrhenius expressions for the six site-specific abstractions by OH radicals are P1,H = 1.90 × 10-18T2.00 exp(-340.87 K/T) cm 3molecule-1s-1 (210-1294 K); P1,D= 2.72 × 10-17 T1.60 exp(-895.57 K/T) cm 3molecule-1s-1 (295-1317 K); S00,H = 4.40 × 10-18 T1.93 exp(121.50 K/T) cm 3molecule-1s-1 (210-1294 K); S00,D = 1.45 × 10-20 T2.69 exp(282.36 K/T) cm 3molecule-1s-1 (295-1341 K); S01,H = 4.65 × 10-17 T1.60 exp(-236.98 K/T) cm 3molecule-1s-1 (235-1407 K); S01,D = 1.26 × 10-18 T2.07 exp(-77.00 K/T) cm 3molecule-1s-1 (294-1412 K). © 2014 American Chemical Society.
Vanícek, Jirí
2011-01-01
Nuclear tunneling and other nuclear quantum effects have been shown to play a significant role in molecules as large as enzymes even at physiological temperatures. I discuss how these quantum phenomena can be accounted for rigorously using Feynman path integrals in calculations of the equilibrium and kinetic isotope effects as well as of the temperature dependence of the rate constant. Because these calculations are extremely computationally demanding, special attention is devoted to increasing the computational efficiency by orders of magnitude by employing efficient path integral estimators.
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
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.
Marcus, R. A.
1962-01-01
Using a theory of electron transfers which takes cognizance of reorganization of the medium outside the inner coordination shell and of changes of bond lengths inside it, relations between electrochemical and related chemical rate constants are deduced and compared with the experimental data. A correlation is found, without the use of arbitrary parameters. Effects of weak complexes with added electrolytes are included under specified conditions. The deductions offer a way of coordinating a variety of data in the two fields, internally as well as with each those in another. For example, the rate of oxidation or reduction of a series of related reactants by one reagent is correlated with that of another and with that of the corresponding electrochemical oxidation-reduction reaction, under certain specified conditions. These correlations may also provide a test for distinguishing an electron from an atom transfer mechanism. (auth)
Mishra, Bhupesh Kumar; Chakrabartty, Arup Kumar; Deka, Ramesh Chandra
2013-06-01
Theoretical investigations are carried out on reaction mechanism of the reactions of CF3CH2NH2 (TFEA) with the OH radical by means of ab initio and DFT methods. The electronic structure information on the potential energy surface for each reaction is obtained at MPWB1K/6-31+G(d,p) level and energetic information is further refined by calculating the energy of the species with a Gaussian-2 method, G2(MP2). The existence of transition states on the corresponding potential energy surface is ascertained by performing intrinsic reaction coordinate (IRC) calculation. Our calculation indicates that the H abstraction from -NH2 group is the dominant reaction channel because of lower energy barrier. The rate constants of the reaction calculated using canonical transition state theory (CTST) utilizing the ab initio data. The agreement between the theoretical and experimental rate constants is good at the measured temperature. From the comparison with CH3CH2NH2, it is shown that the fluorine substution decreases the reactivity of the C-H bond.
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Njoku Uchechukwu Njoku
2015-12-01
Full Text Available The research work was aimed at investigating physiological, biochemical, analgesic and anesthetic indices of dogs anesthetized with propofol-ketamine and maintained with repeat bolus and constant infusions of propofol. Eight dogs, assigned to two groups (n=4, were used in this study. All dogs were pre-medicated with atropine (at 0.03 mg/kg bwt and xylazine (at 2 mg/kg bwt. Anesthesia was induced by a concurrent administration of propofol (at 4 mg/kg bwt and ketamine (at 2.5 mg/kg bwt. Maintenance of anesthesia in Group 1 was done with a repeat bolus of propofol (at 2 mg/kg bwt, while in Group 2 it was done with a constant infusion of propofol (at 0.2 mg/kg bwt/min. Gastrotomy was performed in both groups, and anesthesia was maintained for 60 min. Physiological, analgesic, anesthetic parameters and plasma glucose concentration were measured. There was no significant (P>0.05 difference found in the analgesia and pedal reflex scores, durations of analgesia and recumbency, recovery time and standing time between the groups. The heart rate, respiratory rate and rectal temperature reduced significantly (P0.05 between the groups. In conclusion, both maintenance protocols are suitable for dogs, although the repeat bolus technique produces marked cardiopulmonary depression.
International Nuclear Information System (INIS)
The TROSY principle has been introduced into a HNCA experiment, which is designed for measurements of the intraresidual and sequential Hα-Cα/HN-N dipole/dipole and Hα-Cα/N dipole/CSA cross-correlated relaxation rates. In addition, the new experiment provides values of the 3,4JHαHN coupling constants measured in an E.COSY manner. The conformational restraints for the ψ and φ angles are obtained through the use of the cross-correlated relaxation rates together with the Karplus-type dependencies of the coupling constants. Improved signal-to-noise is achieved through preservation of all coherence transfer pathways and application of the TROSY principle. The application of the [15N,13C]-DQ/ZQ-[15N,1H]-TROSY-E.COSY experiment to the 16 kDa apo-form of the E. coli Heme Chaperon protein CcmE is described. Overall good agreement is achieved between ψ and φ angles measured with the new experiment and the average values determined from an ensemble of 20 NMR conformers
Trapp, Oliver; Bremer, Sabrina; Weber, Sven K
2009-11-01
An extension of the unified equation of chromatography to directly access reaction rate constants k(1) of first-order reaction in on-column chromatography is presented. This extended equation reflects different response factors in the detection of the reaction educt and product which arise from structural changes by elimination or addition, e.g., under pseudo-first-order reaction conditions. The reaction rate constants k(1) and Gibbs activation energies DeltaG(double dagger) of first-order reactions taking place in a chromatographic system can be directly calculated from the chromatographic parameters, i.e., retention times of the educt E and product P (t(R)(A) and t(R)(B)), peak widths at half height (w(A) and w(B)), the relative plateau height (h(p)) of the conversion profile, and the individual response factors f(A) and f(B). The evaluation of on-column reaction gas chromatographic experiments is exemplified by the evaluation of elution profiles obtained by ring-closing metathesis reaction of N,N-diallytrifluoroacetamide in presence of Grubbs second-generation catalyst, dissolved in polydimethylsiloxane (GE SE 30).
Wilczek, Frank
2007-01-01
The notion of ``fundamental constant'' is heavily theory-laden. A natural, fairly precise formulation is possible in the context of the standard model (here defined to include gravity). Some fundamental constants have profound geometric meaning. The ordinary gravitational constant parameterizes the stiffness, or resistance to curvature, of space-time. The cosmological term parameterizes space-time's resistance to expansion -- which may be, and apparently is at present, a {\\it negative} resistance, i.e. a tendency toward expansion. The three gauge couplings of the strong, electromagnetic, and weak interactions parameterize resistance to curvature in internal spaces. The remaining fundamental couplings, of which there are a few dozen, supply an ungainly accommodation of inertia. The multiplicity and variety of fundamental constants are esthetic and conceptual shortcomings in our present understanding of foundational physics. I discuss some ideas for improving the situation. I then briefly discuss additional con...
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.
Barrow, J D
2005-01-01
We review properties of theories for the variation of the gravitation and fine structure 'constants'. We highlight some general features of the cosmological models that exist in these theories with reference to recent quasar data that are consistent with time-variation in the fine structure 'constant' since a redshift of 3.5. The behaviour of a simple class of varying-alpha cosmologies is outlined in the light of all the observational constraints.
International Nuclear Information System (INIS)
Transients generated in situ by advanced oxidation technologies (AOTs) to destroy organic contaminants in ground and drinking water often give large concentrations of chemical by-products. These by-products may have adverse health effects, and can also interfere with the desired chemical removal by competing for the generated transients, thus lowering the overall efficiency of the remediation process. To allow for a quantitative evaluation of the influence of tert-butyl formate (TBF), a major by-product formed in the AOT destruction of methyl tert-butyl ether, rate constants for TBF reaction with the hydroxyl radical, the hydrated electron and the hydrogen atom in aqueous solution were measured in this study. Absolute values of (5.23±0.07)x108, (5.48±0.09)x108 and (3.58±0.07)x106 M-1 s-1, were determined at 22 deg. C, respectively
DEFF Research Database (Denmark)
Christensen, H.; Sehested, K.; Løgager, T.
1994-01-01
The temperature dependence of the rate constants, for the reactions of hydrated electrons with H atoms, OH radicals and H2O2 has been determined. The reaction with H atoms, studied in the temperature range 20-250-degrees-C gives k(20-degrees-C) = 2.4 x 10(10) M-1 s-1 and the activation energy E......(A) = 14.0 kJ mol-1 (3.3 kcal mol-1). For reaction with OH radicals the corresponding values are, k(20-degrees-C) = 3.1 x 10(10) M-1 s-1 and E(A) = 14.7 kJ mol-1 (3.5 kcal mol-1) determined in the temperature range 5-175-degrees-C. For reaction with H2O2 the values are, k(20-degrees-C) = 1.2 x 10(10) M-1 s...
Ziganshin, Ayrat M; Schmidt, Thomas; Lv, Zuopeng; Liebetrau, Jan; Richnow, Hans Hermann; Kleinsteuber, Sabine; Nikolausz, Marcell
2016-10-01
The effects of hydraulic retention time (HRT) reduction at constant high organic loading rate on the activity of hydrogen-producing bacteria and methanogens were investigated in reactors digesting thin stillage. Stable isotope fingerprinting was additionally applied to assess methanogenic pathways. Based on hydA gene transcripts, Clostridiales was the most active hydrogen-producing order in continuous stirred tank reactor (CSTR), fixed-bed reactor (FBR) and anaerobic sequencing batch reactor (ASBR), but shorter HRT stimulated the activity of Spirochaetales. Further decreasing HRT diminished Spirochaetales activity in systems with biomass retention. Based on mcrA gene transcripts, Methanoculleus and Methanosarcina were the predominantly active in CSTR and ASBR, whereas Methanosaeta and Methanospirillum activity was more significant in stably performing FBR. Isotope values indicated the predominance of aceticlastic pathway in FBR. Interestingly, an increased activity of Methanosaeta was observed during shortening HRT in CSTR and ASBR despite high organic acids concentrations, what was supported by stable isotope data.
Energy Technology Data Exchange (ETDEWEB)
Hardison, D.R.; Cooper, William J.; Mezyk, Stephen P. E-mail: smezyk@csulb.edu; Bartels, David M
2002-11-01
Transients generated in situ by advanced oxidation technologies (AOTs) to destroy organic contaminants in ground and drinking water often give large concentrations of chemical by-products. These by-products may have adverse health effects, and can also interfere with the desired chemical removal by competing for the generated transients, thus lowering the overall efficiency of the remediation process. To allow for a quantitative evaluation of the influence of tert-butyl formate (TBF), a major by-product formed in the AOT destruction of methyl tert-butyl ether, rate constants for TBF reaction with the hydroxyl radical, the hydrated electron and the hydrogen atom in aqueous solution were measured in this study. Absolute values of (5.23{+-}0.07)x10{sup 8}, (5.48{+-}0.09)x10{sup 8} and (3.58{+-}0.07)x10{sup 6} M{sup -1} s{sup -1}, were determined at 22 deg. C, respectively.
Energy Technology Data Exchange (ETDEWEB)
Michael, J.V.; Nava, D.F.; Brobst, W.D.; Borkowski, R.P.; Stief, L.J.
1982-01-07
Absolute rate constants for the reaction of hydroxyl radical with hydrogen sulfide were measured at 228, 298, and 437 K by using the flash photolysis-resonance fluorescence method. Hydroxyl radicals were produced by the photolysis of water, and resonance fluorescence from OH were measured by multiscaling techniques. The results at 228, 298, and 437 K were found to be (5.11 +/- 0.39) X 10/sup -12/, (4.42 +/- 0.36) X 10/sup -12/, and (5.57 +/- 0.48) X 10/sup -12/, respectively, all in units of cm/sup 3/ molecule/sup -1/ s/sup -1/. The average value measured was (5.01 +/- 0.55) X 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/, where the uncertainty cited is one standard deviation. The results are discussed theoretically and compared to previous determinations.
Ziganshin, Ayrat M; Schmidt, Thomas; Lv, Zuopeng; Liebetrau, Jan; Richnow, Hans Hermann; Kleinsteuber, Sabine; Nikolausz, Marcell
2016-10-01
The effects of hydraulic retention time (HRT) reduction at constant high organic loading rate on the activity of hydrogen-producing bacteria and methanogens were investigated in reactors digesting thin stillage. Stable isotope fingerprinting was additionally applied to assess methanogenic pathways. Based on hydA gene transcripts, Clostridiales was the most active hydrogen-producing order in continuous stirred tank reactor (CSTR), fixed-bed reactor (FBR) and anaerobic sequencing batch reactor (ASBR), but shorter HRT stimulated the activity of Spirochaetales. Further decreasing HRT diminished Spirochaetales activity in systems with biomass retention. Based on mcrA gene transcripts, Methanoculleus and Methanosarcina were the predominantly active in CSTR and ASBR, whereas Methanosaeta and Methanospirillum activity was more significant in stably performing FBR. Isotope values indicated the predominance of aceticlastic pathway in FBR. Interestingly, an increased activity of Methanosaeta was observed during shortening HRT in CSTR and ASBR despite high organic acids concentrations, what was supported by stable isotope data. PMID:26853042
International Nuclear Information System (INIS)
The actions of tetrodotoxin (TTX) and saxitoxin (STX) in normal water and in deuterium oxide (D20) have been studied in frog myelinated nerve. Substitution of D20 for H20 in normal Ringer's solution has no effect on the potency of TTX in blocking action potentials but increases the potency of STX by approximately 50%. Under voltage clamp, the steady-state inhibition of sodium currents by 1 nM STX is doubled in D20 as a result of a halving of the rate of dissociation of STX from the sodium channel; the rate of block by STX is not measurably changed by D20. Neither steady-state inhibition nor the on- or off-rate constants of TTX are changed by D20 substitution. The isotopic effects on STX binding are observed less than 10 min after the toxin has been added to D20, thus eliminating the possibility that slow-exchange (t 1/2 greater than 10 h) hydrogen-binding sites on STX are involved. The results are consistent with a hypothesis that attributes receptor-toxin stabilization to isotopic changes of hydrogen bonding; this interpretation suggests that hydrogen bonds contribute more to the binding of STX than to that of TTX at the sodium channel
Greives, Nicholas; Zhou, Huan-Xiang
2012-10-01
A method developed by Northrup et al. [J. Chem. Phys. 80, 1517 (1984)], 10.1063/1.446900 for calculating protein-ligand binding rate constants (ka) from Brownian dynamics (BD) simulations has been widely used for rigid molecules. Application to flexible molecules is limited by the formidable computational cost to treat conformational fluctuations during the long BD simulations necessary for ka calculation. Here, we propose a new method called BDflex for ka calculation that circumvents this problem. The basic idea is to separate the whole space into an outer region and an inner region, and formulate ka as the product of kE and bar η _d, which are obtained by separately solving exterior and interior problems. kE is the diffusion-controlled rate constant for the ligand in the outer region to reach the dividing surface between the outer and inner regions; in this exterior problem conformational fluctuations can be neglected. bar η _d is the probability that the ligand, starting from the dividing surface, will react at the binding site rather than escape to infinity. The crucial step in reducing the determination of bar η _d to a problem confined to the inner region is a radiation boundary condition imposed on the dividing surface; the reactivity on this boundary is proportional to kE. By confining the ligand to the inner region and imposing the radiation boundary condition, we avoid multiple-crossing of the dividing surface before reaction at the binding site and hence dramatically cut down the total simulation time, making the treatment of conformational fluctuations affordable. BDflex is expected to have wide applications in problems where conformational fluctuations of the molecules are crucial for productive ligand binding, such as in cases where transient widening of a bottleneck allows the ligand to access the binding pocket, or the binding site is properly formed only after ligand entrance induces the closure of a lid.
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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.
Carl, S. A.; Peeters, J.; Vranckx, S.
2008-01-01
The absolute rate constant for the reaction that is the major source of stratospheric NOx, O(1D)+N2O → products, has been determined in the temperature range 227 K to 719 K, and, in the temperature range 248 K to 600 K, the fraction of the reaction that yields O(3P). Both the rate constants and product yields were determined using a recently-developed chemiluminescence technique for monitoring O(1D) that allows for higher precision determinations for both rate constants, and, particularl...
Dependence of Reaction Rate Constants on Density in Supercritical Fluids%超临界流体中反应速率常数与密度的相互关系
Institute of Scientific and Technical Information of China (English)
王涛; 沈忠耀
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.
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
Bergadano, Alessandra; Andersen, Ole K; Arendt-Nielsen, Lars; Theurillat, Regula; Thormann, Wolfgang; Spadavecchia, Claudia
2009-11-01
This study quantitatively investigated the analgesic action of a low-dose constant-rate-infusion (CRI) of racemic ketamine (as a 0.5 mg kg(-1) bolus and at a dose rate of 10 microg kg(-1) min(-1)) in conscious dogs using a nociceptive withdrawal reflex (NWR) and with enantioselective measurement of plasma levels of ketamine and norketamine. Withdrawal reflexes evoked by transcutaneous single and repeated electrical stimulation (10 pulses, 5 Hz) of the digital plantar nerve were recorded from the biceps femoris muscle using surface electromyography. Ketamine did not affect NWR thresholds or the recruitment curves after a single nociceptive stimulation. Temporal summation (as evaluated by repeated stimuli) and the evoked behavioural response scores were however reduced compared to baseline demonstrating the antinociceptive activity of ketamine correlated with the peak plasma concentrations. Thereafter the plasma levels at pseudo-steady-state did not modulate temporal summation. Based on these experimental findings low-dose ketamine CRI cannot be recommended for use as a sole analgesic in the dog. PMID:18706837
Lin, Shi Ying; Sun, Zhigang; Guo, Hua; Zhang, Dong Hui; Honvault, Pascal; Xie, Daiqian; Lee, Soo-Y
2008-01-31
We present accurate quantum calculations of the integral cross section and rate constant for the H + O2 --> OH + O combustion reaction on a recently developed ab initio potential energy surface using parallelized time-dependent and Chebyshev wavepacket methods. Partial wave contributions up to J = 70 were computed with full Coriolis coupling, which enabled us to obtain the initial state-specified integral cross sections up to 2.0 eV of the collision energy and thermal rate constants up to 3000 K. The integral cross sections show a large reaction threshold due to the quantum endothermicity of the reaction, and they monotonically increase with the collision energy. As a result, the temperature dependence of the rate constant is of the Arrhenius type. In addition, it was found that reactivity is enhanced by reactant vibrational excitation. The calculated thermal rate constant shows a significant improvement over that obtained on the DMBE IV potential, but it still underestimates the experimental consensus.
Sparavigna, Amelia Carolina
2012-01-01
As proposed in a previous paper, the decorations of ancient objects can provide some information on the approximate evaluations of constant {\\pi}, the ratio of circumference to diameter. Here we discuss some disks found in the tomb of Hemaka, the chancellor of a king of the First Dynasty of Egypt, about 3000 BC. The discussion is based on measurements of the dimensionless ratio of lengths.
Energy Technology Data Exchange (ETDEWEB)
Robinson, H.P.; Potter, Elinor
1971-03-01
This collection of mathematical data consists of two tables of decimal constants arranged according to size rather than function, a third table of integers from 1 to 1000, giving some of their properties, and a fourth table listing some infinite series arranged according to increasing size of the coefficients of the terms. The decimal values of Tables I and II are given to 20 D.
Directory of Open Access Journals (Sweden)
S. M. Tebcheran
2003-04-01
in small concentrations as densifying aids for this oxide. In the present study the sintering kinetics of tin oxide was studied considering the effect of sintering atmosphere and of the MnO2 concentration. SnO2-MnO2 systems were prepared from the polymeric precursors method and the obtained powders were characterized by surface area by the BET method. SnO2 powders with varied MnO2 concentrations were pressed in cylindrical shape, and sintered in a dilatometer furnace with constant heating rate and controlled atmospheres. Sintered samples were characterized by scanning electron microscopy. The influence of atmosphere (argon, air or CO2 as well as of the MnO2 concentrations on the sintering kinetics was determined. The kinetics data of linear shrinkage were analyzed in terms of kinetic models for the initial stage of sintering (Woolfrey and Bannister as well as for the global sintering (Su e Johnson allowing the determination of the apparent activation energy. Following the determination of the master sintering curve the apparent activation energy of all sintering process were determined as well as its dependence with the atmosphere and manganese concentrations. Based on these values and on the n exponent, determined by the classical grain growth equation, it was concluded that the most probable sintering mechanism is grain boundary diffusion with surface redistribution controlling the kinetics.
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.
Bidgood, T L; Papich, M G
2005-08-01
Enrofloxacin and marbofloxacin were administered to six healthy dogs in separate crossover experiments as a single oral dose (5 mg/kg) and as a constant rate IV infusion (1.24 and 0.12 mg/h.kg, respectively) following a loading dose (4.47 and 2 mg/kg, respectively) to achieve a steady-state concentration of approximately 1 microg/mL for 8 h. Interstitial fluid (ISF) was collected with an in vivo ultrafiltration device at the same time period as plasma to measure protein unbound drug concentrations at the tissue site and assess the dynamics of drug distribution. Plasma and ISF were analyzed for enrofloxacin, its active metabolite ciprofloxacin, and for marbofloxacin by high performance liquid chromatography (HPLC). Lipophilicity and protein binding of enrofloxacin were higher than for marbofloxacin and ciprofloxacin. Compared to enrofloxacin, marbofloxacin had a longer half-life, higher Cmax, and larger AUC(0-infinity) in plasma and ISF after oral administration. Establishing steady state allowed an assessment of the dynamics of drug concentrations between plasma and ISF. The ISF and plasma-unbound concentrations were similar during the steady-state period despite differences in lipophilicity and pharmacokinetic parameters of the drugs.
Aguado, Delia; Benito, Javier; Gómez de Segura, Ignacio A
2011-07-01
The objective of this study was to determine the effects of a constant rate of infusion of lidocaine and ketamine in combination with either morphine or fentanyl on the minimum alveolar concentration of isoflurane (MAC(ISO)) during ovariohysterectomy in dogs. Female dogs (n=44) were premedicated with acepromazine and midazolam. Anaesthesia was induced with propofol and maintained with isoflurane. Dogs received ketamine (0.6 mg/kg/h) and lidocaine (3 mg/kg/h) together with morphine (0.24 mg/kg/h; MLK) or fentanyl (0.0036 mg/kg/h; FLK). The control group received Ringer's lactate solution. A skin incision was used as the noxious stimulus. The MAC(ISO) value was obtained with Dixon's up-and-down method. MAC(ISO) was 0.7±0.0 vol.% in the control group, 0.3±0.0 vol.% in the MLK group (45% MAC reduction) and 0.0±0.0 vol.% in the FLK group (97% MAC reduction). A combination of fentanyl with lidocaine and ketamine decreased the MAC(ISO) in dogs; this decrease was more pronounced than that produced by morphine, lidocaine and ketamine. PMID:20594878
Zhou, Chong-Wen; Simmie, John M; Pitz, William J; Curran, Henry J
2016-09-15
Theoretical aspects of the development of a chemical kinetic model for the pyrolysis and combustion of a cyclic ketone, cyclopentanone, are considered. Calculated thermodynamic and kinetic data are presented for the first time for the principal species including 2- and 3-oxo-cyclopentyl radicals, which are in reasonable agreement with the literature. These radicals can be formed via H atom abstraction reactions by Ḣ and Ö atoms and ȮH, HȮ2, and ĊH3 radicals, the rate constants of which have been calculated. Abstraction from the β-hydrogen atom is the dominant process when ȮH is involved, but the reverse holds true for HȮ2 radicals. The subsequent β-scission of the radicals formed is also determined, and it is shown that recent tunable VUV photoionization mass spectrometry experiments can be interpreted in this light. The bulk of the calculations used the composite model chemistry G4, which was benchmarked in the simplest case with a coupled cluster treatment, CCSD(T), in the complete basis set limit. PMID:27558073
Manivannan, V.; Padmanaban, R.
2016-08-01
We investigate the initial state-selected dynamics of the title reaction on its ground (1 3A″) and first excited (1 3A‧) triplet potential energy surfaces (PESs) by a time-dependent wavepacket propagation method, employing the ab initio analytical PESs developed by Gamallo et al. (2003). All partial wave contributions up to the total angular momentum J = 140 are found to be necessary for the scattering of NO diatom in its vibrational and rotational ground state up to a collision energy ∼ 0.9 eV. The converged initial state-selected reaction attributes viz., reaction probabilities, integral cross sections and thermal rate constants are obtained within the centrifugal sudden (CS) approximation and the convergence of the results are carefully checked by varying all parameters used in the numerical calculations. The dynamical results are compared with the other reported theoretical and experimental findings. Investigation on the energy-resolved channel-specific reaction probabilities infers that the N2 formation channel is very much favorable than the N-exchange channel. The reaction proceeds via some metastable resonances, observed from the oscillatory probability curves, which is more in the latter channel compared to the former. The effect of rotational and vibrational excitations of the reagent (NO diatom) on the dynamics is examined. We also examine the effect of isotopic substitution of N-atom (14 N by 15 N) on the reaction dynamics.
Columbano, Nicolò; Secci, Fabio; Careddu, Giovanni M; Sotgiu, Giovanni; Rossi, Gabriele; Driessen, Bernd
2012-08-01
The effects of constant rate infusion (CRI) of lidocaine on sevoflurane (SEVO) requirements, autonomic responses to noxious stimulation, and postoperative pain relief were evaluated in dogs undergoing opioid-based balanced anesthesia. Twenty-four dogs scheduled for elective ovariectomy were randomly assigned to one of four groups: BC, receiving buprenorphine without lidocaine; FC, receiving fentanyl without lidocaine; BL, receiving buprenorphine and lidocaine; FL, receiving fentanyl and lidocaine. Dogs were anesthetized with intravenous (IV) diazepam and ketamine and anesthesia maintained with SEVO in oxygen/air. Lidocaine (2mg/kg plus 50 μg/kg/min) or saline were infused in groups BL/FL and BC/FC, respectively. After initiation of lidocaine or saline CRI IV buprenorphine (0.02 mg/kg) or fentanyl (4 μg/kg plus 8 μg/kg/h CRI) were administered IV in BC/BL and FC/FL, respectively. Respiratory and hemodynamic variables, drug plasma concentrations, and end-tidal SEVO concentrations (E'SEVO) were measured. Behaviors and pain scores were subjectively assessed 1 and 2h post-extubation. Lidocaine CRI produced median drug plasma concentrations <0.4 μg/mL during peak surgical stimulation. Lidocaine produced a 14% decrease in E'SEVO in the BL (P<0.01) but none in the FL group and no change in cardio-pulmonary responses to surgery or postoperative behaviors and pain scores in any group. Thus, depending on the opioid used, supplementing opioid-based balanced anesthesia with lidocaine (50 μg/kg/min) may not have any or only a minor impact on anesthetic outcome in terms of total anesthetic dose, autonomic responses to visceral nociception, and postoperative analgesia. PMID:22261004
Energy Technology Data Exchange (ETDEWEB)
Zhang, Ruohui [Department of Radiotherapy, Fourth Hospital of Hebei Medical University (China); Department of Medical Physics, Medical Faculty Mannheim, Heidelberg University (Germany); Fan, Xiaomei; Bai, Wenwen; Han, Chun [Department of Radiotherapy, Fourth Hospital of Hebei Medical University (China)
2014-08-15
Objective: The purpose of this study is to propose an alternative planning approach for VMAT using constant dose rate and gantry speed arc therapy(CDR-CAS-IMAT) implementation on conventional Linac Varian 23EX and used IMRT as a benchmark to evaluate the performance. Methods and materials: Eighteen patients with thoracic esophageal carcinoma who were previously treated with IMRT on Varian 23EX were retrospectively planned for CDR-CAS-IMAT plans. Dose prescription was set to 60 Gy to PTVs in 30 fractions. The planning objectives for PTVs and OAR were corresponding with the IMRT plans. Dose to the PTVs and OAR were compared to IMRT with respect to plan quality, MU, treatment time and delivery accuracy. Results: CDR-CAS-IMAT plans led to equivalent or superior plan quality as compared to IMRT, PTV's CI relative increased 16.2%, while small deviations were observed on minimum dose for PTV. Volumes in the cord receiving 40Gy were increased from 3.6% with IMRT to 7.0%. Treatment times were reduced significantly with CDR-CAS-IMAT(mean 85.7s vs. 232.1s, p < .05), however, MU increased by a factor of 1.3 and lung V10/5/3.5/aver were relative increase 6.7%,12%,17.9%,4.2%, respectively. And increased the E-P low dose area volume decreased the hight dose area. There were no significant difference in Delta4 measurements results between both planning techniques. Conclusion: CDR-CAS-IMAT plans can be implemented smoothly and quickly into a busy cancer center, which improved PTV CI and reduces treatment time but increased the MU and low dose irradiated area. An evaluation of weight loss must be performed during treatment for CDR-CAS-IMAT patients.
Energy Technology Data Exchange (ETDEWEB)
Debreczeny, M.P.
1994-05-01
We have measured and assigned rate constants for energy transfer between chromophores in the light-harvesting protein C-phycocyanin (PC), in the monomeric and trimeric aggregation states, isolated from Synechococcus sp. PCC 7002. In order to compare the measured rate constants with those predicted by Fdrster`s theory of inductive resonance in the weak coupling limit, we have experimentally resolved several properties of the three chromophore types ({beta}{sub 155} {alpha}{sub 84}, {beta}{sub 84}) found in PC monomers, including absorption and fluorescence spectra, extinction coefficients, fluorescence quantum yields, and fluorescence lifetimes. The cpcB/C155S mutant, whose PC is missing the {beta}{sub 155} chromophore, was, useful in effecting the resolution of the chromophore properties and in assigning the experimentally observed rate constants for energy transfer to specific pathways.
Energy Technology Data Exchange (ETDEWEB)
Zhang, R; Bai, W; Chi, Z; Gao, C; Xiaomei, F [The Fourth Hospital of Hebei Medical University, Shijiazhuang, Hebei (China); Gao, Y [Hebei General Hospital, Shijiazhuang, Hebei (China)
2015-06-15
Purpose: Postoperative cervical cancer patients with large target volume and the target shape is concave, treatmented with static intensity-modulated radiotherapy (IMRT) is time consuming. The purpose of this study is to investigate using constant dose rate and gantry speed arc therapy(CDR-CAS-IMAT) on conventional linear accelrator, by comparing with the IMRT technology to evaluate the performance of CDR-CAS-IMAT on postoperative cervical cancer patients. Methods: 18 cervical cancer patients treated with IMRT on Varian 23IX were replanted using CDR-CAS-IMAT. The plans were generated on Oncentra v4.1 planning system, PTV was prescribed to 50.4 Gy in 28 fractions. Plans were evaluated based on the ability to meet the dose volume histogram. The homogeneity index (HI), conformity index (CI) of target volume, the dose of organs at risk, radiation delivery time and monitor units were also compared. SPSS 19.0 software paired T-test analysis was carried out on the two sets of data. Results: Compared with the IMRT plans PTV’s CI (t= 3.85, P =0.001), CTV’s CI, HI, D90, D95, D98, V95, V98, V100 (t=4.21, −3.18, 2.13, 4.65, 7.79, 2.29, 6.00, 2.13, p=0.001, 0.005, 0.049, 0.000, 0.000, 0.035, 0.000, 0.049), and cord D2 and rectum V40 (t=−2.65, −2.47, p= P =0.017, 0.025), and treatment time and MU (t=−36.0, −6.26, P =0.000, 0.000) were better than that of IMRT group. But the IMRT plans in terms of decreasing bladder V50, bowel V30 (t=2.14, 3.00, P =0.048, 0.008) and low dose irradiation volume were superior to that of CDR-CAS-IMAT plans. There were no significant differences in other statistical index. Conclusion: Cervical cancer patients with CDR-CAS-IMAT on Varian Clinical 23IX can get equivalent or superior dose distribution compared with the IMRT technology. IMAT have much less treatment time and MU can reduce the uncertainty factor and patient discomfort in treatment. This work was supported by the Medical Science Foundation of the health department of Hebei
低频脉冲信号的频域恒虚警检测%Constant false alarm rate detection in frequency domain for low-frequency pulse
Institute of Scientific and Technical Information of China (English)
梁增; 马启明; 杜栓平
2016-01-01
To improve the ability of detecting a weak sonar impulse signal form low-frequency background noise, a new detection method with constant false alarm rate (CFAR) in frequency domain is proposed. In this method, the peaks in the frequency domain are taken as the potential pulse signal due to the poor stability and large fluctuation of low-frequency background noise. Then, the detection decision is made through comparing the energy of those peaks and the energy of the background noise. The way of how to get statistic of test, background noise estimation and CFAR threshold is also given. Results of computer simulation and real data processing have confirmed the satisfactory performance of the proposed method in detecting weak sonar pulse signal like CW and CW-LFM, which contain narrow-band components.%为提高低频背景噪声中弱声呐脉冲信号的检测能力,给出了一种频域恒虚警检测方法.该方法针对低频背景噪声平稳性较差、起伏较大的特点,将频域中峰值点或极值点认为是疑似脉冲信号,通过对疑似点能量与历史背景进行比对的方式完成脉冲信号的检测判决,并且给出了相应的检验统计量获取方法、背景噪声估计方法和恒虚警检测门限的计算方法.仿真分析和实际数据处理结果表明,频域恒虚警检测方法对单频脉冲、单频-线性调频组合脉冲等包含窄带成分的弱声呐脉冲信号有非常好的检测性能.
Institute of Scientific and Technical Information of China (English)
李海鹏; 朱元林; 潘卫东
2002-01-01
Uniaxial compressive strength tests were conducted on the saturated frozen Lanzhou silt (loess) at various constant strain rates and at various constant temperatures. It is concluded from the test results that: the compressive strength (σ f) is very sensitive to temperature (θ) and increases with the temperature decreasing as a power law. Compressive strength is sensitive to strain rate () and increases with strain rates increasing within a certain range of strain rates as a power law. Compressive strength decreases when time to failure (tf) increases, also following a power law. Finally, Compressive strength of frozen silt with higher dry density (γd) is higher than that of frozen silt with lower dry density. The difference between them is mainly influenced by strain rate.
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. PMID:24955760
Njoku Uchechukwu Njoku
2015-01-01
The research work was aimed at investigating physiological, biochemical, analgesic and anesthetic indices of dogs anesthetized with propofol-ketamine and maintained with repeat bolus and constant infusions of propofol. Eight dogs, assigned to two groups (n=4), were used in this study. All dogs were pre-medicated with atropine (at 0.03 mg/kg bwt) and xylazine (at 2 mg/kg bwt). Anesthesia was induced by a concurrent administration of propofol (at 4 mg/kg bwt) and ketamine (at 2.5 mg/kg bwt). Ma...
Petros Damos; Polyxeni Soulopoulou
2015-01-01
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-Raphs...
Institute of Scientific and Technical Information of China (English)
黄曦; 张雁秋; 刘伟京; 涂勇; 徐军
2011-01-01
[目的]考察多菌灵初始浓度、臭氧投加量和温度对臭氧氧化降解多茼灵反应表观速率常数的影响.[方法]采用臭氧氧化降解水体中的多菌灵,考察多菌灵降解过程中表现反应速率常数与反应剂量因素的关系.[结果]在不同臭氧投加量和不同初始浓度条件下,多菌灵降解均符合假一级反应动力学.表现速率常数与臭氧投加量呈正相关性,与多菌灵初始浓度呈负相关性.表观速率常数随多菌灵初始浓度的增加而减小,但是反应物的绝对去除量增加,表明增加多菌灵初始浓度有利于提高臭氧的利用效率.表观速率常数随温度的升高而增加,与一般化学反应规律相符合.[结论]为安全有效地降解多菌灵提供了参考.%[ Objective] The effect of the initial concentration of carbenclazim, the adding amount of ozone and temperature on the apparent rate constant in the degradation of carbendazim was researched. [ Method ] The relationship between the apparent rate constant and reaction dose in the process of the carbendazim degradation in water was experimented. [ Results] The results indicated that under the condition of different doses of ozone-adding and initial concentrations the process of carbendazim degradation was matched with the pseudo-first-order kinetic model. The apparent rate constants had the positive relativity with applied ozone dose and negative correlation with initial concentration. The apparent rate constant was decreased with increment of initial concentration. However, the absolute removal rate of the reactants was increased, which indicated that the increment of initial concentration would be beneficial to the improvement of the utilization rate of ozone. The apparent rate constant was increased with the increment of temperature, which was consistent with the general law of chemical reaction. [ Conclusion] The reference for the safety and efficiency degradation of carbendazim was provided
Alajajian, S. H.; Man, K.-F.; Chutjian, A.
1991-01-01
Electron attachment cross sections are reported in the energy range 0-160 meV, and at resolutions of 6.0-6.5 meV (FWHM) for the molecules CF3SO3H (triflic acid), (CF3SO2)2O (triflic anhydride), and CF3I (methyl iodide). Use is made of the Kr photoionization method. Attachment line shapes are deconvoluted from the spectral slit (electron energy) function, and are converted to cross sections by normalization to thermal attachment rate constants at 300 K. Rate constants as a function of mean electron energy are calculated from the cross sections using a Maxwellian electron energy distribution function. Present data are compared with flowing-afterglow, Langmuir-probe results in triflic acid and anhydride, and with high-Rydberg ionization results in CF3I.
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....
Teraji, T.; Arakaki, T.; Suzuka, T.
2012-12-01
Use of artificial sweeteners in beverages and food has been rapidly increasing because of their non-calorie nature. In Japan, aspartame, acesulfame K and sucralose are among the most widely used artificial sweeteners. Because the artificial sweeteners are not metabolized in human bodies, they are directly excreted into the environment without chemical transformations. We initiated a study to better understand the fate of artificial sweeteners in the marine environment. The hydroxyl radical (OH), the most potent reactive oxygen species, reacts with various compounds and determines the environmental oxidation capacity and the life-time of many compounds. The steady-state OH concentration and the reaction rate constants between the compound and OH are used to estimate the life-time of the compound. In this study, we determine the bimolecular rate constants between aspartame, acefulfame K and saccharin and OH at various pH and temperature conditions using a competition kinetics technique. We use hydrogen peroxide as a photochemical source of OH. Bimolecular rate constant we obtained so far for aspartame was (2.6±1.2)×109 M-1 s-1 at pH = 3.0 and (4.9±2.3)×109 M-1 s-1 at pH = 5.5. Little effect was seen by changing the temperatures between 15 and 40 oC. Activation energy (Ea) was calculated to be -1.0 kJ mol-1 at pH = 3.0, +8.5 kJ mol-1 at pH = 5.5, which could be regarded as zero. We will report bimolecular rate constants at different pHs and temperatures for acesulfame K and saccharin, as well. Possible reaction by-products for aspartame will be also reported. We will further discuss the fate of aspartame in the coastal environment.
International Nuclear Information System (INIS)
An understanding of the aqueous radiolysis-induced chemistry in nuclear reactors is an important key to the understanding of materials integrity issues in reactor systems. Significant materials and chemistry issues have emerged in Pressurized Water Reactors (PWR), Boiling Water Reactors (BWR) and CANDU reactors that have required a detailed understanding of the radiation chemistry of the coolant. For each reactor type, specific computer radiolysis models have been developed to gain insight into radiolysis processes and to make chemistry control adjustments to address the particular issues. The objective of this report is to compile and review the radiolysis data now available and, where possible, correct the reported g-values and rate constants to provide a recommendation for the best values to use in high temperature modelling of light water radiolysis up to 350oC. With a few exceptions, the review has been limited to those reactions that occur in slightly acid and slightly alkaline solutions, e.g., it does not address reactions involving the oxide radical anion, O-, or ionized forms of hydrogen peroxide, HO2-, beyond their acid-base equilibria reactions. However, a few reactions have been included where the rate constant for a reaction involving O- is significantly larger than the corresponding hydroxyl radical reaction rate constant and thus can influence the chemistry below the pKA of the hydroxyl radical. (author)
Rolletter, Michael; Fuchs, Hendrik; Novelli, Anna; Ehlers, Christian; Hofzumahaus, Andreas
2016-04-01
Recent studies have shown that the chemistry of gaseous nitrous acid (HONO) in the lower troposphere is not fully understood. Aside from heterogenous reactions, the daytime HONO formation in the gas-phase is not well understood (Li et al., Science, 2014). For a better understanding of HONO in the gas-phase, we have reinvestigated the reaction rate constants of important tropospheric reactions of the HOx radical family (OH and HO2) with nitrogen oxides at realistic conditions of the lower troposphere (at ambient temperature/pressure and in humid air). In this study we apply a direct pump and probe technique with high accuracy, using small radical concentrations to avoid secondary chemistry. Pulsed laser photolysis/laser-induced fluorescence (LP/LIF) was used to investigate the reaction rate constants of OH with CO, NO, NO2, and HO2 with NO2 in synthetic air at different water vapor concentrations (up to 5 x 1017 molecules cm‑3). Photolysis of ozone in the presence of gaseous water was the source of OH. The reactions took place in a flow-tube at room temperature and atmospheric pressure. The chemical decay of the radicals was monitored by laser-induced fluorescence detection in a low-pressure cell, which sampled air continuously from the end of the flow-tube. Knowing the reactant concentrations subsequently allowed to calculate the bimolecular reaction rate constants at 1 atm from the pseudo-first-order decays. In order to observe HO2 reactions, OH was converted into HO2 with an excess of CO in the flow-tube. The newly measured rate constants for OH with CO, NO and NO2 agree very well with current recommendations by NASA/JPL and IUPAC and have an improved accuracy (uncertainty < 5%). These rate coefficients are independent of the presence of water vapour. The measured rate constant of HO2 with NO2 was found to depend significantly on the water-vapour concentration (probably due to formation of HO2*H2O complexes) and to exceed current recommendations by NASA/JPL and
Vredenberg, W.J.
2008-01-01
The fluorescence induction F(t) of dark-adapted chloroplasts has been studied in multi-turnover 1 s light flashes (MTFs). A theoretical expression for the initial fluorescence rise is derived from a set of rate equations that describes the sequence of transfer steps associated with the reduction of
Rate constants for H{sub 2}CO + O{sub 2} {yields} HCO + HO{sub 2} at high temperature
Energy Technology Data Exchange (ETDEWEB)
Michael, J. V.; Su, M.-C.; Sutherland, J. W.; Fang, D.-C.; Harding, L. B.; Wagner, A. F.
2000-01-05
The reaction between H{sub 2}CO and O{sub 2} has been studied in a reflected shock tube apparatus between 1633--2027 K using trioxane, (H{sub 2}CO){sub 3}, as the source of H{sub 2}CO. O-atom atomic resonance absorption spectrometry (ARAS) was used to observe absolute [O]{sub t} under conditions of low [H{sub 2}CO]{sub 0} so that most secondary reactions were negligible. Hence, the observed [O]{sub t} was the direct result of the rate controlling reaction between H{sub 2}CO and O{sub 2}. Ab initio theoretical results indicated that the process, H{sub 2}CO + O{sub 2} {yields} HCO + HO{sub 2}, is the only possible reaction. After rapid HCO and HO{sub 2} dissociations, O-atoms are then instantaneously produced from H + O{sub 2} {yields} O + OH. Using the ab initio result, variational transition state theoretical calculations (CTST) give k{sub 1} = 4.4929 x 10{sup {minus}20} T{sup 2.9116} exp{minus}18692/T cm{sup 3} molecule{sup {minus}1} S{sup {minus}1}. This theoretical result is consistent with the present experimental determinations and those at lower temperatures.
Energy Technology Data Exchange (ETDEWEB)
Bergin, M.S.; Russell, A.G.; Yang, Y.J.; Milford, J.B.; Kirchner, F.; Stockwell, W.R.
1996-07-01
Tropospheric ozone is formed in the atmosphere by a series of reactions involving volatile organic compounds (VOCs) and nitrogen oxides (NO{sub x}). While NOx emissions are primarily composed of only two compounds, nitrogen oxide (NO) and nitrogen dioxide (NO{sub 2}), there are hundreds of different VOCs being emitted. In general, VOCs promote ozone formation, however, the rate and extent of ozone produced by the individual VOCs varies considerably. For example, it is widely acknowledged that formaldehyde (HCHO) is a very reactive VOC, and produces ozone rapidly and efficiently under most conditions. On the other hand, VOCs such as methane, ethane, propane, and methanol do not react as quickly, and are likely to form less urban ozone than a comparable mass of HCHO. The difference in ozone forming potential is one of the bases for the use of alternative fuels. The fuels considered in this study included compressed natural gas, LPG, mixtures of methanol and gasoline, ethanol and gasoline, and a reformulated gasoline.
Energy Technology Data Exchange (ETDEWEB)
Debreczeny, M.P.; Sauer, K. (Lawrence Berkeley Lab., CA (United States) Univ. of California, Berkeley, CA (United States)); Zhou, J.; Bryant, D.A. (Pennsylvania State Univ., University Park, PA (United States))
1993-09-23
At both room temperature (RT) and 77 K, the absorption and fluorescence spectra of the three individual chromophore types ([alpha][sub 84], [beta][sub 84], and [beta][sub 155]) found in monomeric C-phycocyanin ([alpha][sup PC][beta][sup PC]), isolated from the cyanobacterium Synechococcus sp. PCC 7002, were resolved along with the rates of energy transfer between the chromophores. The cpcB/C155S mutant, whose PC is missing the [beta][sub 155] chromophore, was useful in effecting this resolution. At RT, the single broad peak in the visible region of the absorption spectrum of ([alpha][sup PC][beta][sup PC]) was resolved into its three-component spectra by comparing the steady-state absorption spectra of the isolated wild-type [alpha] subunit of PC ([alpha][sup PC]) (containing only the [alpha][sub 84] chromophore) with those of the monomeric PCs isolated from the mutant strain ([alpha][sup PC][beta]*) and the wild-type strain ([alpha][sup PC][beta][sup PC]). At 77 K, the visible region of the absorption spectrum of ([alpha][sup PC][beta][sup PC]) splits into two peaks. This partial resolution at 77 K of the chromophore spectra of ([alpha][sup PC][beta][sup PC]) when compared with the 77 K absorption spectra of [alpha][sup PC], [beta][sup PC], and ([alpha][sup PC][beta]*) provided a confirmation of our RT assignments of the chromophore absorption spectra. 38 refs., 9 figs., 6 tabs.
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.
International Nuclear Information System (INIS)
Accurate quantum total reaction probabilities for the collinear reaction X + F2 (upsilon = 0.1) → XF + F (X = Mu, H, D, T) have been used to calculate collinear rate constants and activation energies. Comparison is made with collinear quasi-classical trajectory calculations and transition state theory assuming classical motion along a separable reaction coordinate and vibrational adiabaticity. Considerable differences between the quantum and quasi-classical and transition state theory results are found only for the Mu reaction at low temperatures. 5 figures, 35 references, 6 tables
Cosmological Hubble constant and nuclear Hubble constant
International Nuclear Information System (INIS)
The evolution of the Universe after the Big Bang and the evolution of the dense and highly excited nuclear matter formed by relativistic nuclear collisions are investigated and compared. Values of the Hubble constants for cosmological and nuclear processes are obtained. For nucleus-nucleus collisions at high energies the nuclear Hubble constant is obtained in the frame of different models involving the hydrodynamic flow of the nuclear matter. Significant difference in the values of the two Hubble constant - cosmological and nuclear - is observed
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。
Institute of Scientific and Technical Information of China (English)
陈书鸿; 张丽莹; 乐艳; 侯健; 文强; 李廷真
2016-01-01
改进了电导法测定乙酸乙酯皂化反应速率常数实验的反应器和反应物混合方式。采用了一种改进的双层恒温烧杯作为反应器，可以准确地控制反应温度。用单通道移液器量取分析纯乙酸乙酯加入反应器，使用磁力搅拌器快速混合反应物。改进后的实验能够方便地测量κ0和κt，学生通过实验可以得到较为准确的速率常数和较好的数据拟合相关系数。%The study aims to improve the mixing mode and reactor of the experiment for determining rate constant of acetic ether saponification using electric conductant method. By using a double layer thermostatic beaker as the reactor, the reaction temperature can be efficient controlled. The analytically pure acetic ether has been poured into reactor by micro pipettes, after that the reactants have been quickly mixed with a magnetic stirrer. The κ0 and κt are measured easily with this improvement in experiment. It enables students to obtain comparatively accurate rate constant and better correlation coefficients.
Ion exchange equilibrium constants
Marcus, Y
2013-01-01
Ion Exchange Equilibrium Constants focuses on the test-compilation of equilibrium constants for ion exchange reactions. The book first underscores the scope of the compilation, equilibrium constants, symbols used, and arrangement of the table. The manuscript then presents the table of equilibrium constants, including polystyrene sulfonate cation exchanger, polyacrylate cation exchanger, polymethacrylate cation exchanger, polysterene phosphate cation exchanger, and zirconium phosphate cation exchanger. The text highlights zirconium oxide anion exchanger, zeolite type 13Y cation exchanger, and
De Fazio, Dario
2014-06-21
In this work, we present a quantum mechanical scattering study of the title reaction from 1 mK to 2000 K. Total integral cross sections and thermal rate constants are compared with previous theoretical and experimental data and with simpler theoretical models to understand the range of validity of the approximations used in the previous studies. The obtained quantum reactive observables have been found to be nearly insensitive to the roto-vibrational energy of the reactants at high temperatures. More sensitive to the reactant's roto-vibrational energy are the data in the cold and ultra-cold regimes. The implications of the new data presented here in the early universe scenario are also discussed and analyzed. PMID:24810283
Institute of Scientific and Technical Information of China (English)
HE Jian-Feng; CHEN Feng; LI Jing
2006-01-01
@@ A quasiclassical trajectory study with the sixth-order explicit symplectic algorithm for the N(4S)+O2 (X3∑-g ) →NO (X2Ⅱ)+O(3P) reaction has been reported by employing a new ground potential energy surface. We have discussed the influence of the relative translational energy, the vibrational and rotational levels of O2 molecules on the total reaction cross section. Thermal rate constants at temperatures 300, 600, and 1000 K determined in this work for the reaction are 4.4 × 107, 1.8 × 1010, and 3.1 × 1011 cm3mol-1s-1, respectively. It is found that they are in better agreement with the experimental data than previous theoretical values.
Institute of Scientific and Technical Information of China (English)
许立滨; 尹晓
2011-01-01
In this paper, under the effect of the variance of the dead population on the internal and environmental toxicant density, a Gallopin' s resource-consumer system with constant-rate harvesting in polluted environment was studied. By using comparison theory, the sufficient condition for β-persistence ,β-extinction and zero-extinction was proved.%在考虑死亡种群对环境毒素影响的情况下,研究了污染环境中具有常数收获率的Gallopin资源-消费者种群的生存问题.利用比较原理,给出了种群β生存、β绝灭、零绝灭的充分条件.
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.
Energy Technology Data Exchange (ETDEWEB)
Zanchet, Alexandre; Bulut, Niyazi; Roncero, Octavio [Instituto de Fisica Fundamental (IFF-CSIC), C.S.I.C., Serrano 123, E-28006 Madrid (Spain); Godard, B.; Cernicharo, Jose [Centro de Astrobilogia, CSIC-INTA, Torrejon de Ardoz, Madrid (Spain); Halvick, Philippe, E-mail: octavio.roncero@csic.es [Institut des Sciences Moleculaires, Universite de Bordeaux, CNRS UMR 5255, 351 cours de la Liberation, F-33405 Talence Cedex (France)
2013-04-01
State-to-state rate constants for the title reaction are calculated using the electronic ground state potential energy surface and an accurate quantum wave-packet method. The calculations are performed for H{sub 2} in different rovibrational states, v = 0, 1 and J = 0 and 1. The simulated reaction cross section for v = 0 shows a rather good agreement with the experimental results of Gerlich et al., both with a threshold of 0.36 eV and within the experimental error of 20%. The total reaction rate coefficients simulated for v = 1 are two times smaller than those estimated by Hierl et al. from cross sections measured at different temperatures and neglecting the contribution from v > 1 with an uncertainty factor of two. Thus, part of the disagreement is attributed to the contributions of v > 1. The computed state-to-state rate coefficients are used in our radiative transfer model code applied to the conditions of the Orion Bar photodissociation region, and leads to an increase of the line fluxes of high-J lines of CH{sup +}. This result partially explains the discrepancies previously found with measurements and demonstrates that CH{sup +} excitation is mostly driven by chemical pumping.
Cosmological Constant, Fine Structure Constant and Beyond
Wei, Hao; Li, Hong-Yu; Xue, Dong-Ze
2016-01-01
In this work, we consider the cosmological constant model $\\Lambda\\propto\\alpha^{-6}$, which is well motivated from three independent approaches. As is well known, the evidence of varying fine structure constant $\\alpha$ was found in 1998. If $\\Lambda\\propto\\alpha^{-6}$ is right, it means that the cosmological constant $\\Lambda$ should be also varying. In this work, we try to develop a suitable framework to model this varying cosmological constant $\\Lambda\\propto\\alpha^{-6}$, in which we view it from an interacting vacuum energy perspective. We propose two types of models to describe the evolutions of $\\Lambda$ and $\\alpha$. Then, we consider the observational constraints on these models, by using the 293 $\\Delta\\alpha/\\alpha$ data from the absorption systems in the spectra of distant quasars, and the data of type Ia supernovae (SNIa), cosmic microwave background (CMB), baryon acoustic oscillation (BAO). We find that the model parameters can be tightly constrained to the narrow ranges of ${\\cal O}(10^{-5})$ t...
Ouk, Chanda-Malis; Zvereva-Loëte, Natalia; Scribano, Yohann; Bussery-Honvault, Béatrice
2012-10-30
Multireference single and double configuration interaction (MRCI) calculations including Davidson (+Q) or Pople (+P) corrections have been conducted in this work for the reactants, products, and extrema of the doublet ground state potential energy surface involved in the N((2)D) + CH(4) reaction. Such highly correlated ab initio calculations are then compared with previous PMP4, CCSD(T), W1, and DFT/B3LYP studies. Large relative differences are observed in particular for the transition state in the entrance channel resolving the disagreement between previous ab initio calculations. We confirm the existence of a small but positive potential barrier (3.86 ± 0.84 kJ mol(-1) (MR-AQCC) and 3.89 kJ mol(-1) (MRCI+P)) in the entrance channel of the title reaction. The correlation is seen to change significantly the energetic position of the two minima and five saddle points of this system together with the dissociation channels but not their relative order. The influence of the electronic correlation into the energetic of the system is clearly demonstrated by the thermal rate constant evaluation and it temperature dependance by means of the transition state theory. Indeed, only MRCI values are able to reproduce the experimental rate constant of the title reaction and its behavior with temperature. Similarly, product branching ratios, evaluated by means of unimolecular RRKM theory, confirm the NH production of Umemoto et al., whereas previous works based on less accurate ab initio calculations failed. We confirm the previous findings that the N((2)D) + CH(4) reaction proceeds via an insertion-dissociation mechanism and that the dominant product channels are CH(2)NH + H and CH(3) + NH.
Sadeghi, N.; Setser, D. W.; Francis, A.; Czarnetzki, U.; Döbele, H. F.
2001-08-01
The total quenching rate constants of argon atoms in the 4p'[1/2]0, 4p[1/2]0, 4p[3/2]2, and 4p[5/2]2 states (2p1, 2p5, 2p6, and 2p8, respectively, in the Paschen numbering system) by rare gases, H2, D2, N2, CO, NO, O2, F2, Cl2, CO2, NO2, CH4, C2H2, C2H4, C2H6, CF4, CHF3, and SF6 have been determined at room temperature. These four excited states of argon (energy 13.09-13.48 eV) were selectively prepared by two-photon excitation from the ground state using VUV (184-190 nm range) laser pulses. The total quenching rates were deduced from the pressure dependence of the decay times of the excited-state atoms, measured by observing their fluorescence emission intensities in the presence of added reagents. The quenching constants increase from values of ≅0.01×10-10 cm3 atom-1 s-1 for Ne, to ≅0.1×10-10 cm3 atom-1 s-1 for He and Ar, and to very large values, (5-15)×10-10 cm3 atom-1 s-1, for most polyatomic molecules, F2, Cl2, and O2. The quenching mechanisms of the Ar(4p,4p') atoms are briefly discussed and compared to the reactions of the Ar(4s,4s') metastable and resonance state atoms, 11.55-11.83 eV, which can serve as a reference.
Directory of Open Access Journals (Sweden)
Ricardo Peraça Toralles
2008-03-01
Full Text Available O ácido ascórbico, vitamina C, é usado extensivamente na indústria de alimentos, não só devido ao seu valor nutricional, mas devido a suas contribuições funcionais na qualidade do produto. Existem muitos estudos sobre a estabilidade cinética do ácido ascórbico em bebidas, mas nenhum estudo foi encontrado sobre as constantes cinéticas de degradação do ácido ascórbico adicionado em purê de pêssego. Neste trabalho, estudou-se a cinética de degradação do ácido ascórbico em purê de pêssego da cultivar Jade, em condições anaeróbicas e na faixa de 70 a 90 °C. As concentrações de purês testadas foram 12, 22 e 32 °Brix. A análise cinética dos dados sugere que a degradação foi significativamente representada pelos modelos cinéticos de zero e primeira ordem. A velocidade de degradação do ácido ascórbico foi dependente da temperatura. A energia de ativação média foi de 45 kJ.mol-1 e independente da concentração de sólidos solúveis.Ascorbic acid (vitamin C is extensively used in the food industry, not only for its nutritional value, but also for its many functional contributions to product quality. There have been many studies on the stability of ascorbic acid in different beverages, but no study was found on the reaction rate constants for ascorbic acid degradation in peach purée. In this work, the degradation of ascorbic acid in Jade peach purée was studied in anaerobic conditions and from 70-90 °C. The peach purée concentrations tested were 12, 22 and 32 °Brix. The kinetic analysis of the data suggests that the degradation was significantly represented by zero and first-order kinetic models. The rate of ascorbic acid degradation in peach purée was temperature dependent. The average activation energy was 45 kJ.mol-1 and independent of the concentration of soluble solids.
Boehmite Dissolution Model Based on Simulant Data
International Nuclear Information System (INIS)
Several of the Hanford waste tanks contain significant quantities of boehmite. This boehmite will be dissolved through caustic leaching as part of the Hanford Tank Waste Treatment and Immobilization Plant currently under construction. Therefore, it is important to fully understand the nature of this dissolution process so that caustic leaching can be effectively deployed on the Hanford tank wastes. This research determined the impact of primary control parameters such as temperature, hydroxide concentration, approach to solubility, and stirring rate on the boehmite dissolution rate.
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。
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.
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
1995-08-01
about the distances to galaxies and thereby about the expansion rate of the Universe. A simple way to determine the distance to a remote galaxy is by measuring its redshift, calculate its velocity from the redshift and divide this by the Hubble constant, H0. For instance, the measured redshift of the parent galaxy of SN 1995K (0.478) yields a velocity of 116,000 km/sec, somewhat more than one-third of the speed of light (300,000 km/sec). From the universal expansion rate, described by the Hubble constant (H0 = 20 km/sec per million lightyears as found by some studies), this velocity would indicate a distance to the supernova and its parent galaxy of about 5,800 million lightyears. The explosion of the supernova would thus have taken place 5,800 million years ago, i.e. about 1,000 million years before the solar system was formed. However, such a simple calculation works only for relatively ``nearby'' objects, perhaps out to some hundred million lightyears. When we look much further into space, we also look far back in time and it is not excluded that the universal expansion rate, i.e. the Hubble constant, may have been different at earlier epochs. This means that unless we know the change of the Hubble constant with time, we cannot determine reliable distances of distant galaxies from their measured redshifts and velocities. At the same time, knowledge about such change or lack of the same will provide unique information about the time elapsed since the Universe began to expand (the ``Big Bang''), that is, the age of the Universe and also its ultimate fate. The Deceleration Parameter q0 Cosmologists are therefore eager to determine not only the current expansion rate (i.e., the Hubble constant, H0) but also its possible change with time (known as the deceleration parameter, q0). Although a highly accurate value of H0 has still not become available, increasing attention is now given to the observational determination of the second parameter, cf. also the Appendix at the
Variation of Fundamental Constants
Flambaum, V. V.
2006-11-01
Theories unifying gravity with other interactions suggest temporal and spatial variation of the fundamental ``constants'' in expanding Universe. The spatial variation can explain a fine tuning of the fundamental constants which allows humans (and any life) to appear. We appeared in the area of the Universe where the values of the fundamental constants are consistent with our existence. We present a review of recent works devoted to the variation of the fine structure constant α, strong interaction and fundamental masses. There are some hints for the variation in quasar absorption spectra. Big Bang nucleosynthesis, and Oklo natural nuclear reactor data. A very promising method to search for the variation of the fundamental constants consists in comparison of different atomic clocks. Huge enhancement of the variation effects happens in transition between accidentally degenerate atomic and molecular energy levels. A new idea is to build a ``nuclear'' clock based on the ultraviolet transition between very low excited state and ground state in Thorium nucleus. This may allow to improve sensitivity to the variation up to 10 orders of magnitude! Huge enhancement of the variation effects is also possible in cold atomic and molecular collisions near Feshbach resonance.
Institute of Scientific and Technical Information of China (English)
杜玉林
2012-01-01
The assumption of constant risk-free interest rate in Black-Scholes formula cannot be satisfied in market. In this paper , we find the option price interval assuming the risk-free lies within a given interval. First we transform this financia/ problem to a stochastic optimal control problem, then obtain options＂ maximum and minimum price models through dynamic programming principle. We then discuss how to solve the nonlinear PDE model and how to narrow the price interval through optima/static hedging. We conclude this paper by giving its applieations in U. S. A option market through BaiDu options,comparing with Black-scholes, and giving a method how to identify arbitrage opportunity in option markets.%Black—Scholes公式中无风险利率的常数假设与现实不符。本文假设无风险利率在一个区间中变动，讨论求期权价格区间问题。首先将此问题归结为一个随机最优控制问题，然后利用动态规划原理得到期权价格区间上下限满足的模型以及模型解法，并利用最优静态对冲缩小此价格区间，最后以BaiDu股票期权为例给出了模型在期权市场上的应用，提供了一种期权市场上的套利识别方法并与Black—Scholes公式的结果做了比较。
The 1% concordance Hubble constant
Energy Technology Data Exchange (ETDEWEB)
Bennett, C. L.; Larson, D.; Weiland, J. L. [Johns Hopkins University, 3400 North Charles Street, Baltimore, MD 21218 (United States); Hinshaw, G., E-mail: cbennett@jhu.edu [Department of Physics and Astronomy, University of British Columbia, Vancouver, BC V6T 1Z1 (Canada)
2014-10-20
The determination of the Hubble constant has been a central goal in observational astrophysics for nearly a hundred years. Extraordinary progress has occurred in recent years on two fronts: the cosmic distance ladder measurements at low redshift and cosmic microwave background (CMB) measurements at high redshift. The CMB is used to predict the current expansion rate through a best-fit cosmological model. Complementary progress has been made with baryon acoustic oscillation (BAO) measurements at relatively low redshifts. While BAO data do not independently determine a Hubble constant, they are important for constraints on possible solutions and checks on cosmic consistency. A precise determination of the Hubble constant is of great value, but it is more important to compare the high and low redshift measurements to test our cosmological model. Significant tension would suggest either uncertainties not accounted for in the experimental estimates or the discovery of new physics beyond the standard model of cosmology. In this paper we examine in detail the tension between the CMB, BAO, and cosmic distance ladder data sets. We find that these measurements are consistent within reasonable statistical expectations and we combine them to determine a best-fit Hubble constant of 69.6 ± 0.7 km s{sup –1} Mpc{sup –1}. This value is based upon WMAP9+SPT+ACT+6dFGS+BOSS/DR11+H {sub 0}/Riess; we explore alternate data combinations in the text. The combined data constrain the Hubble constant to 1%, with no compelling evidence for new physics.
Radiographic constant exposure technique
DEFF Research Database (Denmark)
Domanus, Joseph Czeslaw
1985-01-01
The constant exposure technique has been applied to assess various industrial radiographic systems. Different X-ray films and radiographic papers of two producers were compared. Special attention was given to fast film and paper used with fluorometallic screens. Radiographic image quality...... was tested by the use of ISO wire IQI's and ASTM penetrameters used on Al and Fe test plates. Relative speed and reduction of kilovoltage obtained with the constant exposure technique were calculated. The advantages of fast radiographic systems are pointed out...
Algorithm for structure constants
Paiva, F M
2011-01-01
In a $n$-dimensional Lie algebra, random numerical values are assigned by computer to $n(n-1)$ especially selected structure constants. An algorithm is then created, which calculates without ambiguity the remaining constants, obeying the Jacobi conditions. Differently from others, this algorithm is suitable even for poor personal computer. ------------- En $n$-dimensia algebro de Lie, hazardaj numeraj valoroj estas asignitaj per komputilo al $n(n-1)$ speciale elektitaj konstantoj de strukturo. Tiam algoritmo estas kreita, kalkulante senambigue la ceterajn konstantojn, obeante kondicxojn de Jacobi. Malsimile al aliaj algoritmoj, tiu cxi tauxgas ecx por malpotenca komputilo.
Huchra, John P.
1992-01-01
The Hubble constant is the constant of proportionality between recession velocity and distance in the expanding universe. It is a fundamental property of cosmology that sets both the scale and the expansion age of the universe. It is determined by measurement of galaxy radial velocities and distances. Although there has been considerable progress in the development of new techniques for the measurements of galaxy distances, both calibration uncertainties and debates over systematic errors remain. Current determinations still range over nearly a factor of 2; the higher values favored by most local measurements are not consistent with many theories of the origin of large-scale structure and stellar evolution.
Scott, Tricia
2015-11-01
Compassion is a powerful word that describes an intense feeling of commiseration and a desire to help those struck by misfortune. Most people know intuitively how and when to offer compassion to relieve another person's suffering. In health care, compassion is a constant; it cannot be rationed because emergency nurses have limited time or resources to manage increasing demands.
Constant Proportion Debt Obligations (CPDOs)
DEFF Research Database (Denmark)
Cont, Rama; Jessen, Cathrine
2012-01-01
Constant Proportion Debt Obligations (CPDOs) are structured credit derivatives that generate high coupon payments by dynamically leveraging a position in an underlying portfolio of investment-grade index default swaps. CPDO coupons and principal notes received high initial credit ratings from...... the major rating agencies, based on complex models for the joint transition of ratings and spreads for all names in the underlying portfolio. We propose a parsimonious model for analysing the performance of CPDO strategies using a top-down approach that captures the essential risk factors of the CPDO. Our...... approach allows us to compute default probabilities, loss distributions and other tail risk measures for the CPDO strategy and analyse the dependence of these risk measures on various parameters describing the risk factors. We find that the probability of the CPDO defaulting on its coupon payments can...
Variation of fundamental constants
Flambaum, V V
2006-01-01
We present a review of recent works devoted to the variation of the fine structure constant alpha, strong interaction and fundamental masses. There are some hints for the variation in quasar absorption spectra, Big Bang nucleosynthesis, and Oklo natural nuclear reactor data. A very promising method to search for the variation of the fundamental constants consists in comparison of different atomic clocks. Huge enhancement of the variation effects happens in transition between accidentally degenerate atomic and molecular energy levels. A new idea is to build a ``nuclear'' clock based on the ultraviolet transition between very low excited state and ground state in Thorium nucleus. This may allow to improve sensitivity to the variation up to 10 orders of magnitude! Huge enhancement of the variation effects is also possible in cold atomic and molecular collisions near Feschbach resonance.
Institute of Scientific and Technical Information of China (English)
赵庆孝; 常兆华; 杨鹏飞
2012-01-01
目的 验证一种定功率变流量以维持T0.2(距射频针0.2 cm处的温度)于设定值的气冷射频消融方式的可行性及有效性.方法 以土豆为实验对象,设计了针对不同T0.2预设值、氮气压力、射频功率的3组实验,通过考察射频针周围组织升温幅度及升温速度确定上述3个参数对消融效果的影响.结果 T0.2预设值越高,周围组织升温幅度越大；如能维持T0.2于预设值,则升温效果与氮气压力无关；同样时间内,升温幅度随功率增大而增大,但超过一定功率值后,由于消融时间缩短,升温幅度反而逐渐减小.结论 定功率变流量的气冷射频消融方式优于同工况下的传统气冷射频消融方式,实验结果可为气冷射频技术的优化提供参考.%Objective To verify the feasibility and efficacy of a new radiofrequency ablation ( RFA) mode with constant power and varying gas flow rate to keep T0.2(the temperature 0. 2 cm away from the RF probe) at the presetting temperature. Methods Three groups of experiments were performed according to different presetting value of T0.2, gas pressure and RF power in potatoes. The effects of the former 3 parameters mentioned above on ablation efficacy were evaluated by the degree and the rate of temperature rise of the tissue around the probe. Results The higher the presetting value of T0.2, the larger the degree of temperature rise of tissues was; If T0.2 could be kept at the preset value, the temperature rise was not related to the nitrogen pressure; In the same ablation duration, the degree of temperature rise was in direct proportion to the power. But when the power reached a certain level, the former was in contrast with the latter because of the ablation duration getting shorter. Conclusion The new RFA mode is superior to the regular one. The results provide helpful references for the optimization of gas-cooled RFA technology.
Institute of Scientific and Technical Information of China (English)
李尚俊; 谈宁馨; 姚倩; 李泽荣; 李象远
2015-01-01
Intramolecular hydrogen migration in alkylperoxy reactions is one of the most important reaction classes in hydrocarbon combustion at low temperatures. In this study, the kinetic parameters for reactions in this class were calculated using the isodesmic reaction method. The geometries for al the reactants, transition states, and products were optimized at the B3LYP/6-311+G(d,p) level. A criterion based on conservation of the reaction-center geometry of the transition state was proposed for the reaction class, and the intramolecular hydrogen migration reactions studied were divided into four classes, i.e., (1,3), (1,4), (1,5), and (1,n) (n=6, 7, 8) hydrogen migration. The simplest reaction system for each reaction class was defined as the principal reaction;the approximate single-point energies were obtained at the low level of B3LYP/6-311+G(d,p) and accurate single-point energies were obtained at the high level of CBS-QB3. The other reactions in this class were chosen as the target reactions and the approximate single-point energies were obtained at the B3LYP/6-311+G(d,p) level. The energy barriers and rate constants of these target reactions were corrected using the isodesmic reaction method. The results showed that accurate energy barriers and rate constants for the reactions of large molecules can be obtained by a relatively low level method using the isodesmic reaction method. In this study, classification of the basic isodesmic reaction showed the essential features of the reaction classes. The present work provides accurate kinetic parameters for modeling intramolecular hydrogen migration reactions of hydrocarbons at low temperatures.%过氧烷基自由基分子内氢迁移是低温燃烧反应中的一类重要基元反应。本文用等键反应方法计算了该类反应的动力学参数。所有反应物、过渡态、产物的几何结构均在B3LYP/6-311+G(d,p)水平下优化得到。本文提出了用过渡态反应中心几何结构守恒作为反
Directory of Open Access Journals (Sweden)
Neal Jackson
2015-09-01
Full Text Available I review the current state of determinations of the Hubble constant, which gives the length scale of the Universe by relating the expansion velocity of objects to their distance. There are two broad categories of measurements. The first uses individual astrophysical objects which have some property that allows their intrinsic luminosity or size to be determined, or allows the determination of their distance by geometric means. The second category comprises the use of all-sky cosmic microwave background, or correlations between large samples of galaxies, to determine information about the geometry of the Universe and hence the Hubble constant, typically in a combination with other cosmological parameters. Many, but not all, object-based measurements give H_0 values of around 72–74 km s^–1 Mpc^–1, with typical errors of 2–3 km s^–1 Mpc^–1. This is in mild discrepancy with CMB-based measurements, in particular those from the Planck satellite, which give values of 67–68 km s^–1 Mpc^–1 and typical errors of 1–2 km s^–1 Mpc^–1. The size of the remaining systematics indicate that accuracy rather than precision is the remaining problem in a good determination of the Hubble constant. Whether a discrepancy exists, and whether new physics is needed to resolve it, depends on details of the systematics of the object-based methods, and also on the assumptions about other cosmological parameters and which datasets are combined in the case of the all-sky methods.
Approximations to Euler's constant
International Nuclear Information System (INIS)
We study a problem of finding good approximations to Euler's constant γ=lim→∞ Sn, where Sn = Σk=Ln (1)/k-log(n+1), by linear forms in logarithms and harmonic numbers. In 1995, C. Elsner showed that slow convergence of the sequence Sn can be significantly improved if Sn is replaced by linear combinations of Sn with integer coefficients. In this paper, considering more general linear transformations of the sequence Sn we establish new accelerating convergence formulae for γ. Our estimates sharpen and generalize recent Elsner's, Rivoal's and author's results. (author)
The ideal Kolmogorov inertial range and constant
Zhou, YE
1993-01-01
The energy transfer statistics measured in numerically simulated flows are found to be nearly self-similar for wavenumbers in the inertial range. Using the measured self-similar form, an 'ideal' energy transfer function and the corresponding energy flux rate were deduced. From this flux rate, the Kolmogorov constant was calculated to be 1.5, in excellent agreement with experiments.
Decay constants in geochronology
Institute of Scientific and Technical Information of China (English)
IgorM.Villa; PaulR.Renne
2005-01-01
Geologic time is fundamental to the Earth Sciences, and progress in many disciplines depends critically on our ability to measure time with increasing accuracy and precision. Isotopic geochronology makes use of the decay of radioactive nuclides as a help to quantify the histories of rock, minerals, and other materials. Both accuracy and precision of radioisotopic ages are, at present, limited by those of radioactive decay constants. Modem mass spectrometers can measure isotope ratios with a precision of 10-4 or better. On the other hand, the uncertainties associated with direct half-life determinations are, in most cases, still at the percent level. The present short note briefly summarizes progress and problems that have been encountered during the Working Group's activity.
Ricardo Peraça Toralles; João Luiz Vendruscolo; Claire Tondo Vendruscolo; Francisco Augusto Burkert Del Pino; Pedro Luiz Antunes
2008-01-01
O ácido ascórbico, vitamina C, é usado extensivamente na indústria de alimentos, não só devido ao seu valor nutricional, mas devido a suas contribuições funcionais na qualidade do produto. Existem muitos estudos sobre a estabilidade cinética do ácido ascórbico em bebidas, mas nenhum estudo foi encontrado sobre as constantes cinéticas de degradação do ácido ascórbico adicionado em purê de pêssego. Neste trabalho, estudou-se a cinética de degradação do ácido ascórbico em purê de pêssego da cult...
Poole, R K; Salmon, I; Chance, B
1994-05-01
Cytochromes b and o in membrane vesicles from aerobically grown Escherichia coli were readily reduced by succinate; one cytochrome, which we propose should be called cytochrome o', reacted with CO in the Fe(II) state to give a photodissociable CO adduct. The photodissociation spectrum (photolysed minus pre-photolysis) at sub-zero temperatures had a relatively high gamma/alpha absorbance ratio, indicating a high-spin haem, which, in the reduced state, probably contributes little to the sharp alpha absorbance of the oxidase complex in membranes. Reaction with oxygen of the unliganded high-spin haem between -132 degrees C and -95 degrees C following photolytic activation gave a product that is identified as the oxygenated form, being spectrally similar to, but not identical with, the CO adduct. In membranes, the forward velocity constant at -95 degrees C was 61 M-1s-1, and the dissociation constant was 1.6 x 10(-5) M O2, as it is in intact cells. These data clearly distinguish the oxygen-trapping strategy of the cytochrome o' in this oxidase from that of cytochrome a3 and also suggest that the presence of the soluble flavohaemoglobin (Hmp) in intact cells is without effect on such measurements of the primary oxygen reaction. In view of recent findings that this oxidase complex contains predominantly one mole of haem O and one of haem B, a revised nomenclature for the oxidase complex is proposed, namely, cytochrome bo'. PMID:8025668
The Interacting and Non-constant Cosmological Constant
Verma, Murli Manohar
2009-01-01
We propose a time-varying cosmological constant with a fixed equation of state, which evolves mainly through its interaction with the background during most of the long history of the universe. However, such interaction does not exist in the very early and the late-time universe and produces the acceleration during these eras when it becomes very nearly a constant. It is found that after the initial inflationary phase, the cosmological constant, that we call as lambda parameter, rolls down from a large constant value to another but very small constant value and further dominates the present epoch showing up in form of the dark energy driving the acceleration.
Adelic Universe and Cosmological Constant
Makhaldiani, Nugzar
2003-01-01
In the quantum adelic field (string) theory models, vacuum energy -- cosmological constant vanish. The other (alternative ?) mechanism is given by supersymmetric theories. Some observations on prime numbers, zeta -- function and fine structure constant are also considered.
Quantum Theory without Planck's Constant
Ralston, John P
2012-01-01
Planck's constant was introduced as a fundamental scale in the early history of quantum mechanics. We find a modern approach where Planck's constant is absent: it is unobservable except as a constant of human convention. Despite long reference to experiment, review shows that Planck's constant cannot be obtained from the data of Ryberg, Davisson and Germer, Compton, or that used by Planck himself. In the new approach Planck's constant is tied to macroscopic conventions of Newtonian origin, which are dispensable. The precision of other fundamental constants is substantially improved by eliminating Planck's constant. The electron mass is determined about 67 times more precisely, and the unit of electric charge determined 139 times more precisely. Improvement in the experimental value of the fine structure constant allows new types of experiment to be compared towards finding "new physics." The long-standing goal of eliminating reliance on the artifact known as the International Prototype Kilogram can be accompl...
Chandra Independently Determines Hubble Constant
2006-08-01
A critically important number that specifies the expansion rate of the Universe, the so-called Hubble constant, has been independently determined using NASA's Chandra X-ray Observatory. This new value matches recent measurements using other methods and extends their validity to greater distances, thus allowing astronomers to probe earlier epochs in the evolution of the Universe. "The reason this result is so significant is that we need the Hubble constant to tell us the size of the Universe, its age, and how much matter it contains," said Max Bonamente from the University of Alabama in Huntsville and NASA's Marshall Space Flight Center (MSFC) in Huntsville, Ala., lead author on the paper describing the results. "Astronomers absolutely need to trust this number because we use it for countless calculations." Illustration of Sunyaev-Zeldovich Effect Illustration of Sunyaev-Zeldovich Effect The Hubble constant is calculated by measuring the speed at which objects are moving away from us and dividing by their distance. Most of the previous attempts to determine the Hubble constant have involved using a multi-step, or distance ladder, approach in which the distance to nearby galaxies is used as the basis for determining greater distances. The most common approach has been to use a well-studied type of pulsating star known as a Cepheid variable, in conjunction with more distant supernovae to trace distances across the Universe. Scientists using this method and observations from the Hubble Space Telescope were able to measure the Hubble constant to within 10%. However, only independent checks would give them the confidence they desired, considering that much of our understanding of the Universe hangs in the balance. Chandra X-ray Image of MACS J1149.5+223 Chandra X-ray Image of MACS J1149.5+223 By combining X-ray data from Chandra with radio observations of galaxy clusters, the team determined the distances to 38 galaxy clusters ranging from 1.4 billion to 9.3 billion
Institute of Scientific and Technical Information of China (English)
黄燕玲
2012-01-01
Abstract: In this paper, we study a cubic kolmogorov system with constant-rata prey stocking(dx)/(dt)=x(a0+a1x-a2x2-a3y-a4y2-a5xy)+k,(dy)/(dt)=y(bx2-d)The sufficient conditions of the existence and nonexistence of limit cycles areobtained.%对一类食饵种群具有常数存放率的三次kolmogorov系统：（dx）/（dt）=x（a0＋a1x-a2x2-a3y-a4y2-a5xy）＋k,（dy）/（dt）=y（bx2-d）,进行定性分析,得到该系统不存在极限环和存在极限环的充分条件.
Sofia de Amorim Cerejo; Ewaldo de Mattos Júnior; Lilian Toshiko Nishimura; Carolina Quarterone; Leandro Guimarães Franco
2013-01-01
Constant rate infusion (CRI) shows several advantages in balanced anesthesia, such as reduction of requirement for inhaled anesthetics and control of pain. The most commonly used drugs in these protocols are local anesthetics, dissociative, and opioids, which may be administered alone or in combinations. We evaluated the records of 200 dogs that underwent various surgical procedures with anesthetic or analgesic CRI in the perioperative period during 2011 and 2012 at the Veterinary Hospital of...
Institute of Scientific and Technical Information of China (English)
李亚; 赵鑫; 李振亮; 许玮
2013-01-01
An auto air leakage volume test system based on constant pressure method was designed. Using standard orifice plate as throttle device,after testing some original data such as the differential pressure between both sides of the throttle device,temperature of the dry-bulb and the wet-bulb,and so on,the auto air leakage volume can be calculated. The formulas and methods involved were demonstrated in detail and the experiment was designed based on an analysis of the measurement theory. According to the result of the experiment,this method proved stable and reliable and can satisfy the requirement of the measurement.% 设计了基于恒压法的汽车整车漏风量测试系统。采用标准孔板作为节流件，通过测量节流件上下游的压力差、干球温度和湿球温度等基础数据，经过计算可得到整车漏风量。在分析测量原理的基础上，详细给出了计算漏风量的公式和方法，并进行了实验。实验结果表明，该计算方法稳定可靠，可满足测量要求。
Forward recursions and normalizing constant
Guyon, Xavier; Hardouin, Cécile
2009-01-01
Maximum likelihood parameter estimation is frequently replaced by various techniques because of its intractable normalizing constant. In the same way, the literature displays various alternatives for distributions involving such unreachable constants. In this paper, we consider a Gibbs distribution $\\pi $ and present a recurrence formula allowing a recursive calculus of the marginals of $\\pi $ and in the same time its normalizing constant$.$ The numerical performance of this algorithm is eval...
Basic constant of matter world
International Nuclear Information System (INIS)
It was analysed how to gain constant 46 hidden among elementary units of matter world, which is divided into, 1, 2, 4, 8, 16, 8, 4, 2, 1. Here it shows the unity of opposites on philosophy and simple symmetric beauty of mathphysics. The constant specifically shows that scope constant 44 in nuclides layer of matter world and chromosome number of mankind is 23 pairs, which is the highest form of matter motion, the basic cause of existing constant 46 is that matter exists in space-time with 4-dimensions, and it obeys the principle of the most lower energy
Spectrophotometric determination of association constant
DEFF Research Database (Denmark)
Spanget-Larsen, Jens
2016-01-01
Least-squares 'Systematic Trial-and-Error Procedure' (STEP) for spectrophotometric evaluation of association constant (equilibrium constant) K and molar absorption coefficient E for a 1:1 molecular complex, A + B = C, with error analysis according to Conrow et al. (1964). An analysis of the Charge...
Energy Technology Data Exchange (ETDEWEB)
Michael, J. V.; Sutherland, J. W.; Harding, L. B.; Wagner, A. F.
1999-11-02
The reaction between H{sub 2} and O{sub 2} has been studied in a reflected shock tube apparatus between 1662--2097 K. O-atom atomic resonance absorption spectrometry (ARAS) was used to observe absolute [O]{sub t} under conditions of low [H{sub 2}]{sub 0} so that most secondary reactions were negligible. Hence, the observed [O]{sub t}, was the direct result of the rate controlling reaction between H{sub 2} and O{sub 2}. Three different reactions were considered, but experimental and ab initio theoretical results both indicated that the process, H{sub 2} + O{sub 2} {yields} H + HO{sub 2}, is the only possible reaction. After rapid HO{sub 2} dissociation, O-atoms are then instantaneously produced by H + O{sub 2} {yields} O + OH. Using the ab initio result, conventional transition state theoretical calculations (CTST) with tunneling corrections give the expression: k = 1.228 x 10{sup {minus}18} T{sup 2.4328} exp({minus}26926 K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}, applicable between 400 and 2,300 K. This theoretical result agrees with the present experimental determinations and those at lower temperature, derived from earlier work on the reverse reaction.
Bose-Einstein condensation at constant temperature
Erhard, M.; Schmaljohann, H.; Kronjäger, J.; Bongs, K.; Sengstock, K.
2004-09-01
We present an experimental approach to Bose-Einstein condensation by increasing the particle number of the system at almost constant temperature. In particular, the emergence of a new condensate is observed in multicomponent F=1 spinor condensates of Rb87 . Furthermore, we develop a simple rate-equation model for multicomponent Bose-Einstein condensate thermodynamics at finite temperature which well reproduces the measured effects.
Varying constants, Gravitation and Cosmology
Uzan, Jean-Philippe
2010-01-01
Fundamental constants are a cornerstone of our physical laws. Any constant varying in space and/or time would reflect the existence of an almost massless field that couples to matter. This will induce a violation of the universality of free fall. It is thus of utmost importance for our understanding of gravity and of the domain of validity of general relativity to test for their constancy. We thus detail the relations between the constants, the tests of the local position invariance and of the universality of free fall. We then review the main experimental and observational constraints that have been obtained from atomic clocks, the Oklo phenomenon, Solar system observations, meteorites dating, quasar absorption spectra, stellar physics, pulsar timing, the cosmic microwave background and big bang nucleosynthesis. At each step we describe the basics of each system, its dependence with respect to the constants, the known systematic effects and the most recent constraints that have been obtained. We then describ...
Institute of Scientific and Technical Information of China (English)
曾斌; 张鸣生
2015-01-01
Objective To study the relationship between the constant work rate exercises and dynamic hyperinflation in patients with stable COPD. Methods Routine lung ventilation function and 80%Wmax constant power bicycle ergometer exercises were tested in 30 stable COPD patients. We analyzed the correlation coefficient of Time of tolerant exercise , degree of dyspnea , VO2 max%, VO2 @kgmax% and IC%. Results All COPD patients existed varying degrees of exercise capacity accompaning with dynamic hyperinflation in the bicycle ergometer exercises. By Spearman correlation analysis , the VO2 @kg% of constant power exercises in patients with COPD is correlated with the DH% (r = -0.480, P = 0.007) and ICq% (r = 0.667, P = 0.01). Conclusion Dynamic hyperinflation is probably the prominent factors for the capability of constant work rate exercises in patients with stable COPD. Inhibition of dynamic hyperinflation may help improve exercise capability in patients with constant power exercise.%目的:观察稳定期慢性阻塞性肺疾病(COPD)患者的恒定功率运动表现与动态过度充气间的相互关系.方法:对30例中度以上稳定期COPD患者进行常规肺通气功能、80%Wmax恒定功率自行车运动测试,分析运动耐受时间、呼吸困难程度、最大摄氧量量及最大公斤摄氧量百分比与深吸气量百分比变化值之间的相互关系. 结果:COPD患者均出现不同程度的运动能力下降,且在恒定功率运动中伴随显著的动态过度充气;相关分析提示,恒定功率运动最大公斤摄氧量百分比与动态过度充气百分比呈负相关(r = -0.480, P = 0.007),而与静息深吸气量百分比呈正相关(r=0.667,P=0.01).结论:动态过度充气可能是COPD患者恒定功率运动受限的重要影响因子,抑制动态过度充气可能有助于改善患者的恒定功率运动表现.
Fundamental Constants and Conservation Laws
Roh, Heui-Seol
2001-01-01
This work describes underlying features of the universe such as fundamental constants and cosmological parameters, conservation laws, baryon and lepton asymmetries, etc. in the context of local gauge theories for fundamental forces under the constraint of the flat universe. Conservation laws for fundamental forces are related to gauge theories for fundamental forces, their resulting fundamental constants are quantitatively analyzed, and their possible violations at different energy scales are...
Inflation and the cosmological constant
Directory of Open Access Journals (Sweden)
FENG Chaojun
2014-08-01
Full Text Available By assuming the cosmological “constant” is no longer a constant during the inflation epoch,it is found that the cosmological constant fine-tuning problem is solved.In the meanwhile,inflation models could predict a large tensor-to-scalar ratio,correct power spectral index and a larger running of it.Furthermore,the e-folding number is large enough to overcome the horizon,flatness problems in the Big Bang cosmology.
Varying Constants, Gravitation and Cosmology
Uzan, Jean-Philippe
2011-12-01
Fundamental constants are a cornerstone of our physical laws. Any constant varying in space and/or time would reflect the existence of an almost massless field that couples to matter. This will induce a violation of the universality of free fall. Thus, it is of utmost importance for our understanding of gravity and of the domain of validity of general relativity to test for their constancy. We detail the relations between the constants, the tests of the local position invariance and of the universality of free fall. We then review the main experimental and observational constraints that have been obtained from atomic clocks, the Oklo phenomenon, solar system observations, meteorite dating, quasar absorption spectra, stellar physics, pulsar timing, the cosmic microwave background and big bang nucleosynthesis. At each step we describe the basics of each system, its dependence with respect to the constants, the known systematic effects and the most recent constraints that have been obtained. We then describe the main theoretical frameworks in which the low-energy constants may actually be varying and we focus on the unification mechanisms and the relations between the variation of different constants. To finish, we discuss the more speculative possibility of understanding their numerical values and the apparent fine-tuning that they confront us with.
Varying Constants, Gravitation and Cosmology
Directory of Open Access Journals (Sweden)
Jean-Philippe Uzan
2011-03-01
Full Text Available Fundamental constants are a cornerstone of our physical laws. Any constant varying in space and/or time would reflect the existence of an almost massless field that couples to matter. This will induce a violation of the universality of free fall. Thus, it is of utmost importance for our understanding of gravity and of the domain of validity of general relativity to test for their constancy. We detail the relations between the constants, the tests of the local position invariance and of the universality of free fall. We then review the main experimental and observational constraints that have been obtained from atomic clocks, the Oklo phenomenon, solar system observations, meteorite dating, quasar absorption spectra, stellar physics, pulsar timing, the cosmic microwave background and big bang nucleosynthesis. At each step we describe the basics of each system, its dependence with respect to the constants, the known systematic effects and the most recent constraints that have been obtained. We then describe the main theoretical frameworks in which the low-energy constants may actually be varying and we focus on the unification mechanisms and the relations between the variation of different constants. To finish, we discuss the more speculative possibility of understanding their numerical values and the apparent fine-tuning that they confront us with.
From the Rydberg constant to the fundamental constants metrology
International Nuclear Information System (INIS)
This document reviews the theoretical and experimental achievements of the author since the beginning of his scientific career. This document is dedicated to the spectroscopy of hydrogen, deuterium and helium atoms. The first part is divided into 6 sub-sections: 1) the principles of hydrogen spectroscopy, 2) the measurement of the 2S-nS/nD transitions, 3) other optical frequency measurements, 4) our contribution to the determination of the Rydberg constant, 5) our current experiment on the 1S-3S transition, 6) the spectroscopy of the muonic hydrogen. Our experiments have improved the accuracy of the Rydberg Constant by a factor 25 in 15 years and we have achieved the first absolute optical frequency measurement of a transition in hydrogen. The second part is dedicated to the measurement of the fine structure constant and the last part deals with helium spectroscopy and the search for optical references in the near infrared range. (A.C.)
Effective cosmological constant induced by stochastic fluctuations of Newton's constant
de Cesare, Marco; Lizzi, Fedele; Sakellariadou, Mairi
2016-09-01
We consider implications of the microscopic dynamics of spacetime for the evolution of cosmological models. We argue that quantum geometry effects may lead to stochastic fluctuations of the gravitational constant, which is thus considered as a macroscopic effective dynamical quantity. Consistency with Riemannian geometry entails the presence of a time-dependent dark energy term in the modified field equations, which can be expressed in terms of the dynamical gravitational constant. We suggest that the late-time accelerated expansion of the Universe may be ascribed to quantum fluctuations in the geometry of spacetime rather than the vacuum energy from the matter sector.
Effective cosmological constant induced by stochastic fluctuations of Newton's constant
de Cesare, Marco; Sakellariadou, Mairi
2016-01-01
We consider implications of the microscopic dynamics of spacetime for the evolution of cosmological models. We argue that quantum geometry effects may lead to stochastic fluctuations of the gravitational constant, which is thus considered as a macroscopic effective dynamical quantity. Consistency with Riemannian geometry entails the presence of a time-dependent dark energy term in the modified field equations, which can be expressed in terms of the dynamical gravitational constant. We suggest that the late-time accelerated expansion of the Universe may be ascribed to quantum fluctuations in the geometry of spacetime rather than the vacuum energy from the matter sector.
How fundamental are fundamental constants?
Duff, M. J.
2015-01-01
I argue that the laws of physics should be independent of one's choice of units or measuring apparatus. This is the case if they are framed in terms of dimensionless numbers such as the fine structure constant, ?. For example, the standard model of particle physics has 19 such dimensionless parameters whose values all observers can agree on, irrespective of what clock, rulers or scales? they use to measure them. Dimensional constants, on the other hand, such as ?, c, G, e and k ?, are merely human constructs whose number and values differ from one choice of units to the next. In this sense, only dimensionless constants are 'fundamental'. Similarly, the possible time variation of dimensionless fundamental 'constants' of nature is operationally well defined and a legitimate subject of physical enquiry. By contrast, the time variation of dimensional constants such as ? or ? on which a good many (in my opinion, confusing) papers have been written, is a unit-dependent phenomenon on which different observers might disagree depending on their apparatus. All these confusions disappear if one asks only unit-independent questions. We provide a selection of opposing opinions in the literature and respond accordingly.
How fundamental are fundamental constants?
Duff, M J
2014-01-01
I argue that the laws of physics should be independent of one's choice of units or measuring apparatus. This is the case if they are framed in terms of dimensionless numbers such as the fine structure constant, alpha. For example, the Standard Model of particle physics has 19 such dimensionless parameters whose values all observers can agree on, irrespective of what clock, rulers, scales... they use to measure them. Dimensional constants, on the other hand, such as h, c, G, e, k..., are merely human constructs whose number and values differ from one choice of units to the next. In this sense only dimensionless constants are "fundamental". Similarly, the possible time variation of dimensionless fundamental "constants" of nature is operationally well-defined and a legitimate subject of physical enquiry. By contrast, the time variation of dimensional constants such as c or G on which a good many (in my opinion, confusing) papers have been written, is a unit-dependent phenomenon on which different observers might...
Nonminimal coupling and the cosmological constant problem
Glavan, Dražen
2015-01-01
We consider a universe with a positive effective cosmological constant and a nonminimally coupled scalar field. When the coupling constant is negative, the scalar field exhibits linear growth at asymptotically late times, resulting in a decaying effective cosmological constant. The Hubble rate in the Jordan frame reaches a self-similar solution, $H=1/(\\epsilon t)$, where the principal slow roll parameter $\\epsilon$ depends on $\\xi$, reaching maximally $\\epsilon=2$ (radiation era scaling) in the limit when $\\xi\\rightarrow -\\infty$. Similar results are found in the Einstein frame (E), with $H_E=1/(\\epsilon_E t)$, but now $\\epsilon_E \\rightarrow 4/3$ as $\\xi\\rightarrow -\\infty$. Therefore in the presence of a nonminimally coupled scalar de Sitter is not any more an attractor, but instead (when $\\xi4/3$ at a rate $\\Gamma\\gg H$, the scaling changes to that of matter, $\\epsilon\\rightarrow \\epsilon_m$, and the energy density in the effective cosmological becomes a fixed fraction of the matter energy density, $M_{\\rm...
Learning Read-constant Polynomials of Constant Degree modulo Composites
DEFF Research Database (Denmark)
Chattopadhyay, Arkadev; Gavaldá, Richard; Hansen, Kristoffer Arnsfelt;
2011-01-01
is not known to be learnable in any reasonable learning model. In this paper, we provide a deterministic polynomial time algorithm for learning Boolean functions represented by polynomials of constant degree over arbitrary finite rings from membership queries, with the additional constraint that each variable...
Energy Technology Data Exchange (ETDEWEB)
Nez, F
2005-06-15
This document reviews the theoretical and experimental achievements of the author since the beginning of his scientific career. This document is dedicated to the spectroscopy of hydrogen, deuterium and helium atoms. The first part is divided into 6 sub-sections: 1) the principles of hydrogen spectroscopy, 2) the measurement of the 2S-nS/nD transitions, 3) other optical frequency measurements, 4) our contribution to the determination of the Rydberg constant, 5) our current experiment on the 1S-3S transition, 6) the spectroscopy of the muonic hydrogen. Our experiments have improved the accuracy of the Rydberg Constant by a factor 25 in 15 years and we have achieved the first absolute optical frequency measurement of a transition in hydrogen. The second part is dedicated to the measurement of the fine structure constant and the last part deals with helium spectroscopy and the search for optical references in the near infrared range. (A.C.)
Constant force extensional rheometry of polymer solutions
DEFF Research Database (Denmark)
Szabo, Peter; McKinley, Gareth H.; Clasen, Christian
2012-01-01
We revisit the rapid stretching of a liquid filament under the action of a constant imposed tensile force, a problem which was first considered by Matta and Tytus [J. Non-Newton. Fluid Mech. 35 (1990) 215–229]. A liquid bridge formed from a viscous Newtonian fluid or from a dilute polymer solution...... filament can be probed. In particular, we show that with this constant force pull (CFP) technique it is possible to readily impose very large material strains and strain rates so that the maximum extensibility of the polymer molecules may be quantified. This unique characteristic of the experiment...... mass is developed for simple viscous filaments. Based on these theoretical considerations we develop an expression that enables estimation of the finite extensibility parameter characterizing the polymer solution in terms of quantities that can be extracted directly from simple measurement of the time...
Mirror QCD and Cosmological Constant
Pasechnik, Roman; Teryaev, Oleg
2016-01-01
An analog of Quantum Chromo Dynamics (QCD) sector known as mirror QCD (mQCD) can affect the cosmological evolution and help in resolving the Cosmological Constant problem. In this work, we explore an intriguing possibility for a compensation of the negative QCD vacuum contribution to the ground state energy density of the universe by means of a positive contribution from the chromomagnetic gluon condensate in mQCD. The trace anomaly compensation condition and the form of the mQCD coupling constant in the infrared limit have been proposed by analysing a partial non-perturbative solution of the Einstein--Yang-Mills equations of motion.
Czechowski, Grzegorz; Zywucki, B.; Jadzyn, Jan
1993-10-01
The Frederiks transitions for the n-octyloxycyanobiphenyl (8-OCB) placed in the external magnetic and electric field as a function of the temperature have been studied. On the basis of threshold values Bc and Uc, the elastic constants for splay, bend and twist modes are determined. The magnetic anisotropy of 8-OCB as a function of temperature has been determined. The K11 and K33 elastic constants show the pretransitional nematic- smectic A effect. The values of critical exponents obtained from the temperature dependence of K11 and K33 in the vicinity of N-SA phase transition are discussed.
On constant elasticities of demand
Andrés Vázquez
1998-01-01
While the Slutsky matrix and duality theory have been used to establish that constant elasticity demand functions imply unitary income elasticities, zero cross price elasticities and own price elasticities equal to minus one, this note shows that these results can also be straightforwardly derived from the simple assumption that demand functions satisfy the budget constraint with strict equality.
Institute of Scientific and Technical Information of China (English)
张欣; 丁祥欢; 朱雪焱; 叶建农
2001-01-01
利用具有高分辩率和高灵敏度的毛细管电泳－电化学检测方法测定乳糖、麦芽糖及其水解产物的浓度随反应时间变化的规律。在H2SO4催化下,对不同温度时乳糖、麦芽糖水解反应速率进行了测定,在85℃、90℃和95℃时乳糖的水解反应速率常数分别为13.3×10－3、30.1×10－3和52.5×10－3min－1；而麦芽糖在85℃、95℃和100℃时的反应速率常数分别为17.7×10－3、84.6×10－3和150×10－3min－1；并据此分别求得反应活化能Ea为161.1kJ/mol、194.7kJ/mol。%The concentration of lactose and maltose and their hydrolysisproducts were monitored by ca-pillary electrophoresis-electrochemical detection due to its high resolution and high sensitivity of detection. The reaction rate constant of lactose and maltose hydrolysis at different temperature in 0.75 mol/L H2SO4 were obtained from the concentration change of lactose and maltose during the process of hydrolysis. At 85 ℃ , 90 ℃ and 95 ℃ , the measured rate constants of lactose hydrolysis were 13.3× 10-3 min-1, 30.1× 10-3 min-1 and 52.5× 10-3 min-1, respectively, from which the activation energy of the reaction(Ea) value of 161.1 kJ/mol was derived. At 85 ℃ , 95 ℃ and 100 ℃ , the measured rate constants of maltose hydrolysis were 17.7× 10-3 min-1, 84.6×10-3 min-1 and 150× 10-3 min-1, respectively, Ea value obtained was 194.7 kJ/mol.
Variation of fundamental constants: theory
Flambaum, Victor
2008-05-01
Theories unifying gravity with other interactions suggest temporal and spatial variation of the fundamental ``constants'' in expanding Universe. There are some hints for the variation of different fundamental constants in quasar absorption spectra and Big Bang nucleosynthesis data. A large number of publications (including atomic clocks) report limits on the variations. We want to study the variation of the main dimensionless parameters of the Standard Model: 1. Fine structure constant alpha (combination of speed of light, electron charge and Plank constant). 2. Ratio of the strong interaction scale (LambdaQCD) to a fundamental mass like electron mass or quark mass which are proportional to Higgs vacuum expectation value. The proton mass is propotional to LambdaQCD, therefore, the proton-to-electron mass ratio comes into this second category. We performed necessary atomic, nuclear and QCD calculations needed to study variation of the fundamental constants using the Big Bang Nucleosynthsis, quasar spectra, Oklo natural nuclear reactor and atomic clock data. The relative effects of the variation may be enhanced in transitions between narrow close levels in atoms, molecules and nuclei. If one will study an enhanced effect, the relative value of systematic effects (which are not enhanced) may be much smaller. Note also that the absolute magnitude of the variation effects in nuclei (e.g. in very narrow 7 eV transition in 229Th) may be 5 orders of magnitude larger than in atoms. A different possibility of enhancement comes from the inversion transitions in molecules where splitting between the levels is due to the quantum tunneling amplitude which has strong, exponential dependence on the electron to proton mass ratio. Our study of NH3 quasar spectra has already given the best limit on the variation of electron to proton mass ratio.
WHY IS THE SOLAR CONSTANT NOT A CONSTANT?
International Nuclear Information System (INIS)
In order to probe the mechanism of variations of the solar constant on the inter-solar-cycle scale, the total solar irradiance (TSI; the so-called solar constant) in the time interval of 1978 November 7 to 2010 September 20 is decomposed into three components through empirical mode decomposition and time-frequency analyses. The first component is the rotation signal, counting up to 42.31% of the total variation of TSI, which is understood to be mainly caused by large magnetic structures, including sunspot groups. The second is an annual-variation signal, counting up to 15.17% of the total variation, the origin of which is not known at this point in time. Finally, the third is the inter-solar-cycle signal, counting up to 42.52%, which is inferred to be caused by the network magnetic elements in quiet regions, whose magnetic flux ranges from (4.27-38.01) × 1019 Mx.
Varying Fine-Structure Constant and the Cosmological Constant Problem
Fujii, Y
2003-01-01
We start with a brief account of the latest analysis of the Oklo phenomenon providing the still most stringent constraint on time-variability of the fine- structure constant $\\alpha$. Comparing this with the recent result from the measurement of distant QSO's appears to indicate a non-uniform time-dependence, which we argue to be related to another recent finding of the accelerating universe. This view is implemented in terms of the scalar-tensor theory, applied specifically to the small but nonzero cosmological constant. Our detailed calculation shows that these two phenomena can be understood in terms of a common origin, a particular behavior of the scalar field, dilaton. We also sketch how this theoretical approach makes it appropriate to revisit non- Newtonian gravity featuring small violation of Weak Equivalence Principle at medium distances.
Varying Fine-Structure Constant and the Cosmological Constant Problem
Fujii, Yasunori
We start with a brief account of the latest analysis of the Oklo phenomenon providing the still most stringent constraint on time variability of the fine-structure constant α. Comparing this with the recent result from the measurement of distant QSO's appears to indicate a non-uniform time-dependence, which we argue to be related to another recent finding of the accelerating universe. This view is implemented in terms of the scalar-tensor theory, applied specifically to the small but nonzero cosmological constant. Our detailed calculation shows that these two phenomena can be understood in terms of a common origin, a particular behavior of the scalar field, dilaton. We also sketch how this theoretical approach makes it appropriate to revisit non-Newtonian gravity featuring small violation of Weak Equivalence Principle at medium distances.
New Quasar Studies Keep Fundamental Physical Constant Constant
2004-03-01
Very Large Telescope sets stringent limit on possible variation of the fine-structure constant over cosmological time Summary Detecting or constraining the possible time variations of fundamental physical constants is an important step toward a complete understanding of basic physics and hence the world in which we live. A step in which astrophysics proves most useful. Previous astronomical measurements of the fine structure constant - the dimensionless number that determines the strength of interactions between charged particles and electromagnetic fields - suggested that this particular constant is increasing very slightly with time. If confirmed, this would have very profound implications for our understanding of fundamental physics. New studies, conducted using the UVES spectrograph on Kueyen, one of the 8.2-m telescopes of ESO's Very Large Telescope array at Paranal (Chile), secured new data with unprecedented quality. These data, combined with a very careful analysis, have provided the strongest astronomical constraints to date on the possible variation of the fine structure constant. They show that, contrary to previous claims, no evidence exist for assuming a time variation of this fundamental constant. PR Photo 07/04: Relative Changes with Redshift of the Fine Structure Constant (VLT/UVES) A fine constant To explain the Universe and to represent it mathematically, scientists rely on so-called fundamental constants or fixed numbers. The fundamental laws of physics, as we presently understand them, depend on about 25 such constants. Well-known examples are the gravitational constant, which defines the strength of the force acting between two bodies, such as the Earth and the Moon, and the speed of light. One of these constants is the so-called "fine structure constant", alpha = 1/137.03599958, a combination of electrical charge of the electron, the Planck constant and the speed of light. The fine structure constant describes how electromagnetic forces hold
PECVD of low-dielectric constant films for ULSI
Shimogaki, Yukihiro
1998-10-01
We studied the reduction mechanism of the dielectric constant of F-doped silicon oxide films prepared by PECVD from SiH_4/N_2O/CF4 mixture. From the estimation of the dielectric constant at various frequencies, ranging from 1MHz to 100THz, using CV measurement, Kramers-Kronig relation and the square of the refractive index, we suggest that the dielectric constant due to ionic and electronic polarization is not the dominant factor in decreasing the dielectric constant. It is important to remove -OH in films to obtain very low dielectric constant F-doped silicon oxide films, because Si-OH is the main factor of the orientational polarization in silicon oxide films made by PECVD. To investigate the reaction mechanism which controls the film structure, we changed the residence time of gas in chamber by varying the flow rate. When the residence time in chamber decreases, the film deposition rate increases. We tried to explain flow rate dependency of the deposition rate using a simple CSTR (continuous stirred tank reactor) model. It can be concluded that there are two paths to deposit the films. One route is a deposition by the precursors with poor step coverage profile, and the other route is deposition through intermediates formed by gas phase reactions that contribute to have better step coverage. The overall gas phase reaction rate constant was estimated from these kinetic studies. Same approach was also carried out on the PECVD of C:F film deposition.
Institute of Scientific and Technical Information of China (English)
徐光甫; 李洪霞
2004-01-01
研究了具有定常人为故障率(human error rates)和通常故障率(common-cause failure rates),修复时间任意分布的可修复系统的数学模型.首先将此系统转换为Banach空间下的Volterra积分方程,得到了系统非负解的存在性和唯一性结果.
Wormholes and the cosmological constant
International Nuclear Information System (INIS)
We review Coleman's wormhole mechanism for the vanishing of the cosmological constant. We show that in a minisuperspace model wormhole-connected universes dominate the path integral. We also provide evidence that the euclidean path integral over geometries with spherical topology is unstable with respect to formation of infinitely many wormhole-connected 4-spheres. Consistency is restored by summing over all topologies, which leads to Coleman's result. Coleman's argument for determination of other parameters is reviewed and applied to the mass of the pion. A discouraging result is found that the pion mass is driven to zero. We also consider qualitatively the implications of the wormhole theory for cosmology. We argue that a small number of universes containing matter and energy may exist in contact with infinitely many cold and empty universes. Contact with the cold universes insures that the cosmological constant in the warm ones is zero. (orig.)
Quaternions as astrometric plate constants
Jefferys, William H.
1987-01-01
A new method for solving problems in relative astrometry is proposed. In it, the relationship between the measured quantities and the components of the position vector of a star is modeled using quaternions, in effect replacing the plate constants of a standard four-plate-constant solution with the four components of a quaternion. The method allows a direct solution for the position vectors of the stars, and hence for the equatorial coordinates. Distortions, magnitude, and color effects are readily incorporated into the formalism, and the method is directly applicable to overlapping-plate problems. The advantages of the method include the simplicity of the resulting equations, their freedom from singularities, and the fact that trigonometric functions and tangential point transformations are not needed to model the plate material. A global solution over the entire sky is possible.
Three pion nucleon coupling constants
Ruiz Arriola, E.; Amaro, J. E.; Navarro Pérez, R.
2016-08-01
There exist four pion nucleon coupling constants, fπ0pp, ‑ fπ0nn, fπ+pn/2 and fπ‑np/2 which coincide when up and down quark masses are identical and the electron charge is zero. While there is no reason why the pion-nucleon-nucleon coupling constants should be identical in the real world, one expects that the small differences might be pinned down from a sufficiently large number of independent and mutually consistent data. Our discussion provides a rationale for our recent determination fp2 = 0.0759(4),f 02 = 0.079(1),f c2 = 0.0763(6), based on a partial wave analysis of the 3σ self-consistent nucleon-nucleon Granada-2013 database comprising 6713 published data in the period 1950-2013.
Three pion nucleon coupling constants
Arriola, E Ruiz; Perez, R Navarro
2016-01-01
There exist four pion nucleon coupling constants, $f_{\\pi^0, pp}$, $-f_{\\pi^0, nn}$, $f_{\\pi^+, pn} /\\sqrt{2}$ and $ f_{\\pi^-, np} /\\sqrt{2}$ which coincide when up and down quark masses are identical and the electron charge is zero. While there is no reason why the pion-nucleon-nucleon coupling constants should be identical in the real world, one expects that the small differences might be pinned down from a sufficiently large number of independent and mutually consistent data. Our discussion provides a rationale for our recent determination $$f_p^2 = 0.0759(4) \\, , \\quad f_{0}^2 = 0.079(1) \\,, \\quad f_{c}^2 = 0.0763(6) \\, , $$ based on a partial wave analysis of the $3\\sigma$ self-consistent nucleon-nucleon Granada-2013 database comprising 6713 published data in the period 1950-2013.
Time-Varying Fundamental Constants
Olive, Keith
2003-04-01
Recent data from quasar absorption systems can be interpreted as arising from a time variation in the fine-structure constant. However, there are numerous cosmological, astro-physical, and terrestrial bounds on any such variation. These includes bounds from Big Bang Nucleosynthesis (from the ^4He abundance), the Oklo reactor (from the resonant neutron capture cross-section of Sm), and from meteoretic lifetimes of heavy radioactive isotopes. The bounds on the variation of the fine-structure constant are significantly strengthened in models where all gauge and Yukawa couplings vary in a dependent manner, as would be expected in unified theories. Models which are consistent with all data are severly challenged when Equivalence Principle constraints are imposed.
Henry's law constants of polyols
Compernolle, S.; J.-F. Müller
2014-01-01
Henry's law constants (HLC) are derived for several polyols bearing between 2 and 6 hydroxyl groups, based on literature data for water activity, vapour pressure and/or solubility. While deriving HLC and depending on the case, also infinite dilution activity coefficients (IDACs), solid state vapour pressures or activity coefficient ratios are obtained as intermediate results. An error analysis on the intermediate quantities and the obtained HLC is included....
Henry's law constants of polyols
Compernolle, S.; J.-F. Müller
2014-01-01
Henry's law constants (HLC) are derived for several polyols bearing between 2 and 6 hydroxyl groups, based on literature data for water activity, vapour pressure and/or solubility. Depending on the case, infinite dilution activity coefficients (IDACs), solid state pressures or activity coefficient ratios are obtained as intermediary results. For most compounds, these are the first values reported, while others compare favourably with literature data in most ...
Cosmology with New Astrophysical Constants
Alfonso-Faus, Antonio
2008-01-01
It is shown that Einstein field equations give two solutions for cosmology. The first one is the standard well known representative of the present status of cosmology. We identify it with the local point of view of a flat Universe with the values for the cosmological omega parameters (k = 0, lambda = 2/3, m = 1/3). The second one is a new one that we identify with a cosmic point of view, as given by free photons, neutrinos, tachyons and gravity quanta. We apply a wave to particle technique to find the matter propagation equation. Then we prove that all gravitational radii are constant, regardless of the possible time variations of the physical properties like the speed of light c, the gravitational constant G or the mass m of fundamental particles. We find two cosmological constants, c^3 /G and mc, with the condition that the field equations be derived from the action principle. With this result, and the integration of the Bianchi identity, we prove the existence of the two solutions for cosmology. We then va...
MARTENSITIC TRANSFORMATION AND ELASTIC CONSTANTS
Suzuki, T
1985-01-01
The deformation energy barrier for the martensitic transformation is estimated from the data of the elastic constants. The deformation energy barrier for B.C.C → F.C.C martensitic transformation is, at most, of the order of the thermal energy at room temperature. The deformation energy barrier between B.C.C. and F.C.C can be surmounted by thermal energy at temperatures higher than Ms. The martensitic transformation is proposed to be understood as the freezing process of the non-linear lattice...
Exact constants in approximation theory
Korneichuk, N
1991-01-01
This book is intended as a self-contained introduction for non-specialists, or as a reference work for experts, to the particular area of approximation theory that is concerned with exact constants. The results apply mainly to extremal problems in approximation theory, which in turn are closely related to numerical analysis and optimization. The book encompasses a wide range of questions and problems: best approximation by polynomials and splines; linear approximation methods, such as spline-approximation; optimal reconstruction of functions and linear functionals. Many of the results are base
Henry's law constants of polyols
Directory of Open Access Journals (Sweden)
S. Compernolle
2014-05-01
Full Text Available Henry's law constants (HLC are derived for several polyols bearing between 2 and 6 hydroxyl groups, based on literature data for water activity, vapour pressure and/or solubility. Depending on the case, infinite dilution activity coefficients (IDACs, solid state pressures or activity coefficient ratios are obtained as intermediary results. For most compounds, these are the first values reported, while others compare favourably with literature data in most cases. Using these values and those from a previous work (Compernolle and Müller, 2014, an assessment is made on the partitioning of polyols, diacids and hydroxy acids to droplet and aqueous aerosol.
Kepler's Constant and WDS Orbit
Siregar, S
2012-01-01
The aim of this work are to find a Kepler's constant by using polynomial regression of the angular separation \\rho = \\rho(t) and the position angle \\theta = \\theta(t). The Kepler's constant obtained is used to derive the element of orbit. As a case study the angular separation and the position angle of the WDS 00063 +5826 and the WDS 04403-5857 were investigated. For calculating the element of orbit the Thiele-Innes van den Bos method is used. The rough data of the angular separation \\rho(t) and the position angle \\theta(t) are taken from the US Naval Observatory, Washington. This work also presents the masses and absolute bolometric magnitudes of each star.These stars include into the main-sequence stars with the spectral class G5V for WDS04403-5857and the type of spectrum G3V for WDS 00063+5826. The life time of the primary star and the secondary star of WDS 04403-5857 nearly equal to 20 Gyr. The life time of the primary star and the secondary star of WDS 00063+5826 are 20 Gyr and 19 Gyr, respectively.
Cosmological constant and curved 5D geometry
Ito, M
2002-01-01
We study the value of cosmological constant in de Sitter brane embedded in five dimensions with positive, vanishing and negative bulk cosmological constant. In the case of negative bulk cosmological constant, we show that not zero but tiny four-dimensional cosmological constant can be realized by tiny deviation from bulk curvature of the Randall-Sundrum model.
The fundamental constants a mystery of physics
Fritzsch, Harald
2009-01-01
The speed of light, the fine structure constant, and Newton's constant of gravity — these are just three among the many physical constants that define our picture of the world. Where do they come from? Are they constant in time and across space? In this book, physicist and author Harald Fritzsch invites the reader to explore the mystery of the fundamental constants of physics in the company of Isaac Newton, Albert Einstein, and a modern-day physicist
Henry's law constants of polyols
Compernolle, S.; Müller, J.-F.
2014-12-01
Henry's law constants (HLC) are derived for several polyols bearing between 2 and 6 hydroxyl groups, based on literature data for water activity, vapour pressure and/or solubility. While deriving HLC and depending on the case, also infinite dilution activity coefficients (IDACs), solid state vapour pressures or activity coefficient ratios are obtained as intermediate results. An error analysis on the intermediate quantities and the obtained HLC is included. For most compounds, these are the first values reported, while others compare favourably with literature data in most cases. Using these values and those from a previous work (Compernolle and Müller, 2014), an assessment is made on the partitioning of polyols, diacids and hydroxy acids to droplet and aqueous aerosol.
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.
The Hubble Constant and the Expanding Universe
Freedman, Wendy
2003-01-01
In 1929 Edwin Hubble proved that our universe is expanding by showing that the farther a galaxy is from us, the faster it is speeding away into space. This velocity-distance relation came to be called Hubble's law, and the value that describes the rate of expansion is known as the Hubble constant, or H0 . Like the speed of light, H0 is a fundamental constant, and it is a key parameter needed to estimate both the age and size of the universe. Since the late 1950s astronomers have been arguing for an H0 value between 50 to 100 kilometers per second per megaparsec, a lack of precision that produced an unacceptably wide range of ages for the universe—anywhere from 10 to 20 billion years. Using the Hubble Space Telescope, Freedman and her colleagues measured H0 to an unprecedented level of accuracy, deriving a value of 72, with an uncertainty of 10 percent—a milestone achievement in cosmology. The new result suggests that our universe is about 13 billion years old, give or take a billion years, and it's a value that sits comfortably alongside the 12 billion years estimated for the age of the oldest stars.
Dimensionless constants, cosmology and other dark matters
Tegmark, M; Rees, M; Wilczek, F; Tegmark, Max; Aguirre, Anthony; Rees, Martin; Wilczek, Frank
2006-01-01
We identify 31 dimensionless physical constants required by particle physics and cosmology, and emphasize that both microphysical constraints and selection effects might help elucidate their origin. Axion cosmology provides an instructive example, in which these two kinds of arguments must both be taken into account, and work well together. If a Peccei-Quinn phase transition occurred before or during inflation, then the axion dark matter density will vary from place to place with a probability distribution. By calculating the net dark matter halo formation rate as a function of all four relevant cosmological parameters and assessing other constraints, we find that this probability distribution, computed at stable solar systems, is arguably peaked near the observed dark matter density. If cosmologically relevant WIMP dark matter is discovered, then one naturally expects comparable densities of WIMPs and axions, making it important to follow up with precision measurements to determine whether WIMPs account for ...
Institute of Scientific and Technical Information of China (English)
任庆云; 杨晓磊; 王松涛
2014-01-01
Using Visual Basic 6.0 and a least squares straight line fit program to compile for the experimental data of measuring rate constant of saponification of ethyl acetate with electric conductivity instrument , more correct and scientific results including date and figures can be achieved and printed.This experimental method had the merits of precise experiment , simple operation and accurate result.The executable files of the software can operate independently without Visual Basic environment.%以Visual Basic 6.0为开发工具，结合最小二乘法直线拟合，对“电导法测定乙酸乙酯皂化反应速率常数”实验进行数据处理，得到更科学准确的实验结果，能够打印出计算结果和图形。此实验方法具有实验精密、操作简单、方便、测量结果准确等优点。经编译此实验数据处理程序的可执行文件能在脱离Visual Basic的环境下独立运行，程序的实用性和便利性较强。
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。
A Variant of Davenport's Constant
Indian Academy of Sciences (India)
R Thangadurai
2007-05-01
Let be a prime number. Let be a finite abelian -group of exponent (written additively) and be a non-empty subset of $]n[:=\\{1,2,\\ldots,n\\}$ such that elements of are incongruent modulo and non-zero modulo . Let $k ≥ D(G)/|A|$ be any integer where () denotes the well-known Davenport’s constant. In this article, we prove that for any sequence $g_1,g_2,\\ldots,g_k$ (not necessarily distinct) in , one can always extract a subsequence $g_{i_1},g_{i_2},\\ldots,g_{i_l}$ with $1 ≤ l ≤ k$ such that $$\\sum\\limits_{j=1}^l a_j g_{i_j}=0 \\text{in} G,$$ where $a_j\\in A$ for all . We provide examples where this bound cannot be improved. Furthermore, for the cyclic groups, we prove some sharp results in this direction. In the last section, we explore the relation between this problem and a similar problem with prescribed length. The proof of Theorem 1 uses group-algebra techniques, while for the other theorems, we use elementary number theory techniques.
Implications of the Cosmological Constant for Spherically Symmetric Mass Distributions
Zubairi, Omair; Weber, Fridolin
2013-04-01
In recent years, scientists have made the discovery that the expansion rate of the Universe is increasing rather than decreasing. This acceleration leads to an additional term in Albert Einstein's field equations which describe general relativity and is known as the cosmological constant. This work explores the aftermath of a non-vanishing cosmological constant for relativistic spherically symmetric mass distributions, which are susceptible to change against Einstein's field equations. We introduce a stellar structure equation known as the Tolman-Oppenhiemer-Volkoff (TOV) equation modified for a cosmological constant, which is derived from Einstein's modified field equations. We solve this modified TOV equation for these spherically symmetric mass distributions and obtain stellar properties such as mass and radius and investigate changes that may occur depending on the value of the cosmological constant.
Vacuum energy and the cosmological constant
Bass, Steven D
2015-01-01
The accelerating expansion of the Universe points to a small positive value for the cosmological constant or vacuum energy density. We discuss recent ideas that the cosmological constant plus LHC results might hint at critical phenomena near the Planck scale.
Temporal variation of coupling constants and nucleosynthesis
Oberhummer, Heinz; Fairbairn, M; Schlattl, H; Sharma, M M
2003-01-01
We investigate the triple-alpha process and the Oklo phenomenon to obtain constraints on possible cosmological time variations of fundamental constants. Specifically we study cosmological temporal constraints for the fine structure constant and nucleon and meson masses.
Temporal variation of coupling constants and nucleosynthesis
Oberhummer, H.; Csótó, A.; Fairbairn, M.; Schlattl, H.; Sharma, M. M.
2003-05-01
We investigate the triple-alpha process and the Oklo phenomenon to obtain constraints on possible cosmological time variations of fundamental constants. Specifically we study cosmological temporal constraints for the fine structure constant and nucleon and meson masses.
Surfaces of a Constant Negative Curvature
Directory of Open Access Journals (Sweden)
G. M. Gharib
2012-01-01
Full Text Available I study the geometric notion of a differential system describing surfaces of a constant negative curvature and describe a family of pseudospherical surfaces for the nonlinear partial differential equations with constant Gaussian curvature .
Anderegg, G
2013-01-01
Critical Survey of Stability Constants of EDTA Complexes focuses on the computations, values, and characteristics of stability constants. The book emphasizes that for a critical discussion of experimentally determined stability constants, it is important to consider the precision of the values that manifests the self-consistency of the constant, taking into consideration the random errors. The publication reviews the stability constants of metal complexes. The numerical calculations affirm the reactions and transformations of metal ions when exposed to varying conditions. The text also present
Constant global population with demographic heterogeneity
Cohen, Joel E.
2008-01-01
To understand better a possible future constant global population that is demographically heterogeneous, this paper analyzes several models. Classical theory of stationary populations generally fails to apply. However, if constant global population size P(global) is the sum of all country population sizes, and if constant global annual number of births B(global) is the sum of the annual number of births of all countries, and if constant global life expectancy at birth e(global) is the populat...
Origin of cosmological constant from Bulk manifold
International Nuclear Information System (INIS)
The problem about cosmological constant is a difficult and important problem, people even don't know what it is really originated from. In this letter, the authors show up a kind of origin of the cosmological constant from the viewpoint of some extra dimensional spaces, obtain different values of the cosmological constant under different circumstances, acquire the evolution function with time t. And we achieve a cosmological constant that may be fitted with modern astronomic observation. (authors)
Institute of Scientific and Technical Information of China (English)
邢波
2012-01-01
在此研究中,采用一系列具有相似结构的气态饱和单胺和二胺作为研究对象,应用Gaussian03计算化学软件,在DFT/B3LYP水平上,使用6-311＋G（d）基组优化处于基态的胺分子结构并使用CIS/6-311＋G（d）优化处于激发态胺分子的结构,计算激发能量、激发波长,以及S1←S0振子强度f。通过查得文献中已有的气态饱和胺的荧光寿命以及得到的荧光辐射速率常数实验数据,比较计算得出的振子强度f,得出结论：双胺的荧光寿命明显长于单胺;若f=0,表明跃迁禁阻,像DMPZ,DABCO,它们的荧光寿命很长,超过了770ns;若f〉0,则允许跃迁,饱和胺分子荧光寿命小于60ns。可由计算得出的f值,初步判断荧光物质在UV辐射作用下的荧光寿命长短。并得到振子强度f与荧光辐射速率常数线性关系。与基态分子结构比较,激发态的饱和胺分子结构发生改变。%In this research,a series of saturated monoamines and diamines with similar molecule structures are investigated.The Gaussian03 DFT/B3LYP/6-311＋G（d） method was carried out to optimize the molecular structures in ground state.CIS/6-311＋G（d） was used to optimize the S1 molecular structures and calculate the S1←S0 oscillator strengths（f values）.The excitation energies,excitation wavelengths and S1←S0 oscillator strengths were calculated.The calculated oscillator strengths with the experimental lifetimes and radiative rate constants were compared.It concluded that the fluorescence lifetimes of diamines are much longer than that of monoamines.If f=0,for example,DMPZ and DABCO,the transition is forbidden and their fluorescence lifetimes exceed 770ns.If f0,the transition is allowed and the fluorescence lifetimes of these amines are less than 60ns.Using f values can estimate the fluorescence lifetimes under UV radiation.The oscillator strengths（f values） are linear with the fluorescence radiative rate constants.The geometries of
Local Experiments See Cosmologically Varying Constants
Shaw, D J; Barrow, John D.; Shaw, Douglas J.
2006-01-01
We describe a rigorous construction, using matched asymptotic expansions, which establishes under very general conditions that local terrestrial and solar-system experiments will measure the effects of varying `constants' of Nature occurring on cosmological scales to computable precision. In particular, `constants' driven by scalar fields will still be found to evolve in time when observed within virialised structures like clusters, galaxies, and planetary systems. This provides a justification for combining cosmological and terrestrial constraints on the possible time variation of many assumed `constants' of Nature, including the fine structure constant and Newton's gravitation constant.
Cosmological Constant and Soft Terms in Supergravity
Choi, Kiwoon; Kim, Jihn E.; Nilles, Hans Peter, Ramos-S\\xe1nchez, Sa\\xfal
1994-01-01
Some of the soft SUSY breaking parameters in hidden sector supergravity model depend on the expectation value of the hidden sector scalar potential, $$, whose tree level value is equal to the tree level cosmological constant. The current practice of calculating soft parameters assumes that $=0$. Quantum correction to the cosmological constant can differ from the correction to $$ by an amount of order $m^2_{3/2}M_{Pl}^2/8\\pi$. This implies that, for the vanishing cosmological constant, the $$-...
A small but nonzero cosmological constant
Ng, Y J
1999-01-01
Recent astrophysical observations seem to indicate that the cosmological constant is small but nonzero and positive. The old cosmological constant problem asks why it is so small; we must now ask, in addition, why it is nonzero, and why it is positive. In this essay, we try to kill these three metaphorical birds with one stone. That stone is the unimodular theory of gravity, which is the canonical theory of gravity, except for the way the cosmological constant arises in the theory.
Cosmological Constant and Axions in String Theory
Energy Technology Data Exchange (ETDEWEB)
Svrcek, Peter; /Stanford U., Phys. Dept. /SLAC
2006-08-18
String theory axions appear to be promising candidates for explaining cosmological constant via quintessence. In this paper, we study conditions on the string compactifications under which axion quintessence can happen. For sufficiently large number of axions, cosmological constant can be accounted for as the potential energy of axions that have not yet relaxed to their minima. In compactifications that incorporate unified models of particle physics, the height of the axion potential can naturally fall close to the observed value of cosmological constant.
Bubble Universes With Different Gravitational Constants
Takamizu, Yu-ichi; Maeda, Kei-ichi
2015-01-01
We argue a scenario motivated by the context of string landscape, where our universe is produced by a new vacuum bubble embedded in an old bubble and these bubble universes have not only different cosmological constants, but also their own different gravitational constants. We study these effects on the primordial curvature perturbations. In order to construct a model of varying gravitational constants, we use the Jordan-Brans-Dicke (JBD) theory where different expectation values of scalar fi...
ZEMO system for generating group constants
International Nuclear Information System (INIS)
The code system ZEMO for generating 26 group and 140-group constant sets for fast breeder reactors neutronics is considered. Group constant libraries, calculational techniques, formats of generated group constant sets and code control parameters are described. Results of one-dimensional model calculations for some critical assemblies and results of investigation of sodium void reactivity effect calculational error caused by 26-group approximation for two-dimensional model of BN-800 are presented. 14 refs.; 1 fig.; 3 tabs
A natural cosmological constant from chameleons
Energy Technology Data Exchange (ETDEWEB)
Nastase, Horatiu, E-mail: nastase@ift.unesp.br [Instituto de Física Teórica, UNESP-Universidade Estadual Paulista, R. Dr. Bento T. Ferraz 271, Bl. II, Sao Paulo 01140-070, SP (Brazil); Weltman, Amanda, E-mail: amanda.weltman@uct.ac.za [Astrophysics, Cosmology & Gravity Center, Department of Mathematics and Applied Mathematics, University of Cape Town, Private Bag, Rondebosch 7700 (South Africa)
2015-07-30
We present a simple model where the effective cosmological constant appears from chameleon scalar fields. For a Kachru–Kallosh–Linde–Trivedi (KKLT)-inspired form of the potential and a particular chameleon coupling to the local density, patches of approximately constant scalar field potential cluster around regions of matter with density above a certain value, generating the effect of a cosmological constant on large scales. This construction addresses both the cosmological constant problem (why Λ is so small, yet nonzero) and the coincidence problem (why Λ is comparable to the matter density now)
Surprises in numerical expressions of physical constants
Amir, Ariel; Tokieda, Tadashi
2016-01-01
In science, as in life, `surprises' can be adequately appreciated only in the presence of a null model, what we expect a priori. In physics, theories sometimes express the values of dimensionless physical constants as combinations of mathematical constants like pi or e. The inverse problem also arises, whereby the measured value of a physical constant admits a `surprisingly' simple approximation in terms of well-known mathematical constants. Can we estimate the probability for this to be a mere coincidence, rather than an inkling of some theory? We answer the question in the most naive form.
Institute of Scientific and Technical Information of China (English)
杨洋; 刘伟; 林金官; 张玉林
2014-01-01
Consider two dependent renewal risk models with constant interest rate.By using some methods in the risk theory, uniform asymptotics for finite-time ruin probability is derived in a non-compound risk model, where claim sizes are upper tail asymptotically independent random variables with dominatedly varying tails, claim inter-arrival times follow the widely lower orthant dependent structure, and the total amount of premiums is a nonnegative stochastic process.Based on the obtained result, using the method of analysis for the tail probability of random sums, a similar result in a more complex and reasonable compound risk model is also obtained, where individual claim sizes are specialized to be extended negatively dependent and accident inter-arrival times are still widely lower orthant dependent, and both the claim sizes and the claim number have dominatedly varying tails.%考虑了2个带有常数利息率的相依更新风险模型。首先研究了非复合风险模型，其中索赔额是上尾渐近独立且带有控制变换尾分布的非负随机变量，索赔时间间隔是宽下象限相依的，保费收入过程是一个非负的随机过程，利用风险理论中的方法，得到了有限时破产概率在某个有界区间上的一致渐近性。在此基础上，利用随机和尾渐近性的分析方法，进一步研究获得了更为复杂且合理的复合相依更新风险模型中有限时破产概率的一致渐近性公式，其中单个索赔额特殊化为广义负相依的，并且事故时间间隔仍然保持宽下象限相依的，索赔额和索赔次数均为控制变换尾的。
Habitable sphere and fine structure constant
Kozlovskii, Miroslaw P; Kozlowski, Miroslaw; Marciak-Kozlowska, Janina
2005-01-01
Future space missions, TPF and Darwin will focus on searches of signatures of life on extrasolar planets. In this paper we look for model independ definition of the habitable zone. It will be shown that the radius of the habitable sphere depends only on the constants of the Nature. Key words: Habitable sphere, fine structure constant.
Fullerene derivatives with increased dielectric constants
Jahani, Fatemeh; Torabi, Solmaz; Chiechi, Ryan C; Koster, L Jan Anton; Hummelen, Jan C
2014-01-01
The invention of new organic materials with high dielectric constants is of extreme importance for the development of organic-based devices such as organic solar cells. We report on a synthetic way to increase the dielectric constant of fullerene derivatives. It is demonstrated that introducing trie
Atomic hydrogen and fundamental physical constants
International Nuclear Information System (INIS)
Techniques are described which allow the study, in undergraduate laboratories, of the spectrum of atomic hydrogen. The Rydberg constant, the electron-proton mass ratio, and the fine-structure constant are evaluated from the measurements. The key to the series of experiments is a discharge tube in which atomic lines dominate over the molecular lines. (author)
Bubble Universes With Different Gravitational Constants
Takamizu, Yu-ichi
2015-01-01
We argue a scenario motivated by the context of string landscape, where our universe is produced by a new vacuum bubble embedded in an old bubble and these bubble universes have not only different cosmological constants, but also their own different gravitational constants. We study these effects on the primordial curvature perturbations. In order to construct a model of varying gravitational constants, we use the Jordan-Brans-Dicke (JBD) theory where different expectation values of scalar fields produce difference of constants. In this system, we investigate the nucleation of bubble universe and dynamics of the wall separating two spacetimes. In particular, the primordial curvature perturbation on superhorizon scales can be affected by the wall trajectory as the boundary effect. We show the effect of gravitational constant in the exterior bubble universe can provide a peak like a bump feature at a large scale in a modulation of power spectrum.
String theory, cosmology and varying constants
Damour, Thibault
In string theory the coupling `constants' appearing in the low-energy effective Lagrangian are determined by the vacuum expectation values of some (a priori) massless scalar fields (dilaton, moduli). This naturally leads one to expect a correlated variation of all the coupling constants, and an associated violation of the equivalence principle. We review some string-inspired theoretical models which incorporate such a 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 a very unnatural fine-tuning 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.
String theory, cosmology and varying constants
Damour, Thibault Marie Alban Guillaume
2002-01-01
In string theory the coupling ``constants'' appearing in the low-energy effective Lagrangian are determined by the vacuum expectation values of some (a priori) massless scalar fields (dilaton, moduli). This naturally leads one to expect a correlated variation of all the coupling constants, and an associated violation of the equivalence principle. We review some string-inspired theoretical models which incorporate such a 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 a very unnatural fine-tuning 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 universa...
EFFECTS OF CONSTANT EXCITATION ON LOCAL BIFURCATION
Institute of Scientific and Technical Information of China (English)
WU Zhi-qiang; CHEN Yu-shu
2006-01-01
The effects of the constant excitation on the local bifurcation of the periodic solutions in the 1:2 internal resonant systems were analyzed based on the singularity theory. It is shown that the constant excitation make influence only when there exist some nonlinear terms, in the oscillator with lower frequency. Besides acting as main bifurcation parameter, the constant excitation, together with coefficients of some nonlinear terms,may change the values of unfolding parameters and the type of the bifurcation. Under the non-degenerate cases, the effect of the third order terms can be neglected.
On the constants for some Sobolev imbeddings
Directory of Open Access Journals (Sweden)
Pizzocchero Livio
2001-01-01
Full Text Available We consider the imbedding inequality is the Sobolev space (or Bessel potential space of type and (integer or fractional order . We write down upper bounds for the constants , using an argument previously applied in the literature in particular cases. We prove that the upper bounds computed in this way are in fact the sharp constants if , , and exhibit the maximising functions. Furthermore, using convenient trial functions, we derive lower bounds on for in many cases these are close to the previous upper bounds, as illustrated by a number of examples, thus characterizing the sharp constants with little uncertainty.
The Determination of the Strong Coupling Constant
Dissertori, Günther
2016-10-01
The strong coupling constant is one of the fundamental parameters of the Standard Theory of particle physics. In this review I will briefly summarise the theoretical framework, within which the strong coupling constant is defined and how it is connected to measurable observables. Then I will give an historical overview of its experimental determinations and discuss the current status and world average value. Among the many different techniques used to determine this coupling constant in the context of quantum chromodynamics, I will focus in particular on a number of measurements carried out at the Large Electron-Positron Collider (LEP) and the Large Hadron Collider (LHC) at CERN.
Some Zero-Sum Constants with Weights
Indian Academy of Sciences (India)
S D Adhikari; R Balasubramanian; F Pappalardi; P Rath
2008-05-01
For an abelian group , the Davenport constant () is defined to be the smallest natural number such that any sequence of elements in has a non-empty subsequence whose sum is zero (the identity element). Motivated by some recent developments around the notion of Davenport constant with weights, we study them in some basic cases. We also define a new combinatorial invariant related to $(\\mathbb{Z}/n\\mathbb{Z})^d$, more in the spirit of some constants considered by Harborth and others and obtain its exact value in the case of $(\\mathbb{Z}/n\\mathbb{Z})^2$ where is an odd integer.
On geometrically unified fields and universal constants
Fabbri, Luca
2013-07-01
We consider the Cartan extension of Riemann geometry as the basis upon which to build the Sciama-Kibble completion of Einstein gravity, developing the most general theory in which torsion and metric have two independent coupling constants: the main problem of the ESK theory was that torsion, having the Newton constant, was negligible beyond the Planck scale, but in this {ESK}2 theory torsion, with its own coupling constant, may be relevant much further Planck scales; further consequences of these torsionally-induced interactions will eventually be discussed.
Global stability of an SEIR epidemic model with constant immigration
International Nuclear Information System (INIS)
An SEIR epidemic model with the infectious force in the latent (exposed), infected and recovered period is studied. It is assumed that susceptible and exposed individuals have constant immigration rates. The model exhibits a unique endemic state if the fraction p of infectious immigrants is positive. If the basic reproduction number R is greater than 1, sufficient conditions for the global stability of the endemic equilibrium are obtained by the compound matrix theory
Solution to the Cosmological Constant Problem by Gauge Theory of Gravity
Institute of Scientific and Technical Information of China (English)
WU Ning; Germano Resconi; ZHENG Zhi-Peng; XU Zhan; ZHANG Da-Hua; RUAN Tu-Nan
2003-01-01
Based on geometry picture of gravitational gauge theory, the cosmological constant is determined theoreti-cally. The cosmological constant is related to the average energy density of gravitational gauge field. Because the energydensity of gravitational gauge field is negative, the cosmological constant is positive, which generates repulsive force onstars to make the expansion rate of the Universe accelerated. A rough estimation of it gives out its magnitude of theorder of about 10-52m-2, which is well consistent with experimental results.
Denny, Mark
2016-05-01
The physics of a weather balloon is analyzed. The surprising aspect of the motion of these balloons is that they ascend to great altitudes (typically 35 km) at a more or less constant rate. Such behavior is not surprising near the ground—say for a helium-filled party balloon rising from street level to the top of the Empire State building—but it is unexpected for a balloon that rises to altitudes where the air is rarefied. We show from elementary physical laws why the ascent rate is approximately constant.
Interacting universes and the cosmological constant
Energy Technology Data Exchange (ETDEWEB)
Alonso-Serrano, A. [Centro de Física “Miguel Catalán”, Instituto de Física Fundamental, Consejo Superior de Investigaciones Científicas, Serrano 121, 28006 Madrid (Spain); Estación Ecológica de Biocosmología, Pedro de Alvarado 14, 06411 Medellín (Spain); Bastos, C. [Instituto de Plasmas e Fusão Nuclear, Instituto Superior Técnico, Avenida Rovisco Pais 1, 1049-001 Lisboa (Portugal); Bertolami, O. [Instituto de Plasmas e Fusão Nuclear, Instituto Superior Técnico, Avenida Rovisco Pais 1, 1049-001 Lisboa (Portugal); Departamento de Física e Astronomia, Faculdade de Ciências da Universidade do Porto, Rua do Campo Alegre 687, 4169-007 Porto (Portugal); Robles-Pérez, S., E-mail: salvarp@imaff.cfmac.csic.es [Centro de Física “Miguel Catalán”, Instituto de Física Fundamental, Consejo Superior de Investigaciones Científicas, Serrano 121, 28006 Madrid (Spain); Estación Ecológica de Biocosmología, Pedro de Alvarado 14, 06411 Medellín (Spain); Física Teórica, Universidad del País Vasco, Apartado 644, 48080 Bilbao (Spain)
2013-02-12
In this Letter it is studied the effects that an interaction scheme among universes can have in the values of their cosmological constants. In the case of two interacting universes, the value of the cosmological constant of one of the universes becomes very close to zero at the expense of an increasing value of the cosmological constant of the partner universe. In the more general case of a chain of N interacting universes with periodic boundary conditions, the spectrum of the Hamiltonian splits into a large number of levels, each of them associated with a particular value of the cosmological constant, that can be occupied by single universes revealing a collective behavior that plainly shows that the multiverse is much more than the mere sum of its parts.
An improved dosimeter having constant flow pump
International Nuclear Information System (INIS)
A dosemeter designed for individual use which can be used to monitor toxic radon gas and toxic related products of radon gas in mines and which incorporates a constant air stream flowing through the dosimeter is described. (U.K.)
The time constant of the somatogravic illusion
Correia Grácio, B.J.; Winkel, K.N. de; Groen, E.L.; Wentink, M.; Bos, J.E.
2013-01-01
Met desdemona hebben we gevonden dat de tijd constante van de somatografische illusie rond twee seconden is. Dit resultaat verschilt van wat was gevonden in ander onderzoek dat gebruikt maakt van een gewone centrifuge
Determination of the gravitational constant G
Institute of Scientific and Technical Information of China (English)
HU Zhong-kun; LIU Qi; LUO Jun
2006-01-01
A precise knowledge of the Newtonian gravitational constant G has an important role in physics and is of considerable meteorological interest.Although G was the first physical constant to be introduced and measured in the history of science,it is still the least precisely determined of all the fundamental constants of nature.The 2002 CODATA recommended value for G,G=(6.6742±0.0010)×10-11m3·kg-1·s-2,has an uncertainty of 150 parts per million (ppm),much larger than that of all other fundamental constants.Reviewed here is the status of our knowledge of the absolute value of G,methods for determining G,and recent high precision experiments for determining G.
Canonoid transformations and constants of motion
International Nuclear Information System (INIS)
The necessary and sufficient conditions for a canonoid transformation with respect to a given Hamiltonian are obtained in terms of the Lagrange brackets of the trasformation. The relation of these conditions with the constants of motion is discussed. (Author)
Black holes with constant topological Euler density
Bargueño, Pedro
2016-01-01
A class of four dimensional spherically symmetric and static geometries with constant topological Euler density is studied. These geometries are shown to solve the coupled Einstein-Maxwell system when non-linear Born-Infeld-like electrodynamics is employed.
Local experiments see cosmologically varying constants
International Nuclear Information System (INIS)
We describe a rigorous matched asymptotic expansion, which establishes under very general conditions that local terrestrial and solar-system experiments will measure any variations in 'constants' of Nature occurring on cosmological scales
Cosmology with a time dependent cosmological constant
International Nuclear Information System (INIS)
In the context of the scalar-tensor theories we consider cosmological models with a time dependent cosmological constant. Several toy models are obtained among them there are solutions without singularity and accelerating. (Author)
Hydrolysis and formation constants at 250C
International Nuclear Information System (INIS)
A database consisting of hydrolysis and formation constants for about 20 metals associated with the disposal of nuclear waste is given. Complexing ligands for the various ionic species of these metals include OH, F, Cl, SO4, PO4 and CO3. Table 1 consists of tabulated calculated and experimental values of log K/sub xy/, mainly at 250C and various ionic strengths together with references to the origin of the data. Table 2 consists of a column of recommended stability constants at 250C and zero ionic strength tabulated in the column headed log K/sub xy/(0); other columns contain coefficients for an extended Debye-Huckel equation to permit calculations of stability constants up to 3 ionic strength, and up to 0.7 ionic strength using the Davies equation. Selected stability constants calculated with these coefficients for various ionic strengths agree to an average of +- 2% when compared with published experimental and calculated values
The Origin of the Constant Carbohydrate Diet
Directory of Open Access Journals (Sweden)
Charles Herbert Read
2009-01-01
Full Text Available The Constant Carbohydrate diet, based entirely on carbohydrate exchanges, is now widely used in the dietary treatment of diabetes mellitus. Being based on sound scientific principles and simple in design, the Constant Carabohydrate diet is appropriate for all those having diabetes mellitus, young or old, no matter their ethncity. This report describes why and how it was developed in 1951. Its simplicity makes it adaptable to all ethnic diets.
The Origin of the Constant Carbohydrate Diet
Directory of Open Access Journals (Sweden)
Read CharlesHerbert
2008-01-01
Full Text Available The Constant Carbohydrate diet, based entirely on carbohydrate exchanges, is now widely used in the dietary treatment of diabetes mellitus. Being based on sound scientific principles and simple in design, the Constant Carabohydrate diet is appropriate for all those having diabetes mellitus, young or old, no matter their ethncity. This report describes why and how it was developed in 1951. Its simplicity makes it adaptable to all ethnic diets.
Holographic dark energy with varying gravitational constant
Jamil, Mubasher; Saridakis, Emmanuel N.; Setare, M. R.
2009-08-01
We investigate the holographic dark energy scenario with a varying gravitational constant, in flat and non-flat background geometry. We extract the exact differential equations determining the evolution of the dark energy density-parameter, which include G-variation correction terms. Performing a low-redshift expansion of the dark energy equation of state, we provide the involved parameters as functions of the current density parameters, of the holographic dark energy constant and of the G-variation.
Holographic dark energy with varying gravitational constant
International Nuclear Information System (INIS)
We investigate the holographic dark energy scenario with a varying gravitational constant, in flat and non-flat background geometry. We extract the exact differential equations determining the evolution of the dark energy density-parameter, which include G-variation correction terms. Performing a low-redshift expansion of the dark energy equation of state, we provide the involved parameters as functions of the current density parameters, of the holographic dark energy constant and of the G-variation.
Holographic dark energy with varying gravitational constant
Jamil, Mubasher; Setare, M R
2009-01-01
We investigate the holographic dark energy scenario with a varying gravitational constant, in flat and non-flat background geometry. We extract the exact differential equations determining the evolution of the dark energy density-parameter, which include $G$-variation correction terms. Performing a low-redshift expansion of the dark energy equation of state, we provide the involved parameters as functions of the current density parameters, of the holographic dark energy constant and of the $G$-variation.
Siegel-Veech constants in H(2)
Lelièvre, Samuel
2005-01-01
Abelian differentials on Riemann surfaces can be seen as translation surfaces, which are flat surfaces with cone-type singularities. Closed geodesics for the associated flat metrics form cylinders whose number under a given maximal length generically has quadratic asymptotics in this length, with a common coefficient constant for the quadratic asymptotics called a Siegel--Veech constant which is shared by almost all surfaces in each moduli space of translation surfaces. Square-tiled surfaces ...
Emergent Gravity And The Cosmological Constant Problem
Yang, Hyun Seok
2007-01-01
We address issues on the origin of gravity and the cosmological constant problem based on a recent understanding about the correspondence between noncommutative field theory and gravity. We suggest that the cosmological constant problem can be resolved in a natural way if gravity emerges from a gauge theory in noncommutative spacetime. Especially, we elucidate why the emergent gravity implies that vacuum energy does not gravitate but only fluctuations around the vacuum generate gravity. That ...
Optimization for Hue Constant RGB Sensors
Finlayson, Graham D.; Süsstrunk, Sabine
2002-01-01
We present an optimization technique to find hue constant RGB sensors. The hue representation is based on a log RGB opponent color space that is invariant to brightness and gamma. While modeling the visual response did not derive the opponent space, the hue definition is similar to the ones found in CIE Lab and IPT. Finding hue constant RGB sensors through this optimization might be applicable in color engineering applications such as finding RGB sensors for color image encodings.
A constant elasticity of profit production function
Beard, Rodney
2007-01-01
Impact analysis of changes in production inputs may be simplified if one can apply a constant adjustment factor to profit. In particular, if a production function can be found for which the elasticity of profit is constant and this function has desirable properties, then one can use the input elasticity of profit to study the impact of input changes on profit. In this paper such a production function is derived from first principles.
Beyond lensing by the cosmological constant
Faraoni, Valerio
2016-01-01
The long-standing problem of whether the cosmological constant affects directly the deflection of light caused by a gravitational lens is reconsidered. We use a new approach based on the Hawking quasilocal mass of a sphere grazed by light rays and on its splitting into local and cosmological parts. Previous literature restricted to the cosmological constant is extended to any form of dark energy accelerating the universe in which the gravitational lens is embedded.
Prime rings with PI rings of constants
Kharchenko, V K; Rodríguez-Romo, S
1996-01-01
It is shown that if the ring of constants of a restricted differential Lie algebra with a quasi-Frobenius inner part satisfies a polynomial identity (PI) then the original prime ring has a generalized polynomial identitiy (GPI). If additionally the ring of constants is semiprime then the original ring is PI. The case of a non-quasi-Frobenius inner part is also considered.
RNA structure and scalar coupling constants
Energy Technology Data Exchange (ETDEWEB)
Tinoco, I. Jr.; Cai, Z.; Hines, J.V.; Landry, S.M.; SantaLucia, J. Jr.; Shen, L.X.; Varani, G. [Univ. of California, Berkeley, CA (United States)
1994-12-01
Signs and magnitudes of scalar coupling constants-spin-spin splittings-comprise a very large amount of data that can be used to establish the conformations of RNA molecules. Proton-proton and proton-phosphorus splittings have been used the most, but the availability of {sup 13}C-and {sup 15}N-labeled molecules allow many more coupling constants to be used for determining conformation. We will systematically consider the torsion angles that characterize a nucleotide unit and the coupling constants that depend on the values of these torsion angles. Karplus-type equations have been established relating many three-bond coupling constants to torsion angles. However, one- and two-bond coupling constants can also depend on conformation. Serianni and coworkers measured carbon-proton coupling constants in ribonucleosides and have calculated their values as a function of conformation. The signs of two-bond coupling can be very useful because it is easier to measure a sign than an accurate magnitude.
Teraji, T.; Arakaki, T.
2011-12-01
Use of artificial sweeteners in drinks and food has been rapidly increasing because of their non-calorie nature. In Japan, aspartame, acesulfame K and sucralose are among the most widely used artificial sweeteners. Because the artificial sweeteners are not metabolized in human bodies, they are directly excreted into the environment without chemical transformations. We initiated a study to better understand the fate of artificial sweeteners in the marine environment. In particular, we focused on the fate of aspartame by determining its bimolecular rate constants with hydroxyl radicals at various pH and temperature conditions and reaction by-products. The hydroxyl radical (OH), the most potent reactive oxygen species, reacts with various compounds and determines the environmental oxidation capacity and the life-time of many compounds. The steady-state OH concentration and the reaction rate constants between the compound and OH are used to estimate the life-time of the compound. In this study, we determine the bimolecular rate constants between aspartame and OH at various pH and temperature conditions using a competition kinetics technique. We use hydrogen peroxide as a photochemical source of OH. Bimolecular rate constant we obtained so far was (2.6±1.2)×109 M-1 s-1 at pH = 3.0. Little effect was seen by changing the temperatures between 15 and 40 °C. Activation energy (Ea) was calculated to be -1.0 kJ mol-1 at pH = 3.0, which could be regarded as zero. We will report reaction rate constants at different pHs and reaction by-products which will be analyzed by GC-MS. We will further discuss the fate of aspartame in the coastal environment.
Environment-Dependent Fundamental Physical Constants
Terazawa, Hidezumi
2012-01-01
A theory of special inconstancy, in which some fundamental physical constants such as the fine-structure and gravitational constants may vary, is proposed in pregeometry. In the special theory of inconstancy, the \\alpha-G relation of \\alpha=3\\pi/[16ln(4\\pi/5GM_W^2)] between the varying fine-structure and gravitaional constants (where M_W is the charged weak boson mass) is derived from the hypothesis that both of these constants are related to the same fundamental length scale in nature. Furthermore, it leads to the prediction of dot{{\\alpha}}/\\alpha=(-0.8\\pm2.5)\\times10^{-14}yr^{-1} from the most precise limit of dot{G}/G=(-0.6\\pm2.0)\\times10^{-12}yr^{-1} by Thorsett, which is not only consistent with the recent observation of dot{{\\alpha}}/\\alpha=(0.5\\pm0.5)\\times10^{-14}yr^{-1} by Webb et al. but also feasible for future experimental tests. Also a theory of general inconstancy, in which any fundamental physical constants may vary, is proposed in "more general relativity", by assuming that the space-time is ...
Estimation of Stability Constants of Complex Compounds
Directory of Open Access Journals (Sweden)
Raos, N.
Full Text Available The stability constant of a complex generally depends on the electronic, stereochemical and steric factors, as well as on the chelate effect and interaction of the complex, metal and ligand with water. In the first part of the paper we discuss the Irving-Williams order of stability of bivalent transition metal ion complexes from Mn2+ to Zn2+, along with the HSAB model (hard and soft acids and bases of stability. The second part describes three kinds of models for the estimation of the stability constants of complex compounds. First are those based on molecular mechanics, which were used mainly for the estimation of the enantioselectivity effect, i. e. Gibbs energy differences between MLL and MDL isomers. The second kind of models are mechanistic, that rest on the presumption of linear dependence of measured stability constants of the complexes with the same ligand (stability constants of mono- and bis-complexes, protonation constants, etc.. The third kind of models are heuristic (QSPR, which encompass molecular descriptors calculated by the method of overlapping spheres (OS, as well as topological indices. Among the variety of topological indices, connectivity indices proved best. They were calculated for the ligand and various representations of the coordination compound structure.
Directory of Open Access Journals (Sweden)
Sofia de Amorim Cerejo
2013-09-01
Full Text Available Constant rate infusion (CRI shows several advantages in balanced anesthesia, such as reduction of requirement for inhaled anesthetics and control of pain. The most commonly used drugs in these protocols are local anesthetics, dissociative, and opioids, which may be administered alone or in combinations. We evaluated the records of 200 dogs that underwent various surgical procedures with anesthetic or analgesic CRI in the perioperative period during 2011 and 2012 at the Veterinary Hospital of Franca University (Unifran, and identified possible complications during the transoperative period. Records evaluated included clinical state, laboratory tests, drugs used in premedication and induction, and CRI protocol. Acepromazine and morphine were the main drugs used in premedication. Propofol was used to induce anesthesia alone or in combination with other agents. We evaluated records of the 25 different CRI protocols. Fentanyl was the main drug employed in CRI, either alone or in combination. There were 128 episodes of anesthetic complications during CRI;the most common were hypotension, hypertension, and tachycardia, which occurred in 43 (32%, 35 (26.3%, and 19 (14.2% dogs, respectively. Cardiac arrhythmia was reported in only 4 dogs. Signs of respiratory depression were present in dogs treated with 6 different CRI protocols. The consumption of isoflurane (vol % reduced between 15.7% and 21.05% after 30minutes of the CRI in the fentanyl and fentanyl–lidocaine–ketamine CRI groups (pO uso de técnicas de infusão contínua (IC possui inúmeras vantagens na anestesia balanceada, como a redução do requerimento de anestésicos inalatórios e controle da dor. Os fármacos mais comumente utilizados nestes protocolos são os anestésicos locais, dissociativos e opioides, que podem ser administrados isoladamente ou em associações. Foram avaliados os prontuários de 200 cães que foram submetidos a diversos procedimentos cirúrgicos com IC de anest
Directory of Open Access Journals (Sweden)
Gudapati Sreedevi
Full Text Available Temperature-driven development and survival rates of the mealybug, Phenacoccussolenopsis Tinsley (Hemiptera: Pseudococcidae were examined at nine constant temperatures (15, 20, 25, 27, 30, 32, 35 and 40°C on hibiscus (Hibiscusrosa -sinensis L.. Crawlers successfully completed development to adult stage between 15 and 35°C, although their survival was affected at low temperatures. Two linear and four nonlinear models were fitted to describe developmental rates of P. solenopsis as a function of temperature, and for estimating thermal constants and bioclimatic thresholds (lower, optimum and upper temperature thresholds for development: Tmin, Topt and Tmax, respectively. Estimated thresholds between the two linear models were statistically similar. Ikemoto and Takai's linear model permitted testing the equivalence of lower developmental thresholds for life stages of P. solenopsis reared on two hosts, hibiscus and cotton. Thermal constants required for completion of cumulative development of female and male nymphs and for the whole generation were significantly lower on hibiscus (222.2, 237.0, 308.6 degree-days, respectively compared to cotton. Three nonlinear models performed better in describing the developmental rate for immature instars and cumulative life stages of female and male and for generation based on goodness-of-fit criteria. The simplified β type distribution function estimated Topt values closer to the observed maximum rates. Thermodynamic SSI model indicated no significant differences in the intrinsic optimum temperature estimates for different geographical populations of P. solenopsis. The estimated bioclimatic thresholds and the observed survival rates of P. solenopsis indicate the species to be high-temperature adaptive, and explained the field abundance of P. solenopsis on its host plants.
Sreedevi, Gudapati; Prasad, Yenumula Gerard; Prabhakar, Mathyam; Rao, Gubbala Ramachandra; Vennila, Sengottaiyan; Venkateswarlu, Bandi
2013-01-01
Temperature-driven development and survival rates of the mealybug, Phenacoccussolenopsis Tinsley (Hemiptera: Pseudococcidae) were examined at nine constant temperatures (15, 20, 25, 27, 30, 32, 35 and 40°C) on hibiscus (Hibiscusrosa -sinensis L.). Crawlers successfully completed development to adult stage between 15 and 35°C, although their survival was affected at low temperatures. Two linear and four nonlinear models were fitted to describe developmental rates of P. solenopsis as a function of temperature, and for estimating thermal constants and bioclimatic thresholds (lower, optimum and upper temperature thresholds for development: Tmin, Topt and Tmax, respectively). Estimated thresholds between the two linear models were statistically similar. Ikemoto and Takai's linear model permitted testing the equivalence of lower developmental thresholds for life stages of P. solenopsis reared on two hosts, hibiscus and cotton. Thermal constants required for completion of cumulative development of female and male nymphs and for the whole generation were significantly lower on hibiscus (222.2, 237.0, 308.6 degree-days, respectively) compared to cotton. Three nonlinear models performed better in describing the developmental rate for immature instars and cumulative life stages of female and male and for generation based on goodness-of-fit criteria. The simplified β type distribution function estimated Topt values closer to the observed maximum rates. Thermodynamic SSI model indicated no significant differences in the intrinsic optimum temperature estimates for different geographical populations of P. solenopsis. The estimated bioclimatic thresholds and the observed survival rates of P. solenopsis indicate the species to be high-temperature adaptive, and explained the field abundance of P. solenopsis on its host plants.
The case for the cosmological constant
Indian Academy of Sciences (India)
Varun Sahni
2000-07-01
I present a short overview of current observational results and theoretical models for a cosmological constant. The main motivation for invoking a small cosmological constant (or -term) at the present epoch has to do with observations of high redshift Type Ia supernovae which suggest an accelerating universe. A ﬂat accelerating universe is strongly favoured by combining supernovae observations with observations of CMB anisotropies on degree scales which give the `best-ﬁt’ values ≃ 0.7 and m ≃ 0.3. A time dependent cosmological -term can be generated by scalar ﬁeld models with exponential and power law potentials. Some of these models can alleviate the `ﬁne tuning’ problem which faces the cosmological constant.
Bounds on Gromov Hyperbolicity Constant in Graphs
Indian Academy of Sciences (India)
José M Rodríguez; José M Sigarreta
2012-02-01
If is a geodesic metric space and 1,2,3 $\\in$ , a geodesic triangle ={1,2,3} is the union of the three geodesics [1,2], [2,3] and [31] in . The space is -hyperbolic (in the Gromov sense) if any side of is contained in a -neighborhood of the union of two other sides, for every geodesic triangle in . If is hyperbolic, we denote by () the sharp hyperbolicity constant of , i.e. ()=$inf{$≥ 0$ : is -hyperbolic}. In this paper we relate the hyperbolicity constant of a graph with some known parameters of the graph, as its independence number, its maximum and minimum degree and its domination number. Furthermore, we compute explicitly the hyperbolicity constant of some class of product graphs.
Gravitational Interactions and Fine-Structure Constant
Jentschura, U D; Nandori, I
2015-01-01
Electromagnetic and gravitational central-field problems are studied with relativistic quantum mechanics on curved space-time backgrounds. Corrections to the transition current are identified. Analogies of the gravitational and electromagnetic spectra suggest the definition of a gravitational fine-structure constant. The electromagnetic and gravitational coupling constants enter the Einstein-Hilbert-Maxwell Lagrangian. We postulate that the variational principle holds with regard to a global dilation transformation of the space-time coordinates. The variation suggests is consistent with a functional relationship of the form alpha_QED being proportional to alpha_G^(1/2), where alpha_QED is the electrodynamic fine-structure constant, and alpha_G its gravitational analogue.
New concepts in constant wavelength neutron powder diffractometry
International Nuclear Information System (INIS)
Complete text of publication follows. Neutron powder diffraction is an important tool in the determination of atomic structures of materials. It has become increasingly important to improve the current constant wavelength powder diffractometers to handle the increasing demand. Where once a single diffraction pattern of a 10 gram sample was the entire experiment, today the demand is for experiments using smaller samples in multiple environments (temperature, pressure, magnetic field,...). A new type of constant wavelength diffractometer is proposed using position sensitive detectors (PSD) and advanced collimators. The PSD's allow a larger out-of-scattering plane area to be collected while still affording good peak shapes; hence good resolution at increased collection rates can be obtained. With miniaturisation of many of the detector electronics, the entire system could be affordable and compact. A system of 360 x 40 cm long PSD's is envisaged. This increased density (over the typically 64 detectors) is made possible by use of new advances in neutron collimation. (author)
Cosmic Explosions, Life in the Universe, and the Cosmological Constant.
Piran, Tsvi; Jimenez, Raul; Cuesta, Antonio J; Simpson, Fergus; Verde, Licia
2016-02-26
Gamma-ray bursts (GRBs) are copious sources of gamma rays whose interaction with a planetary atmosphere can pose a threat to complex life. Using recent determinations of their rate and probability of causing massive extinction, we explore what types of universes are most likely to harbor advanced forms of life. We use cosmological N-body simulations to determine at what time and for what value of the cosmological constant (Λ) the chances of life being unaffected by cosmic explosions are maximized. Life survival to GRBs favors Lambda-dominated universes. Within a cold dark matter model with a cosmological constant, the likelihood of life survival to GRBs is governed by the value of Λ and the age of the Universe. We find that we seem to live in a favorable point in this parameter space that minimizes the exposure to cosmic explosions, yet maximizes the number of main sequence (hydrogen-burning) stars around which advanced life forms can exist.
The Cosmological Constant Problem (2/2)
CERN. Geneva
2015-01-01
I will review the cosmological constant problem as a serious challenge to our notion of naturalness in Physics. Weinberg’s no go theorem is worked through in detail. I review a number of proposals possibly including Linde's universe multiplication, Coleman's wormholes, the fat graviton, and SLED, to name a few. Large distance modifications of gravity are also discussed, with causality considerations pointing towards a global modification as being the most sensible option. The global nature of the cosmological constant problem is also emphasized, and as a result, the sequestering scenario is reviewed in some detail, demonstrating the cancellation of the Standard Model vacuum energy through a global modification of General Relativity.
The Cosmological Constant Problem (1/2)
CERN. Geneva
2015-01-01
I will review the cosmological constant problem as a serious challenge to our notion of naturalness in Physics. Weinberg’s no go theorem is worked through in detail. I review a number of proposals possibly including Linde's universe multiplication, Coleman's wormholes, the fat graviton, and SLED, to name a few. Large distance modifications of gravity are also discussed, with causality considerations pointing towards a global modification as being the most sensible option. The global nature of the cosmological constant problem is also emphasized, and as a result, the sequestering scenario is reviewed in some detail, demonstrating the cancellation of the Standard Model vacuum energy through a global modification of General Relativity.
Coulomb field in a constant electromagnetic background
Adorno, T C; Shabad, A E
2016-01-01
Nonlinear Maxwell equations are written up to the third-power deviations from a constant-field background, valid within any local nonlinear electrodynamics including QED with Euler-Heisenberg effective Lagrangian. Linear electric response to imposed static finite-sized charge is found in the vacuum filled by an arbitrary combination of constant and homogeneous electric and magnetic fields. The modified Coulomb field, corrections to the total charge and to the charge density are given in terms of derivatives of the effective Lagrangian with respect to the field invariants.
Black Hole Constraints on Varying Fundamental Constants
International Nuclear Information System (INIS)
We apply the generalized second law of thermodynamics and derive upper limits on the variation in the fundamental constants. The maximum variation in the electronic charge permitted for black holes accreting and emitting in the present cosmic microwave background corresponds to a variation in the fine-structure constant of Δα/α≅2x10-23 per second. This value matches the variation measured by Webb et al. [Phys. Rev. Lett. 82, 884 (1999); Phys. Rev. Lett. 87, 091301 (2001)] using absorption lines in the spectra of distant quasars and suggests the variation mechanism may be a coupling between the electron and the cosmic photon background
Atomic weights: no longer constants of nature
Coplen, Tyler B.; Holden, Norman E.
2011-01-01
Many of us were taught that the standard atomic weights we found in the back of our chemistry textbooks or on the Periodic Table of the Chemical Elements hanging on the wall of our chemistry classroom are constants of nature. This was common knowledge for more than a century and a half, but not anymore. The following text explains how advances in chemical instrumentation and isotopic analysis have changed the way we view atomic weights and why they are no longer constants of nature
Stringy mechanism for a small cosmological constant
International Nuclear Information System (INIS)
Based on the probability distributions of products of random variables, we propose a simple stringy mechanism that prefers the meta-stable vacua with a small cosmological constant. We state some relevant properties of the probability distributions of functions of random variables. We then illustrate the mechanism within the flux compactification models in Type IIB string theory. As a result of the stringy dynamics, we argue that the generic probability distribution for the meta-stable vacua typically peaks with a divergent behavior at the zero value of the cosmological constant. However, its suppression in the single modulus model studied here is modest
Optimizing constant wavelength neutron powder diffractometers
Cussen, Leo D.
2016-06-01
This article describes an analytic method to optimize constant wavelength neutron powder diffractometers. It recasts the accepted mathematical description of resolution and intensity in terms of new variables and includes terms for vertical divergence, wavelength and some sample scattering effects. An undetermined multiplier method is applied to the revised equations to minimize the RMS value of resolution width at constant intensity and fixed wavelength. A new understanding of primary spectrometer transmission (presented elsewhere) can then be applied to choose beam elements to deliver an optimum instrument. Numerical methods can then be applied to choose the best wavelength.
Hermite's Constant for Quadratic Number Fields
Baeza, Ricardo; Coulangeon, Renaud; Icaza, Maria Ines; O'Ryan, Manuel
2001-01-01
We develop a method to compute the Hermite-Humbert constants $\\gam_{K,n}$ of a real quadratic number field $K$, the analogue of the classical Hermite constant $\\gam_n$ when $\\funnyQ$ is replaced by a quadratic extension. In the case $n=2$, the problem is equivalent to the determination of lowest points of fundamental domains in $\\H^2$ for the Hilbert modular group over $K$, that had been studied experimentally by H. Cohn. We establish the results he conjectured for the...
Can compactifications solve the cosmological constant problem?
Hertzberg, Mark P.; Masoumi, Ali
2016-06-01
Recently, there have been claims in the literature that the cosmological constant problem can be dynamically solved by specific compactifications of gravity from higher-dimensional toy models. These models have the novel feature that in the four-dimensional theory, the cosmological constant Λ is much smaller than the Planck density and in fact accumulates at Λ = 0. Here we show that while these are very interesting models, they do not properly address the real cosmological constant problem. As we explain, the real problem is not simply to obtain Λ that is small in Planck units in a toy model, but to explain why Λ is much smaller than other mass scales (and combinations of scales) in the theory. Instead, in these toy models, all other particle mass scales have been either removed or sent to zero, thus ignoring the real problem. To this end, we provide a general argument that the included moduli masses are generically of order Hubble, so sending them to zero trivially sends the cosmological constant to zero. We also show that the fundamental Planck mass is being sent to zero, and so the central problem is trivially avoided by removing high energy physics altogether. On the other hand, by including various large mass scales from particle physics with a high fundamental Planck mass, one is faced with a real problem, whose only known solution involves accidental cancellations in a landscape.
The Alpha Constant from Relativistic Groups
González-Martin, G R
2000-01-01
The value of the alpha constant, known to be equal to an algebraic expression in terms of pi and entire numbers related to certain group volumes, is derived from the relativistic structure group of a geometric unified theory, its subgroups and corresponding symmetric space quotients.
Timelike Constant Mean Curvature Surfaces with Singularities
DEFF Research Database (Denmark)
Brander, David; Svensson, Martin
2014-01-01
We use integrable systems techniques to study the singularities of timelike non-minimal constant mean curvature (CMC) surfaces in the Lorentz–Minkowski 3-space. The singularities arise at the boundary of the Birkhoff big cell of the loop group involved. We examine the behavior of the surfaces at ...
Pion decay constants in dense skyrmion matter
Directory of Open Access Journals (Sweden)
Lee H.-J.
2010-10-01
Full Text Available According to the QCD, the hadronic matter can have various phases with matter density and temperature. In general, when there is phase transition in a matter, it is known that a symmetry in the matter changes. In case of the hadronic matter, the chiral symmetry in the matter is expected to be restored when the matter density (or temperature increases. The actual order parameter with respect to the chiral symmetry in the hadronic matter is known as the quark condensate from the QCD, but the pion decay constant, corresponding to the radius of the chiral circle, plays the role of the order parameter in an eﬀective ﬁeld theoretical approach to the QCD. In this paper, by using the skyrmion model which is an eﬀective theory to the QCD, we construct the skyrmion matter as a model of the hadronic matter (nuclear matter and calculate the pion decay constant in the matter. Because of presence of the matter, the pion decay constant is split into the two components, the temporal component and the spatial component. We discuss the phase transition in the skyrmion matter and behavior of the two components of the decay constant for massless pion with density of the skyrmion matter.
Teaching Nanochemistry: Madelung Constants of Nanocrystals
Baker, Mark D.; Baker, A. David
2010-01-01
The Madelung constants for binary ionic nanoparticles are determined. The computational method described here sums the Coulombic interactions of each ion in the particle without the use of partial charges commonly used for bulk materials. The results show size-dependent lattice energies. This is a useful concept in teaching how properties such as…
Discrete Higgs and the Cosmological Constant
Amore, Paolo; Diaz-Cruz, J Lorenzo
2008-01-01
It is proposed that the Higgs vacuum possesses a small-scale structure that can explain the large discrepancy between the predicted electroweak vacuum energy density and the observed cosmological constant. An effective Lagrangian description is employed to obtain modifications to the Standard Model predictions that can be tested at collider experiments.
Varying Constants: Constraints from Seasonal Variations
Shaw, Douglas J
2010-01-01
We analyse the constraints obtained from new atomic clock data on the possible time variation of the fine structure `constant' and the electron-proton mass ratio and show how they are strengthened when the seasonal variation of Sun's gravitational field at the Earth's surface is taken into account.
Variation of the fine structure constant
Lipovka, Anton A
2016-01-01
In present paper we evaluate the fine structure constant variation which should take place as the Universe is expanded and its curvature is changed adiabatically. This changing of the fine structure constant is attributed to the energy lost by physical system (consist of baryonic component and electromagnetic field) due to expansion of our Universe. Obtained ratio (d alpha)/alpha = 1. 10{-18} (per second) is only five times smaller than actually reported experimental limit on this value. For this reason this variation can probably be measured within a couple of years. To argue the correctness of our approach we calculate the Planck constant as adiabatic invariant of electromagnetic field, from geometry of our Universe in the framework of the pseudo- Riemannian geometry. Finally we discuss the double clock experiment based on Al+ and Hg+ clocks carried out by T. Rosenband et al. (Science 2008). We show that in this particular case there is an error in method and this way the fine structure constant variation c...
The Cosmological Constant and its Interpretation
Liddle, A.; Murdin, P.
2002-12-01
The cosmological constant was first introduced into the equations of general relativity by Einstein himself, who later famously criticized this move as his `greatest blunder'. His main motivation had been to allow cosmological models featuring a static universe, but this possibility swiftly became redundant with Edwin Hubble's discovery of the expansion of the universe. Despite this, it has period...
The Elastic Constants for Wrought Aluminum Alloys
Templin, R L; Hartmann, E C
1945-01-01
There are several constants which have been devised as numerical representations of the behavior of metals under the action of loadings which stress the metal within the range of elastic action. Some of these constants, such as Young's modulus of elasticity in tension and compression, shearing modulus of elasticity, and Poisson's ratio, are regularly used in engineering calculations. Precise tests and experience indicate that these elastic constants are practically unaffected by many of the factors which influence the other mechanical properties of materials and that a few careful determinations under properly controlled conditions are more useful and reliable than many determinations made under less favorable conditions. It is the purpose of this paper to outline the methods employed by the Aluminum Research Laboratories for the determination of some of these elastic constants, to list the values that have been determined for some of the wrought aluminum alloys, and to indicate the variations in the values that may be expected for some of the commercial products of these alloys.
Monopoly price discrimination with constant elasticity demand
Aguirre Pérez, Iñaki; Cowan, Simon George
2013-01-01
This paper presents new results on the welfare e¤ects of third-degree price discrimination under constant elasticity demand. We show that when both the share of the strong market under uniform pricing and the elasticity di¤erence between markets are high enough,then price discrimination not only can increase social welfare but also consumer surplus.
Supersymmetry Breaking and the Cosmological Constant
Banks, T
2014-01-01
I review three attempts to explain the small value of the cosmological constant, and their connection to SUSY breaking. They are The String Landscape, Supersymmetric Large Extra Dimensions (SLED), and the Holographic Space-time Formalism invented by Fischler and myself.
International Nuclear Information System (INIS)
Statistical shape fluctuations can be calculated with two alternative assumptions: (a) the temperature remains constant as the shape fluctuates, or (b) the energy remains constant as the shape fluctuates. These two possibilities are compared for a simple model, the Landau theory, and the finite-temperature HFB cranking theory. Average electric quadrupole moments are compared for these two constraints. (orig.)
Frequency Dependence of Attenuation Constant of Dielectric Materials
Directory of Open Access Journals (Sweden)
A. S. Zadgaonkar
1975-01-01
Full Text Available Different dielectric materials have been studied for frequency dependence of attenuation constant. The sensitive cathode ray oscillograph method has been used to evaluate to the dielectric constant and loss factor, and from these attenuation constants have been calculated. The temperature remaining constant, a regular increase has been observed in attenuation constant, at higher frequencies of electro-magnetic propagating wave.
The information carrying capacity of a cosmological constant
Simidzija, Petar
2016-01-01
We analyze the exchange of information in different cosmological backgrounds when sender and receiver are timelike separated and communicate through massless fields (without the exchange of light-signals). Remarkably, we show that the dominance of a cosmological constant makes the amount of recoverable information imprinted in the field by the sender extremely resilient: it does not decay in time or with the spatial separation of sender and receiver, and it actually increases with the rate of expansion of the Universe. This is in stark contrast with the information carried by conventional light-signals and with previous results on timelike communication through massless fields in matter dominated cosmologies.
On recent SFR calibrations and the constant SFR approximation
Cervino, M; Hidalgo, S
2016-01-01
Star Formation Rate (SFR) inferences are based in the so-called constant SFR approximation, where synthesis models are require to provide a calibration; we aims to study the key points of such approximation to produce accurate SFR inferences. We use the intrinsic algebra used in synthesis models, and we explore how SFR can be inferred from the integrated light without any assumption about the underling Star Formation history (SFH). We show that the constant SFR approximation is actually a simplified expression of more deeper characteristics of synthesis models: It is a characterization of the evolution of single stellar populations (SSPs), acting the SSPs as sensitivity curve over different measures of the SFH can be obtained. As results, we find that (1) the best age to calibrate SFR indices is the age of the observed system (i.e. about 13Gyr for z=0 systems); (2) constant SFR and steady-state luminosities are not requirements to calibrate the SFR; (3) it is not possible to define a SFR single time scale ove...
Evaluation of Rice Seedling Tolerance to Constant and Intermittent Low Temperature Stress
Institute of Scientific and Technical Information of China (English)
Sang-Ic KIM; Dong-min KIM; Thomas H.TAI
2012-01-01
M202,IR50 and advanced backcross (BC4F6) lines carrying the cold tolerance QTLs qCTS4 and qCTS12 were evaluated using three low temperature stress assays (constant,intermittent and constant with recovery period).Under constant stress,two BC4F6 lines (MIb 4853-9 and MIb 6885-2) exhibited differences in seedling growth and accumulation of stress-related compounds although both carry the two QTLs in the IR50 background.Differences between these lines were also observed in the constant with recovery period assay,although both of them performed comparably under intermittent stress.MIb 6885-2 performed more similarly to M202 in the constant and constant with recovery period assays,suggesting that this line contains an introgressed region(s) not present in Mlb 4853-9.The three assays were also applied to assess variations in cold tolerance in a set of diverse germplasms.Performance metrics and visual ratings were comparable for evaluating tolerance to constant stress.However,differences in response to intermittent stress were more evident from growth and total chlorophyll measurements than from visual ratings.With regard to the constant with recovery period assay,about 15％ of the germplasm accessions did not recover.However,some lines which exhibited chilling injuries of comparable severity were able to overcome them.This recovery phenotype may improve rice performance in the field and warrant further investigation.
Hyperscaling violation and the shear diffusion constant
Kolekar, Kedar S.; Mukherjee, Debangshu; Narayan, K.
2016-09-01
We consider holographic theories in bulk (d + 1)-dimensions with Lifshitz and hyperscaling violating exponents z , θ at finite temperature. By studying shear gravitational modes in the near-horizon region given certain self-consistent approximations, we obtain the corresponding shear diffusion constant on an appropriately defined stretched horizon, adapting the analysis of Kovtun, Son and Starinets. For generic exponents with d - z - θ > - 1, we find that the diffusion constant has power law scaling with the temperature, motivating us to guess a universal relation for the viscosity bound. When the exponents satisfy d - z - θ = - 1, we find logarithmic behaviour. This relation is equivalent to z = 2 +deff where deff =di - θ is the effective boundary spatial dimension (and di = d - 1 the actual spatial dimension). It is satisfied by the exponents in hyperscaling violating theories arising from null reductions of highly boosted black branes, and we comment on the corresponding analysis in that context.
Fat Euclidean Gravity with Small Cosmological Constant
Sundrum, Raman
2003-01-01
The cosmological constant problem is usually considered an inevitable feature of any effective theory capturing well-tested gravitational and matter physics, without regard to the details of short-distance gravitational couplings. In this paper, a subtle effective description avoiding the problem is presented in a first quantized language, consistent with experiments and the Equivalence Principle. First quantization allows a minimal domain of validity to be carved out by cutting on the proper length of particle worldlines. This is facilitated by working in (locally) Euclidean spacetime, although considerations of unitarity are still addressed by analytic continuation from Lorentzian spacetime. The new effective description demonstrates that the cosmological constant problem {\\it is} sensitive to short-distance details of gravity, which can be probed experimentally. ``Fat Gravity'' toy models are presented, illustrating how gravity might shut off at short but testable distances, in a generally covariant manner...
Negative Energy Cosmology and the Cosmological Constant
Prokopec, Tomislav
2011-01-01
It is well known that string theories naturally compactify on anti-de Sitter spaces, and yet cosmological observations show no evidence of a negative cosmological constant in the early Universe's evolution. In this letter we present two simple nonlocal modifications of the standard Friedmann cosmology that can lead to observationally viable cosmologies with an initial (negative) cosmological constant. The nonlocal operators we include are toy models for the quantum cosmological backreaction. In Model I an initial quasiperiodic oscillatory epoch is followed by inflation and a late time matter era, representing a dark matter candidate. The backreaction in Model II quickly compensates the negative cosmological term such that the Ricci curvature scalar rapidly approaches zero, and the Universe ends up in a late time radiation era.
Cosmological Constant or Variable Dark Energy?
Institute of Scientific and Technical Information of China (English)
XU Li-Xin; ZHANG Cheng-Wu; LIU Hong-Ya
2007-01-01
@@ Selection statics of the Akaike information criterion (AIC) model and the Bayesian information criterion (BIC)model are applied to the Λ-cold dark matter (ΛCDM) cosmological model, the constant equation of state of dark energy, w =constant, and the parametrized equation of state of dark energy, w(z) = w0 + w1z/(1 + z),to determine which one is the better cosmological model to describe the evolution of the universe by combining the recent cosmic observational data including Sne Ia, the size of baryonic acoustic oscillation (BAO) peak from SDSS, the three-year WMAP CMB shift parameter. The results show that AIC, BIC and current datasets are not powerful enough to discriminate one model from the others, though odds suggest differences between them.
Regular Black Holes with Cosmological Constant
Institute of Scientific and Technical Information of China (English)
MO Wen-Juan; CAI Rong-Gen; SU Ru-Keng
2006-01-01
We present a class of regular black holes with cosmological constant Λ in nonlinear electrodynamics. Instead of usual singularity behind black hole horizon, all fields and curvature invariants are regular everywhere for the regular black holes. Through gauge invariant approach, the linearly dynamical stability of the regular black hole is studied. In odd-parity sector, we find that the Λ term does not appear in the master equations of perturbations, which shows that the regular black hole is stable under odd-parity perturbations. On the other hand, for the even-parity sector, the master equations are more complicated than the case without the cosmological constant. We obtain the sufficient conditions for stability of the regular black hole. We also investigate the thermodynamic properties of the regular black hole, and find that those thermodynamic quantities do not satisfy the differential form of first law of black hole thermodynamics. The reason for violating the first law is revealed.
Quantum Exclusion of Positive Cosmological Constant?
Dvali, Gia
2014-01-01
We show that a positive cosmological constant is incompatible with the quantum-corpuscular resolution of de Sitter metric in form of a coherent state. The reason is very general and is due to the quantum self-destruction of the coherent state because of the scattering of constituent graviton quanta. This process creates an irreversible quantum clock, which precludes eternal de Sitter. It also eliminates the possibility of Boltzmann brains and Poincare recurrences. This effect is expected to be part of any microscopic theory that takes into account the quantum corpuscular structure of the cosmological background. This observation puts the cosmological constant problem in a very different light, promoting it, from a naturalness problem, into a question of quantum consistency. We are learning that quantum gravity cannot tolerate exceedingly-classical sources.
The Value of the Cosmological Constant
Barrow, John D
2011-01-01
We make the cosmological constant, {\\Lambda}, into a field and restrict the variations of the action with respect to it by causality. This creates an additional Einstein constraint equation. It restricts the solutions of the standard Einstein equations and is the requirement that the cosmological wave function possess a classical limit. When applied to the Friedmann metric it requires that the cosmological constant measured today, t_{U}, be {\\Lambda} ~ t_{U}^(-2) ~ 10^(-122), as observed. This is the classical value of {\\Lambda} that dominates the wave function of the universe. Our new field equation determines {\\Lambda} in terms of other astronomically measurable quantities. Specifically, it predicts that the spatial curvature parameter of the universe is {\\Omega}_{k0} \\equiv -k/a_(0)^(2)H^2= -0.0055, which will be tested by Planck Satellite data. Our theory also creates a new picture of self-consistent quantum cosmological history.
Pole placement with constant gain output feedback
Sridhar, B.; Lindorff, D. P.
1972-01-01
Given a linear time invariant multivariable system with m inputs and p outputs, it was shown that p closed loop poles of the system can be preassigned arbitrarily using constant gain output feedback provided (A circumflex, B circumflex) is controllable. These data show that if (A circumflex, B circumflex, C circumflex) is controllable and observable, and Rank B circumflex = m, Rank C circumflex = p, then max (m,p) poles of the system can be assigned arbitarily using constant gain output feedback. Further, it is shown that in some cases more than max (m,p) poles can be arbitrarily assigned. A least square design technique is outlined to approximate the desired pole locations when it is not possible to place all the poles.
Some Dynamical Effects of the Cosmological Constant
Axenides, M.; Floratos, E. G.; Perivolaropoulos, L.
Newton's law gets modified in the presence of a cosmological constant by a small repulsive term (antigravity) that is proportional to the distance. Assuming a value of the cosmological constant consistent with the recent SnIa data (Λ~=10-52 m-2), we investigate the significance of this term on various astrophysical scales. We find that on galactic scales or smaller (less than a few tens of kpc), the dynamical effects of the vacuum energy are negligible by several orders of magnitude. On scales of 1 Mpc or larger however we find that the vacuum energy can significantly affect the dynamics. For example we show that the velocity data in the local group of galaxies correspond to galactic masses increased by 35% in the presence of vacuum energy. The effect is even more important on larger low density systems like clusters of galaxies or superclusters.
Incompressible flows with piecewise constant density
Danchin, Raphaël
2012-01-01
We investigate the incompressible Navier-Stokes equations with variable density. The aim is to prove existence and uniqueness results in the case of discontinuous ini- tial density. In dimension n = 2, 3, assuming only that the initial density is bounded and bounded away from zero, and that the initial velocity is smooth enough, we get the local-in-time existence of unique solutions. Uniqueness holds in any dimension and for a wider class of velocity fields. Let us emphasize that all those results are true for piecewise constant densities with arbitrarily large jumps. Global results are established in dimension two if the density is close enough to a positive constant, and in n-dimension if, in addition, the initial velocity is small. The Lagrangian formula- tion for describing the flow plays a key role in the analysis that is proposed in the present paper.
Lectures on the Cosmological Constant Problem
Padilla, Antonio
2015-01-01
These lectures on the cosmological constant problem were prepared for the X Mexican School on Gravitation and Mathematical Physics. The problem itself is explained in detail, emphasising the importance of radiative instability and the need to repeatedly fine tune as we change our effective description. Weinberg's no go theorem is worked through in detail. I review a number of proposals including Linde's universe multiplication, Coleman's wormholes, the fat graviton, and SLED, to name a few. Large distance modifications of gravity are also discussed, with causality considerations pointing towards a global modification as being the most sensible option. The global nature of the cosmological constant problem is also emphasized, and as a result, the sequestering scenario is reviewed in some detail, demonstrating the cancellation of the Standard Model vacuum energy through a global modification of General Relativity.
Variable energy constant current accelerator structure
Anderson, O.A.
1988-07-13
A variable energy, constant current ion beam accelerator structure is disclosed comprising an ion source capable of providing the desired ions, a pre-accelerator for establishing an initial energy level, a matching/pumping module having means for focusing means for maintaining the beam current, and at least one main accelerator module for continuing beam focus, with means capable of variably imparting acceleration to the beam so that a constant beam output current is maintained independent of the variable output energy. In a preferred embodiment, quadrupole electrodes are provided in both the matching/pumping module and the one or more accelerator modules, and are formed using four opposing cylinder electrodes which extend parallel to the beam axis and are spaced around the beam at 90/degree/ intervals with opposing electrodes maintained at the same potential. 12 figs., 3 tabs.
The fine structure constant and numerical alchemy
Dattoli, Giuseppe
2010-01-01
We comment on past and more recent efforts to derive a formula yielding the fine structure constant in terms of integers and transcendent numbers. We analyse these "exoteric" attitudes and describe the myths regarding {\\alpha}, which seems to have very ancient roots, tracing back to Cabbala and to medieval alchemic conceptions. We discuss the obsession for this constant developed by Pauli and the cultural "environment" in which such an "obsession" grew. We also derive a simple formula for {\\alpha} in terms of two numbers {\\pi} and 137 only. The formula we propose reproduces the experimental values up to the last significant digit, it has not any physical motivation and is the result of an alchemic combination of numbers. We make a comparison with other existing formulae, discuss the relevant limits of validity by comparison with the experimental values and discuss a criterion to recover a physical meaning, if existing, from their mathematical properties.
Varying fine-structure and gravitational constants
International Nuclear Information System (INIS)
A simple relation between the time-dependent fine-structure and gravitational constants of alpha/alpha2 approx G/G is derived from the hypothesis that both of these fundamental constants are related to the more fundamental length scale of nature as in he unified pregauge and pregeometric theory of all fundamental forces. From the latest observation of alpha/alpha = (-1.91 ± 0.54) centre dot 10-15yr-1 by Webb et al., it leads to the prediction of G/G = (-0.154 ± 0.044) centre dot 10-12yr-1, which is not only consistent with the most precise limit of G/G = (-0.6 ± 2.0) centre dot 10-12yr-1 by Thorsett but also feasible for future experimental tests
Daylight calculations using constant luminance curves
Energy Technology Data Exchange (ETDEWEB)
Betman, E. [CRICYT, Mendoza (Argentina). Laboratorio de Ambiente Humano y Vivienda
2005-02-01
This paper presents a simple method to manually estimate daylight availability and to make daylight calculations using constant luminance curves calculated with local illuminance and irradiance data and the all-weather model for sky luminance distribution developed in the Atmospheric Science Research Center of the University of New York (ARSC) by Richard Perez et al. Work with constant luminance curves has the advantage that daylight calculations include the problem's directionality and preserve the information of the luminous climate of the place. This permits accurate knowledge of the resource and a strong basis to establish conclusions concerning topics related to the energy efficiency and comfort in buildings. The characteristics of the proposed method are compared with the method that uses the daylight factor. (author)
Why all these prejudices against a constant?
Bianchi, Eugenio
2010-01-01
The expansion of the observed universe appears to be accelerating. A simple explanation of this phenomenon is provided by the non-vanishing of the cosmological constant in the Einstein equations. Arguments are commonly presented to the effect that this simple explanation is not viable or not sufficient, and therefore we are facing the "great mystery" of the "nature of a dark energy". We argue that these arguments are unconvincing, or ill-founded.
Comoving suppression mechanism and cosmological constant problem
Shen, Jian Qi
2004-01-01
In this paper, we assume that the observer is fixed in a comoving frame of reference with $g_{00}=\\frac{\\lambda}{\\Lambda}$, where $\\lambda$ and $\\Lambda$ denote the comoving parameter and the cosmological constant, respectively. By using the {\\it comoving suppression mechanism} and {\\it Mach's principle} (the latter of which is used to determine the comoving parameter $\\lambda$), we calculate the vacuum energy density of quantum fluctuation field in the above-mentioned comoving frame of refer...
Constant fraction timing with scintillation detectors
International Nuclear Information System (INIS)
A model is presented for constant fraction pick-off timing with scintillator-photomultiplier detectors based on a statistical method for leading edge timing. Many of the essential features of this technique are obtained such as prompt time-response, the dependence of FWHM on dynamic range of pulse heights and on maximum energy deposited in scintillator; also the effect of delay time on the optimum resolution in CFPHT and ARC timing. The Walk component in this technique is also satisfactory reproduced
Standard-model coupling constants from compositeness
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 unifica...
Elastic constants from microscopic strain fluctuations
Sengupta, Surajit; Nielaba, Peter; Rao, Madan; Binder, K.
1999-01-01
Fluctuations of the instantaneous local Lagrangian strain $\\epsilon_{ij}(\\bf{r},t)$, measured with respect to a static ``reference'' lattice, are used to obtain accurate estimates of the elastic constants of model solids from atomistic computer simulations. The measured strains are systematically coarse- grained by averaging them within subsystems (of size $L_b$) of a system (of total size $L$) in the canonical ensemble. Using a simple finite size scaling theory we predict the behaviour of th...
Physical Basis for a Constant Lag Time
Socrates, Aristotle
2012-01-01
We show that the constant time lag prescription for tidal dissipation follows directly from the equations of motion of a tidally-forced fluid body, given some basic assumptions. They are (i) the equilibrium structure of the forced body is spherically-symmetric (ii) the tidal forcing is weak and non-resonant (iii) dissipation is weak. The lag time is an intrinsic property of the tidally-forced body and is independent of the orbital configuration.
Running cosmological constant with observational tests
Geng, Chao-Qiang; Lee, Chung-Chi; Zhang, Kaituo
2016-01-01
We investigate the running cosmological constant model with dark energy linearly proportional to the Hubble parameter, $\\Lambda = \\sigma H + \\Lambda_0$, in which the $\\Lambda$CDM limit is recovered by taking $\\sigma=0$. We derive the linear perturbation equations of gravity under the Friedmann-Lema\\"itre-Robertson-Walker cosmology, and show the power spectra of the CMB temperature and matter density distribution. By using the Markov chain Monte Carlo method, we fit the model to the current ob...
Linear polarization constant of $\\R^n$
Matolcsi, Mate
2006-01-01
The present work contributes to the determination of the $n$-th linear polarization constant $c_n(H)$ of an $n$-dimensional real Hilbert space $H$. We provide some new lower bounds on the value of $\\sup_{\\|y\\|=1}| x_1,y >... x_n,y |$, where $x_1, ..., x_n$ are unit vectors in $H$. In particular, the results improve an earlier estimate of Marcus. However, the intriguing conjecture $c_n(H)=n^{n/2}$ remains open.
Noteworthy dimensionless constant in gravitation theory
Energy Technology Data Exchange (ETDEWEB)
Fayos, F.; Lobo, J.A.; Llanta, E.
1986-01-01
A simple problem of gravitation is studied classically and in the Schwarzchild framework. A relationship is found between the parameters that define the trajectories of two particles (the first in radial motion and the second in a circular orbit) which are initially together and meet again after one revolution of particle 2. Dimensional analysis is the clue to explain the appearance of a dimensionless constant in the Newtonian case.
Some constant solutions to Zamolodchikov's tetrahedron equations
Hietarinta, Jarmo
1992-01-01
In this letter we present constant solutions to the tetrahedron equations proposed by Zamolodchikov. In general, from a given solution of the Yang-Baxter equation there are two ways to construct solutions to the tetrahedron equation. There are also other kinds of solutions. We present some two-dimensional solutions that were obtained by directly solving the equations using either an upper triangular or Zamolodchikov's ansatz.
Fractional constant elasticity of variance model
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.
Chiral Heterotic Strings with Positive Cosmological Constant
Florakis, Ioannis
2016-01-01
We present explicit examples of semi-realistic heterotic models with spontaneously broken supersymmetry, which dynamically lead to breaking scales much smaller than $M_{\\rm Planck}$ and exponentially small positive values for the cosmological constant. Contrary to field theoretic intuition, we find that the global structure of the effective potential is significantly affected by contributions of massive and non-level matched string states and we investigate the conditions that dynamically ensure a number of desired properties.
A constant current source for extracellular microiontophoresis.
Walker, T; Dillman, N; Weiss, M L
1995-12-01
A sophisticated constant-current source suitable for extracellular microiontophoresis of tract-tracing substances, such as Phaseolus vulgaris leucoagglutinin, Biocytin or Fluoro-Gold, is described. This design uses a flyback switched-mode power supply to generate controllable high-voltage and operational amplifier circuitry to regulate current and provide instrumentation. Design features include a fast rise time, +/- 2000 V supply (stable output in current and voltage monitoring, and separate pumping and holding current settings. Three features of this constant-current source make it especially useful for extracellular microiontophoresis. First, the output voltage monitor permits one to follow changes in the microelectrode resistance during current injection. Second, the voltage-limit (or out-of-compliance) indicator circuitry will sound an alarm when the iontophoretic pump is unable to generate the desired current, such as when the micropipette is blocked. Third, the high-compliance voltage power supply insures up to +/- 20 microA of current through 100 M omega resistance. This device has proven itself to be a reliable constant-current source for extracellular microiontophoresis in the laboratory. PMID:8788057
When is the growth index constant?
Polarski, David; Giacomini, Hector
2016-01-01
The growth index $\\gamma$ is an interesting tool to assess the phenomenology of dark energy (DE) models, in particular of those beyond general relativity (GR). We investigate the possibility for DE models to allow for a constant $\\gamma$ during the entire matter and DE dominated stages. It is shown that if DE is described by quintessence (a scalar field minimally coupled to gravity), this behaviour of $\\gamma$ is excluded either because it would require a transition to a phantom behaviour at some finite moment of time, or, in the case of tracking DE at the matter dominated stage, because the relative matter density $\\Omega_m$ appears to be too small. An infinite number of solutions, with $\\Omega_m$ and $\\gamma$ both constant, are found with $w_{DE}=0$ corresponding to Einstein-de Sitter universes. For all modified gravity DE models satisfying $G_{\\rm eff}\\ge G$, among them the $f(R)$ DE models suggested in the literature, the condition to have a constant $w_{DE}$ is strongly violated at the present epoch. In ...
Fundamental constants and high resolution spectroscopy
Bonifacio, P; Whitmore, J B; Wendt, M; Centurion, M; Molaro, P; Srianand, R; Murphy, M T; Petitjean, P; Agafonova, I I; D'Odorico, S; Evans, T M; Levshakov, S A; Lopez, S; Martins, C J A P; Reimers, D; Vladilo, G
2013-01-01
Absorption-line systems detected in high resolution quasar spectra can be used to compare the value of dimensionless fundamental constants such as the fine-structure constant, alpha, and the proton-to-electron mass ratio, mu = m_p/m_e, as measured in remote regions of the Universe to their value today on Earth. In recent years, some evidence has emerged of small temporal and also spatial variations in alpha on cosmological scales which may reach a fractional level of 10 ppm . We are conducting a Large Programme of observations with VLT UVES to explore these variations. We here provide a general overview of the Large Programme and report on the first results for these two constants, discussed in detail in Molaro et al. and Rahmani et al. A stringent bound for Delta(alpha)/Alpha is obtained for the absorber at_abs = 1.6919 towards HE 2217-2818. The absorption profile is complex with several very narrow features, and is modeled with 32 velocity components. The relative variation in alpha in this system is +1.3+-...
Stability constants for silicate adsorbed to ferrihydrite
DEFF Research Database (Denmark)
Hansen, Hans Christian Bruun; Wetche, T.P.; Raulund-Rasmussen, Karsten;
1994-01-01
required days-weeks, both reactions probably being diffusion controlled. Applying the values for specific surface area and site densities for ferrihydrite used by Dzombak & Morel (1990) (600 m2 g-1, 3.4 mumole m-2) the constants pK(al)intr 6.93 +/- 0.12, pK(a2)intr = 8.72 +/- 0.17 and log K(Si) = 3.62 were...... calculated by using the FITEQL optimization routine. Use of the specific surface area actually measured (269 m2 g-1) gave a poorer fit of the experimental data. Due to the slow adsorption of silicate and hence long shaking times, changes in the surface characteristics of the ferrihydrite seem to take place......Intrinsic surface acidity constants (K(a1)intr, K(a2)intr) and surface complexation constant for adsorption of orthosilicate onto synthetic ferrihydrite (K(Si) for the complex = FeOSi(OH)3) have been determined from acid/base titrations in 0.001-0.1 m NaClO4 electrolytes and silicate adsorption...
Twelve Elastic Constants of Betula platyphylla Suk.
Institute of Scientific and Technical Information of China (English)
Wang Liyu; Lu Zhenyou
2004-01-01
Wood elastic constants are needed to describe the elastic behaviors of wood and be taken as an important design parameter for wood-based composite materials and structural materials. This paper clarified the relationships between compliance coefficients and engineering elastic constants combined with orthotropic properties of wood, and twelve elastic constants of Betula platyphylla Suk. were measured by electrical strain gauges. Spreading the adhesive quantity cannot be excessive or too little when the strain flakes were glued. If excessive, the glue layer was too thick which would influence the strain flakes' performance, and if too little, glues plastered were not firm, which could not accurately transmit the strain. Wood as an orthotropic material, its modulus of elasticity and poisson's ratios are related by two formulas:μij /Ei =μji /Ej and μij 0.95) between the reciprocal of elastic modulus MOE-1 and the square of the ratio of depth to length (h/l)2, which indicate that shear modulus values measured were reliable by three point bending experiment.
Fundamental Constants as Monitors of the Universe
Thompson, Rodger I
2016-01-01
Astronomical observations have a unique ability to determine the laws of physics at distant times in the universe. They, therefore, have particular relevance in answering the basic question as to whether the laws of physics are invariant with time. The dimesionless fundamental constants, such as the proton to electron mass ratio and the fine structure constant are key elements in the investigation. If they vary with time then the answer is clearly that the laws of physics are not invariant with time and significant new physics must be developed to describe the universe. Limits on their variance, on the other hand, constrains the parameter space available to new physics that requires a variation with time of basic physical law. There are now observational constraints on the time variation of the proton to electron mass ratio mu at the 1.E-7 level. Constraints on the variation of the fine structure constant alpha are less rigorous, 1E-5, but are imposed at higher redshift. The implications of these limits on ne...
Time Variation of the Fine Structure Constant Driven by Quintessence
Anchordoqui, L A; Anchordoqui, Luis; Goldberg, Haim
2003-01-01
There are indications from the study of quasar absorption spectra that the fine structure constant $\\alpha$ may have been measurably smaller for redshifts $z>2.$ Analyses of other data ($^{149}$Sm fission rate for the Oklo natural reactor, variation of $^{187}$Re $\\beta$-decay rate in meteorite studies, atomic clock measurements) which probe variations of $\\alpha$ in the more recent past imply much smaller deviations from its present value. In this work we tie the variation of $\\alpha$ to the evolution of the quintessence field proposed by Albrecht and Skordis, and show that agreement with all these data, as well as consistency with WMAP observations, can be achieved for a range of parameters. Some definite predictions follow for upcoming space missions searching for violations of the equivalence principle.
Time variation of the fine structure constant driven by quintessence
Anchordoqui, Luis; Goldberg, Haim
2003-10-01
There are indications from the study of quasar absorption spectra that the fine structure constant α may have been measurably smaller for redshifts z>2. Analyses of other data (149Sm fission rate for the Oklo natural reactor, variation of 187Re β-decay rate in meteorite studies, atomic clock measurements) which probe variations of α in the more recent past imply much smaller deviations from its present value. In this work we tie the variation of α to the evolution of the quintessence field proposed by Albrecht and Skordis, and show that agreement with all these data, as well as consistency with Wilkinson Microwave Anisotropy Probe observations, can be achieved for a range of parameters. Some definite predictions follow for upcoming space missions searching for violations of the equivalence principle.