A digital, constant-frequency pulsed phase-locked-loop instrument for real-time, absolute ultrasonic phase measurements

Science.gov (United States)

Haldren, H. A.; Perey, D. F.; Yost, W. T.; Cramer, K. E.; Gupta, M. C.

2018-05-01

A digitally controlled instrument for conducting single-frequency and swept-frequency ultrasonic phase measurements has been developed based on a constant-frequency pulsed phase-locked-loop (CFPPLL) design. This instrument uses a pair of direct digital synthesizers to generate an ultrasonically transceived tone-burst and an internal reference wave for phase comparison. Real-time, constant-frequency phase tracking in an interrogated specimen is possible with a resolution of 0.000 38 rad (0.022°), and swept-frequency phase measurements can be obtained. Using phase measurements, an absolute thickness in borosilicate glass is presented to show the instrument's efficacy, and these results are compared to conventional ultrasonic pulse-echo time-of-flight (ToF) measurements. The newly developed instrument predicted the thickness with a mean error of -0.04 μm and a standard deviation of error of 1.35 μm. Additionally, the CFPPLL instrument shows a lower measured phase error in the absence of changing temperature and couplant thickness than high-resolution cross-correlation ToF measurements at a similar signal-to-noise ratio. By showing higher accuracy and precision than conventional pulse-echo ToF measurements and lower phase errors than cross-correlation ToF measurements, the new digitally controlled CFPPLL instrument provides high-resolution absolute ultrasonic velocity or path-length measurements in solids or liquids, as well as tracking of material property changes with high sensitivity. The ability to obtain absolute phase measurements allows for many new applications than possible with previous ultrasonic pulsed phase-locked loop instruments. In addition to improved resolution, swept-frequency phase measurements add useful capability in measuring properties of layered structures, such as bonded joints, or materials which exhibit non-linear frequency-dependent behavior, such as dispersive media.

Reactions of sulfur atoms. XV. Absolute rate parameters for the S(3P210) + alkyne reactions

International Nuclear Information System (INIS)

van Roodselaar, A.; Safarik, I.; Strausz, O.P.; Gunning, H.E.

1978-01-01

Using flash photolysis with vacuum uv kinetic absorption spectroscopy, absolute rate constants and Arrhenius parameters have been measured for the addition of ground state S( 3 P 2 , 1 , 0 ) atoms to alkynes. The decay of sulfur atoms in COS, alkyne, and CO 2 -diluent mixtures is first order in sulfur atom concentration and the first-order decay rate constants are proportional to the alkyne concentration. The following rate constants were determined at room temperature: k(C 2 H 2 ) = k(C 2 D 2 ) + (2.3 +- 0.4) x 10 8 ; k(CHCCH 3 ) = (4.8 +- 0.2) x 10 9 ; k(CHCC 2 H 5 ) = (3.3 +- 0.2) x 10 9 ; k(CH 3 CCCH 3 ) = 1.6 +- 0.2) x 10 10 ; k(CH 3 CCC 2 C 5 ) = 1.8 +- 0.3) x 10 10 ; and k(CF 3 CCCF 3 ) = (2.1 +- 0.4) x 10 8 L mol -1 s -1 . The Arrhenius parameters determined are k(C 2 H 2 ) = (3.4 +- 1.9) x 10 10 exp[(-3000 +- 400)/RT] L mol -1 s -1 and k(CHCCH 3 ) = (2.0 +- 1.2) x 10 10 exp[(-900 +- 200)/RT] L mol -1 s -1 where error limits represent standard deviations. The rate parameters are compared to those obtained for the addition of other electrophilic reagents to alkynes and the results discussed in terms of structural and kinetic factors. Theoretical treatment of the secondary H/D isotope effect in the acetylene reaction satisfactorily reproduces the experimental value. 5 tables, 4 figures, 59 references

Rate constant for the reaction of O(3P) with diacetylene from 210 to 423 K

Science.gov (United States)

Mitchell, M. B.; Nava, D. F.; Stief, L. J.

1986-01-01

The absolute rate constant for the reaction of O(3P) with diacetylene (C4H2) has been measured as a function of pressure and temperature by the flash-photolysis/resonance-fluorescence method. At 298 K and below, no pressure dependence of the rate constant was observed, but at 423 K a moderate (factor-of-2) increase was detected in the range 3 to 75 torr Ar.Results at or near the high-pressure limit are represented by an Arrhenius expression over the temperature range 210 to 423 K. The results are compared with previous determinations, all of which employed the discharge-flow/mass-spectrometry technique. The mechanism of the reaction is considered, including both primary and secondary processes. The heats of formation of the reactants, adducts, and products for the O(3P) + C4H2 reaction are discussed and contrasted with those for O(3P) + C2H2.

Rate constant for the reaction of OH with CH3CCl2F (HCFC-141b) determined by relative rate measurements with CH4 and CH3CCl3

Science.gov (United States)

Huder, Karin; Demore, William B.

1993-01-01

Determination of accurate rate constants for OH abstraction is of great importance for the calculation of lifetimes for HCFCs and their impact on the atmosphere. For HCFC-141b there has been some disagreement in the literature for absolute measurements of this rate constant. In the present work rate constant ratios for HCFC-141b were measured at atmospheric pressure in the temperature range of 298-358 K, with CH4 and CH3CCl3 as reference gases. Ozone was photolyzed at 254 nm in the presence of water vapor to produce OH radicals. Relative depletions of 141b and the reference gases were measured by FTIR. Arrhenius expressions for 141b were derived from each reference gas and found to be in good agreement with each other. The combined expression for HCFC-141b which we recommend is 1.4 x 10 exp -12 exp(-1630/T) with k at 298 K being 5.9 x 10 exp -15 cu cm/molec-s. This value is in excellent agreement with the JPL 92-20 recommendation.

Sensitivity of molecular vibrational dynamics to energy exchange rate constants

International Nuclear Information System (INIS)

Billing, G D; Coletti, C; Kurnosov, A K; Napartovich, A P

2003-01-01

The sensitivity of molecular vibrational population dynamics, governing the CO laser operated in fundamental and overtone transitions, to vibration-to-vibration rate constants is investigated. With this aim, three rate constant sets have been used, differing in their completeness (i.e. accounting for single-quantum exchange only, or for multi-quantum exchange with a limited number of rate constants obtained by semiclassical calculations, and, finally, with an exhaustive set of rate constants including asymmetric exchange processes, as well) and in the employed interaction potential. The most complete set among these three is introduced in this paper. An existing earlier kinetic model was updated to include the latter new data. Comparison of data produced by kinetic modelling with the above mentioned sets of rate constants shows that the vibrational distribution function, and, in particular, the CO overtone laser characteristics, are very sensitive to the choice of the model. The most complete model predicts slower evolution of the vibrational distribution, in qualitative agreement with experiments

Absolute rate constants for the reaction of CF3O2 and CF3O radicals with NO at 295 K

DEFF Research Database (Denmark)

Sehested, J.; Nielsen, O.J.

1993-01-01

Using a pulse radiolysis UV absorption technique and subsequent simulations of experimental NO2 and FNO absorption transients, rate constants for reaction between CF3O and CF3O2 radicals with NO were determined, CF3O2+NO-->CF3O+NO2 (3), CF3O+NO-->CF2O+FNO (5). k3 was derived to be (1.68+/-0.26)x10...

Rate Constant of the Reaction between CH3O2 Radicals and OH Radicals Revisited.

Science.gov (United States)

Assaf, Emmanuel; Song, Bo; Tomas, Alexandre; Schoemaecker, Coralie; Fittschen, Christa

2016-11-17

The reaction between CH 3 O 2 and OH radicals has been studied in a laser photolysis cell using the reaction of F atoms with CH 4 and H 2 O for the simultaneous generation of both radicals, with F atoms generated through 248 nm photolysis of XeF 2 . An experimental setup combining cw-Cavity Ring Down Spectroscopy (cw-CRDS) and high repetition rate laser-induced fluorescence (LIF) to a laser photolysis cell has been used. The absolute concentration of CH 3 O 2 was measured by cw-CRDS, while the relative concentration of OH(v = 0) radicals was determined by LIF. To remove dubiety from the quantification of CH 3 O 2 by cw-CRDS in the near-infrared, its absorption cross section has been determined at 7489.16 cm -1 using two different methods. A rate constant of k 1 = (1.60 ± 0.4) × 10 -10 cm 3 s -1 has been determined at 295 K, nearly a factor of 2 lower than an earlier determination from our group ((2.8 ± 1.4) × 10 -10 cm 3 s -1 ) using CH 3 I photolysis as a precursor. Quenching of electronically excited I atoms (from CH 3 I photolysis) in collision with OH(v = 0) is suspected to be responsible for a bias in the earlier, fast rate constant.

Absolute NMR shielding scales and nuclear spin–rotation constants in {sup 175}LuX and {sup 197}AuX (X = {sup 19}F, {sup 35}Cl, {sup 79}Br and {sup 127}I)

Energy Technology Data Exchange (ETDEWEB)

Demissie, Taye B., E-mail: taye.b.demissie@uit.no; Komorovsky, Stanislav; Repisky, Michal; Ruud, Kenneth [Centre for Theoretical and Computational Chemistry, Department of Chemistry, UiT The Arctic University of Norway, N-9037 Tromsø (Norway); Jaszuński, Michał [Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01 224 Warszawa (Poland)

2015-10-28

We present nuclear spin–rotation constants, absolute nuclear magnetic resonance (NMR) shielding constants, and shielding spans of all the nuclei in {sup 175}LuX and {sup 197}AuX (X = {sup 19}F, {sup 35}Cl, {sup 79}Br, {sup 127}I), calculated using coupled-cluster singles-and-doubles with a perturbative triples (CCSD(T)) correction theory, four-component relativistic density functional theory (relativistic DFT), and non-relativistic DFT. The total nuclear spin–rotation constants determined by adding the relativistic corrections obtained from DFT calculations to the CCSD(T) values are in general in agreement with available experimental data, indicating that the computational approach followed in this study allows us to predict reliable results for the unknown spin–rotation constants in these molecules. The total NMR absolute shielding constants are determined for all the nuclei following the same approach as that applied for the nuclear spin–rotation constants. In most of the molecules, relativistic effects significantly change the computed shielding constants, demonstrating that straightforward application of the non-relativistic formula relating the electronic contribution to the nuclear spin–rotation constants and the paramagnetic contribution to the shielding constants does not yield correct results. We also analyze the origin of the unusually large absolute shielding constant and its relativistic correction of gold in AuF compared to the other gold monohalides.

Selected hydraulic test analysis techniques for constant-rate discharge tests

International Nuclear Information System (INIS)

Spane, F.A. Jr.

1993-03-01

The constant-rate discharge test is the principal field method used in hydrogeologic investigations for characterizing the hydraulic properties of aquifers. To implement this test, the aquifer is stressed by withdrawing ground water from a well, by using a downhole pump. Discharge during the withdrawal period is regulated and maintained at a constant rate. Water-level response within the well is monitored during the active pumping phase (i.e., drawdown) and during the subsequent recovery phase following termination of pumping. The analysis of drawdown and recovery response within the stress well (and any monitored, nearby observation wells) provides a means for estimating the hydraulic properties of the tested aquifer, as well as discerning formational and nonformational flow conditions (e.g., wellbore storage, wellbore damage, presence of boundaries, etc.). Standard analytical methods that are used for constant-rate pumping tests include both log-log type-curve matching and semi-log straight-line methods. This report presents a current ''state of the art'' review of selected transient analysis procedures for constant-rate discharge tests. Specific topics examined include: analytical methods for constant-rate discharge tests conducted within confined and unconfined aquifers; effects of various nonideal formation factors (e.g., anisotropy, hydrologic boundaries) and well construction conditions (e.g., partial penetration, wellbore storage) on constant-rate test response; and the use of pressure derivatives in diagnostic analysis for the identification of specific formation, well construction, and boundary conditions

Absolute instabilities of travelling wave solutions in a Keller-Segel model

OpenAIRE

Davis, P. N.; van Heijster, P.; Marangell, R.

2016-01-01

We investigate the spectral stability of travelling wave solutions in a Keller-Segel model of bacterial chemotaxis with a logarithmic chemosensitivity function and a constant, sublinear, and linear consumption rate. Linearising around the travelling wave solutions, we locate the essential and absolute spectrum of the associated linear operators and find that all travelling wave solutions have essential spectrum in the right half plane. However, we show that in the case of constant or sublinea...

Accurate and approximate thermal rate constants for polyatomic chemical reactions

International Nuclear Information System (INIS)

Nyman, Gunnar

2007-01-01

In favourable cases it is possible to calculate thermal rate constants for polyatomic reactions to high accuracy from first principles. Here, we discuss the use of flux correlation functions combined with the multi-configurational time-dependent Hartree (MCTDH) approach to efficiently calculate cumulative reaction probabilities and thermal rate constants for polyatomic chemical reactions. Three isotopic variants of the H 2 + CH 3 → CH 4 + H reaction are used to illustrate the theory. There is good agreement with experimental results although the experimental rates generally are larger than the calculated ones, which are believed to be at least as accurate as the experimental rates. Approximations allowing evaluation of the thermal rate constant above 400 K are treated. It is also noted that for the treated reactions, transition state theory (TST) gives accurate rate constants above 500 K. TST theory also gives accurate results for kinetic isotope effects in cases where the mass of the transfered atom is unchanged. Due to neglect of tunnelling, TST however fails below 400 K if the mass of the transferred atom changes between the isotopic reactions

Rate constant for reaction of atomic hydrogen with germane

Science.gov (United States)

Nava, David F.; Payne, Walter A.; Marston, George; Stief, Louis J.

1990-01-01

Due to the interest in the chemistry of germane in the atmospheres of Jupiter and Saturn, and because previously reported kinetic reaction rate studies at 298 K gave results differing by a factor of 200, laboratory measurements were performed to determine the reaction rate constant for H + GeH4. Results of the study at 298 K, obtained via the direct technique of flash photolysis-resonance fluorescence, yield the reaction rate constant, k = (4.08 + or - 0.22) x 10(exp -12) cu cm/s.

High-temperature rate constant measurements for OH+xylenes

KAUST Repository

Elwardani, Ahmed Elsaid

2015-06-01

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

Study on the effect factor of the absolute fission rates measured by depleted uranium fission chamber

International Nuclear Information System (INIS)

Jiang Li; Liu Rong; Wang Dalun; Wang Mei; Lin Jufang; Wen Zhongwei

2003-01-01

The absolute fission rates was measured by the depleted uranium fission chamber. The efficiency of the fission fragments recorded in the fission chamber was analyzed. The factor influencing absolute fission rates was studied in the experiment, including the disturbing effect between detectors and the effect of the structural of the fission chamber, etc

The time dependence of rate constants of esub(aq)sup(-) reactions

International Nuclear Information System (INIS)

Burcl, R.; Byakov, V.M.; Grafutin, V.I.

1982-01-01

Published data about the time dependence of rate constants k(esub(aq)sup(-)+Ac) of esub(aq)sup(-) reactions with the acceptor Ac are analyzed, using the results of rate constant k(Ps+Ac) measurements for positronium reactions. It is shown that neither esub(aq)sup(-) nor Ps reaction rate constants depend on time in the observable range. Experimentally found concentration dependence of k(esub(aq)sup(-)+Ac) is due to other factors, connected with the existence of electric charge of esub(aq)sup(-), e.g. ionic strength, tunnelling effect etc. (author)

Reaction F + C2H4: Rate Constant and Yields of the Reaction Products as a Function of Temperature over 298-950 K.

Science.gov (United States)

Bedjanian, Yuri

2018-03-29

The kinetics and products of the reaction of F + C 2 H 4 have been studied in a discharge flow reactor combined with an electron impact ionization mass spectrometer at nearly 2 Torr total pressure of helium in the temperature range 298-950 K. The total rate constant of the reaction, k 1 = (1.78 ± 0.30) × 10 -10 cm 3 molecule -1 s -1 , determined under pseudo-first-order conditions, monitoring the kinetics of F atom consumption in excess of C 2 H 4 , was found to be temperature independent in the temperature range used. H, C 2 H 3 F, and HF were identified as the reaction products. Absolute measurements of the yields of these species allowed to determine the branching ratios, k 1b / k 1 = (0.73 ± 0.07) exp(-(425 ± 45)/ T) and k 1a / k 1 = 1 - (0.73 ± 0.07) exp(-(425 ± 45)/ T) and partial rate constants for addition-elimination (H + C 2 H 3 F) and H atom abstraction (HF + C 2 H 3 ) pathways of the title reaction: k 1a = (0.80 ± 0.07) × 10 -10 exp(189 ± 37/ T) and k 1b = (1.26 ± 0.13) × 10 -10 exp(-414 ± 45/ T) cm 3 molecule -1 s -1 , respectively, at T = 298-950 K and with 2σ quoted uncertainties. The overall reaction rate constant can be adequately described by both the temperature independent value and as a sum of k 1a and k 1b . The kinetic and mechanistic data from the present study are discussed in comparison with previous absolute and relative measurements and theoretical calculations.

Rate constant for reaction of hydroxyl radicals with bicarbonate ions

International Nuclear Information System (INIS)

Buxton, G.V.; Elliot, A.J.

1986-01-01

The rate constant for reaction of hydroxyl radicals with the bicarbonate ion has been determined to be 8.5 x 10 6 dm 3 mol -1 s -1 . This value was calculated from: the measured rate of formation of the CO 3 - radical in pulsed electron irradiation of bicarbonate solutions over the pH range 7.0 to 9.4; the pK for the equilibrium HCO 3 - = CO 3 2- + H + ; and the rate constant for hydroxyl radicals reacting with the carbonate ion. (author)

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.

Glucose consumption and rate constants for 18F-fluorodeoxyglucose in human gliomas

International Nuclear Information System (INIS)

Ishikawa, Masatsune; Kikuchi, Haruhiko; Nagata, Izumi; Yamagata, Sen; Taki, Waro; Yonekura, Yoshiharu; Nishizawa, Sadahiko; Iwasaki, Yasushi; Mukai, Takao

1990-01-01

To investigate the value of direct measurement of the rate constants by performing 18 F-labeled fluorodeoxyglucose (FDG) studies of glucose consumption in human gliomas in vivo, a kinetic method with 3- and 4-parameter rate constant models for FDG uptake was used to analyze data from dynamic scans obtained by positron emission tomography after injection of FDG into 14 patients with glioma. The results were compared with those obtained by the autoradiographic method using 3- and 4-parameter rate constant models. There were no significant differences in the glucose consumption calculated by the four different methods both in the gliomas and in the contralateral intact cortex. It was found that the rate constant k4 could be neglected in calculation of glucose consumption in gliomas as well as in the contralateral intact cortex. The rate constant k3, an index of hexokinase function, was higher in malignant gliomas than in benign gliomas and was close to that in the contralateral cortex. This study indicates that the 3-parameter autoradiographic method, which is the most common one used in clinical practice, is reliable for the calculation of glucose consumption in human gliomas. Furthermore, direct measurement of the regional rate constants for FDG by the kinetic method was found to be useful for evaluation of the biochemical and physiological characteristics of human gliomas in vivo. (author)

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

KAUST Repository

Badra, Jihad; Elwardani, Ahmed Elsaid; Farooq, Aamir

2014-01-01

-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

Determination of Biological Oxygen Demand Rate Constant and ...

African Journals Online (AJOL)

Determination of Biological Oxygen Demand Rate Constant and Ultimate Biological Oxygen Demand for Liquid Waste Generated from Student Cafeteria at Jimma University: A Tool for Development of Scientific Criteria to Protect Aquatic Health in the Region.

Rate Constant and Temperature Dependence for the Reaction of Hydroxyl Radicals with 2-Flouropropane (FC-281ea) and Comparison with an Estimated Rate Constant

Science.gov (United States)

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.

VMATc: VMAT with constant gantry speed and dose rate

International Nuclear Information System (INIS)

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

2015-01-01

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

Impact of Constant Rate Factor on Objective Video Quality Assessment

Directory of Open Access Journals (Sweden)

Juraj Bienik

2017-01-01

Full Text Available This paper deals with the impact of constant rate factor value on the objective video quality assessment using PSNR and SSIM metrics. Compression efficiency of H.264 and H.265 codecs defined by different Constant rate factor (CRF values was tested. The assessment was done for eight types of video sequences depending on content for High Definition (HD, Full HD (FHD and Ultra HD (UHD resolution. Finally, performance of both mentioned codecs with emphasis on compression ratio and efficiency of coding was compared.

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

Science.gov (United States)

Badra, Jihad; Elwardany, Ahmed E; Farooq, Aamir

2014-06-28

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 (C=O) 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 (C=O), and the prime is used to differentiate different neighboring environments of a methylene group):

Constrained least squares methods for estimating reaction rate constants from spectroscopic data

NARCIS (Netherlands)

Bijlsma, S.; Boelens, H.F.M.; Hoefsloot, H.C.J.; Smilde, A.K.

2002-01-01

Model errors, experimental errors and instrumental noise influence the accuracy of reaction rate constant estimates obtained from spectral data recorded in time during a chemical reaction. In order to improve the accuracy, which can be divided into the precision and bias of reaction rate constant

Estimating reaction rate constants: comparison between traditional curve fitting and curve resolution

NARCIS (Netherlands)

Bijlsma, S.; Boelens, H. F. M.; Hoefsloot, H. C. J.; Smilde, A. K.

2000-01-01

A traditional curve fitting (TCF) algorithm is compared with a classical curve resolution (CCR) approach for estimating reaction rate constants from spectral data obtained in time of a chemical reaction. In the TCF algorithm, reaction rate constants an estimated from the absorbance versus time data

Dissociative electron attachment to ozone: rate constant

International Nuclear Information System (INIS)

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

2002-01-01

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

Absolute calibration of the Rh-103(n,n')Rh-103m reaction rate

International Nuclear Information System (INIS)

Taylor, W.H.; Murphy, M.F.; March, M.R.

1979-05-01

The uncertainties in determining the absolute values of the Rh-103(n, n') Rh-103m reaction rate (which is widely used as a neutron damage flux monitor) have been reduced to approximately +-5%. This has been achieved with the use of a calibrated source of Pd-103-Rh-103m activity supplied by the IAEA. Agreement to within 3% between measured and calculated values of the reaction rate (normalised to the U-238 fission rate) has been achieved. (author)

Glucose consumption and rate constants for sup 18 F-fluorodeoxyglucose in human gliomas

Energy Technology Data Exchange (ETDEWEB)

Ishikawa, Masatsune; Kikuchi, Haruhiko; Nagata, Izumi; Yamagata, Sen; Taki, Waro; Yonekura, Yoshiharu; Nishizawa, Sadahiko; Iwasaki, Yasushi; Mukai, Takao [Kyoto Univ. (Japan). Faculty of Medicine

1990-06-01

To investigate the value of direct measurement of the rate constants by performing {sup 18}F-labeled fluorodeoxyglucose (FDG) studies of glucose consumption in human gliomas in vivo, a kinetic method with 3- and 4-parameter rate constant models for FDG uptake was used to analyze data from dynamic scans obtained by positron emission tomography after injection of FDG into 14 patients with glioma. The results were compared with those obtained by the autoradiographic method using 3- and 4-parameter rate constant models. There were no significant differences in the glucose consumption calculated by the four different methods both in the gliomas and in the contralateral intact cortex. It was found that the rate constant k4 could be neglected in calculation of glucose consumption in gliomas as well as in the contralateral intact cortex. The rate constant k3, an index of hexokinase function, was higher in malignant gliomas than in benign gliomas and was close to that in the contralateral cortex. This study indicates that the 3-parameter autoradiographic method, which is the most common one used in clinical practice, is reliable for the calculation of glucose consumption in human gliomas. Furthermore, direct measurement of the regional rate constants for FDG by the kinetic method was found to be useful for evaluation of the biochemical and physiological characteristics of human gliomas in vivo. (author).

Lifespan metabolic potential of the unicellular organisms expressed by Boltzmann constant, absolute temperature and proton mass

Science.gov (United States)

Atanasov, Atanas Todorov

2016-12-01

The unicellular organisms and phages are the first appeared fundamental living organisms on the Earth. The total metabolic energy (Els, J) of these organisms can be expressed by their lifespan metabolic potential (Als, J/kg) and body mass (M, kg): Els =Als M. In this study we found a different expression - by Boltzmann's constant (k, J/K), nucleon mass (mp+, kg) of protons (and neutrons), body mass (M, kg) of organism or mass (Ms) of biomolecules (proteins, nucleotides, polysaccharides and lipids) building organism, and the absolute temperature (T, K). The found equations are: Els= (M/mp+)kT for phages and Els=(Ms/mp+)kT for the unicellular organisms. From these equations the lifespan metabolic potential can be expressed as: Als=Els/M= (k/mp+)T for phages and Als=Els/M= (k/3.3mp+)T for unicellular organisms. The temperature-normated lifespan metabolic potential (Als/T, J/K.kg) is equals to the ratio between Boltzmann's constant and nucleon mass: Als/T=k/mp+ for phages and Als/T=k/3.3mp+ for unicellular organisms. The numerical value of the k/mp+ ratio is equals to 8.254×103 J/K.kg, and the numerical value of k/3.3mp+ ratio is equal to 2.497×103 J/K.kg. These values of temperature-normated lifespan metabolic potential could be considered fundamental for the unicellular organisms.

High-temperature rate constant measurements for OH+xylenes

KAUST Repository

Elwardani, Ahmed Elsaid; Badra, Jihad; Farooq, Aamir

2015-01-01

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

Absolute calibration of the Rh-103 (n, n') Rh-103m reaction rate

International Nuclear Information System (INIS)

Taylor, W.H.; Murphy, M.F.; March, M.R.

1979-05-01

The uncertainties in determining the absolute values of the Rh-103 (n, n') Rh-103m reaction rate (which is widely used as a neutron damage flux monitor) have been reduced to ∼±5%. This has been achieved with the use of a calibrated source of Pd-103-Rh-103m activity supplied by the I.A.E.A. Agreement to within 3% between measured and calculated values of the reaction rate (normalised to the U-238 fission rate) has been achieved. (author)

Constant displacement rate testing at elevated temperatures

International Nuclear Information System (INIS)

Pepe, J.J.; Gonyea, D.C.

1989-01-01

A short time test has been developed which is capable of determining the long time notch sensitivity tendencies of CrMoV rotor forging materials. This test is based on Constant Displacement Rate (CDR) testing of a specific notch bar specimen at 1200 0 F at 2 mils/in/hour displacement rate. These data were correlated to conventional smooth and notch bar rupture behavior for a series of CrMoV materials with varying long time ductility tendencies. The purpose of this paper is to describe the details of this new test procedure and some of the relevant mechanics of material information generated during its development

Higher success rate with transcranial electrical stimulation of motor-evoked potentials using constant-voltage stimulation compared with constant-current stimulation in patients undergoing spinal surgery.

Science.gov (United States)

Shigematsu, Hideki; Kawaguchi, Masahiko; Hayashi, Hironobu; Takatani, Tsunenori; Iwata, Eiichiro; Tanaka, Masato; Okuda, Akinori; Morimoto, Yasuhiko; Masuda, Keisuke; Tanaka, Yuu; Tanaka, Yasuhito

2017-10-01

During spine surgery, the spinal cord is electrophysiologically monitored via transcranial electrical stimulation of motor-evoked potentials (TES-MEPs) to prevent injury. Transcranial electrical stimulation of motor-evoked potential involves the use of either constant-current or constant-voltage stimulation; however, there are few comparative data available regarding their ability to adequately elicit compound motor action potentials. We hypothesized that the success rates of TES-MEP recordings would be similar between constant-current and constant-voltage stimulations in patients undergoing spine surgery. The objective of this study was to compare the success rates of TES-MEP recordings between constant-current and constant-voltage stimulation. This is a prospective, within-subject study. Data from 100 patients undergoing spinal surgery at the cervical, thoracic, or lumbar level were analyzed. The success rates of the TES-MEP recordings from each muscle were examined. Transcranial electrical stimulation with constant-current and constant-voltage stimulations at the C3 and C4 electrode positions (international "10-20" system) was applied to each patient. Compound muscle action potentials were bilaterally recorded from the abductor pollicis brevis (APB), deltoid (Del), abductor hallucis (AH), tibialis anterior (TA), gastrocnemius (GC), and quadriceps (Quad) muscles. The success rates of the TES-MEP recordings from the right Del, right APB, bilateral Quad, right TA, right GC, and bilateral AH muscles were significantly higher using constant-voltage stimulation than those using constant-current stimulation. The overall success rates with constant-voltage and constant-current stimulations were 86.3% and 68.8%, respectively (risk ratio 1.25 [95% confidence interval: 1.20-1.31]). The success rates of TES-MEP recordings were higher using constant-voltage stimulation compared with constant-current stimulation in patients undergoing spinal surgery. Copyright © 2017

A calculation of the surface recombination rate constant for hydrogen isotopes on metals

International Nuclear Information System (INIS)

Baskes, M.J.

1980-01-01

The surface recombination rate constant for hydrogen isotopes on a metal has been calculated using a simple model whose parameters may be determined by direct experimental measurements. Using the experimental values for hydrogen diffusivity, solubility, and sticking coefficient at zero surface coverage a reasonable prediction of the surface recombination constant may be made. The calculated recombination constant is in excellent agreement with experiment for bcc iron. A heuristic argument is developed which, along with the rate constant calculation, shows that surface recombination is important in those metals in which hydrogen has an exothermic heat of solution. (orig.)

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

Directory of Open Access Journals (Sweden)

Dániel Kozma

2012-01-01

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

Convergence analysis of Chauvin's PCA learning algorithm with a constant learning rate

International Nuclear Information System (INIS)

Lv Jiancheng; Yi Zhang

2007-01-01

The convergence of Chauvin's PCA learning algorithm with a constant learning rate is studied in this paper by using a DDT method (deterministic discrete-time system method). Different from the DCT method (deterministic continuous-time system method), the DDT method does not require that the learning rate converges to zero. An invariant set of Chauvin's algorithm with a constant learning rate is obtained so that the non-divergence of this algorithm can be guaranteed. Rigorous mathematic proofs are provided to prove the local convergence of this algorithm

Determination of reaction rate constants for alkylation of 4-(p-nitrobenzyl) pyridine by different alkylating agents.

Science.gov (United States)

Walles, S A

1980-02-01

The rate constants have been determined for the reaction between some different alkylating agents and 4-(p-nitrobenzyl) pyridine (NBP) in methanol. These constants have been compared with those for alkylation of aniline in water. All the constants were lower in methanol than in water but in different degrees. The rate constants of the different alkylating agents have been calculated at a nucleophilic strength n=2. The genetic risk defined as the degree of alkylation of a nucleophile (n=2) is equivalent to the rate constant kn=2 and the target dose. The dependence of the genetic risk on the rate constant (kn=2) is discussed.

Rate constants and temperature effects for reactions of Cl2sm-bullet- with unsaturated alcohols and hydrocarbons in aqueous and acetonitrile/water solutions

International Nuclear Information System (INIS)

Padmaja, S.; Neta, P.; Huie, R.E.

1992-01-01

Absolute rate constants for reactions of the dichlorine radical anion, Cl 2 sm-bullet- , with unsaturated alcohols and hydrocarbons have been measured at various temperatures. The alcohol reactions were measured in aqueous solutions and the hydrocarbon reactions in 1:1 aqueous acetonitirle (ACN) solutions. The rate constants for two alcohols and one hydrocarbon were also examined as a function of solvent composition. The room temperature rate constants varied between 10 6 and 10 9 M -1 s -1 . The pre-exponential factors, A, were about (1-5) x 10 9 M -1 s -1 for the alcohols in aqueous solutions and about (0.1-1) x 10 9 M -1 s -1 for the hydrocarbons in aqueous ACN solutions. The activation energies, E a , varied considerably, between 4 and 12 kJ mol -1 for the alcohols and between 2 and 8 kJ mol -1 for the hydrocarbons. The rate constants, k 298 , decrease with increasing ionization potential (IP) of the unsaturated compound, in agreement with an electrophilic addition mechanism. The activation energies for the unsaturated alcohols decrease when the IP decreases from 9.7 to 9.1 eV but appear to level off at lower IP. Most alkenes studied had IP a . Upon addition of ACN to the aqueous solution, the values of log k 298 decreased linearly by more than 1 order of magnitude with increasing ACN mole fraction. This decrease appears to result from a combination of changes in the activation energy and in the pre-exponential factor. The reason for these changes may lie in changes in the solvation shell of the Cl 2 sm-bullet- radical, which will affect the A factor, in combination with changes in solvation of Cl - , which will affect the energetics of the reactions as well. 20 refs., 7 figs., 6 tabs

The reaction of atomic hydrogen with germane - Temperature dependence of the rate constant and implications for germane photochemistry in the atmospheres of Jupiter and Saturn

Science.gov (United States)

Nava, David F.; Payne, Walter A.; Marston, George; Stief, Louis J.

1993-01-01

Studies of the formation and loss processes for GeH4 are required in order to provide data to help determine the major chemical form in which germanium exists in the atmospheres of Jupiter and Saturn. The reaction of hydrogen atoms with germane is one of the most important of these reactions. The absolute rate constant for this reaction as a function of temperature and pressure is studied. Flash photolysis of dilute mixtures of GeH4 in argon, combined with time-resolved detection of H atoms via Lyman alpha resonance fluorescence, is employed to measure the reaction rate. The reaction is shown to be moderately rapid, independent of total pressure, but possessing a positive temperature dependence.

Applications of the absolute reaction rate theory to biological responses in electric and magnetic fields

International Nuclear Information System (INIS)

Brannen, J.P.; Wayland, J.R.

1976-01-01

This paper develops a theoretical foundation for the study of biological responses of electric and magnetic fields. The basis of the development is the absolute reaction rate theory and the effects of fields on reaction rates. A simple application to the response of Bacillus subtilis var niger in a microwave field is made. Potential areas of application are discussed

Absolute calibration of the Rh-103 (n, n') Rh-103m reaction rate

Energy Technology Data Exchange (ETDEWEB)

Taylor, W.H.; Murphy, M.F.; March, M.R. [Reactor Physics Division, Atomic Energy Establishment, Winfrith, Dorchester, Dorset (United Kingdom)

1979-05-15

The uncertainties in determining the absolute values of the Rh-103 (n, n') Rh-103m reaction rate (which is widely used as a neutron damage flux monitor) have been reduced to {approx}{+-}5%. This has been achieved with the use of a calibrated source of Pd-103-Rh-103m activity supplied by the I.A.E.A. Agreement to within 3% between measured and calculated values of the reaction rate (normalised to the U-238 fission rate) has been achieved. (author)

Reaction rate constants of HO2 + O3 in the temperature range 233-400 K

Science.gov (United States)

Wang, Xiuyan; Suto, Masako; Lee, L. C.

1988-01-01

The reaction rate constants of HO2 + O3 were measured in the temperature range 233-400 K using a discharge flow system with photofragment emission detection. In the range 233-253 K, the constants are approximately a constant value, and then increase with increasing temperature. This result suggests that the reaction may have two different channels. An expression representing the reaction rate constants is presented.

Semiclassical Calculation of Reaction Rate Constants for Homolytical Dissociations

Science.gov (United States)

Cardelino, Beatriz H.

2002-01-01

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

Constant rate natural gas production from a well in a hydrate reservoir

International Nuclear Information System (INIS)

Ji Chuang; Ahmadi, Goodarz; Smith, Duane H.

2003-01-01

Using a computational model, production of natural gas at a constant rate from a well that is drilled into a confined methane hydrate reservoir is studied. It is assumed that the pores in the reservoir are partially saturated with hydrate. A linearized model for an axisymmetric condition with a fixed well output is used in the analysis. For different reservoir temperatures and various well outputs, time evolutions of temperature and pressure profiles, as well as the gas flow rate in the hydrate zone and the gas region, are evaluated. The distance of the decomposition front from the well as a function of time is also computed. It is shown that to maintain a constant natural gas production rate, the well pressure must be decreased with time. A constant low production rate can be sustained for a long duration of time, but a high production rate demands unrealistically low pressure at the well after a relatively short production time. The simulation results show that the process of natural gas production in a hydrate reservoir is a sensitive function of reservoir temperature and hydrate zone permeability

Radiative lifetimes and two-body collisional deactivation rate constants in argon for Kr(4p 55p) and Kr(4p 55p') states

International Nuclear Information System (INIS)

Chang, R.S.F.; Horiguchi, H.; Setser, D.W.

1980-01-01

The radiative lifetimes and collisional deactivation rate constants, in argon, of eight Kr(4p 5 [ 2 P/sub 1/2/]5p and [ 2 P/sub 3/2/]5p) levels have been measured by a time-resolved laser-induced fluorescence technique in a flowing afterglow apparatus. The measured radiative lifetimes are compared with other experimental values and with theoretical calculations. Radiative branching ratios of these excited states also were measured in order to assign the absolute transition probabilities of the Kr(5p,5p'--5s, 5s') transition array from the radiative lifetimes. In addition to the total deactivation rate constants, product states from two-body collisions between Kr(5p and 5p') atoms and ground state argon atoms were identified from the laser-induced emission spectra, and product formation rate constants were assigned. Two-body intermultiplet transfer from Kr(4p 5 [ 2 P/sub 1/2/]5p) to the Kr(4p 5 [ 2 P/sub 3/2/]4d) levels occurs with ease. Intermultiplet transfer from the lowest level in the (4p 5 5p) configuration to the Kr(4p 5 5s and 5s') manifold was fast despite the large energy defect. However, this was the only Kr(5p) level that gave appreciable transfer to the Kr(5s or 5s') manifold. Generally the favored product states are within a few kT of the entrance channel

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

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

Science.gov (United States)

Zhao, Jiao; Ridgway, Douglas; Broderick, Gordon; Kovalenko, Andriy; Ellison, Michael

2008-01-01

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 minima and uncertainty

Absolute measurement and international intercomparison of 0.1-0.8 MeV monoenergetic neutron fluence rate

International Nuclear Information System (INIS)

Ma Hongchang; Lu Hanlin; Rong Chaofan

1988-01-01

The methods for absolute measurement of 0.1-18MeV monoenergetic neutron fluence rate are described. Which include proton recoil telescope, semicoducetor telescope, hydrogen filled proportional counter and associated particale method. A long counter used as secondary recent international intercomparison of neutron fluence rate organized by BIPM, and the results were given

Feasibility studies of high-pressure 4π proportional counter for absolute activity measurement

International Nuclear Information System (INIS)

Hino, Y.; Kawada, Y.

1988-01-01

A high-pressure proportional counter system is constructed. The high pressure 4πβ counter system constructed is made of aluminum and is divided into two 2π counters. The gas pressure is controlled with a pressure regulator and very fine leak valves to keep the balance of a stable pressure and constant flow rate. Investigation of characteristics of th counter shows that there is an almost linear relation between voltage and pressure. The linearlity of gas gain of this counter to the electron energies is measured with different gas pressures. Quite good linear gas multiplication is obtained at 0.9 MPa. Another investigation is made of application of to activity measurement of 109 Cd. When the gas pressure is over 0.5 MPa, the proportion of collected conversion electrons to absolute activity comes to a constant value of 96 %. This is quite good agreement with the decay data of 96.4 % conversion electron emission rate. The study indicated many excellent features for activity measurement. Especially the efficiency variation technique is good for automatic data acquisition with a programmable high voltage supplier. Moreover, since it is possible to obtain absolute activity with only one sample, it will be quite useful for limited samples experiments. (N.K.)

Experimental determination of the high-temperature rate constant for the reaction of OH with sec-butanol.

Science.gov (United States)

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

2012-10-04

The overall rate constant for the reaction of OH with sec-butanol [CH(3)CH(OH)CH(2)CH(3)] was determined from measurements of the near-first-order OH decay in shock-heated mixtures of tert-butylhydroperoxide (as a fast source of OH) with sec-butanol in excess. Three kinetic mechanisms from the literature describing sec-butanol combustion were used to examine the sensitivity of the rate constant determination to secondary kinetics. The overall rate constant determined can be described by the Arrhenius expression 6.97 × 10(-11) exp(-1550/T[K]) cm(3) molecule(-1) s(-1), valid over the temperature range of 888-1178 K. Uncertainty bounds of ±30% were found to adequately account for the uncertainty in secondary kinetics. To our knowledge, the current data represent the first efforts toward an experimentally determined rate constant for the overall reaction of OH with sec-butanol at combustion-relevant temperatures. A rate constant predicted using a structure-activity relationship from the literature was compared to the current data and previous rate constant measurements for the title reaction at atmospheric-relevant temperatures. The structure-activity relationship was found to be unable to correctly predict the measured rate constant at all temperatures where experimental data exist. We found that the three-parameter fit of 4.95 × 10(-20)T(2.66) exp(+1123/T[K]) cm(3) molecule(-1) s(-1) better describes the overall rate constant for the reaction of OH with sec-butanol from 263 to 1178 K.

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

KAUST Repository

Badra, Jihad

2014-01-01

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

Phototransformation rate constants of PAHs associated with soot particles

International Nuclear Information System (INIS)

Kim, Daekyun; Young, Thomas M.; Anastasio, Cort

2013-01-01

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 (k p 0 ), the effective diffusion coefficients (D eff ), and the light penetration depths (z 0.5 ) for PAHs on soot layers of variable thickness were determined by fitting experimental data with a model of coupled photolysis and diffusion. The overall disappearance rates of irradiated low molecular weight PAHs (with 2–3 rings) on soot particles were influenced by fast photodegradation and fast diffusion kinetics, while those of high molecular weight PAHs (with 4 or more rings) were apparently controlled by either the combination of slow photodegradation and slow diffusion kinetics or by very slow diffusion kinetics alone. The value of z 0.5 is more sensitive to the soot layer thickness than the k p 0 value. As the thickness of the soot layer increases, the z 0.5 values increase, but the k p 0 values are almost constant. The effective diffusion coefficients calculated from dark experiments are generally higher than those from the model fitting method for illumination experiments. Due to the correlation between k p 0 and z 0.5 in thinner layers, D eff should be estimated by an independent method for better accuracy. Despite some limitations of the model used in this study, the fitted parameters were useful for describing empirical results of photodegradation of soot-associated PAHs. - Highlights: ► PAHs on soot were evaluated by a model of coupled photolysis and diffusion. ► Photodegradation rate at the surface, diffusion coefficient, and light penetration path were determined. ► Low MW PAHs were influenced by fast photodegradation and fast diffusion. ► High MW PAHs were controlled either by slow

From the Rydberg constant to the fundamental constants metrology; De la constante de Rydberg a la metrologie des constantes fondamentales

Energy Technology Data Exchange (ETDEWEB)

Nez, F

2005-06-15

This document reviews the theoretical and experimental achievements of the author since the beginning of his scientific career. This document is dedicated to the spectroscopy of hydrogen, deuterium and helium atoms. The first part is divided into 6 sub-sections: 1) the principles of hydrogen spectroscopy, 2) the measurement of the 2S-nS/nD transitions, 3) other optical frequency measurements, 4) our contribution to the determination of the Rydberg constant, 5) our current experiment on the 1S-3S transition, 6) the spectroscopy of the muonic hydrogen. Our experiments have improved the accuracy of the Rydberg Constant by a factor 25 in 15 years and we have achieved the first absolute optical frequency measurement of a transition in hydrogen. The second part is dedicated to the measurement of the fine structure constant and the last part deals with helium spectroscopy and the search for optical references in the near infrared range. (A.C.)

A first-passage scheme for determination of overall rate constants for non-diffusion-limited suspensions

Science.gov (United States)

Lu, Shih-Yuan; Yen, Yi-Ming

2002-02-01

A first-passage scheme is devised to determine the overall rate constant of suspensions under the non-diffusion-limited condition. The original first-passage scheme developed for diffusion-limited processes is modified to account for the finite incorporation rate at the inclusion surface by using a concept of the nonzero survival probability of the diffusing entity at entity-inclusion encounters. This nonzero survival probability is obtained from solving a relevant boundary value problem. The new first-passage scheme is validated by an excellent agreement between overall rate constant results from the present development and from an accurate boundary collocation calculation for the three common spherical arrays [J. Chem. Phys. 109, 4985 (1998)], namely simple cubic, body-centered cubic, and face-centered cubic arrays, for a wide range of P and f. Here, P is a dimensionless quantity characterizing the relative rate of diffusion versus surface incorporation, and f is the volume fraction of the inclusion. The scheme is further applied to random spherical suspensions and to investigate the effect of inclusion coagulation on overall rate constants. It is found that randomness in inclusion arrangement tends to lower the overall rate constant for f up to the near close-packing value of the regular arrays because of the inclusion screening effect. This screening effect turns stronger for regular arrays when f is near and above the close-packing value of the regular arrays, and consequently the overall rate constant of the random array exceeds that of the regular array. Inclusion coagulation too induces the inclusion screening effect, and leads to lower overall rate constants.

Application of accelerated evaluation method of alteration temperature and constant dose rate irradiation on bipolar linear regulator LM317

International Nuclear Information System (INIS)

Deng Wei; Wu Xue; Wang Xin; Zhang Jinxin; Zhang Xiaofu; Zheng Qiwen; Ma Wuying; Lu Wu; Guo Qi; He Chengfa

2014-01-01

With different irradiation methods including high dose rate irradiation, low dose rate irradiation, alteration temperature and constant dose rate irradiation, and US military standard constant high temperature and constant dose rate irradiation, the ionizing radiation responses of bipolar linear regulator LM317 from three different companies were investigated under the operating and zero biases. The results show that compared with constant high temperature and constant dose rate irradiation method, the alteration temperature and constant dose rate irradiation method can not only very rapidly and accurately evaluate the dose rate effect of three bipolar linear regulators, but also well simulate the damage of low dose rate irradiation. Experiment results make the alteration temperature and constant dose rate irradiation method successfully apply to bipolar linear regulator. (authors)

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

Science.gov (United States)

Brunning, J.; Stief, L.

1986-01-01

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

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

DEFF Research Database (Denmark)

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

2002-01-01

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

Absolute E0 and E2 transition rates and collective states in 116Sn

International Nuclear Information System (INIS)

Kantele, J.; Julin, R.; Luontama, M.; Passoja, A.; Poikolainen, T.; Baecklin, A.; Jonsson, N.-G.

1978-08-01

Absolute E0 and E2 transition rates in 116 Sn have been measured using several newly developed techniques. Many E2 transitions are observed to have a collective character with B(E2) values of up to 60 W.u. The presence of deformed excited states in 116 Sn is discussed in view of the results obtained. (author)

Communication: The absolute shielding scales of oxygen and sulfur revisited

Energy Technology Data Exchange (ETDEWEB)

Komorovsky, Stanislav; Repisky, Michal; Malkin, Elena; Ruud, Kenneth, E-mail: kenneth.ruud@uit.no [Centre for Theoretical and Computational Chemistry, University of Tromsø — The Arctic University of Norway, N-9037 Tromsø (Norway); Gauss, Jürgen [Institut für Physikalische Chemie, Johannes Gutenberg-Universität Mainz, Duesbergweg 10-14, D-55128 Mainz (Germany)

2015-03-07

We present an updated semi-experimental absolute shielding scale for the {sup 17}O and {sup 33}S nuclei. These new shielding scales are based on accurate rotational microwave data for the spin–rotation constants of H{sub 2}{sup 17}O [Puzzarini et al., J. Chem. Phys. 131, 234304 (2009)], C{sup 17}O [Cazzoli et al., Phys. Chem. Chem. Phys. 4, 3575 (2002)], and H{sub 2}{sup 33}S [Helgaker et al., J. Chem. Phys. 139, 244308 (2013)] corrected both for vibrational and temperature effects estimated at the CCSD(T) level of theory as well as for the relativistic corrections to the relation between the spin–rotation constant and the absolute shielding constant. Our best estimate for the oxygen shielding constants of H{sub 2}{sup 17}O is 328.4(3) ppm and for C{sup 17}O −59.05(59) ppm. The relativistic correction for the sulfur shielding of H{sub 2}{sup 33}S amounts to 3.3%, and the new sulfur shielding constant for this molecule is 742.9(4.6) ppm.

a comparative study of the drying rate constant, drying efficiency

African Journals Online (AJOL)

The drying rate constants for the solar dryer and open- air sun dried bitter leaf were 0.8 and ... of cost benefit but the poorest when other considerations ... J. I. Eze, National Centre for Energy Research and Development (NCERD), University of ...

Non Lyapunov stability of the constant spatially developing 1-D gas flow in presence of solutions having strictly positive exponential growth rate

Science.gov (United States)

Balint, Stefan; Balint, Agneta M.

2017-01-01

Different types of stabilities (global, local) and instabilities (global absolute, local convective) of the constant spatially developing 1-D gas flow are analyzed in the phase space of continuously differentiable functions, endowed with the usual algebraic operations and the topology generated by the uniform convergence on the real axis. For this purpose the Euler equations linearized at the constant flow are used. The Lyapunov stability analysis was presented in [1] and this paper is a continuation of [1].

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.

Arrhenius Rate: constant volume burn

Energy Technology Data Exchange (ETDEWEB)

Menikoff, Ralph [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2017-12-06

A constant volume burn occurs for an idealized initial state in which a large volume of reactants at rest is suddenly raised to a high temperature and begins to burn. Due to the uniform spatial state, there is no fluid motion and no heat conduction. This reduces the time evolu tion to an ODE for the reaction progress variable. With an Arrhenius reaction rate, two characteristics of thermal ignition are illustrated: induction time and thermal runaway. The Frank-Kamenetskii approximation then leads to a simple expression for the adiabatic induction time. For a first order reaction, the analytic solution is derived and used to illustrate the effect of varying the activation temperature; in particular, on the induction time. In general, the ODE can be solved numerically. This is used to illustrate the effect of varying the reaction order. We note that for a first order reaction, the time evolution of the reaction progress variable has an exponential tail. In contrast, for a reaction order less than one, the reaction completes in a nite time. The reaction order also affects the induction time.

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 ...

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

KAUST Repository

Badra, Jihad

2015-01-01

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

The correlation schemes in calculations of the rate constants of some radiation chemical reactions

International Nuclear Information System (INIS)

Zagorets, P.A.; Shostenko, A.G.; Kim, V.

1983-01-01

The various correlation relationships of the evaluation of the rate constants of radiation chemical reactions of addition, abstraction and isomerization were considered. It was shown that neglection of the influence of solvent can result in errors in calculations of rate constants equalling two orders in magnitude. Several examples of isokinetic relationship are given. The methods of calculation of transmission coefficient of reaction addition have been discussed. (author)

From the Rydberg constant to the fundamental constants metrology

International Nuclear Information System (INIS)

Nez, F.

2005-06-01

This document reviews the theoretical and experimental achievements of the author since the beginning of his scientific career. This document is dedicated to the spectroscopy of hydrogen, deuterium and helium atoms. The first part is divided into 6 sub-sections: 1) the principles of hydrogen spectroscopy, 2) the measurement of the 2S-nS/nD transitions, 3) other optical frequency measurements, 4) our contribution to the determination of the Rydberg constant, 5) our current experiment on the 1S-3S transition, 6) the spectroscopy of the muonic hydrogen. Our experiments have improved the accuracy of the Rydberg Constant by a factor 25 in 15 years and we have achieved the first absolute optical frequency measurement of a transition in hydrogen. The second part is dedicated to the measurement of the fine structure constant and the last part deals with helium spectroscopy and the search for optical references in the near infrared range. (A.C.)

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

NARCIS (Netherlands)

Juraszek, J.; Bolhuis, P.G.

2008-01-01

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

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

NARCIS (Netherlands)

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

2009-01-01

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

Big bang nucleosynthesis with a varying fine structure constant and nonstandard expansion rate

International Nuclear Information System (INIS)

Ichikawa, Kazuhide; Kawasaki, Masahiro

2004-01-01

We calculate the primordial abundances of light elements produced during big bang nucleosynthesis when the fine structure constant and/or the cosmic expansion rate take nonstandard values. We compare them with the recent values of observed D, 4 He, and 7 Li abundances, which show a slight inconsistency among themselves in the standard big bang nucleosynthesis scenario. This inconsistency is not solved by considering either a varying fine structure constant or a nonstandard expansion rate separately but solutions are found by their simultaneous existence

Convergence analysis of Chauvin's PCA learning algorithm with a constant learning rate

Energy Technology Data Exchange (ETDEWEB)

Lv Jiancheng [Computational Intelligence Laboratory, School of Computer Science and Engineering, University of Electronic Science and Technology of China, Chengdu 610054 (China); Yi Zhang [Computational Intelligence Laboratory, School of Computer Science and Engineering, University of Electronic Science and Technology of China, Chengdu 610054 (China)]. E-mail: zhangyi@uestc.edu.cn

2007-05-15

The convergence of Chauvin's PCA learning algorithm with a constant learning rate is studied in this paper by using a DDT method (deterministic discrete-time system method). Different from the DCT method (deterministic continuous-time system method), the DDT method does not require that the learning rate converges to zero. An invariant set of Chauvin's algorithm with a constant learning rate is obtained so that the non-divergence of this algorithm can be guaranteed. Rigorous mathematic proofs are provided to prove the local convergence of this algorithm.

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

DEFF Research Database (Denmark)

Zhou, Teng; Jhamb, Spardha; Liang, Xiaodong

2018-01-01

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

Determination of rate constants for the oxygen reduction reaction

Energy Technology Data Exchange (ETDEWEB)

Racz, A.; Walter, T.; Stimming, U. [Munich Technical Univ., Garching (Germany). Dept. of Physics

2008-07-01

The oxygen reduction reaction (ORR) in fuel cells is a complex and fundamental electrochemical reaction. However, greater insight is needed into this multi-electron reaction in order to develop efficient and innovative catalysts. The rotating ring disc electrode (RRDE) is a useful tool for studying reaction intermediates of the ORR and to better understand the reaction pathway. Carbon materials such as carbon nanofilaments-platelets (CNF-PL) have high electrical conductivity and may be considered for fuel cells. In particular Pt and RuSe{sub x}, deposited on CNF-PL materials could act as efficient catalysts in fuel cells. This study used the RRDE to evaluate the oxygen reduction kinetics of these catalysts in oxygen-saturated, diluted sulphuric acid at room temperature. Kinetic data and hydrogen peroxide formation were determined by depositing a thin-film of the catalyst on the Au disc. The values for the constants k1, k2 and k3 were obtained using diagnostic criteria and expressions to calculate the rate constants of the cathodic oxygen reduction reaction for RuSe on new carbon supports. A potential dependency of the constants k1 and k2 for RuSe{sub x}/CNF-PL was observed. The transition of the Tafel slopes for this catalyst was obtained. 4 refs., 1 fig.

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

Science.gov (United States)

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

2014-06-01

Augmenting leachate before recirculation with peroxidase enzymes is a novel method to increase the available carbon, and therefore the food supply to microorganisms at the declining phase of the anaerobic landfill bioreactor operation. In order to optimize the enzyme-catalyzed leachate recirculation process, it is necessary to identify the reaction mechanisms and determine rate constants. This paper presents a kinetic model developed to ascertain the reaction mechanisms and determine the rate constants for enzyme catalyzed anaerobic waste degradation. The maximum rate of reaction (Vmax) for MnP enzyme-catalyzed reactors was 0.076 g(TOC)/g(DS).day. The catalytic turnover number (k(cat)) of the MnP enzyme-catalyzed was 506.7 per day while the rate constant (k) of the un-catalyzed reaction was 0.012 per day. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

Science.gov (United States)

Höhna, Sebastian

2014-01-01

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 to be

Measuring Protein Synthesis Rate In Living Object Using Flooding Dose And Constant Infusion Methods

OpenAIRE

Ulyarti, Ulyarti

2018-01-01

Constant infusion is a method used for measuring protein synthesis rate in living object which uses low concentration of amino acid tracers. Flooding dose method is another technique used to measure the rate of protein synthesis which uses labelled amino acid together with large amount of unlabelled amino acid.  The latter method was firstly developed to solve the problem in determination of precursor pool arise from constant infusion method.  The objective of this writing is to com...

Absolute instrumental neutron activation analysis at Lawrence Livermore Laboratory

International Nuclear Information System (INIS)

Heft, R.E.

1977-01-01

The Environmental Science Division at Lawrence Livermore Laboratory has in use a system of absolute Instrumental Neutron Activation Analysis (INAA). Basically, absolute INAA is dependent upon the absolute measurement of the disintegration rates of the nuclides produced by neutron capture. From such disintegration rate data, the amount of the target element present in the irradiated sample is calculated by dividing the observed disintegration rate for each nuclide by the expected value for the disintegration rate per microgram of the target element that produced the nuclide. In absolute INAA, the expected value for disintegration rate per microgram is calculated from nuclear parameters and from measured values of both thermal and epithermal neutron fluxes which were present during irradiation. Absolute INAA does not depend on the concurrent irradiation of elemental standards but does depend on the values for thermal and epithermal neutron capture cross-sections for the target nuclides. A description of the analytical method is presented

Frost heave susceptibility of saturated soil under constant rate of freezing

Science.gov (United States)

Ryokai, K.; Iguro, M.; Yoneyama, K.

Introduced are the results of experiments carried out to quantitatively obtain the frost heave pressure and displacement of soil subjected to artificial freezing or freezing around in-ground liquefied natural gas storage tanks. This experiment is conducted to evaluate the frost heave susceptibility of saturated soil under overconsolidation. In other words, this experiment was carried out to obtain the relation of the over-burden pressure and freezing rate to the frost heave ratio by observing the frost heave displacement and freezing time of specimens by freezing the specimens at a constant freezing rate under a constant overburden pressure, while letting water freely flow in and out of the system. Introduced are the procedures for frost heave test required to quantitatively obtain the frost heave displacement and pressure of soil. Furthermore, the relation between the frost heave susceptibility and physical properties of soil obtained by this test is reported.

The reaction O((3)P) + HOBr: Temperature dependence of the rate constant and importance of the reaction as an HOBr stratospheric loss process

Science.gov (United States)

Nesbitt, F. L.; Monks, P. S.; Payne, W. A.; Stief, L. J.; Toumi, R.

1995-01-01

The absolute rate constant for the reaction O((3)P) + HOBr has been measured between T = 233K and 423K using the discharge-flow kinetic technique coupled to mass spectrometric detection. The value of the rate coefficient at room temperature is (2.5 +/- 0.6) x 10(exp -11)cu cm/molecule/s and the derived Arrhenius expression is (1.4 +/- 0.5) x 10(exp -10) exp((-430 +/- 260)/T)cu cm/molecule/s. From these rate data the atmospheric lifetime of HOBr with respect to reaction with O((3)P) is about 0.6h at z = 25 km which is comparable to the photolysis lifetime based on recent measurements of the UV cross section for HOBr. Implications for HOBr loss in the stratosphere have been tested using a 1D photochemical box model. With the inclusion of the rate parameters and products for the O + HOBr reaction, calculated concentration profiles of BrO increase by up to 33% around z = 35 km. This result indicates that the inclusion of the O + HOBr reaction in global atmospheric chemistry models may have an impact on bromine partitioning in the middle atmosphere.

The absolute counting of red cell-derived microparticles with red cell bead by flow rate based assay.

Science.gov (United States)

Nantakomol, Duangdao; Imwong, Malika; Soontarawirat, Ingfar; Kotjanya, Duangporn; Khakhai, Chulalak; Ohashi, Jun; Nuchnoi, Pornlada

2009-05-01

Activation of red blood cell is associated with the formation of red cell-derived microparticles (RMPs). Analysis of circulating RMPs is becoming more refined and clinically useful. A quantitative Trucount tube method is the conventional method uses for quantitating RMPs. In this study, we validated a quantitative method called "flow rate based assay using red cell bead (FCB)" to measure circulating RMPs in the peripheral blood of healthy subjects. Citrated blood samples collected from 30 cases of healthy subjects were determined the RMPs count by using double labeling of annexin V-FITC and anti-glycophorin A-PE. The absolute RMPs numbers were measured by FCB, and the results were compared with the Trucount or with flow rate based calibration (FR). Statistical correlation and agreement were analyzed using linear regression and Bland-Altman analysis. There was no significant difference in the absolute number of RMPs quantitated by FCB when compared with those two reference methods including the Trucount tube and FR method. The absolute RMPs count obtained from FCB method was highly correlated with those obtained from Trucount tube (r(2) = 0.98, mean bias 4 cell/microl, limit of agreement [LOA] -20.3 to 28.3 cell/microl), and FR method (r(2) = 1, mean bias 10.3 cell/microl, and LOA -5.5 to 26.2 cell/microl). This study demonstrates that FCB is suitable and more affordable for RMPs quantitation in the clinical samples. This method is a low cost and interchangeable to latex bead-based method for generating the absolute counts in the resource-limited areas. (c) 2008 Clinical Cytometry Society.

Simultaneous estimation of lithospheric uplift rates and absolute sea level change in southwest Scandinavia from inversion of sea level data

DEFF Research Database (Denmark)

Nielsen, Lars; Hansen, Jens Morten; Hede, Mikkel Ulfeldt

2014-01-01

the relative sea level data. Similar independent data do not exist for ancient times. The purpose of this study is to test two simple inversion approaches for simultaneous estimation of lithospheric uplift rates and absolute sea level change rates for ancient times in areas where a dense coverage of relative...... sea level data exists and well-constrained average lithospheric movement values are known from, for example glacial isostatic adjustment (GIA) models. The inversion approaches are tested and used for simultaneous estimation of lithospheric uplift rates and absolute sea level change rates in southwest...... Scandinavia from modern relative sea level data series that cover the period from 1900 to 2000. In both approaches, a priori information is required to solve the inverse problem. A priori information about the average vertical lithospheric movement in the area of interest is critical for the quality...

Determination of the Absolute Disintegration Rate of Cs-137 sources by the Tracer Method

Energy Technology Data Exchange (ETDEWEB)

Hellstroem, S; Brune, D

1963-07-15

{sup 137}Cs - sources were absolutely measured by the 'tracer method', with {sup 82}Br as a tracer nuclide and with application of the 4{pi} {beta}-{gamma} coincidence technique. A self-absorption of 6 % was found in sources obtained from a solution with a carrier-content of 400 {mu}g/ml. The precision of the method for the determination of the {beta}-emission rate was estimated to {+-} 1 %. The results were compared with those of other works.

Determination of the Absolute Disintegration Rate of Cs-137 sources by the Tracer Method

International Nuclear Information System (INIS)

Hellstroem, S.; Brune, D.

1963-07-01

137 Cs - sources were absolutely measured by the 'tracer method', with 82 Br as a tracer nuclide and with application of the 4π β-γ coincidence technique. A self-absorption of 6 % was found in sources obtained from a solution with a carrier-content of 400 μg/ml. The precision of the method for the determination of the β-emission rate was estimated to ± 1 %. The results were compared with those of other works

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

DEFF Research Database (Denmark)

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

Microextraction (HS-SPME) was applied directly on the test systems to measure substrate depletion by biodegradation relative to abiotic controls. HS-SPME was also applied to determine air to water partitioning ratios. Water phase biodegradation rate constants, kwater, were up to 72 times higher than test system...

On the estimate of the rate constant in the homogeneous dissolution model

Czech Academy of Sciences Publication Activity Database

Čupera, Jakub; Lánský, Petr

2013-01-01

Roč. 39, č. 10 (2013), s. 1555-1561 ISSN 0363-9045 Institutional support: RVO:67985823 Keywords : dissolution * estimation * rate constant Subject RIV: FR - Pharmacology ; Medidal Chemistry Impact factor: 2.006, year: 2013

Rate constant measurements for the overall reaction of OH + 1-butanol → products from 900 to 1200 K.

Science.gov (United States)

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

2012-03-15

The rate constant for the overall reaction OH + 1-butanol → products was determined in the temperature range 900 to 1200 K from measurements of OH concentration time histories in reflected shock wave experiments of tert-butyl hydroperoxide (TBHP) as a fast source of OH radicals with 1-butanol in excess. Narrow-linewidth laser absorption was employed for the quantitative OH concentration measurement. A detailed kinetic mechanism was constructed that includes updated rate constants for 1-butanol and TBHP kinetics that influence the near-first-order OH concentration decay under the present experimental conditions, and this mechanism was used to facilitate the rate constant determination. The current work improves upon previous experimental studies of the title rate constant by utilizing a rigorously generated kinetic model to describe secondary reactions. Additionally, the current work extends the temperature range of experimental data in the literature for the title reaction under combustion-relevant conditions, presenting the first measurements from 900 to 1000 K. Over the entire temperature range studied, the overall rate constant can be expressed in Arrhenius form as 3.24 × 10(-10) exp(-2505/T [K]) cm(3) molecule(-1) s(-1). The influence of secondary reactions on the overall OH decay rate is discussed, and a detailed uncertainty analysis is performed yielding an overall uncertainty in the measured rate constant of ±20% at 1197 K and ±23% at 925 K. The results are compared with previous experimental and theoretical studies on the rate constant for the title reaction and reasonable agreement is found when the earlier experimental data were reinterpreted.

Multi-target QSPR modeling for simultaneous prediction of multiple gas-phase kinetic rate constants of diverse chemicals

Science.gov (United States)

Basant, Nikita; Gupta, Shikha

2018-03-01

The reactions of molecular ozone (O3), hydroxyl (•OH) and nitrate (NO3) radicals are among the major pathways of removal of volatile organic compounds (VOCs) in the atmospheric environment. The gas-phase kinetic rate constants (kO3, kOH, kNO3) are thus, important in assessing the ultimate fate and exposure risk of atmospheric VOCs. Experimental data for rate constants are not available for many emerging VOCs and the computational methods reported so far address a single target modeling only. In this study, we have developed a multi-target (mt) QSPR model for simultaneous prediction of multiple kinetic rate constants (kO3, kOH, kNO3) of diverse organic chemicals considering an experimental data set of VOCs for which values of all the three rate constants are available. The mt-QSPR model identified and used five descriptors related to the molecular size, degree of saturation and electron density in a molecule, which were mechanistically interpretable. These descriptors successfully predicted three rate constants simultaneously. The model yielded high correlations (R2 = 0.874-0.924) between the experimental and simultaneously predicted endpoint rate constant (kO3, kOH, kNO3) values in test arrays for all the three systems. The model also passed all the stringent statistical validation tests for external predictivity. The proposed multi-target QSPR model can be successfully used for predicting reactivity of new VOCs simultaneously for their exposure risk assessment.

A new analytical method for estimating lumped parameter constants of linear viscoelastic models from strain rate tests

Science.gov (United States)

Mattei, G.; Ahluwalia, A.

2018-04-01

We introduce a new function, the apparent elastic modulus strain-rate spectrum, E_{app} ( \\dot{ɛ} ), for the derivation of lumped parameter constants for Generalized Maxwell (GM) linear viscoelastic models from stress-strain data obtained at various compressive strain rates ( \\dot{ɛ}). The E_{app} ( \\dot{ɛ} ) function was derived using the tangent modulus function obtained from the GM model stress-strain response to a constant \\dot{ɛ} input. Material viscoelastic parameters can be rapidly derived by fitting experimental E_{app} data obtained at different strain rates to the E_{app} ( \\dot{ɛ} ) function. This single-curve fitting returns similar viscoelastic constants as the original epsilon dot method based on a multi-curve global fitting procedure with shared parameters. Its low computational cost permits quick and robust identification of viscoelastic constants even when a large number of strain rates or replicates per strain rate are considered. This method is particularly suited for the analysis of bulk compression and nano-indentation data of soft (bio)materials.

Critical Review of rate constants for reacitons of hydrated electrons

International Nuclear Information System (INIS)

Buxton, G.V.; Greenstock, C.L.; Phillips Helman, W.; Ross, A.B.

1988-01-01

Kinetic data for the radicals Hx and xOH in aqueous solution,and the corresponding radical anions, xO - and e/sub =/, have been critically reviewed. Reactions of the radicals in aqueous solution have been studied by pulse radiolysis, flash photolysis and other methods. Rate constants for over 3500 reaction are tabulated, including reaction with molecules, ions and other radicals derived from inorganic and organic solutes

Dose rate constant and energy spectrum of interstitial brachytherapy sources

International Nuclear Information System (INIS)

Chen Zhe; Nath, Ravinder

2001-01-01

In the past two years, several new manufacturers have begun to market low-energy interstitial brachytherapy seeds containing 125 I and 103 Pd. Parallel to this development, the National Institute of Standards and Technology (NIST) has implemented a modification to the air-kerma strength (S K ) standard for 125 I seeds and has also established an S K standard for 103 Pd seeds. These events have generated a considerable number of investigations on the determination of the dose rate constants (Λ) of interstitial brachytherapy seeds. The aim of this work is to study the general properties underlying the determination of Λ and to develop a simple method for a quick and accurate estimation of Λ. As the dose rate constant of clinical seeds is defined at a fixed reference point, we postulated that Λ may be calculated by treating the seed as an effective point source when the seed's source strength is specified in S K and its source characteristics are specified by the photon energy spectrum measured in air at the reference point. Using a semi-analytic approach, an analytic expression for Λ was derived for point sources with known photon energy spectra. This approach enabled a systematic study of Λ as a function of energy. Using the measured energy spectra, the calculated Λ for 125 I model 6711 and 6702 seeds and for 192 Ir seed agreed with the AAPM recommended values within ±1%. For the 103 Pd model 200 seed, the agreement was 5% with a recently measured value (within the ±7% experimental uncertainty) and was within 1% with the Monte Carlo simulations. The analytic expression for Λ proposed here can be evaluated using a programmable calculator or a simple spreadsheet and it provides an efficient method for checking the measured dose rate constant for any interstitial brachytherapy seed once the energy spectrum of the seed is known

Extrapolation of rate constants of reactions producing H2 and O2 in radiolysis of water at high temperatures

International Nuclear Information System (INIS)

Leblanc, R.; Ghandi, K.; Hackman, B.; Liu, G.

2014-01-01

One target of our research is to extrapolate known data on the rate constants of reactions and add corrections to estimate the rate constants at the higher temperatures reached by the SCWR reactors. The focus of this work was to extrapolate known data on the rate constants of reactions that produce Hydrogen or Oxygen with a rate constant below 10 10 mol -1 s -1 at room temperature. The extrapolation is done taking into account the change in the diffusion rate of the interacting species and the cage effect with thermodynamic conditions. The extrapolations are done over a wide temperature range and under isobaric conditions. (author)

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

KAUST Repository

Badra, Jihad

2015-02-01

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

Absolute in vivo translation rates of individual codons in Escherichia coli: The two glutamic acid codons GAA and GAG are translated with a threefold difference in rate

DEFF Research Database (Denmark)

Sørensen, M.A.; Pedersen, Steen

1991-01-01

We have determined the absolute translation rates for four individual codons in Escherichia coli. We used our previously described system for direct measurements of in vivo translation rates using small, in-frame inserts in the lacZ gene. The inserts consisted of multiple synthetic 30 base-pair D...

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

Study on absolute humidity influence of NRL-1 measuring apparatus for radon

International Nuclear Information System (INIS)

Shan Jian; Xiao Detao; Zhao Guizhi; Zhou Qingzhi; Liu Yan; Qiu Shoukang; Meng Yecheng; Xiong Xinming; Liu Xiaosong; Ma Wenrong

2014-01-01

The absolute humidity and temperature's effects on the NRL-1 measuring apparatus for radon were studied in this paper. By controlling the radon activity concentration of the radon laboratory in University of South China and improving the temperature and humidity adjust strategy, different correction factor values under different absolute humidities were obtained. Moreover, a correction curve between 1.90 and 14.91 g/m"3 was also attained. The results show that in the case of absolute humidity, when it is less than 2.4 g/m"3, collection efficiency of the NRL-1 measuring apparatus for radon tends to be constant, and the correction factor of the absolute humidity closes to 1. However, the correction factor increases nonlinearly along with the absolute humidity. (authors)

Free energy correlation of rate constants for electron transfer between organic systems in aqueous solutions

Energy Technology Data Exchange (ETDEWEB)

Meisel, D

1975-07-15

Recent experimental data concerning the rate constants for electron transfer reactions of organic systems in aqueous solutions and their equilibrium constants is examined for possible correlation. The data is correlated quite well by the Marcus theory, if a reorganization parameter, lambda, of 18 kcal/mole is used. Assuming that the only contribution to lambda is the free energy of rearrangement of the water molecules, an effective radius of 5 A for the reacting entities is estimated. For the zero free energy change reaction, i.e., electron exchange between a radical ion and its parent molecule, a rate constant of about 5 X 10/sup 7/ M/sup -1/ s/sup -1/ is predicted. (auth)

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

Science.gov (United States)

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

2016-07-13

If for a chemical reaction with a known reaction mechanism the concentration profiles are accessible only for certain species, e.g. only for the main product, then often the reaction rate constants cannot uniquely be determined from the concentration data. This is a well-known fact which includes the so-called slow-fast ambiguity. This work combines the question of unique or non-unique reaction rate constants with factor analytic methods of chemometrics. The idea is to reduce the rotational ambiguity of pure component factorizations by considering only those concentration factors which are possible solutions of the kinetic equations for a properly adapted set of reaction rate constants. The resulting set of reaction rate constants corresponds to those solutions of the rate equations which appear as feasible factors in a pure component factorization. The new analysis of the ambiguity of reaction rate constants extends recent research activities on the Area of Feasible Solutions (AFS). The consistency with a given chemical reaction scheme is shown to be a valuable tool in order to reduce the AFS. The new methods are applied to model and experimental data. Copyright © 2016 Elsevier B.V. All rights reserved.

Mathematical basis for the measurement of absolute and fractional cardiac output with diffusible tracers by compartmental analysis methods

International Nuclear Information System (INIS)

Charkes, N.D.

1984-01-01

Using compartmental analysis methods, a mathematical basis is given for the measurement of absolute and fractional cardiac output with diffusible tracers. Cardiac output is shown to be the product of the blood volume and the sum of the rate constants of tracer egress from blood, modified by a factor reflecting transcapillary diffusibility, the transfer fraction. The return of tracer to the blood and distant (intracellular) events are shown to play no role in the solution. Fractional cardiac output is the ratio of the rate constant of tracer egress from blood to an organ, divided by the sum of the egress constants from blood. Predominantly extracellular ions such as sodium or bromide are best suited for this technique, although theoretically any diffusible tracer whose compartmental model can be solved may be used. It is shown that fractional cardiac output is independent of the transfer fraction, and therefore can be measured accurately by tracers which are not freely diffusible

Determination of rate constants in second-order kinetics using UV-visible spectroscopy

NARCIS (Netherlands)

Bijlsma, S.; Boelens, H. F. M.; Smilde, A. R.

2001-01-01

A general method for estimating reaction rate constants of chemical reactions using ultraviolet-visible (UV-vis) spectroscopy is presented. The only requirement is that some of the chemical components involved be spectroscopically active. The method uses the combination of spectroscopic measurements

Bibliographies on radiation chemistry: Pt. 12; Rate constants for reactions of nonmetallic inorganic radicals in aqueous solution

Energy Technology Data Exchange (ETDEWEB)

Helman, W P; Ross, A B [Notre Dame Univ., IN (USA). Radiation Chemistry Data Center

1990-01-01

Rate constants have been determined by pulse radiolysis, flash photolysis, and other methods, for a wide variety of reactions involving transient radicals in aqueous solution. Reliable rate constants have been established for reactions of radicals from water (e{sub aq}{sup -}, {center dot}H, {center dot}OH/{center dot}O{sup -}) and the data have been tabulated (Buxton, 1988) through 1986. Kinetic data for HO{sub 2}{center dot}/O{sub 2}{center dot}{sup -} were tabulated. (Bielski, 1985) from papers published through 1983. A compilation of rate constants, from the literature through Mid-1987, for other nonmetallic inorganic radicals has also appeared recently (Neta, 1988). Together, these compilations contain rate constants for more than 6,000 different reactions, reported in about 2,000 references. The present bibliography provides a list of relevant references which have been collected since the publication of the above-mentioned compilations. The list contains references received through the end of December, 1989. (author).

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

DEFF Research Database (Denmark)

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

1993-01-01

Rate constant ratios of the reactions of CF3O radicals with a number of hydrocarbons have been determined at 298 +/- 2 K and atmospheric pressure using a relative rate method. Using a previously determined value k(CF30 + C2H6) = 1.2 x 10(-12) cm3 molecule-1 s-1 these rate constant ratios provide...... estimates of the rate constants: k(CF3O + CH4) = (1.2 +/- 0.1) x 10(-14), k(CF3O + c-C3H6) = (3.6 +/- 0.2) x 10(-13), k(CF3O + C3H8) = (4.7 +/- 0.7) x 10(-12), k(CF3O + (CH3)3CH) = (7.2 +/- 0.5) x 10(-12), k(CF3O + C2H4) = (3.0 +/- 0.1) x 10(-11) and k(CF3O + C6H6) = (3.6 +/- 0.1) x 10(-11) cm3 molecule-1 s......-1. The importance of the reactions of CF3O radicals with hydrocarbons under atmospheric conditions is discussed....

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

Science.gov (United States)

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

2015-12-01

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

Rate constants for the reaction of e-aq with EDTA and some metal EDTA-complexes

International Nuclear Information System (INIS)

Buitenhuis, R.; Bakker, C.M.N.; Stock, F.R.; Louwrier, P.W.F.

1977-01-01

The rate constants for the reaction e - aq + EDTA were measured as a function of the pH by the pulse-radiolysis technique. Between pH = 6and pH = 10 this rate constant can be represented by the equation k = 4.7 x 10 6 x (fraction of HEDTA 3- )+1.0 x 10 8 x (fraction H 2 EDTA 2 -)M -1 s -1 . Also the rate constants for reactions of e - aq with the following metal-EDTA complexes were measured: CuEDTA 2- , HgEDTA 2- , CoEDTA 2- , InEDTA - , NiEDTA 2- , GaEDTA - , MnEDTA 2- , ZnEDTA 2- , CdEDTA 2- , PbEDTA 2- . Ionic strength variation indicates that the reacting ions are not hydrolized to an appreciable amount at pH = 11.5. It is found that some of the products show light absorption in the region between 300 and 400 nm. (orig.) [de

Linear free energy relationships between aqueous phase hydroxyl radical reaction rate constants and free energy of activation.

Science.gov (United States)

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.

Absolute measurement of a tritium standard

International Nuclear Information System (INIS)

Hadzisehovic, M.; Mocilnik, I.; Buraei, K.; Pongrac, S.; Milojevic, A.

1978-01-01

For the determination of a tritium absolute activity standard, a method of internal gas counting has been used. The procedure involves water reduction by uranium and zinc further the measurement of the absolute disintegration rate of tritium per unit of the effective volume of the counter by a compensation method. Criteria for the choice of methods and procedures concerning the determination and measurement of gaseous 3 H yield, parameters of gaseous hydrogen, sample mass of HTO and the absolute disintegration rate of tritium are discussed. In order to obtain gaseous sources of 3 H (and 2 H), the same reversible chemical reaction was used, namely, the water - uranium hydride - hydrogen system. This reaction was proved to be quantitative above 500 deg C by measuring the yield of the gas obtained and the absolute activity of an HTO standard. A brief description of the measuring apparatus is given, as well as a critical discussion of the brass counter quality and the possibility of obtaining equal working conditions at the counter ends. (T.G.)

Studies on the catalytic rate constant of ribosomal peptidyltransferase.

Science.gov (United States)

Synetos, D; Coutsogeorgopoulos, C

1987-02-20

A detailed kinetic analysis of a model reaction for the ribosomal peptidyltransferase is described, using fMet-tRNA or Ac-Phe-tRNA as the peptidyl donor and puromycin as the acceptor. The initiation complex (fMet-tRNA X AUG X 70 S ribosome) or (Ac-Phe-tRNA X poly(U) X 70 S ribosome) (complex C) is isolated and then reacted with excess puromycin (S) to give fMet-puromycin or Ac-Phe-puromycin. This reaction (puromycin reaction) is first order at all concentrations of S tested. An important asset of this kinetic analysis is the fact that the relationship between the first order rate constant kobs and [S] shows hyperbolic saturation and that the value of kobs at saturating [S] is a measure of the catalytic rate constant (k cat) of peptidyltransferase in the puromycin reaction. With fMet-tRNA as the donor, this kcat of peptidyltransferase is 8.3 min-1 when the 0.5 M NH4Cl ribosomal wash is present, compared to 3.8 min-1 in its absence. The kcat of peptidyltransferase is 2.0 min-1 when Ac-Phe-tRNA replaces fMet-tRNA in the presence of the ribosomal wash and decreases to 0.8 min-1 in its absence. This kinetic procedure is the best method available for evaluating changes in the activity of peptidyltransferase in vitro. The results suggest that peptidyltransferase is subjected to activation by the binding of fMet-tRNA to the 70 S initiation complex.

Constant Growth Rate Can Be Supported by Decreasing Energy Flux and Increasing Aerobic Glycolysis

Directory of Open Access Journals (Sweden)

Nikolai Slavov

2014-05-01

Full Text Available 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 roles in yeast batch cultures by quantifying O2 consumption, CO2 production, amino acids, mRNAs, proteins, posttranslational modifications, and stress sensitivity in the course of nine doublings at constant rate. During this course, the cells support a constant biomass-production rate with decreasing rates of respiration and ATP production but also decrease their stress resistance. As the respiration rate decreases, so do the levels of enzymes catalyzing rate-determining reactions of the tricarboxylic-acid cycle (providing NADH for respiration and of mitochondrial folate-mediated NADPH production (required for oxidative defense. The findings demonstrate that exponential growth can represent not a single metabolic/physiological state but a continuum of changing states and that aerobic glycolysis can reduce the energy demands associated with respiratory metabolism and stress survival.

Rate Constants for the Reactions of Hydroxyl Radical with Several Alkanes, Cycloalkanes, and Dimethyl Ether

Science.gov (United States)

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.

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

Science.gov (United States)

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

2012-08-15

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

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.

Low-Temperature Experimental and Theoretical Rate Constants for the O(1D) + H2 Reaction.

Science.gov (United States)

Hickson, Kevin M; Suleimanov, Yury V

2017-03-09

In the present joint experimental and theoretical study, we report thermal rate constants for the O( 1 D) + H 2 reaction within the 50-300 K temperature range. Experimental kinetics measurements were performed using a continuous supersonic flow reactor coupled with pulsed laser photolysis for O( 1 D) production and pulsed laser-induced fluorescence in the vacuum ultraviolet wavelength range (VUV LIF) for O( 1 D) detection. Theoretical rate constants were obtained using the ring polymer molecular dynamics (RPMD) approach over the two lowest potential energy surfaces 1 1 A' and 1 1 A″, which possess barrierless and thermally activated energy profiles, respectively. Both the experimental and theoretical rate constants exhibit a weak temperature dependence. The theoretical results show the dominant role of the 1 1 A' ground state and that contribution of the 1 1 A″ excited state to the total thermal rate decreases dramatically at lower temperature. Agreement between the experimental and theoretical results is good, and the discrepancy does not exceed 25%. It is argued that these differences are likely to be due to nonadiabatic couplings between the 1 1 A' and 2 1 A' surfaces.

Determination of hydroxyl rate constants by a high-throughput fluorimetric assay: towards a unified reactivity scale for antioxidants

International Nuclear Information System (INIS)

Louit, G.; Renault, J.P.; Pin, S.; Coffigny, H.; Hanedanian, M.; Taran, F.; Renault, J.P.; Pin, S.

2009-01-01

We describe in this article the development of a new method for the determination of rate constants of reaction of the hydroxyl radical, generated by radiolysis of water, with almost any possible molecule. It has been designed to provide a fast and reliable screening of antioxidant banks using microplates. Our particular approach is based on the use of the coumarin molecule as a competitor against the tested molecules: after a fast pulse of low dose irradiation, the fluorescence of 7-hydroxycoumarin produced by the oxidation of coumarin is measured and is inversely proportional to the scavenging ability of the tested antioxidant. We have validated our protocol using 32 molecules whose rate constants with HO . had already been evaluated and found a good agreement between our rate constants and the latter ones. The scopes and limitations of our method, as well as those of other rate constant determination methods, are discussed. (authors)

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

Science.gov (United States)

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

2014-07-01

Ultrasound has been used as an advanced oxidation method for wastewater treatment. Sonochemical degradation of organic compounds in aqueous solution occurs by pyrolysis and/or reaction with hydroxyl radicals. Moreover, kinetics of sonochemical degradation has been proposed. However, the effect of ultrasonic frequency on degradation rate has not been investigated. In our previous study, a simple model for estimating the apparent degradation rate of methylene blue was proposed. In this study, sonochemical degradation of methylene blue was performed at various frequencies. Apparent degradation rate constant was evaluated assuming that sonochemical degradation of methylene blue was a first-order reaction. Specifically, we focused on effects of ultrasonic frequency and power on rate constant, and the applicability of our proposed model was demonstrated. Using this approach, maximum sonochemical degradation rate was observed at 490 kHz, which agrees with a previous investigation into the effect of frequency on the sonochemical efficiency value evaluated by KI oxidation dosimetry. Degradation rate increased with ultrasonic power at every frequency. It was also observed that threshold power must be reached for the degradation reaction to progress. The initial methylene blue concentration and the apparent degradation rate constant have a relation of an inverse proportion. Our proposed model for estimating the apparent degradation rate constant using ultrasonic power and sonochemical efficiency value can apply to this study which extended the frequency and initial concentration range. Copyright © 2013 Elsevier B.V. All rights reserved.

Constant savings rates and quasi-arithmetic population growth under exhaustible resource constraints

NARCIS (Netherlands)

Asheim, G.B.; Buchholz, W.; Hartwick, J.M.; Mitra, T.; Withagen, C.A.A.M.

2007-01-01

In the Dasgupta–Heal–Solow–Stiglitz (DHSS) model of capital accumulation and resource depletion we show the following equivalence: if an efficient path has constant (gross and net of population growth) savings rates, then population growth must be quasi-arithmetic and the path is a maximin or a

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

Directory of Open Access Journals (Sweden)

Kircher Michael

2015-09-01

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

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...

The Rate Constant for the Reaction H + C2H5 at T = 295 - 150K

Science.gov (United States)

Pimentel, Andre S.; Payne, Walter A.; Nesbitt, Fred L.; Cody, Regina J.; Stief, Louis J.

2004-01-01

The reaction between the hydrogen atom and the ethyl (C2H3) radical is predicted by photochemical modeling to be the most important loss process for C2H5 radicals in the atmospheres of Jupiter and Saturn. This reaction is also one of the major sources for the methyl radicals in these atmospheres. These two simplest hydrocarbon radicals are the initial species for the synthesis of larger hydrocarbons. Previous measurements of the rate constant for the H + C2H5 reaction varied by a factor of five at room temperature, and some studies showed a dependence upon temperature while others showed no such dependence. In addition, the previous studies were at higher temperatures and generally higher pressures than that needed for use in planetary atmospheric models. The rate constant for the reaction H + C2H5 has been measured directly at T = 150, 202 and 295 K and at P = 1.0 Torr He for all temperatures and additionally at P = 0.5 and 2.0 Torr He at T = 202 K. The measurements were performed in a discharge - fast flow system. The decay of the C2H5 radical in the presence of excess hydrogen was monitored by low-energy electron impact mass spectrometry under pseudo-first order conditions. H atoms and C2H5 radicals were generated rapidly and simultaneously by the reaction of fluorine atoms with H2 and C2H6, respectively. The total rate constant was found to be temperature and pressure independent. The measured total rate constant at each temperature are: k(sub 1)(295K) = (1.02+/-0.24)x10(exp -10), k(sub 1)(202K) = (1.02+/-0.22)x10(exp -10) and k(sub 1)(150K) = (0.93+/-0.21)x10(exp -10), all in units of cu cm/molecule/s. The total rate constant derived from all the combined measurements is k(sub 1) = (l.03+/-0.17)x10(exp -10) cu cm/molecule/s. At room temperature our results are about a factor of two higher than the recommended rate constant and a factor of three lower than the most recently published study.

On determining absolute entropy without quantum theory or the third law of thermodynamics

Science.gov (United States)

Steane, Andrew M.

2016-04-01

We employ classical thermodynamics to gain information about absolute entropy, without recourse to statistical methods, quantum mechanics or the third law of thermodynamics. The Gibbs-Duhem equation yields various simple methods to determine the absolute entropy of a fluid. We also study the entropy of an ideal gas and the ionization of a plasma in thermal equilibrium. A single measurement of the degree of ionization can be used to determine an unknown constant in the entropy equation, and thus determine the absolute entropy of a gas. It follows from all these examples that the value of entropy at absolute zero temperature does not need to be assigned by postulate, but can be deduced empirically.

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

KAUST Repository

Regnery, J.

2015-05-29

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

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

Science.gov (United States)

Regnery, J; Wing, A D; Alidina, M; Drewes, J E

2015-08-01

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

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

KAUST Repository

Wu, Junjun; Khaled, Fathi; Ning, Hongbo; Ma, Liuhao; Farooq, Aamir; Ren, Wei

2017-01-01

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

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

KAUST Repository

Wu, Junjun

2017-08-03

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

Empirical correlation for prediction of the elutriation rate constant

Directory of Open Access Journals (Sweden)

Stojkovski Valentino

2003-01-01

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

Extrapolation of rate constants of reactions producing H{sub 2} and O{sub 2} in radiolysis of water at high temperatures

Energy Technology Data Exchange (ETDEWEB)

Leblanc, R.; Ghandi, K.; Hackman, B.; Liu, G. [Mount Allison Univ., Sackville, NB (Canada)

2014-07-01

One target of our research is to extrapolate known data on the rate constants of reactions and add corrections to estimate the rate constants at the higher temperatures reached by the SCWR reactors. The focus of this work was to extrapolate known data on the rate constants of reactions that produce Hydrogen or Oxygen with a rate constant below 10{sup 10} mol{sup -1} s{sup -1} at room temperature. The extrapolation is done taking into account the change in the diffusion rate of the interacting species and the cage effect with thermodynamic conditions. The extrapolations are done over a wide temperature range and under isobaric conditions. (author)

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

Directory of Open Access Journals (Sweden)

Jan Moestedt

2015-01-01

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

Reaction rate constant of HO2+O3 measured by detecting HO2 from photofragment fluorescence

Science.gov (United States)

Manzanares, E. R.; Suto, Masako; Lee, Long C.; Coffey, Dewitt, Jr.

1986-01-01

A room-temperature discharge-flow system investigation of the rate constant for the reaction 'HO2 + O3 yields OH + 2O2' has detected HO2 through the OH(A-X) fluorescence produced by photodissociative excitation of HO2 at 147 nm. A reaction rate constant of 1.9 + or - 0.3 x 10 to the -15th cu cm/molecule per sec is obtained from first-order decay of HO2 in excess O3; this agrees well with published data.

QSARs for phenols and phenolates: oxidation potential as a predictor of reaction rate constants with photochemically produced oxidants.

Science.gov (United States)

Arnold, William A; Oueis, Yan; O'Connor, Meghan; Rinaman, Johanna E; Taggart, Miranda G; McCarthy, Rachel E; Foster, Kimberley A; Latch, Douglas E

2017-03-22

Quantitative structure-activity relationships (QSARs) for prediction of the reaction rate constants of phenols and phenolates with three photochemically produced oxidants, singlet oxygen, carbonate radical, and triplet excited state sensitizers/organic matter, are developed. The predictive variable is the one-electron oxidation potential (E 1 ), which is calculated for each species using density functional theory. The reaction rate constants are obtained from the literature, and for singlet oxygen, are augmented with new experimental data. Calculated E 1 values have a mean unsigned error compared to literature values of 0.04-0.06 V. For singlet oxygen, a single linear QSAR that includes both phenols and phenolates is developed that predicts experimental rate constants, on average, to within a factor of three. Predictions for only 6 out of 87 compounds are off by more than a factor of 10. A more limited data set for carbonate radical reactions with phenols and phenolates also gives a single linear QSAR with prediction of rate constant being accurate to within a factor of three. The data for the reactions of phenols with triplet state sensitizers demonstrate that two sensitizers, 2-acetonaphthone and methylene blue, most closely predict the reactivity trend of triplet excited state organic matter with phenols. Using sensitizers with stronger reduction potentials could lead to overestimation of rate constants and thus underestimation of phenolic pollutant persistence.

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

Science.gov (United States)

Allison, Thomas C

2016-03-03

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

Determination of photoformation rates and scavenging rate constants of hydroxyl radicals in natural waters using an automatic light irradiation and injection system

International Nuclear Information System (INIS)

Nakatani, Nobutake; Hashimoto, Norichika; Shindo, Hirotaka; Yamamoto, Masatoshi; Kikkawa, Megumi; Sakugawa, Hiroshi

2007-01-01

Photoformation rates and scavenging rate constants of hydroxyl radicals (·OH) in natural water samples were determined by an automatic determination system. After addition of benzene as a chemical probe to a water sample in a reaction cell, light irradiation and injection of irradiated water samples into an HPLC as a function of time were performed automatically. Phenol produced by the reaction between ·OH and the benzene added to the water sample was determined to quantify the ·OH formation rate. The rate constants of ·OH formation from the photolysis of nitrate ions, nitrite ions and hydrogen peroxide were comparable with those obtained in previous studies. The percent of expected ·OH photoformation rate from added nitrate ion were high in drinking water (97.4%) and river water (99.3%). On the other hand, the low percent (65.0%) was observed in seawater due to the reaction of ·OH with the high concentrations of chloride and bromide ions. For the automatic system, the coefficient of variance for the determination of the ·OH formation rate was less than 5.0%, which is smaller than that in the previous report. When the complete time sequence of analytical cycle was 40 min for one sample, the detection limit of the photoformation rate and the sample throughput were 8 x 10 -13 M s -1 and 20 samples per day, respectively. The automatic system successfully determined the photoformation rates and scavenging rate constants of ·OH in commercial drinking water and the major source and sink of ·OH were identified as nitrate and bicarbonate ions, respectively

Recent developments in semiclassical mechanics: eigenvalues and reaction rate constants

International Nuclear Information System (INIS)

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

Absolute analytical prediction of photonic crystal guided mode resonance wavelengths

DEFF Research Database (Denmark)

Hermannsson, Pétur Gordon; Vannahme, Christoph; Smith, Cameron

2014-01-01

numerically with methods such as rigorous coupled wave analysis. Here it is demonstrated how the absolute resonance wavelengths of such structures can be predicted by analytically modeling them as slab waveguides in which the propagation constant is determined by a phase matching condition. The model...... is experimentally verified to be capable of predicting the absolute resonance wavelengths to an accuracy of within 0.75 nm, as well as resonance wavelength shifts due to changes in cladding index within an accuracy of 0.45 nm across the visible wavelength regime in the case where material dispersion is taken...

The bolometric, infrared and visual absolute magnitudes of Mira variables

International Nuclear Information System (INIS)

Robertson, B.S.C.; Feast, M.W.

1981-01-01

Statistical parallaxes, as well as stars with individually known distances are used to derive bolometric and infrared absolute magnitudes of Mira (Me) variables. The derived bolometric magnitudes are in the mean about 0.75 mag fainter than recent estimates. The problem of determining the pulsation constant is discussed. Miras with periods greater than 150 days probably pulsate in the first overtone. Those of shorter periods are anomalous and may be fundamental pulsators. It is shown that the absolute visual magnitudes at mean light of Miras with individually determined distances are consistent with values derived by Clayton and Feast from statistical parallaxes. (author)

Relative and absolute risk in epidemiology and health physics

International Nuclear Information System (INIS)

Goldsmith, R.; Peterson, H.T. Jr.

1983-01-01

The health risk from ionizing radiation commonly is expressed in two forms: (1) the relative risk, which is the percentage increase in natural disease rate and (2) the absolute or attributable risk which represents the difference between the natural rate and the rate associated with the agent in question. Relative risk estimates for ionizing radiation generally are higher than those expressed as the absolute risk. This raises the question of which risk estimator is the most appropriate under different conditions. The absolute risk has generally been used for radiation risk assessment, although mathematical combinations such as the arithmetic or geometric mean of both the absolute and relative risks, have also been used. Combinations of the two risk estimators are not valid because the absolute and relative risk are not independent variables. Both human epidemiologic studies and animal experimental data can be found to illustrate the functional relationship between the natural cancer risk and the risk associated with radiation. This implies that the radiation risk estimate derived from one population may not be appropriate for predictions in another population, unless it is adjusted for the difference in the natural disease incidence between the two populations

Effects of the anion salt nature on the rate constants of the aqueous proton exchange reactions.

Science.gov (United States)

Paredes, Jose M; Garzon, Andres; Crovetto, Luis; Orte, Angel; Lopez, Sergio G; Alvarez-Pez, Jose M

2012-04-28

The proton-transfer ground-state rate constants of the xanthenic dye 9-[1-(2-methyl-4-methoxyphenyl)]-6-hydroxy-3H-xanthen-3-one (TG-II), recovered by Fluorescence Lifetime Correlation Spectroscopy (FLCS), have proven to be useful to quantitatively reflect specific cation effects in aqueous solutions (J. M. Paredes, L. Crovetto, A. Orte, J. M. Alvarez-Pez and E. M. Talavera, Phys. Chem. Chem. Phys., 2011, 13, 1685-1694). Since these phenomena are more sensitive to anions than to cations, in this paper we have accounted for the influence of salts with the sodium cation in common, and the anion classified according to the empirical Hofmeister series, on the proton transfer rate constants of TG-II. We demonstrate that the presence of ions accelerates the rate of the ground-state proton-exchange reaction in the same order than ions that affect ion solvation in water. The combination of FLCS with a fluorophore undergoing proton transfer reactions in the ground state, along with the desirable feature of a pseudo-dark state when the dye is protonated, allows one unique direct determination of kinetic rate constants of the proton exchange chemical reaction. This journal is © the Owner Societies 2012

The fading American dream: Trends in absolute income mobility since 1940.

Science.gov (United States)

Chetty, Raj; Grusky, David; Hell, Maximilian; Hendren, Nathaniel; Manduca, Robert; Narang, Jimmy

2017-04-28

We estimated rates of "absolute income mobility"-the fraction of children who earn more than their parents-by combining data from U.S. Census and Current Population Survey cross sections with panel data from de-identified tax records. We found that rates of absolute mobility have fallen from approximately 90% for children born in 1940 to 50% for children born in the 1980s. Increasing Gross Domestic Product (GDP) growth rates alone cannot restore absolute mobility to the rates experienced by children born in the 1940s. However, distributing current GDP growth more equally across income groups as in the 1940 birth cohort would reverse more than 70% of the decline in mobility. These results imply that reviving the "American dream" of high rates of absolute mobility would require economic growth that is shared more broadly across the income distribution. Copyright © 2017, American Association for the Advancement of Science.

Pseudo-extravasation rate constant of dynamic susceptibility contrast-MRI determined from pharmacokinetic first principles.

Science.gov (United States)

Li, Xin; Varallyay, Csanad G; Gahramanov, Seymur; Fu, Rongwei; Rooney, William D; Neuwelt, Edward A

2017-11-01

Dynamic susceptibility contrast-magnetic resonance imaging (DSC-MRI) is widely used to obtain informative perfusion imaging biomarkers, such as the relative cerebral blood volume (rCBV). The related post-processing software packages for DSC-MRI are available from major MRI instrument manufacturers and third-party vendors. One unique aspect of DSC-MRI with low-molecular-weight gadolinium (Gd)-based contrast reagent (CR) is that CR molecules leak into the interstitium space and therefore confound the DSC signal detected. Several approaches to correct this leakage effect have been proposed throughout the years. Amongst the most popular is the Boxerman-Schmainda-Weisskoff (BSW) K 2 leakage correction approach, in which the K 2 pseudo-first-order rate constant quantifies the leakage. In this work, we propose a new method for the BSW leakage correction approach. Based on the pharmacokinetic interpretation of the data, the commonly adopted R 2 * expression accounting for contributions from both intravascular and extravasating CR components is transformed using a method mathematically similar to Gjedde-Patlak linearization. Then, the leakage rate constant (K L ) can be determined as the slope of the linear portion of a plot of the transformed data. Using the DSC data of high-molecular-weight (~750 kDa), iron-based, intravascular Ferumoxytol (FeO), the pharmacokinetic interpretation of the new paradigm is empirically validated. The primary objective of this work is to empirically demonstrate that a linear portion often exists in the graph of the transformed data. This linear portion provides a clear definition of the Gd CR pseudo-leakage rate constant, which equals the slope derived from the linear segment. A secondary objective is to demonstrate that transformed points from the initial transient period during the CR wash-in often deviate from the linear trend of the linearized graph. The inclusion of these points will have a negative impact on the accuracy of the leakage

Adjustment of a two-block X-ray interferometer and absolute measurement of lattice spacing

International Nuclear Information System (INIS)

Nakayama, Kan

1994-01-01

X-ray interferometer was invented in 1965 by Bonse and Hart, and it uses the lattice surface of a silicon single crystal as a three-dimensional diffraction lattice. It divides X-ray coherently, changes direction, combines and causes interference. It made for the first time the interference effect of X-ray into the usable form in macroscopic world. As an example of the application of X-ray interferometers to basic science, there is the absolute measurement of lattice spacing. This is the method of simultaneously measuring the same displacement with an X-ray interferometer and a light wave interferometer, and doing the absolute measurement of the lattice spacing of crystals with light wavelength. Avogadro constant is the constant that becomes the foundation of chemistry, and its relation with other basic constants is shown. The principle of X-ray interferometers is explained. As the elementary technologies for the absolute measurement of lattice spacing, the adjustment of X-ray interferometers, parallel movement table and angular adjustment table, light wave interferometer and the prevention of vibration and temperature change are described. The example of the measurement is reported. In order to improve the accuracy, the improvement of the equipment and the measurement in vacuum are prepared at present. (K.I.)

Rate constants for the reactions of OH with HFC-134a (CF3CH2F) and HFC-134 (CHF2CHF2)

Science.gov (United States)

Demore, W. B.

1993-01-01

Measurements of rate constants for HFC-134 (CF2HCF2H) relative to CH3CCl3, HFC-125, and HFC-134a are reported. The measurements were made in a slow-flow, temperature controlled photochemical reactor, and were based on relative rates of disappearance of the parent compounds as measured by FTIR spectroscopy. Hydroxyl radicals were generated by 254-nm photolysis of O3 in the presence of water vapor. NASA/JPL rate constants for the reference compounds are used to derive temperature-dependent rate constants of both compounds. Rate constants obtained from the different reference compounds are in excellent agreement. The presently recommended rate constant for HFC-134a is about 25 percent too high.

Structure and Absolute Configuration of Nyasol and Hinokiresinol via Synthesis and Vibrational Circular Dichroism Spectroscopy

DEFF Research Database (Denmark)

Lassen, Peter Rygaard

2005-01-01

The absolute configuration of the norlignan (+)-nyasol was determined to be S by comparison of the experimental vibrational circular dichroism data with first-principle calculations taking into account the eight lowest energy conformations. The established absolute configuration of (+)-nyasol...... enables establishment of the absolute configuration of (-)-hinokiresinol, which is concluded to be S. A total synthesis and resolution of hinokiresinol has been performed to resolve the conflicting reports of the coupling constant of the vinylic protons of the disubstituted double bond in this molecule...

Cylindrical Taylor states conserving total absolute magnetic helicity

Science.gov (United States)

Low, B. C.; Fang, F.

2014-09-01

The Taylor state of a three-dimensional (3D) magnetic field in an upright cylindrical domain V is derived from first principles as an extremum of the total magnetic energy subject to a conserved, total absolute helicity Habs. This new helicity [Low, Phys. Plasmas 18, 052901 (2011)] is distinct from the well known classical total helicity and relative total helicity in common use to describe wholly-contained and anchored fields, respectively. A given field B, tangential along the cylindrical side of V, may be represented as a unique linear superposition of two flux systems, an axially extended system along V and a strictly transverse system carrying information on field-circulation. This specialized Chandrasekhar-Kendall representation defines Habs and permits a neat formulation of the boundary-value problem (BVP) for the Taylor state as a constant-α force-free field, treating 3D wholly-contained and anchored fields on the same conceptual basis. In this formulation, the governing equation is a scalar integro-partial differential equation (PDE). A family of series solutions for an anchored field is presented as an illustration of this class of BVPs. Past treatments of the constant-α field in 3D cylindrical geometry are based on a scalar Helmholtz PDE as the governing equation, with issues of inconsistency in the published field solutions discussed over time in the journal literature. The constant-α force-free equation reduces to a scalar Helmholtz PDE only as special cases of the 3D integro-PDE derived here. In contrast, the constant-α force-free equation and the scalar Helmholtz PDE are absolutely equivalent in the spherical domain as discussed in Appendix. This theoretical study is motivated by the investigation of the Sun's corona but the results are also relevant to laboratory plasmas.

Gravitational constant is likely dependent on the absolute velocity of galaxy

Science.gov (United States)

Chen, Shao-Guang

({2) -1}m (({2) -1}\\underline{m}) and only arises when ({2) -1}m(A) and ({2) -1}m(B) to be superposed. Though the turn-advance values U of ({2) -1}m had been counteracted, but when ({2) -1}m(A) superposes with ({2) -1}m (B) the ne(0) (A) of ({2) -1}m (A) and the ne (0) (B) of ({2) -1} m(B) can interact directly. The interaction shows as the piπ exchange force with the short-distance and saturation characters as the covalence. One nucleon has two ({2) -1}m (nuclear valences), the nuclear structure stability is dependent on the conjugation state of nuclear valences (to constitute nucleus). When two nuclear valences of all nucleons are conjugated entirely in the valences saturation state, then it is most stabilization and this element in a large natural abundance. The cubic with 4 angles, hexagon with 6 angles, double floor hexagon with 10 angles and three floor hexagon with 14 angles four kinds formation are all nuclear valences in saturation state, each angle also may be two or four particles, so that these elements: He (4) , Li, Be, B, C (12) , N (14) , O (16) , Ne (20) , Mg (24) , Si (28) , Fe (56) , Ni (58) , Ni (62) , Sn (112) ,Pb (208) are abundance, it accord to the fact. The charge q is the turn quantity U, and the mass m is absolute value of U. From \\underline{P} • \\underline{P} = 0: m (0) = e (0) = ±± (1/2 (1/2) ) (E (0) /c (2) ), q _{0} = e _{0} (nuυ _{0} (0) nuυ) = 2 (1/2) 2 e (0) = 2 (1/2) 2 q (0) . The electromagnetic (weak) interaction constant is alphaα = q _{℮} q _{℮} /h c (betaβ = q (0) q (0) /h c). The electronic outside layer is one _{0}nuυ (1 q (0) ) and one e = 9 e _{0} (nuυ _{0} (0) nuυ) = 9 q _{0}, q _{℮} = 9.5q _{0} = 19*2 (1/2) q (0) . The alphaα / betaβ = (q _{℮} (2) / h c) / (q (0) (2) /h c) = (19 *2 (1/2) ) (2) = 722. To take alphaα = 1/137.0302, then betaβ = alphaα / 722 = 1.010756*10 (-5) , alphaα is about 10 _{0}nuυ /(10 _{0}nuυ + 1359 nuυ _{0}). Because of the ne (0) of nucleon inside layer (5) m, (4) m

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

Science.gov (United States)

Ivanov, Mikhail V; Babikov, Dmitri

2012-05-14

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

Variational transition-state theory study of the rate constant of the DMS·OH scavenging reaction by O2.

Science.gov (United States)

Ramírez-Anguita, Juan M; González-Lafont, Àngels; Lluch, José M

2011-07-30

The chemical tropospheric dimethyl sulfide (DMS, CH3SCH3) degradation involves several steps highly dependent on the environmental conditions. So, intensive efforts have been devoted during the last years to enhance the understanding of the DMS oxidation mechanism under different conditions. The reaction of DMS with OH is considered to be the most relevant process that initiates the whole oxidation process. The experimental observations have been explained by a two-channel mechanism consisting of a H-abstraction process leading to CH3S(O)CH3 and HO2 and an addition reaction leading to the DMS·OH adduct. In the presence of O2, the DMS·OH adduct is competitively scavenged increasing the contribution of the addition channel to the overall DMS oxidation. Recent experimental measurements have determined from a global fit that the rate constant of this scavenging process is independent of pressure and temperature but this rate constant cannot be directly measured. In this article, a variational transition-state theory calculation of the low- and high-pressure rate constants for the reaction between DMS·OH and O2 has been carried out as a function of temperature. Our proposal is that the slight temperature dependence of the scavenging rate constant can only be explained if the H-abstraction bottleneck is preceded by a dynamical bottleneck corresponding to the association process between the DMS·OH adduct and the O2 molecule. The agreement between the low-pressure and high-pressure rate constants confirms the experimental observations. Copyright © 2011 Wiley Periodicals, Inc.

Overspecification of colour, pattern, and size: Salience, absoluteness, and consistency

OpenAIRE

Sammie eTarenskeen; Mirjam eBroersma; Mirjam eBroersma; Bart eGeurts

2015-01-01

The rates of overspecification of colour, pattern, and size are compared, to investigate how salience and absoluteness contribute to the production of overspecification. Colour and pattern are absolute attributes, whereas size is relative and less salient. Additionally, a tendency towards consistent responses is assessed. Using a within-participants design, we find similar rates of colour and pattern overspecification, which are both higher than the rate of size overspecification. Using a bet...

Overspecification of color, pattern, and size: salience, absoluteness, and consistency

OpenAIRE

Tarenskeen, S.L.; Broersma, M.; Geurts, B.

2015-01-01

The rates of overspecification of color, pattern, and size are compared, to investigate how salience and absoluteness contribute to the production of overspecification. Color and pattern are absolute and salient attributes, whereas size is relative and less salient. Additionally, a tendency toward consistent responses is assessed. Using a within-participants design, we find similar rates of color and pattern overspecification, which are both higher than the rate of size overspecification. Usi...

Atmospheric fate of a series of carbonyl nitrates: photolysis frequencies and OH-oxidation rate constants.

Science.gov (United States)

Suarez-Bertoa, R; Picquet-Varrault, B; Tamas, W; Pangui, E; Doussin, J-F

2012-11-20

Multifunctional organic nitrates are potential NO(x) reservoirs whose atmospheric chemistry is somewhat little known. They could play an important role in the spatial distribution of reactive nitrogen species and consequently in ozone formation and distribution in remote areas. In this work, the rate constants for the reaction with OH radical and the photolysis frequencies of α-nitrooxyacetone, 3-nitrooxy-2-butanone, and 3-methyl-3-nitrooxy-2-butanone have been determined at room temperature at 1000 mbar total pressure of synthetic air. The rate constants for the OH oxidation were measured using the relative rate technique, with methanol as reference compound. The following rate constants were obtained for the reaction with OH: k(OH) = (6.7 ± 2.5) × 10(-13) cm(3) molecule(-1) s(-1) for α-nitrooxyacetone, (10.6 ± 4.1) × 10(-13) cm(3) molecule(-1) s(-1) for 3-nitrooxy-2-butanone, and (2.6 ± 0.9) × 10(-13) cm(3) molecule(-1) s(-1) for 3-methyl-3-nitrooxy-2-butanone. The corresponding photolysis frequencies extrapolated to typical atmospheric conditions for July first at noon at 40° latitude North were (4.8 ± 0.3) × 10(-5) s(-1), (5.7 ± 0.3) × 10(-5) s(-1), and (7.4 ± 0.2) × 10(-5) s(-1), respectively. The data show that photolysis is a major atmospheric sink for these organic nitrates.

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

KAUST Repository

Badra, Jihad; Farooq, Aamir

2015-01-01

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

Constant resolution of time-dependent Hartree--Fock phase ambiguity

International Nuclear Information System (INIS)

Lichtner, P.C.; Griffin, J.J.; Schultheis, H.; Schultheis, R.; Volkov, A.B.

1978-01-01

The customary time-dependent Hartree--Fock problem is shown to be ambiguous up to an arbitrary function of time additive to H/sub HF/, and, consequently, up to an arbitrary time-dependent phase for the solution, PHI(t). The ''constant'' (H)'' phase is proposed as the best resolution of this ambiguity. It leads to the following attractive features: (a) the time-dependent Hartree--Fock (TDHF) Hamiltonian, H/sub HF/, becomes a quantity whose expectation value is equal to the average energy and, hence, constant in time; (b) eigenstates described exactly by determinants, have time-dependent Hartree--Fock solutions identical with the exact time-dependent solutions; (c) among all possible TDHF solutions this choice minimizes the norm of the quantity (H--i dirac constant delta/delta t) operating on the ket PHI, and guarantees optimal time evolution over an infinitesimal period; (d) this choice corresponds both to the stationary value of the absolute difference between (H) and (i dirac constant delta/delta t) and simultaneously to its absolute minimal value with respect to choice of the time-dependent phase. The source of the ambiguity is discussed. It lies in the time-dependent generalization of the freedom to transform unitarily among the single-particle states of a determinant at the (physically irrelevant for stationary states) cost of altering only a factor of unit magnitude

Extension of the master sintering curve for constant heating rate modeling

Science.gov (United States)

McCoy, Tammy Michelle

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

Absolute measurement of the desintegration rate of 137 Cs by 4Π (BS) e--X coincidence method

International Nuclear Information System (INIS)

Koskinas, M.F.; Dias, M.S.

1989-01-01

The method developed by the Nuclear Metrology Laboratory for the absolute measurement of the desintegration rate of 137 Cs by 4Π(BS)e - -X is described. The conversion electron are measured by a pair of surface barrier detectors with 200mm 2 of active area and 1000μm of depletion depth. The X-rays are measured by two 50.8mm diameter and 1.0mm thick NaI (Tl) scintillation counters. (author) [pt

Some chaotic behaviors in a MCA learning algorithm with a constant learning rate

International Nuclear Information System (INIS)

Lv Jiancheng; Yi Zhang

2007-01-01

Douglas's minor component analysis algorithm with a constant learning rate has both stability and chaotic dynamical behavior under some conditions. The paper explores such dynamical behavior of this algorithm. Certain stability and chaos of this algorithm are derived. Waveform plots, Lyapunov exponents and bifurcation diagrams are presented to illustrate the existence of chaotic behavior

Accelerated Testing Methodology in Constant Stress-Rate Testing for Advanced Structural Ceramics: A Preloading Technique

Science.gov (United States)

Choi, Sung R.; Gyekenyesi, John P.; Huebert, Dean; Bartlett, Allen; Choi, Han-Ho

2001-01-01

Preloading technique was used as a means of an accelerated testing methodology in constant stress-rate (dynamic fatigue) testing for two different brittle materials. The theory developed previously for fatigue strength as a function of preload was further verified through extensive constant stress-rate testing for glass-ceramic and CRT glass in room temperature distilled water. The preloading technique was also used in this study to identify the prevailing failure mechanisms at elevated temperatures, particularly at lower test rates in which a series of mechanisms would be associated simultaneously with material failure, resulting in significant strength increase or decrease. Two different advanced ceramics including SiC whisker-reinforced composite silicon nitride and 96 wt% alumina were used at elevated temperatures. It was found that the preloading technique can be used as an additional tool to pinpoint the dominant failure mechanism that is associated with such a phenomenon of considerable strength increase or decrease.

Noninvasive optical quantification of absolute blood flow, blood oxygenation, and oxygen consumption rate in exercising skeletal muscle

Science.gov (United States)

Gurley, Katelyn; Shang, Yu; Yu, Guoqiang

2012-07-01

This study investigates a method using novel hybrid diffuse optical spectroscopies [near-infrared spectroscopy (NIRS) and diffuse correlation spectroscopy (DCS)] to obtain continuous, noninvasive measurement of absolute blood flow (BF), blood oxygenation, and oxygen consumption rate (\\Vdot O2) in exercising skeletal muscle. Healthy subjects (n=9) performed a handgrip exercise to increase BF and \\Vdot O2 in forearm flexor muscles, while a hybrid optical probe on the skin surface directly monitored oxy-, deoxy-, and total hemoglobin concentrations ([HbO2], [Hb], and THC), tissue oxygen saturation (StO2), relative BF (rBF), and relative oxygen consumption rate (r\\Vdot O2). The rBF and r\\Vdot O2 signals were calibrated with absolute baseline BF and \\Vdot O2 obtained through venous and arterial occlusions, respectively. Known problems with muscle-fiber motion artifacts in optical measurements during exercise were mitigated using a novel gating algorithm that determined muscle contraction status based on control signals from a dynamometer. Results were consistent with previous findings in the literature. This study supports the application of NIRS/DCS technology to quantitatively evaluate hemodynamic and metabolic parameters in exercising skeletal muscle and holds promise for improving diagnosis and treatment evaluation for patients suffering from diseases affecting skeletal muscle and advancing fundamental understanding of muscle and exercise physiology.

Rate constant computation on some elementary reactions of Hg during combustion

Energy Technology Data Exchange (ETDEWEB)

Wang, Qing; Yang, Bo-wen; Bai, Jing-ru [Northeast Dianli Univ., Jilin (China). Inst. of Energy and Power Engineering

2013-07-01

The geometry optimizations of reactants, products and transition states were made by the quantum chemistry MP2 method at the SDD basis function level for Hg, and 6-311++G(3df, 3pd) for others. The properties of stable minimums were validated by vibration frequencies analysis. Furthermore, the microcosmic chemical reaction mechanisms of reactions were investigated by ab initio calculations of quantum chemistry. On the basis of the geometry optimization, reaction rate constants within 298-2,000 K are calculated neither from experimental data nor by estimated, but directly from Quantum Chemistry software-Khimera.

Absolute El, {delta}K= O Transition Rates in Odd-Mass Pm and Eu-Isotopes

Energy Technology Data Exchange (ETDEWEB)

Malmskog, S G

1967-06-15

The half life of the 5/2{sup -} (532) intrinsic state in {sup 151}Pm, {sup 153}Eu and {sup 155}Eu has been determined by the delayed coincidence method. The absolute E1, {delta}K = 0 transition probabilities between the 5/2{sup -} (532) -> 5/2{sup +} (413) intrinsic states have been deduced and compared with theoretical predictions, using the Nilsson model as a starting point. The effect on the predicted transition probabilities obtained by adding pairing correlations and Coriolis coupling have also been studied. It has been found that the experimental transition rates, which are still strongly enhanced, cannot be explained by these contributions alone. It is therefore suggested that collective dipole contributions like those arising through the octupole excitations are of importance.

Characterization of creatine guanidinium proton exchange by water-exchange (WEX) spectroscopy for absolute-pH CEST imaging in vitro.

Science.gov (United States)

Goerke, Steffen; Zaiss, Moritz; Bachert, Peter

2014-05-01

Chemical exchange saturation transfer (CEST) enables indirect detection of small metabolites in tissue by MR imaging. To optimize and interpret creatine-CEST imaging we characterized the dependence of the exchange-rate constant k(sw) of creatine guanidinium protons in aqueous creatine solutions as a function of pH and temperature T in vitro. Model solutions in the low pH range (pH = 5-6.4) were measured by means of water-exchange (WEX)-filtered ¹H NMR spectroscopy on a 3 T whole-body MR tomograph. An extension of the Arrhenius equation with effective base-catalyzed Arrhenius parameters yielded a general expression for k(sw) (pH, T). The defining parameters were identified as the effective base-catalyzed rate constant k(b,eff) (298.15 K) = (3.009 ± 0.16) × 10⁹  Hz l/mol and the effective activation energy E(A,b,eff)  = (32.27 ± 7.43) kJ/mol at a buffer concentration of c(buffer)  = (1/15) M. As expected, a strong dependence of k(sw) on temperature was observed. The extrapolation of the exchange-rate constant to in vivo conditions (pH = 7.1, T = 37 °C) led to the value of the exchange-rate constant k(sw)  = 1499 Hz. With the explicit function k(sw) (pH, T) available, absolute-pH CEST imaging could be realized and experimentally verified in vitro. By means of our calibration method it is possible to adjust the guanidinium proton exchange-rate constant k(sw) to any desired value by preparing creatine model solutions with a specific pH and temperature. Copyright © 2014 John Wiley & Sons, Ltd.

Piezooptical constants of Rochelle salt crystals

OpenAIRE

V.Yo. Stadnyk; M.O. Romanyuk; V.Yu. Kurlyak; V.F.Vachulovych

2000-01-01

The influence of uniaxial mechanical pressure applied along the principal axes and the corresponding bisectors on the birefringent properties of Rochelle salt (RS) crystals are studied. The temperature (77-300 K) and spectral (300-700 nm) dependencies of the effective and absolute piezooptical constants of the RS crystals are calculated. The intercept of dispersion curves of is revealed in the region of the birefringence sign inversion. This testifies that the anizotropy of the piezooptical ...

Ion-neutral gas reactions in a collision/reaction cell in inductively coupled plasma mass spectrometry: Correlation of ion signal decrease to kinetic rate constants

Energy Technology Data Exchange (ETDEWEB)

Gray, Patrick J. [Trace Element Research Laboratory, School of Earth Sciences, The Ohio State University, 125 S. Oval Mall, Columbus, OH 43210 (United States); Department of Chemistry, The Ohio State University, 120 18th Avenue, Columbus, OH 43210 (United States); Olesik, John W., E-mail: olesik.2@osu.edu [Trace Element Research Laboratory, School of Earth Sciences, The Ohio State University, 125 S. Oval Mall, Columbus, OH 43210 (United States)

2015-03-01

Reaction gas flow rate dependent Ar{sub 2}{sup +} and Ar{sup +} signals are correlated to fundamental kinetic rate coefficients. A simple calculation, assuming that gas exits the reaction cell due only to effusion, is described to estimate the gas pressure in the reaction cell. The value of the product of the kinetic rate constant and the ion residence time in the reaction cell can be determined from experimental measurement of the decrease in an ion signal as a function of reaction gas flow rate. New kinetic rate constants are determined for the reaction of CH{sub 3}F with Ar{sup +} and Ar{sub 2}{sup +}. - Highlights: • How to determine pressure and the product of the kinetic rate constant times the ion residence time in reaction cell • Relate measured ICP-DRC-MS signals versus gas flow rate to kinetic rate constants measured previously using SIFT-MS • Describe how to determine previously unmeasured kinetic rate constants using ICP-DRC-MS.

Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion.

Science.gov (United States)

Soudackov, Alexander V; Hammes-Schiffer, Sharon

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

Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

International Nuclear Information System (INIS)

Soudackov, Alexander V.; Hammes-Schiffer, Sharon

2015-01-01

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

The dissolution rate constant of magnetite in water at different temperatures and neutral or ammoniated chemistry conditions

International Nuclear Information System (INIS)

Mohajery, K.; Lister, D.H.

2012-01-01

In this study, the dissolution rate constants of magnetite were measured at various water chemistry conditions and different temperatures, corresponding to several feedwater conditions of water-cooled reactors. Sintered magnetite pellets were used as the dissolving material and these were mounted in a jet-impingement apparatus in a recirculating water loop. Exposures were carried out at temperatures of 25, 55 and 140 o C and pHs of neutral and 9.2 in which many FAC (Flow Accelerated Corrosion) studies have been conducted. Average dissolution rate constants were estimated by measuring the volume of lost material with a profilometry technique. The excellent correspondent between the calculated value of dissolution rate constant of 2.20 mm/s for the synthesized magnetite and 2.05 mm/s for the single crystal of magnetite at neutral condition shows that the particle removal from the synthesized pellets is not an obstruction in this technique. Also, good agreement between the values calculated in duplicated runs at neutral condition at room temperature supports the accuracy of the method. (author)

Absolute production rate measurements of nitric oxide by an atmospheric pressure plasma jet (APPJ)

International Nuclear Information System (INIS)

Pipa, A V; Bindemann, T; Foest, R; Kindel, E; Roepcke, J; Weltmann, K-D

2008-01-01

Tunable diode laser absorption spectroscopy (TDLAS) has been applied to measure the absolute production rate of NO molecules in the gas phase of an atmospheric pressure plasma jet (APPJ) operating at rf (13.56 MHz) in argon with small (up to 1%) admixtures of air. The resulting NO production rates were found to be in the range (0.1-80) x 10 -3 sccm or (0.05-35) x 10 18 molecules s -1 depending on the experimental conditions. Maximum rates were obtained at 0.2% air. For TDLAS measurements the APPJ was arranged inside an astigmatic multi-pass cell of Herriott type with 100 m absorption length. The insertion into a closed volume differs slightly from the normal, open operation with the jet propagating freely into air. Therefore, the measuring results are compared with optical emission of the open jet to verify equivalent experimental conditions. The dependence of the optical emission of NO (237 nm) on power and gas mixture has been measured. The similar shape of the dependence of absorption and emission signals gives evidence that the comparability of experimental conditions is sufficiently satisfied. It is concluded that the NO production rate of the APPJ in ambient air can be characterized using TDLAS and provides reliable results in spite of differing experimental conditions due to the set-up.

Estimation of Anaerobic Debromination Rate Constants of PBDE Pathways Using an Anaerobic Dehalogenation Model.

Science.gov (United States)

Karakas, Filiz; Imamoglu, Ipek

2017-04-01

This study aims to estimate anaerobic debromination rate constants (k m ) of PBDE pathways using previously reported laboratory soil data. k m values of pathways are estimated by modifying a previously developed model as Anaerobic Dehalogenation Model. Debromination activities published in the literature in terms of bromine substitutions as well as specific microorganisms and their combinations are used for identification of pathways. The range of estimated k m values is between 0.0003 and 0.0241 d -1 . The median and maximum of k m values are found to be comparable to the few available biologically confirmed rate constants published in the literature. The estimated k m values can be used as input to numerical fate and transport models for a better and more detailed investigation of the fate of individual PBDEs in contaminated sediments. Various remediation scenarios such as monitored natural attenuation or bioremediation with bioaugmentation can be handled in a more quantitative manner with the help of k m estimated in this study.

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

Science.gov (United States)

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

2013-10-01

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

Fast, Computer Supported Experimental Determination of Absolute Zero Temperature at School

Science.gov (United States)

Bogacz, Bogdan F.; Pedziwiatr, Antoni T.

2014-01-01

A simple and fast experimental method of determining absolute zero temperature is presented. Air gas thermometer coupled with pressure sensor and data acquisition system COACH is applied in a wide range of temperature. By constructing a pressure vs temperature plot for air under constant volume it is possible to obtain--by extrapolation to zero…

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...

Prediction of ozone tropospheric degradation rate constant of organic compounds by using artificial neural networks

International Nuclear Information System (INIS)

Fatemi, M.H.

2006-01-01

Ozone tropospheric degradation of organic compound is very important in environmental chemistry. The lifetime of organic chemicals in the atmosphere can be calculated from the knowledge of the rate constant of their reaction with free radicals such as OH and NO 3 or O 3 . In the present work, the rate constant for the tropospheric degradation of 137 organic compounds by reaction with ozone, the least widely and successfully modeled degradation process, are predicted by quantitative structure activity relationships modeling based on a variety of theoretical descriptors, which screened and selected by genetic algorithm variable subset selection procedure. These descriptors which can be used as inputs for generated artificial neural networks are; HOMO-LUMO gap, number of double bonds, number of single bonds, maximum net charge on C atom, minimum (>0.1) bond order of C atom and Minimum e-e repulsion of H atom. After generation, optimization and training of artificial neural network, network was used for the prediction of log KO 3 for the validation set. The root mean square error for the neural network calculated log KO 3 for training, prediction and validation set are 0.357, 0.460 and 0.481, respectively, which are smaller than those obtained by multiple linear regressions model (1.217, 0.870 and 0.968, respectively). Results obtained reveal the reliability and good predictivity of neural network model for the prediction of ozone tropospheric degradations rate constant of organic compounds

Absolute disintegration rate and 320 keV {gamma}-ray emission probability of {sup 51}Cr

Energy Technology Data Exchange (ETDEWEB)

Almeida, M.C.M. de [Laboratorio Nacional de Metrologia das Radiacoes Ionizantes /Instituto de Radioprotecao e Dosimetria (LNMRI/ IRD), Avenida Salvador Allende, s/no. Recreio-Rio de Janeiro, CEP 22780-160 (Brazil)], E-mail: candida@ird.gov.br; Iwahara, A.; Poledna, R.; Silva, C.J. da; Delgado, J.U. [Laboratorio Nacional de Metrologia das Radiacoes Ionizantes /Instituto de Radioprotecao e Dosimetria (LNMRI/ IRD), Avenida Salvador Allende, s/no. Recreio-Rio de Janeiro, CEP 22780-160 (Brazil)

2007-09-21

This work describes the procedures for determining absolutely the {sup 51}Cr disintegration rate by using the 4{pi}{beta}-{gamma} coincidence and anti-coincidence counting and the sum-peak methods. A 4''x4''-NaI(Tl) scintillation detector was used in the {gamma}- channel of the 4{pi}{beta}-{gamma} coincidence system for {gamma}-ray counting. In the {beta}-channel, a 4{pi} gas flow proportional counter was used for counting of characteristic X-rays and Auger electrons originating from the electron capture events of the {sup 51}Cr decay scheme. Gamma spectrometry measurements by high-pure planar and coaxial germanium detectors were performed in the sum-peak method and in the determination of the 320 keV {gamma}-emission probability of {sup 51}Cr. This latter determined value agrees with the recent values found in the literature, confirming the reliability of the three methods used in this work for the disintegration rate measurements.

Estimation in adults of the glomerular filtration rate in [99mTc] DTPA renography - the rate constant method

International Nuclear Information System (INIS)

Carlsen, Ove

2004-01-01

The purpose of this study was to design an alternative and robust method for estimation of glomerular filtration rate (GFR) in [ 99 mTc]-diethylenetriaminepentaacetic acid ([ 99 mTc] -DTPA renography with a reliability not significantly lower than that of the conventional Gates' method. Methods: The method is based on renographies lasting 40 min in which regions of interest (ROIs) are manually created over selected parts of certain blood pools (e.g. heart, lungs, spleen, and liver). For each ROI the corresponding time-activity curve (TAC) was generated, decay corrected and exposed to a monoexponential fit in the time interval 10 to 40 min postinjection. The rate constant in min-1 of the monoexponential fit was denoted BETA. Following an iterative procedure comprising usually 5-10 manually created ROIs, the monoexponential fit with the maximum rate constant (BETA max ) was used for estimation of GFR. Results: In a patient material of 54 adult subjects in whom GFR was determined with multiple or one sample techniques with [ 51 Cr]-ethylenediaminetetraacetic acid ([ 51 Cr]-EDTA) the regression curve of standard GFR (GFR std ) (i.e. GFR adjusted to 1.73 m 2 body surface area) showed a close, non-linear relationship with BETA max with a correlation coefficient of 95%. The standard errors of estimate (SEE) were 6.6, 10.6 and 16.8 for GFR std equal to 30, 60, and 120 ml/(min .73 m 2 ), respectively. The corresponding SEE values for almost the same patient material using Gates' method were 8.4, 11.9, and 16.8 ml/(min 1.73 m 2 ). Conclusions: The alternative rate constant method yields estimates of GFR std with SEE values equal to or slightly smaller than in Gates' method. The two methods provide statistically uncorrelated estimates of GFR std . Therefore, pooled estimates of GFR std can be calculated with SEE values approximately 1.41 times smaller than those mentioned above. The reliabilities of the pooled estimate of GFR std separately and of the multiple samples method

Addition and spin exchange rate constants by longitudinal field μSR: the Mu + NO reaction

International Nuclear Information System (INIS)

Senba, Masayoshi; Gonzalez, A.C.; Kempton, J.R.; Arseneau, D.J.; Pan, J.J.; Tempelmann, A.; Fleming, D.G.

1991-01-01

The addition reaction Mu + NO + M → MuNO + M and the spin exchange reaction Mu(↑) + NO(↓)→Mu(↓)+NO(↑) have been measured by longitudinal field μSR at room temperature in the presence of up to 58 atm of N 2 as inert collider. The pressure dependence of the longitudinal relaxation rate due to the addition reaction (λ c ) demonstrates that the system is still in the low pressure regime in this pressure range. The corresponding termolecular rate constant has been determined as k 0.Mu =(1.10±0.25)x10 -32 cm 6 molecules -2 s -1 , almost 4 times smaller than the corresponding H atom reaction k 0,H =3.90x10 -32 cm 6 molecules -2 s -1 . The average value of the spin exchange rate constants in the 2.5-58 atm pressure range, k SE = (3.16±0.06)x10 -10 cm 3 molecule -1 s -1 , is in good agreement with previous values obtained by transverse field μSR. (orig.)

Rate constants for a mechanism including intermediates in the interconversion of ternary complexes by horse liver alcohol dehydrogenase

International Nuclear Information System (INIS)

Sekhar, V.C.; Plapp, B.V.

1990-01-01

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 D 2 O, 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

Determination of subjective similarity for pairs of masses and pairs of clustered microcalcifications on mammograms: Comparison of similarity ranking scores and absolute similarity ratings

International Nuclear Information System (INIS)

Muramatsu, Chisako; Li Qiang; Schmidt, Robert A.; Shiraishi, Junji; Suzuki, Kenji; Newstead, Gillian M.; Doi, Kunio

2007-01-01

The presentation of images that are similar to that of an unknown lesion seen on a mammogram may be helpful for radiologists to correctly diagnose that lesion. For similar images to be useful, they must be quite similar from the radiologists' point of view. We have been trying to quantify the radiologists' impression of similarity for pairs of lesions and to establish a ''gold standard'' for development and evaluation of a computerized scheme for selecting such similar images. However, it is considered difficult to reliably and accurately determine similarity ratings, because they are subjective. In this study, we compared the subjective similarities obtained by two different methods, an absolute rating method and a 2-alternative forced-choice (2AFC) method, to demonstrate that reliable similarity ratings can be determined by the responses of a group of radiologists. The absolute similarity ratings were previously obtained for pairs of masses and pairs of microcalcifications from five and nine radiologists, respectively. In this study, similarity ranking scores for eight pairs of masses and eight pairs of microcalcifications were determined by use of the 2AFC method. In the first session, the eight pairs of masses and eight pairs of microcalcifications were grouped and compared separately for determining the similarity ranking scores. In the second session, another similarity ranking score was determined by use of mixed pairs, i.e., by comparison of the similarity of a mass pair with that of a calcification pair. Four pairs of masses and four pairs of microcalcifications were grouped together to create two sets of eight pairs. The average absolute similarity ratings and the average similarity ranking scores showed very good correlations in the first study (Pearson's correlation coefficients: 0.94 and 0.98 for masses and microcalcifications, respectively). Moreover, in the second study, the correlations between the absolute ratings and the ranking scores were also

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

OpenAIRE

Youhua Chen

2014-01-01

In this brief report, alternative time-varying diversification rate models were fitted onto the phylogeny of global amphibians by considering one-constant-rate (OCR), one-continuous-shift (OCS) and multiplediscrete- shifts (MDS) situations. The OCS diversification model was rejected by γ statistic (γ=-5.556, p⁄ 0.001), implying the existence of shifting diversification rates for global amphibian phylogeny. Through model selection, MDS diversification model outperformed OCS and OCR...

Absolute risk, absolute risk reduction and relative risk

Directory of Open Access Journals (Sweden)

Jose Andres Calvache

2012-12-01

Full Text Available This article illustrates the epidemiological concepts of absolute risk, absolute risk reduction and relative risk through a clinical example. In addition, it emphasizes the usefulness of these concepts in clinical practice, clinical research and health decision-making process.

Ozonation of norfloxacin and levofloxacin in water: Specific reaction rate constants and defluorination reaction.

Science.gov (United States)

Ling, Wencui; Ben, Weiwei; Xu, Ke; Zhang, Yu; Yang, Min; Qiang, Zhimin

2018-03-01

The degradation kinetics and mechanism of two typical fluoroquinolones (FQs), norfloxacin (NF) and levofloxacin (LOF), by ozone in water were investigated. Semi-continuous mode and competition kinetics mode experiments were conducted to determine the reaction rate constants of target FQs with ozone and OH, separately. Results indicate that both NF and LOF were highly reactive toward ozone, and the reactivity was strongly impacted by the solution pH. The specific reaction rate constants of the diprotonated, monoprotonated and deprotonated species were determined to be 7.20 × 10 2 , 8.59 × 10 3 , 4.54 × 10 5  M -1  s -1 respectively for NF and 1.30 × 10 3 , 1.40 × 10 4 , 1.33 × 10 6  M -1  s -1 respectively for LOF. The reaction rate constants of target FQs toward OH were measured to be (4.81-7.41) × 10 9  M -1  s -1 in the pH range of 6.3-8.3. Furthermore, NF was selected as a model compound to clarify the degradation pathways, with a particular focus on the defluorination reaction. The significant release of F - ions and the formation of three F-free organic byproducts indicated that defluorination was a prevalent pathway in ozonation of FQs, while six F-containing organic byproducts indicated that ozone also attacked the piperazinyl and quinolone moieties. Escherichia coli growth inhibition tests revealed that ozonation could effectively eliminate the antibacterial activity of target FQ solutions, and the residual antibacterial activity had a negative linear correlation with the released F - concentration. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

International Nuclear Information System (INIS)

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

2012-01-01

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. - Highlights: ► Photoemission electron attachment ion mobility spectrometry (PE-EA-IMS) was developed to study electron attachment reaction. ► The rate constants of electron attachment to CCl 4 and CHCl 3 were determined. ► The present experimental results are in good agreement with the previously reported data.

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

Science.gov (United States)

Sattar, Simeen

2011-01-01

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

Spin-rotation and NMR shielding constants in HCl

Energy Technology Data Exchange (ETDEWEB)

Jaszuński, Michał, E-mail: michal.jaszunski@icho.edu.pl [Institute of Organic Chemistry, Polish Academy of Sciences, 01-224 Warszawa, Kasprzaka 44 (Poland); Repisky, Michal; Demissie, Taye B.; Komorovsky, Stanislav; Malkin, Elena; Ruud, Kenneth [Centre for Theoretical and Computational Chemistry, University of Tromsø—The Arctic University of Norway, N-9037 Tromsø (Norway); Garbacz, Piotr; Jackowski, Karol; Makulski, Włodzimierz [Laboratory of NMR Spectroscopy, Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw (Poland)

2013-12-21

The spin-rotation and nuclear magnetic shielding constants are analysed for both nuclei in the HCl molecule. Nonrelativistic ab initio calculations at the CCSD(T) level of approximation show that it is essential to include relativistic effects to obtain spin-rotation constants consistent with accurate experimental data. Our best estimates for the spin-rotation constants of {sup 1}H{sup 35}Cl are C{sub Cl}  = −53.914 kHz and C{sub H}  = 42.672 kHz (for the lowest rovibrational level). For the chlorine shielding constant, the ab initio value computed including the relativistic corrections, σ(Cl) = 976.202 ppm, provides a new absolute shielding scale; for hydrogen we find σ(H) = 31.403 ppm (both at 300 K). Combining the theoretical results with our new gas-phase NMR experimental data allows us to improve the accuracy of the magnetic dipole moments of both chlorine isotopes. For the hydrogen shielding constant, including relativistic effects yields better agreement between experimental and computed values.

Spin-rotation and NMR shielding constants in HCl

International Nuclear Information System (INIS)

Jaszuński, Michał; Repisky, Michal; Demissie, Taye B.; Komorovsky, Stanislav; Malkin, Elena; Ruud, Kenneth; Garbacz, Piotr; Jackowski, Karol; Makulski, Włodzimierz

2013-01-01

The spin-rotation and nuclear magnetic shielding constants are analysed for both nuclei in the HCl molecule. Nonrelativistic ab initio calculations at the CCSD(T) level of approximation show that it is essential to include relativistic effects to obtain spin-rotation constants consistent with accurate experimental data. Our best estimates for the spin-rotation constants of 1 H 35 Cl are C Cl   = −53.914 kHz and C H   = 42.672 kHz (for the lowest rovibrational level). For the chlorine shielding constant, the ab initio value computed including the relativistic corrections, σ(Cl) = 976.202 ppm, provides a new absolute shielding scale; for hydrogen we find σ(H) = 31.403 ppm (both at 300 K). Combining the theoretical results with our new gas-phase NMR experimental data allows us to improve the accuracy of the magnetic dipole moments of both chlorine isotopes. For the hydrogen shielding constant, including relativistic effects yields better agreement between experimental and computed values

Ab initio and relativistic DFT study of spin–rotation and NMR shielding constants in XF{sub 6} molecules, X = S, Se, Te, Mo, and W

Energy Technology Data Exchange (ETDEWEB)

Ruud, Kenneth [Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø—The Arctic University of Norway, N-9037 Tromsø (Norway); Demissie, Taye B. [Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø—The Arctic University of Norway, N-9037 Tromsø (Norway); Institute of Physical Chemistry, Polish Academy of Sciences, 01-224 Warszawa, Kasprzaka 44 (Poland); Jaszuński, Michał, E-mail: michal.jaszunski@icho.edu.pl [Institute of Organic Chemistry, Polish Academy of Sciences, 01-224 Warszawa, Kasprzaka 44 (Poland)

2014-05-21

We present an analysis of the spin–rotation and absolute shielding constants of XF{sub 6} molecules (X = S, Se, Te, Mo, W) based on ab initio coupled cluster and four-component relativistic density-functional theory (DFT) calculations. The results show that the relativistic contributions to the spin–rotation and shielding constants are large both for the heavy elements as well as for the fluorine nuclei. In most cases, incorporating the computed relativistic corrections significantly improves the agreement between our results and the well-established experimental values for the isotropic spin–rotation constants and their anisotropic components. This suggests that also for the other molecules, for which accurate and reliable experimental data are not available, reliable values of spin–rotation and absolute shielding constants were determined combining ab initio and relativistic DFT calculations. For the heavy nuclei, the breakdown of the relationship between the spin–rotation constant and the paramagnetic contribution to the shielding constant, due to relativistic effects, causes a significant error in the total absolute shielding constants.

First-Principles Computed Rate Constant for the O + O2 Isotopic Exchange Reaction Now Matches Experiment.

Science.gov (United States)

Guillon, Grégoire; Honvault, Pascal; Kochanov, Roman; Tyuterev, Vladimir

2018-04-19

We show, by performing exact time-independent quantum molecular scattering calculations, that the quality of the ground electronic state global potential energy surface appears to be of utmost importance in accurately obtaining even as strongly averaged quantities as kinetic rate constants. The oxygen isotope exchange reaction, 18 O + 32 O 2 , motivated by the understanding of a complex long-standing problem of isotopic ozone anomalies in the stratosphere and laboratory experiments, is explored in this context. The thermal rate constant for this key reaction is now in quantitative agreement with all experimental data available to date. A significant recent progress at the frontier of three research domains, advanced electronic structure calculations, ultrasensitive spectroscopy, and quantum scattering calculations, has therefore permitted a breakthrough in the theoretical modeling of this crucial collision process from first principles.

Rational functions with maximal radius of absolute monotonicity

KAUST Repository

Loczi, Lajos

2014-05-19

We study the radius of absolute monotonicity R of rational functions with numerator and denominator of degree s that approximate the exponential function to order p. Such functions arise in the application of implicit s-stage, order p Runge-Kutta methods for initial value problems and the radius of absolute monotonicity governs the numerical preservation of properties like positivity and maximum-norm contractivity. We construct a function with p=2 and R>2s, disproving a conjecture of van de Griend and Kraaijevanger. We determine the maximum attainable radius for functions in several one-parameter families of rational functions. Moreover, we prove earlier conjectured optimal radii in some families with 2 or 3 parameters via uniqueness arguments for systems of polynomial inequalities. Our results also prove the optimality of some strong stability preserving implicit and singly diagonally implicit Runge-Kutta methods. Whereas previous results in this area were primarily numerical, we give all constants as exact algebraic numbers.

Telling in-tune from out-of-tune: widespread evidence for implicit absolute intonation.

Science.gov (United States)

Van Hedger, Stephen C; Heald, Shannon L M; Huang, Alex; Rutstein, Brooke; Nusbaum, Howard C

2017-04-01

Absolute pitch (AP) is the rare ability to name or produce an isolated musical note without the aid of a reference note. One skill thought to be unique to AP possessors is the ability to provide absolute intonation judgments (e.g., classifying an isolated note as "in-tune" or "out-of-tune"). Recent work has suggested that absolute intonation perception among AP possessors is not crystallized in a critical period of development, but is dynamically maintained by the listening environment, in which the vast majority of Western music is tuned to a specific cultural standard. Given that all listeners of Western music are constantly exposed to this specific cultural tuning standard, our experiments address whether absolute intonation perception extends beyond AP possessors. We demonstrate that non-AP listeners are able to accurately judge the intonation of completely isolated notes. Both musicians and nonmusicians showed evidence for absolute intonation recognition when listening to familiar timbres (piano and violin). When testing unfamiliar timbres (triangle and inverted sine waves), only musicians showed weak evidence of absolute intonation recognition (Experiment 2). Overall, these results highlight a previously unknown similarity between AP and non-AP possessors' long-term musical note representations, including evidence of sensitivity to frequency.

Estimation of rate constants of PCB dechlorination reactions using an anaerobic dehalogenation model.

Science.gov (United States)

Karakas, Filiz; Imamoglu, Ipek

2017-02-15

This study aims to estimate anaerobic dechlorination rate constants (k m ) of reactions of individual PCB congeners using data from four laboratory microcosms set up using sediment from Baltimore Harbor. Pathway k m values are estimated by modifying a previously developed model as Anaerobic Dehalogenation Model (ADM) which can be applied to any halogenated hydrophobic organic (HOC). Improvements such as handling multiple dechlorination activities (DAs) and co-elution of congeners, incorporating constraints, using new goodness of fit evaluation led to an increase in accuracy, speed and flexibility of ADM. DAs published in the literature in terms of chlorine substitutions as well as specific microorganisms and their combinations are used for identification of pathways. The best fit explaining the congener pattern changes was found for pathways of Phylotype DEH10, which has the ability to remove doubly flanked chlorines in meta and para positions, para flanked chlorines in meta position. The range of estimated k m values is between 0.0001-0.133d -1 , the median of which is found to be comparable to the few available published biologically confirmed rate constants. Compound specific modelling studies such as that performed by ADM can enable monitoring and prediction of concentration changes as well as toxicity during bioremediation. Copyright © 2016 Elsevier B.V. All rights reserved.

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

International Nuclear Information System (INIS)

Matsuoka, Shingo; Nakamura, Hirone; Tamura, Takaaki; Fujii, Toshihiro.

1984-01-01

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 + + NO, N 2 + + NO, He + + N 2 , and SF 6 + e; the results were 5.8 x 10 -10 , 3.9 x 10 -10 , 1.20 x 10 -9 , and 2.1 x 10 -7 cm 3 s -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 6 . Nevertheless, the attachment rate could be determined by fitting the theoretical and experimantal curves in the limited region of the SF 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. (author)

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

Science.gov (United States)

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

2017-12-01

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

H0, q0 and the local velocity field. [Hubble and deceleration constants in Big Bang expansion

Science.gov (United States)

Sandage, A.; Tammann, G. A.

1982-01-01

An attempt is made to find a systematic deviation from linearity for distances that are under the control of the Virgo cluster, and to determine the value of the mean random motion about the systematic flow, in order to improve the measurement of the Hubble and the deceleration constants. The velocity-distance relation for large and intermediate distances is studied, and type I supernovae are calibrated relatively as distance indicators and absolutely to obtain a new value for the Hubble constant. Methods of determining the deceleration constant are assessed, including determination from direct measurement, mean luminosity density, virgocentric motion, and the time scale test. The very local velocity field is investigated, and a solution is preferred with a random peculiar radial velocity of very nearby field galaxies of 90-100 km/s, and a Virgocentric motion of the local group of 220 km/s, leading to an underlying expansion rate of 55, in satisfactory agreement with the global value.

NMR shielding and spin–rotation constants of {sup 175}LuX (X = {sup 19}F, {sup 35}Cl, {sup 79}Br, {sup 127}I) molecules

Energy Technology Data Exchange (ETDEWEB)

Demissie, Taye B. [Centre for Theoretical and Computational Chemistry Department of Chemistry, UiT – The Arctic University of Norway, N-9037 Tromsø (Norway)

2015-12-31

This presentation demonstrates the relativistic effects on the spin-rotation constants, absolute nuclear magnetic resonance (NMR) shielding constants and shielding spans of {sup 175}LuX (X = {sup 19}F, {sup 35}Cl, {sup 79}Br, {sup 127}I) molecules. The results are obtained from calculations performed using density functional theory (non-relativistic and four-component relativistic) and coupled-cluster calculations. The spin-rotation constants are compared with available experimental values. In most of the molecules studied, relativistic effects make an order of magnitude difference on the NMR absolute shielding constants.

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

Science.gov (United States)

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

Global Absolute Poverty: Behind the Veil of Dollars

NARCIS (Netherlands)

Moatsos, M.

2015-01-01

The global absolute poverty rates of the World Bank demonstrate a continued decline of poverty in developing countries between 1983 and 2012. However, the methodology applied to derive these results has received extensive criticism by scholars for requiring the application of PPP exchange rates and

Overspecification of colour, pattern, and size: Salience, absoluteness, and consistency

Directory of Open Access Journals (Sweden)

Sammie eTarenskeen

2015-11-01

Full Text Available The rates of overspecification of colour, pattern, and size are compared, to investigate how salience and absoluteness contribute to the production of overspecification. Colour and pattern are absolute attributes, whereas size is relative and less salient. Additionally, a tendency towards consistent responses is assessed. Using a within-participants design, we find similar rates of colour and pattern overspecification, which are both higher than the rate of size overspecification. Using a between-participants design, however, we find similar rates of pattern and size overspecification, which are both lower than the rate of colour overspecification. This indicates that although many speakers are more likely to include colour than pattern (probably because colour is more salient, they may also treat pattern like colour due to a tendency towards consistency. We find no increase in size overspecification when the salience of size is increased, suggesting that speakers are more likely to include absolute than relative attributes. However, we do find an increase in size overspecification when mentioning the attributes is triggered, which again shows that speakers tend refer in a consistent manner, and that there are circumstances in which even size overspecification is frequently produced.

Measuring the absolute disintegration rate of a radioactive gas with a moveable endplate discharge counter (MEP) and theoretical calculation of wall effect

International Nuclear Information System (INIS)

Jaffey, A.H.; Gray, J.; Bentley, W.C.; Lerner, J.L.

1987-09-01

A precision built moveable endplate Geiger-Mueller counter was used to measure the absolute disintegration rate of a beta-emitting radioactive gas. A Geiger-Mueller counter used for measuring gaseous radioactivity has 85 Kr (beta energy, 0.67 MeV). The wall effect calculation is readily extendable to other beta energies

An absolute- and relative-rate study of the gas-phase reaction of OH radicals and Cl atoms with n-alkyl nitrates

DEFF Research Database (Denmark)

Nielsen, O.J.; Sidebottom, H.W.; Donlon, M.

1991-01-01

combined with kinetic spectroscopy and a conventional photolytic relative-rate method. The Cl rate constants were measured using only the relative-rate method. Evidence is presented from the kinetic studies that reaction of OH radicals with alkyl nitrates may involve both addition and abstraction pathways...

Encasing the Absolutes

Directory of Open Access Journals (Sweden)

Uroš Martinčič

2014-05-01

Full Text Available The paper explores the issue of structure and case in English absolute constructions, whose subjects are deduced by several descriptive grammars as being in the nominative case due to its supposed neutrality in terms of register. This deduction is countered by systematic accounts presented within the framework of the Minimalist Program which relate the case of absolute constructions to specific grammatical factors. Each proposal is shown as an attempt of analysing absolute constructions as basic predication structures, either full clauses or small clauses. I argue in favour of the small clause approach due to its minimal reliance on transformations and unique stipulations. Furthermore, I propose that small clauses project a singular category, and show that the use of two cases in English absolute constructions can be accounted for if they are analysed as depictive phrases, possibly selected by prepositions. The case of the subject in absolutes is shown to be a result of syntactic and non-syntactic factors. I thus argue in accordance with Minimalist goals that syntactic case does not exist, attributing its role in absolutes to other mechanisms.

Rate constant of free electrons and holes recombination in thin films CdSe

International Nuclear Information System (INIS)

Radychev, N.A.; Novikov, G.F.

2006-01-01

Destruction kinetics of electrons generated in thin films CdSe by laser impulse (wave length is 337 nm, period of impulse - 8 nc) is studied by the method of microwave photoconductivity (36 GHz) at 295 K. Model of the process was suggested using the analysis of kinetics of photo-responses decay, and it allowed determination of rate constant of recombination of free electrons and holes in cadmium selenide - (4-6)x10 -11 cm 3 s -1 [ru

Propargyl Recombination: Estimation of the High Temperature, Low Pressure Rate Constant from Flame Measurements

DEFF Research Database (Denmark)

Rasmussen, Christian Lund; Skjøth-Rasmussen, Martin Skov; Jensen, Anker

2005-01-01

The most important cyclization reaction in hydrocarbon flames is probably recombination of propargyl radicals. This reaction may, depending on reaction conditions, form benzene, phenyl or fulvene, as well as a range of linear products. A number of rate measurements have been reported for C3H3 + C3H......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...

Limitations of absolute activity determination of I-125 sources

Energy Technology Data Exchange (ETDEWEB)

Pelled, O; German, U; Kol, R; Levinson, S; Weinstein, M; Laichter, Y [Israel Atomic Energy Commission, Beersheba (Israel). Nuclear Research Center-Negev; Alphasy, Z [Ben-Gurion Univ. of the Negev, Beersheba (Israel)

1996-12-01

A method for absolute determination of the activity of a I-125 source, based on the counting rate values of the 27 keV photons and the coincidence photon peak is given in the literature. It is based on the principle that if a radionuclide emits two photons in coincidence , a measurement of its disintegration rate in the photopeak and in the sum- peak can determinate it`s absolute activity. When using this method , the system calibration is simplified and parameters such as source geometry or source position relative to the detector have no significant influence. However, when the coincidence rate is very low, the application of this method is limited because of the statistics of the coincidence peak (authors).

Non Lyapunov stability of a constant spatially developing 2-D gas flow

Science.gov (United States)

Balint, Agneta M.; Balint, Stefan; Tanasie, Loredana

2017-01-01

Different types of stabilities (global, local) and instabilities (global absolute, local convective) of the constant spatially developing 2-D gas flow are analyzed in a particular phase space of continuously differentiable functions, endowed with the usual algebraic operations and the topology generated by the uniform convergence on the plane. For this purpose the Euler equations linearized at the constant flow are used. The Lyapunov stability analysis was presented in [1] and this paper is a continuation of [1].

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.

Absolute measurement of 85Sr

International Nuclear Information System (INIS)

Miyahara, Hiroshi; Watanabe, Tamaki

1978-01-01

An extension of 4πe.x-γ coincidence technique is described to measure the absolute disintegration rate of 85 Sr. This nuclide shows electron capture-gamma decay, and 514keV level of 85 Rb is a meta-stable state with half life of 0.958 μsec. Therefore, the conventional 4 πe.x-γ coincidence technique with about 1 μsec of resolution time can not be applied to this nuclide. To measure the absolute disintegration rate of this, the delayed 4 πe.x-γ coincidence technique with two different resolution time has been used. The disintegration rate was determined from four counting rates of electron-x ray, gamma ray and two coincidences, and the true disintegration rate could be obtained by extraporation of the electron-x ray detection efficiency to 1. Two resolution time appearing in the calculation formulas were determined from the chance coincidence between electron-x ray and delayed gamma ray signals. When the coincidence countings with three different resolution time were carried out by one coincidence circuit, the results calculated from all combinations did not agree each other. However, when the two coincidence circuits of the same type were used to fix the resolution time, a good coincidence absorption function was obtained and the disintegration rate was determined with accuracy of +- 0.5%. To evaluate the validity of the results the disintegration rates were measured by two NaI (Tl) scintillation detectors whose gamma-ray detection efficiency was previously determined and both results were agreed within accuracy of +- 0.5%. This method can be applied with nearly same accuracy for the beta-gamma decay nuclide possessing a meta-stable state of the half life below about 10 μsec. (auth.)

Absolute advantage

NARCIS (Netherlands)

J.G.M. van Marrewijk (Charles)

2008-01-01

textabstractA country is said to have an absolute advantage over another country in the production of a good or service if it can produce that good or service using fewer real resources. Equivalently, using the same inputs, the country can produce more output. The concept of absolute advantage can

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

International Nuclear Information System (INIS)

Xu, K.Y.

1989-01-01

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

Rate Constants for Reactions of Radiation-Produced Transients in Aqueous Solutions of Actinides

International Nuclear Information System (INIS)

Gordon, S.; Sullivan, J.C.; Ross, A.B.

1986-01-01

Rate constants have been critically compiled for reactions of ions of the actinides Am, Cf, Cm, Np, Pu, Th, and U, as well as the element Tc, in different oxidation states with various chemical species in aqueous solution. The reactants include products of the radiolysis of water (hydrated electrons, hydrogen atoms, hydroxyl radicals, hydrogen peroxide) and transient species derived from other solutes (e.g., carbonate radical). The data are useful in the estimation of migration properties of actinides, which are relevant to waste management studies

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

NARCIS (Netherlands)

Tang, Q.

2004-01-01

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

Rate constant for reaction of vitamin C with protein radicals in γ-irradiated aqueous albumin solution at 295K

International Nuclear Information System (INIS)

Miyazaki, Tetsuo; Yoshimura, Toru; Mita, Kazuya; Suzuki, Keiji; Watanabe, Masami

1995-01-01

When an aqueous solution of albumin (0.1 kg dm -3 ) is irradiated by γ-rays at 295 K, albumin radicals with a long lifetime are observed by ESR. The reaction of vitamin C with the albumin radicals has been studied at 295 K in the albumin solution, which is considered as a model of cells. The rate constant for the reaction of vitamin C with the albumin radicals was measured as 0.014 dm 3 mol -1 S -1 , which is much smaller than the reported constants (10 6 -10 10 dm 3 mol -1 s -1 ) for the reaction of vitamin C with radicals in a dilute aqueous solution. The small rate constant for the reaction of vitamin C is ascribed to the reaction in polymer coils in the albumin solution, since vitamin C and albumin radicals diffuse very slowly in the coils. (author)

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

Science.gov (United States)

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

2015-01-01

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

A photon spectrometric dose-rate constant determination for the Advantage™ Pd-103 brachytherapy source

OpenAIRE

Chen, Zhe Jay; Bongiorni, Paul; Nath, Ravinder

2010-01-01

Purpose: Although several dosimetric characterizations using Monte Carlo simulation and thermoluminescent dosimetry (TLD) have been reported for the new Advantage™ Pd-103 source (IsoAid, LLC, Port Richey, FL), no AAPM consensus value has been established for the dosimetric parameters of the source. The aim of this work was to perform an additional dose-rate constant (Λ) determination using a recently established photon spectrometry technique (PST) that is independent of the published TLD and ...

Pharmacokinetic evaluation of pamidronate after oral administration: a study on dose proportionality, absolute bioavailability, and effect of repeated administration

DEFF Research Database (Denmark)

Hyldstrup, Lars; Flesch, G; Hauffe, S A

1993-01-01

30 minutes at constant infusion rate. Repeated peroral doses (75 and 150 mg) were administered to 12 females (aged 51-70 years) for 10 consecutive days. Urinary excretion of pamidronate after peroral and i.v. administration was used for estimation of pamidronate absorption. Renal excretion...... of pamidronate ranged from 0.01% to 0.35% of dose, with mean values of 0.11, 0.16, and 0.18% for 75, 150, and 300 mg, respectively. After i.v. infusion, the renal excretion of pamidronate was 26-53% of the dose, lower than for other bisphosphonates. The absolute bioavailability was 0.31% (range 0.08-0.7%) after...

Constant Leverage And Constant Cost Of Capital: A Common Knowledge Half-Truth

Directory of Open Access Journals (Sweden)

Ignacio Vélez–Pareja

2008-04-01

In this document we show that for finite cash flows, Ke and hence WACC depend on the discount rate that is used to value the tax shield, TS and as expected, Ke and WACC are not constant with Kd as the discount rate for the tax shield, even if the leverage is constant. We illustrate this situation with a simple example. We analyze five methods: DCF using APV, FCF and traditional and general formulation for WACC, present value of CFE plus debt and Capital Cash Flow, CCF.

Basic study on relationship between estimated rate constants and noise in FDG kinetic analysis

International Nuclear Information System (INIS)

Kimura, Yuichi; Toyama, Hinako; Senda, Michio.

1996-01-01

For accurate estimation of the rate constants in 18 F-FDG dynamic study, the shape of the estimation function (Φ) 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 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 1 ≤0.15, 0.1≤k 2 ≤0.2 and 0.01≤k 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 18 F-FDG dynamic study were used to calculate the Φ. 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 Φ 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)

Constant strain accumulation rate between major earthquakes on the North Anatolian Fault.

Science.gov (United States)

Hussain, Ekbal; Wright, Tim J; Walters, Richard J; Bekaert, David P S; Lloyd, Ryan; Hooper, Andrew

2018-04-11

Earthquakes are caused by the release of tectonic strain accumulated between events. Recent advances in satellite geodesy mean we can now measure this interseismic strain accumulation with a high degree of accuracy. But it remains unclear how to interpret short-term geodetic observations, measured over decades, when estimating the seismic hazard of faults accumulating strain over centuries. Here, we show that strain accumulation rates calculated from geodetic measurements around a major transform fault are constant for its entire 250-year interseismic period, except in the ~10 years following an earthquake. The shear strain rate history requires a weak fault zone embedded within a strong lower crust with viscosity greater than ~10 20  Pa s. The results support the notion that short-term geodetic observations can directly contribute to long-term seismic hazard assessment and suggest that lower-crustal viscosities derived from postseismic studies are not representative of the lower crust at all spatial and temporal scales.

Alternative approach to estimate the hydrolysis rate constant of particulate material from batch data

International Nuclear Information System (INIS)

Koch, Konrad; Drewes, Jörg E.

2014-01-01

Highlights: • An alternative to the commonly used first-order approach is presented. • A relationship between k h and the 1% criterion of the VDI 4630 is deduced. • Equation is proposed to directly calculate k h without the need for data fitting. • Hydrolysis constant k h can then easily be read-off from a table. - Abstract: As anaerobic batch tests are easy to conduct, they are commonly used to assess the effects of different operational factors on the anaerobic digestion process. Hydrolysis of particulate material is often assumed to be the rate limiting step in anaerobic digestion. Its velocity is often estimated by data fitting from batch tests. In this study, a Monod-type alternative to the commonly used first-order approach is presented. The approach was adapted from balancing a continuously stirred-tank reactor and better accommodates the fact that even after a long incubation time, some of the methane potential of the substrate remains untapped in the digestate. In addition, an equation is proposed to directly calculate the hydrolysis constant from the time when the daily gas production is less than 1% of the total gas production. The hydrolysis constant can then easily be read-off from a table when the batch test duration is known

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

Science.gov (United States)

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

2015-07-01

Reaction with hydroxyl radicals (OH) is the major pathway for removal of cyclic volatile methyl siloxanes (cVMS) from air. We present new measurements of second-order rate constants for reactions of the cVMS octamethylcyclotetrasiloxane (D 4 ), decamethylcyclopentasiloxane (D 5 ), and dodecamethylcyclohexasiloxane (D 6 ) with OH determined at temperatures between 313 and 353 K. Our measurements were made using the method of relative rates with cyclohexane as a reference substance and were conducted in a 140-mL gas-phase reaction chamber with online mass spectrometry analysis. When extrapolated to 298 K, our measured reaction rate constants of D 4 and D 5 with the OH radical are 1.9 × 10 -12 (95% confidence interval (CI): (1.7-2.2) × 10 -12 ) and 2.6 × 10 -12 (CI: (2.3-2.9) × 10 -12 ) cm 3 molecule -1 s -1 , respectively, which are 1.9× and 1.7× faster than previous measurements. Our measured rate constant for D 6 is 2.8 × 10 -12 (CI: (2.5-3.2) × 10 -12 ) cm 3 molecule -1 s -1 and to our knowledge there are no comparable laboratory measurements in the literature. Reaction rates for D 5 were 33% higher than for D 4 (CI: 30-37%), whereas the rates for D 6 were only 8% higher than for D 5 (CI: 5-10%). The activation energies of the reactions of D 4 , D 5 , and D 6 with OH were not statistically different and had a value of 4300 ± 2800 J/mol.

Absolutely relative or relatively absolute: violations of value invariance in human decision making.

Science.gov (United States)

Teodorescu, Andrei R; Moran, Rani; Usher, Marius

2016-02-01

Making decisions based on relative rather than absolute information processing is tied to choice optimality via the accumulation of evidence differences and to canonical neural processing via accumulation of evidence ratios. These theoretical frameworks predict invariance of decision latencies to absolute intensities that maintain differences and ratios, respectively. While information about the absolute values of the choice alternatives is not necessary for choosing the best alternative, it may nevertheless hold valuable information about the context of the decision. To test the sensitivity of human decision making to absolute values, we manipulated the intensities of brightness stimuli pairs while preserving either their differences or their ratios. Although asked to choose the brighter alternative relative to the other, participants responded faster to higher absolute values. Thus, our results provide empirical evidence for human sensitivity to task irrelevant absolute values indicating a hard-wired mechanism that precedes executive control. Computational investigations of several modelling architectures reveal two alternative accounts for this phenomenon, which combine absolute and relative processing. One account involves accumulation of differences with activation dependent processing noise and the other emerges from accumulation of absolute values subject to the temporal dynamics of lateral inhibition. The potential adaptive role of such choice mechanisms is discussed.

SU-G-201-06: Directional Low-Dose Rate Brachytherapy: Determination of the TG-43 Dose-Rate Constant Analog for a New Pd-103 Source

Energy Technology Data Exchange (ETDEWEB)

Aima, M; Culberson, W; Hammer, C; Micka, J; DeWerd, L [Department of Medical Physics, School of Medicine and Public Health, University of Wisconsin-Madison, Madison, WI (United States)

2016-06-15

Purpose: The aim of this work is to determine the TG-43 dose-rate constant analog for a new directional low-dose rate brachytherapy source based on experimental methods and comparison to Monte Carlo simulations. The CivaSheet™ is a new commercially available planar source array comprised of a variable number of discrete directional source elements called “CivaDots”. Given the directional nature and non-conventional design of the source, modifications to the AAPM TG-43 protocol for dosimetry are required. As a result, various parameters of the TG-43 dosimetric formalism have to be adapted to accommodate this source. This work focuses on the dose-rate constant analog determination for a CivaDot. Methods: Dose to water measurements of the CivaDot were performed in a polymethyl methacrylate phantom (20×20×12 cm{sup 3}) using thermoluminescent dosimeters (TLDs) and Gafchromic EBT3 film. The source was placed in the center of the phantom, and nine TLD micro-cubes were irradiated along its central axis at a distance of 1 cm. For the film measurements, the TLDs were substituted by a (3×3) cm{sup 2} EBT3 film. Primary air-kerma strength measurements of the source were performed using a variable-aperture free-air chamber. Finally, the source was modeled using the Monte Carlo N-Particle Transport Code 6. Results: Dose-rate constant analog observed for a total of eight CivaDots using TLDs and five CivaDots using EBT3 film was within ±7.0% and ±2.9% of the Monte Carlo predicted value respectively. The average difference observed was −4.8% and −0.1% with a standard deviation of 1.7% and 2.1% for the TLD and the film measurements respectively, which are both within the comparison uncertainty. Conclusion: A preliminary investigation to determine the doserate constant analog for a CivaDot was conducted successfully with good agreement between experimental and Monte Carlo based methods. This work will aid in the eventual realization of a clinically-viable dosimetric

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...... that the entanglement density M/Me of the solution coincided with that of PS 290k melt (M = 290k). After the elongation at the Rouse-based Weissenberg number Wi(R) ~ 3 up to the Hencky strain of 3, the short time stress relaxation of the solution was accelerated by a factor of ~4, which was less significant compared...... and the lack of monotonic thinning observed for the semidilute solutions. Results for less concentrated solutions will be also presented on site....

Subjective evaluation of HDTV stereoscopic videos in IPTV scenarios using absolute category rating

Science.gov (United States)

Wang, K.; Barkowsky, M.; Cousseau, R.; Brunnström, K.; Olsson, R.; Le Callet, P.; Sjöström, M.

2011-03-01

Broadcasting of high definition (HD) stereobased 3D (S3D) TV are planned, or has already begun, in Europe, the US, and Japan. Specific data processing operations such as compression and temporal and spatial resampling are commonly used tools for saving network bandwidth when IPTV is the distribution form, as this results in more efficient recording and transmission of 3DTV signals, however at the same time it inevitably brings quality degradations to the processed video. This paper investigated observers quality judgments of state of the art video coding schemes (simulcast H.264/AVC or H.264/MVC), with or without added temporal and spatial resolution reduction of S3D videos, by subjective experiments using the Absolute Category Rating method (ACR) method. The results showed that a certain spatial resolution reduction working together with high quality video compressing was the most bandwidth efficient way of processing video data when the required video quality is to be judged as "good" quality. As the subjective experiment was performed in two different laboratories in two different countries in parallel, a detailed analysis of the interlab differences was performed.

A photon spectrometric dose-rate constant determination for the Advantage Pd-103 brachytherapy source

International Nuclear Information System (INIS)

Chen, Zhe Jay; Bongiorni, Paul; Nath, Ravinder

2010-01-01

Purpose: Although several dosimetric characterizations using Monte Carlo simulation and thermoluminescent dosimetry (TLD) have been reported for the new Advantage Pd-103 source (IsoAid, LLC, Port Richey, FL), no AAPM consensus value has been established for the dosimetric parameters of the source. The aim of this work was to perform an additional dose-rate constant (Λ) determination using a recently established photon spectrometry technique (PST) that is independent of the published TLD and Monte Carlo techniques. Methods: Three Model IAPD-103A Advantage Pd-103 sources were used in this study. The relative photon energy spectrum emitted by each source along the transverse axis was measured using a high-resolution germanium spectrometer designed for low-energy photons. For each source, the dose-rate constant was determined from its emitted energy spectrum. The PST-determined dose-rate constant ( PST Λ) was then compared to those determined by TLD ( TLD Λ) and Monte Carlo ( MC Λ) techniques. A likely consensus Λ value was estimated as the arithmetic mean of the average Λ values determined by each of three different techniques. Results: The average PST Λ value for the three Advantage sources was found to be (0.676±0.026) cGyh -1 U -1 . Intersource variation in PST Λ was less than 0.01%. The PST Λ was within 2% of the reported MC Λ values determined by PTRAN, EGSnrc, and MCNP5 codes. It was 3.4% lower than the reported TLD Λ. A likely consensus Λ value was estimated to be (0.688±0.026) cGyh -1 U -1 , similar to the AAPM consensus values recommended currently for the Theragenics (Buford, GA) Model 200 (0.686±0.033) cGyh -1 U -1 , the NASI (Chatsworth, CA) Model MED3633 (0.688±0.033) cGyh -1 U -1 , and the Best Medical (Springfield, VA) Model 2335 (0.685±0.033) cGyh -1 U -1 103 Pd sources. Conclusions: An independent Λ determination has been performed for the Advantage Pd-103 source. The PST Λ obtained in this work provides additional information

An exclusion process on a tree with constant aggregate hopping rate

International Nuclear Information System (INIS)

Mottishaw, Peter; Waclaw, Bartlomiej; Evans, Martin R

2013-01-01

We introduce a model of a totally asymmetric simple exclusion process (TASEP) on a tree network where the aggregate hopping rate is constant from level to level. With this choice for hopping rates the model shows the same phase diagram as the one-dimensional case. The potential applications of our model are in the area of distribution networks, where a single large source supplies material to a large number of small sinks via a hierarchical network. We show that mean-field theory (MFT) for our model is identical to that of the one-dimensional TASEP and that this MFT is exact for the TASEP on a tree in the limit of large branching ratio, b (or equivalently large coordination number). We then present an exact solution for the two level tree (or star network) that allows the computation of any correlation function and confirm how mean-field results are recovered as b → ∞. As an example we compute the steady-state current as a function of branching ratio. We present simulation results that confirm these results and indicate that the convergence to MFT with large branching ratio is quite rapid. (paper)

Binomial Distribution Sample Confidence Intervals Estimation 7. Absolute Risk Reduction and ARR-like Expressions

Directory of Open Access Journals (Sweden)

Andrei ACHIMAŞ CADARIU

2004-08-01

Full Text Available Assessments of a controlled clinical trial suppose to interpret some key parameters as the controlled event rate, experimental event date, relative risk, absolute risk reduction, relative risk reduction, number needed to treat when the effect of the treatment are dichotomous variables. Defined as the difference in the event rate between treatment and control groups, the absolute risk reduction is the parameter that allowed computing the number needed to treat. The absolute risk reduction is compute when the experimental treatment reduces the risk for an undesirable outcome/event. In medical literature when the absolute risk reduction is report with its confidence intervals, the method used is the asymptotic one, even if it is well know that may be inadequate. The aim of this paper is to introduce and assess nine methods of computing confidence intervals for absolute risk reduction and absolute risk reduction – like function.Computer implementations of the methods use the PHP language. Methods comparison uses the experimental errors, the standard deviations, and the deviation relative to the imposed significance level for specified sample sizes. Six methods of computing confidence intervals for absolute risk reduction and absolute risk reduction-like functions were assessed using random binomial variables and random sample sizes.The experiments shows that the ADAC, and ADAC1 methods obtains the best overall performance of computing confidence intervals for absolute risk reduction.

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

DEFF Research Database (Denmark)

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

1976-01-01

Pulse radiolysis and gamma radiolysis have been used to study the reaction mechanism in the radiolysis of aqueous solutions of Fe2+ and Cu2+. A reaction scheme has been developed and confirmed by computation of the corresponding complete set of differential equations. The rate constants for some ...... 10^{8}$ and $1.3\\times 10^{8}\\ {\\rm mol}^{-1}\\ {\\rm sec}^{-1}$ in pH 2.1 H2 SO4 and HClO4, respectively.......Pulse radiolysis and gamma radiolysis have been used to study the reaction mechanism in the radiolysis of aqueous solutions of Fe2+ and Cu2+. A reaction scheme has been developed and confirmed by computation of the corresponding complete set of differential equations. The rate constants for some...... of the reactions have been determined at different pH's. $k_{{\\rm Cu}^{+}+{\\rm O}_{2}}=4.6\\times 10^{5}$ and $1.0\\times 10^{6}\\ {\\rm mol}^{-1}\\ {\\rm sec}^{-1}$, $k_{{\\rm Cu}^{+}+{\\rm Fe}^{3+}}=5.5\\times 10^{6}$ and $1.3\\times 10^{7}\\ {\\rm mol}^{-1}\\ {\\rm sec}^{-1}$, $k_{{\\rm Cu}({\\rm III)}+{\\rm Fe}^{2+}}=3.3\\times...

Rate constants and mechanisms for the crystallization of Al nano-goethite under environmentally relevant conditions

Science.gov (United States)

Bazilevskaya, Ekaterina; Archibald, Douglas D.; Martínez, Carmen Enid

2012-07-01

Mobile inorganic and organic nanocolloidal particles originate-from and interact-with bulk solid phases in soil and sediment environments, and as such, they contribute to the dynamic properties of environmental systems. In particular, ferrihydrite and (nano)goethite are the most abundant of nanocolloidal Fe oxy(hydr)oxides in these environments. We therefore investigated the ferrihydrite to goethite phase transformation using experimental reaction conditions that mimicked environmental conditions where the formation of nanocolloidal Fe oxy(hydr)oxides may occur: slow titration of dilute solutions to pH 5 at 25 °C with and without 2 mol% Al. Subsequently, the rate constants from 54-d nano-goethite aging/crystallization experiments at 50 °C were determined using aliquots pulled for vibrational spectroscopy (including multivariate curve resolution, MCR, analyses of infrared spectra) and synchrotron-based X-ray diffraction (XRD). We also present a mechanistic model that accounts for the nano-goethite crystallization observed by the aforementioned techniques, and particle structural characteristics observed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). In contrast to the common assumption that metastable ferrihydrite precipitates first, before it transforms to goethite, the presence of characteristic infrared bands in freshly synthesized nanoparticle suspensions indicate goethite can precipitate directly from solution under environmentally relevant conditions: low Fe concentration, ambient temperature, and pH maintained at 5. However, the presence of 2 mol% Al prevented direct goethite precipitation. Rate constants obtained by fitting the contributions from the MCR-derived goethite-like component to the OH-stretching region were (7.4 ± 1.1) × 10-7 s-1 for 0% Al and (4.2 ± 0.4) × 10-7 s-1 for 2 mol% Al suspensions. Rate constants derived from intensities of OH-bending infrared vibrations (795 and 895 cm-1) showed similar values

Estimation of uptake rate constants for PCB congeners accumulated by semipermeable membrane devices and brown treat (Salmo trutta)

Science.gov (United States)

Meadows, J.C.; Echols, K.R.; Huckins, J.N.; Borsuk, F.A.; Carline, R.F.; Tillitt, D.E.

1998-01-01

The triolein-filled semipermeable membrane device (SPMD) is a simple and effective method of assessing the presence of waterborne hydrophobic chemicals. Uptake rate constants for individual chemicals are needed to accurately relate the amounts of chemicals accumulated by the SPMD to dissolved water concentrations. Brown trout and SPMDs were exposed to PCB- contaminated groundwater in a spring for 28 days to calculate and compare uptake rates of specific PCB congeners by the two matrixes. Total PCB congener concentrations in water samples from the spring were assessed and corrected for estimated total organic carbon (TOC) sorption to estimate total dissolved concentrations. Whole and dissolved concentrations averaged 4.9 and 3.7 ??g/L, respectively, during the exposure. Total concentrations of PCBs in fish rose from 0.06 to 118.3 ??g/g during the 28-day exposure, while concentrations in the SPMD rose from 0.03 to 203.4 ??g/ g. Uptake rate constants (k1) estimated for SPMDs and brown trout were very similar, with k1 values for SPMDs ranging from one to two times those of the fish. The pattern of congener uptake by the fish and SPMDs was also similar. The rates of uptake generally increased or decreased with increasing K(ow), depending on the assumption of presence or absence of TOC.The triolein-filled semipermeable membrane device (SPMD) is a simple and effective method of assessing the presence of waterborne hydrophobic chemicals. Uptake rate constants for individual chemicals are needed to accurately relate the amounts of chemicals accumulated by the SPMB to dissolved water concentrations. Brown trout and SPMDs were exposed to PCB-contaminated groundwater in a spring for 28 days to calculate and compare uptake rates of specific PCB congeners by the two matrixes. Total PCB congener concentrations in water samples from the spring were assessed and corrected for estimated total organic carbon (TOC) sorption to estimate total dissolved concentrations. Whole and

Sedative and cardiorespiratory effects of detomidine constant rate infusion in sheep.

Science.gov (United States)

de Moura, Rauane Sousa; Bittar, Isabela Plazza; da Silva, Luiz Henrique; Villela, Ana Carolina Vasquez; Dos Santos Júnior, Marcelo Borges; Borges, Naida Cristina; Franco, Leandro Guimarães

2018-02-01

The use of sheep in experiments is widespread and is increasing worldwide, and so is the need to develop species-specific anaesthetic techniques to ensure animal safety. Previous studies have mentioned several protocols involving the administration of alpha-2 adrenergic agonists in sheep; however, assessment of the efficacy and safety of these infusion techniques is still relatively new. Thus, the aim of the present study is to assess the effectiveness of detomidine constant rate infusion (CRI) in sheep by measuring the cardiovascular and respiratory parameters, blood gas variables and sedation scores. Eight adult female Santa Inês sheep received 20 µg/kg of detomidine hydrochloride intravenously as a bolus loading dose, followed by an infusion rate of 60 µg/kg/h. The heart rates and respiratory rates changed continuously during the CRI period. No arrhythmias were observed. The reduction in arterial partial pressure of oxygen (PaO 2 ) was not significant, but one animal showed signs of hypoxaemia (minimum PaO 2 of 66.9 mmHg). The arterial partial pressure of carbon dioxide (PaCO 2 ) increased, but the animals did not become hypercapnic. The bicarbonate (HCO 3- ), pH and base excess (BE) tended towards metabolic alkalosis. The cardiac output (CO), stroke volume (SV), cardiac index (CI) and ejection fraction (EF%) showed no significant changes. The fractional shortening (FS%) decreased slightly, starting at T 45min . Sedation scores varied between 3 (0/10) after sedation and during recovery and 7 (0/10) during CRI. We concluded that administering detomidine at an infusion rate of 60 µg/kg/h in Santa Inês sheep is a simple technique that produces satisfactory sedation for minimally invasive procedures.

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

Science.gov (United States)

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

2016-01-01

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

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

Science.gov (United States)

Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie

2015-01-01

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

THE ABSOLUTE RATE OF LGRB FORMATION

Energy Technology Data Exchange (ETDEWEB)

Graham, J. F.; Schady, P. [Max-Planck Institute for Extraterrestrial Physics, Giessenbachstrasse 1, D-85748 Garching (Germany)

2016-06-01

We estimate the long-duration gamma-ray burst (LGRB) progenitor rate using our recent work on the effects of environmental metallically on LGRB formation in concert with supernovae (SNe) statistics via an approach patterned loosely off the Drake equation. Beginning with the cosmic star formation history, we consider the expected number of broad-line Type Ic events (the SNe type associated with LGRBs) that are in low-metallicity host environments adjusted by the contribution of high-metallicity host environments at a much reduced rate. We then compare this estimate to the observed LGRB rate corrected for instrumental selection effects to provide a combined estimate of the efficiency fraction of these progenitors to produce LGRBs and the fraction of which are beamed in our direction. From this we estimate that an aligned LGRB occurs for approximately every 4000 ± 2000 low-metallically broad-lined SNe Ic. Therefore, if one assumes a semi-nominal beaming factor of 100, then only about one such supernova out of 40 produce an LGRB. Finally, we propose an off-axis LGRB search strategy of targeting only broad-line Type Ic events that occur in low-metallicity hosts for radio observation.

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

DEFF Research Database (Denmark)

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

1996-01-01

In situ microcosms (ISM) and laboratory batch microcosms (LBM) were used for determination of the first-order degradation rate constants of benzene, toluene, o-xylene, nitrobenzene, naphthalene, biphenyl, o- and p-dichlorobenzene, 1,1,1 -trichloroethane, tetrachlorometane, trichloroethene......, tetrachloroethene, phenol, o-cresol, 2,4- and 2,6-dichlorophenol, 4,6-o-dichlorocresol, and o- and p-nitrophenol in an aerobic aquifer, All aromatic hydrocarbons were degraded in ISM and LBM experiments. The phenolic hydrocarbons were ail degraded in ISM experiments, but some failed to degrade in LBM experiments....... Chlorinated aliphatic hydrocarbons were degraded neither in ISM nor LBM experiments. Degradation rate constants were determined by a model accounting for kinetic sorption (bicontinuum model), lag phases, and first-order degradation. With a few exceptions, lag phases were less than 2 weeks in both ISM and LBM...

Direct measurements of methoxy removal rate constants for collisions with CH4, Ar, N2, Xe, and CF4 in the temperature range 673--973K

International Nuclear Information System (INIS)

Wantuck, P.J.; Oldenborg, R.C.; Baugchum, S.L.; Winn, K.R.

1988-01-01

Removal rate constants for CH 3 O by CH 4 , Ar, N 2 , Xe, and CF 4 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, N 2 , Xe, and CF 4 ) at elevated temperatures showing that the dissociation and isomerization channels for CH 3 O are indeed important. The total removal rate constant (reaction /plus/ dissociation and/or isomerization) for CH 4 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]cm 3 molecule/sup /minus/1/s/sup /minus/1/. Assuming that the removal rate constant due to dissociation and/or isomerization are similar for CH 4 and CF 4 , the reaction rate constant for CH 3 O /plus/ CH 4 is equal to (1.7 +- 1.0) /times/ 10/sup /minus/10/exp[(/minus/7480 +- 1100)/T]cm 3 molecule/sup /minus/1/s/sup /minus/1/. 7 refs., 4 figs

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

DEFF Research Database (Denmark)

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

2016-01-01

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) f...

Inflation with a smooth constant-roll to constant-roll era transition

Science.gov (United States)

Odintsov, S. D.; Oikonomou, V. K.

2017-07-01

In this paper, we study canonical scalar field models, with a varying second slow-roll parameter, that allow transitions between constant-roll eras. In the models with two constant-roll eras, it is possible to avoid fine-tunings in the initial conditions of the scalar field. We mainly focus on the stability of the resulting solutions, and we also investigate if these solutions are attractors of the cosmological system. We shall calculate the resulting scalar potential and, by using a numerical approach, we examine the stability and attractor properties of the solutions. As we show, the first constant-roll era is dynamically unstable towards linear perturbations, and the cosmological system is driven by the attractor solution to the final constant-roll era. As we demonstrate, it is possible to have a nearly scale-invariant power spectrum of primordial curvature perturbations in some cases; however, this is strongly model dependent and depends on the rate of the final constant-roll era. Finally, we present, in brief, the essential features of a model that allows oscillations between constant-roll eras.

Room-temperature and temperature-dependent QSRR modelling for predicting the nitrate radical reaction rate constants of organic chemicals using ensemble learning methods.

Science.gov (United States)

Gupta, S; Basant, N; Mohan, D; Singh, K P

2016-07-01

Experimental determinations of the rate constants of the reaction of NO3 with a large number of organic chemicals are tedious, and time and resource intensive; and the development of computational methods has widely been advocated. In this study, we have developed room-temperature (298 K) and temperature-dependent quantitative structure-reactivity relationship (QSRR) models based on the ensemble learning approaches (decision tree forest (DTF) and decision treeboost (DTB)) for predicting the rate constant of the reaction of NO3 radicals with diverse organic chemicals, under OECD guidelines. Predictive powers of the developed models were established in terms of statistical coefficients. In the test phase, the QSRR models yielded a correlation (r(2)) of >0.94 between experimental and predicted rate constants. The applicability domains of the constructed models were determined. An attempt has been made to provide the mechanistic interpretation of the selected features for QSRR development. The proposed QSRR models outperformed the previous reports, and the temperature-dependent models offered a much wider applicability domain. This is the first report presenting a temperature-dependent QSRR model for predicting the nitrate radical reaction rate constant at different temperatures. The proposed models can be useful tools in predicting the reactivities of chemicals towards NO3 radicals in the atmosphere, hence, their persistence and exposure risk assessment.

A photon spectrometric dose-rate constant determination for the Advantage Pd-103 brachytherapy source

Energy Technology Data Exchange (ETDEWEB)

Chen, Zhe Jay; Bongiorni, Paul; Nath, Ravinder [Department of Therapeutic Radiology, Yale University School of Medicine, New Haven, Connecticut 06520 (United States)

2010-02-15

Purpose: Although several dosimetric characterizations using Monte Carlo simulation and thermoluminescent dosimetry (TLD) have been reported for the new Advantage Pd-103 source (IsoAid, LLC, Port Richey, FL), no AAPM consensus value has been established for the dosimetric parameters of the source. The aim of this work was to perform an additional dose-rate constant ({Lambda}) determination using a recently established photon spectrometry technique (PST) that is independent of the published TLD and Monte Carlo techniques. Methods: Three Model IAPD-103A Advantage Pd-103 sources were used in this study. The relative photon energy spectrum emitted by each source along the transverse axis was measured using a high-resolution germanium spectrometer designed for low-energy photons. For each source, the dose-rate constant was determined from its emitted energy spectrum. The PST-determined dose-rate constant ({sub PST}{Lambda}) was then compared to those determined by TLD ({sub TLD}{Lambda}) and Monte Carlo ({sub MC}{Lambda}) techniques. A likely consensus {Lambda} value was estimated as the arithmetic mean of the average {Lambda} values determined by each of three different techniques. Results: The average {sub PST}{Lambda} value for the three Advantage sources was found to be (0.676{+-}0.026) cGyh{sup -1} U{sup -1}. Intersource variation in {sub PST}{Lambda} was less than 0.01%. The {sub PST}{Lambda} was within 2% of the reported {sub MC}{Lambda} values determined by PTRAN, EGSnrc, and MCNP5 codes. It was 3.4% lower than the reported {sub TLD}{Lambda}. A likely consensus {Lambda} value was estimated to be (0.688{+-}0.026) cGyh{sup -1} U{sup -1}, similar to the AAPM consensus values recommended currently for the Theragenics (Buford, GA) Model 200 (0.686{+-}0.033) cGyh{sup -1} U{sup -1}, the NASI (Chatsworth, CA) Model MED3633 (0.688{+-}0.033) cGyh{sup -1} U{sup -1}, and the Best Medical (Springfield, VA) Model 2335 (0.685{+-}0.033) cGyh{sup -1} U{sup -1} {sup 103}Pd

Differentiating inflamed and normal lungs by the apparent reaction rate constants of lactate dehydrogenase probed by hyperpolarized (13)C labeled pyruvate.

Science.gov (United States)

Xu, He N; Kadlececk, Stephen; Shaghaghi, Hoora; Zhao, Huaqing; Profka, Harilla; Pourfathi, Mehrdad; Rizi, Rahim; Li, Lin Z

2016-02-01

Clinically translatable hyperpolarized (HP) (13)C-NMR can probe in vivo enzymatic reactions, e.g., lactate dehydrogenase (LDH)-catalyzed reaction by injecting HP (13)C-pyruvate into the subject, which is converted to (13)C labeled lactate by the enzyme. Parameters such as (13)C-lactate signals and lactate-to-pyruvate signal ratio are commonly used for analyzing the HP (13)C-NMR data. However, the biochemical/biological meaning of these parameters remains either unclear or dependent on experimental settings. It is preferable to quantify the reaction rate constants with a clearer physical meaning. Here we report the extraction of the kinetic parameters of the LDH reaction from HP (13)C-NMR data and investigate if they can be potential predictors of lung inflammation. Male Sprague-Dawley rats (12 controls, 14 treated) were used. One dose of bleomycin (2.5 U/kg) was administered intratracheally to the treatment group. The lungs were removed, perfused, and observed by the HP-NMR technique, where a HyperSense dynamic nuclear polarization system was used to generate the HP (13)C-pyruvate for injecting into the lungs. A 20 mm (1)H/(13)C dual-tuned coil in a 9.4-T Varian vertical bore NMR spectrometer was employed to acquire the (13)C spectral data every 1 s over a time period of 300 s using a non-selective, 15-degree radiofrequency pulse. The apparent rate constants of the LDH reaction and their ratio were quantified by applying ratiometric fitting analysis to the time series data of (13)C labeled pyruvate and lactate. The apparent forward rate constant kp =(3.67±3.31)×10(-4) s(-1), reverse rate constant kl =(4.95±2.90)×10(-2) s(-1), rate constant ratio kp /kl =(7.53±5.75)×10(-3) for the control lungs; kp =(11.71±4.35)×10(-4) s(-1), kl =(9.89±3.89)×10(-2) s(-1), and kp /kl =(12.39±4.18)×10(-3) for the inflamed lungs at the 7(th) day post treatment. Wilcoxon rank-sum test showed that the medians of these kinetic parameters of the 7-day cohort were significantly

Rate constant for the H˙ + H2O → ˙OH + H2 reaction at elevated temperatures measured by pulse radiolysis.

Science.gov (United States)

Muroya, Y; Yamashita, S; Lertnaisat, P; Sanguanmith, S; Meesungnoen, J; Jay-Gerin, J-P; Katsumura, Y

2017-11-22

Maintaining the structural integrity of materials in nuclear power plants is an essential issue associated with safe operation. Hydrogen (H 2 ) addition or injection to coolants is a powerful technique that has been widely applied such that the reducing conditions in the coolant water avoid corrosion and stress corrosion cracking (SCC). Because the radiation-induced reaction of ˙OH + H 2 → H˙ + H 2 O plays a crucial role in these systems, the rate constant has been measured at operation temperatures of the reactors (285-300 °C) by pulse radiolysis, generating sufficient data for analysis. The reverse reaction H˙ + H 2 O → ˙OH + H 2 is negligibly slow at ambient temperature; however, it accelerates considerably quickly at elevated temperatures. Although the reverse reaction reduces the effectiveness of H 2 addition, reliable rate constants have not yet been measured. In this study, the rate constants have been determined in a temperature range of 250-350 °C by pulse radiolysis in an aqueous I - solution.

Absolute calibration of TFTR helium proportional counters

International Nuclear Information System (INIS)

Strachan, J.D.; Diesso, M.; Jassby, D.; Johnson, L.; McCauley, S.; Munsat, T.; Roquemore, A.L.; Loughlin, M.

1995-06-01

The TFTR helium proportional counters are located in the central five (5) channels of the TFTR multichannel neutron collimator. These detectors were absolutely calibrated using a 14 MeV neutron generator positioned at the horizontal midplane of the TFTR vacuum vessel. The neutron generator position was scanned in centimeter steps to determine the collimator aperture width to 14 MeV neutrons and the absolute sensitivity of each channel. Neutron profiles were measured for TFTR plasmas with time resolution between 5 msec and 50 msec depending upon count rates. The He detectors were used to measure the burnup of 1 MeV tritons in deuterium plasmas, the transport of tritium in trace tritium experiments, and the residual tritium levels in plasmas following 50:50 DT experiments

ABSOLUTE NEUTRINO MASSES

DEFF Research Database (Denmark)

Schechter, J.; Shahid, M. N.

2012-01-01

We discuss the possibility of using experiments timing the propagation of neutrino beams over large distances to help determine the absolute masses of the three neutrinos.......We discuss the possibility of using experiments timing the propagation of neutrino beams over large distances to help determine the absolute masses of the three neutrinos....

Theoretical growth rates, periods, and pulsation constants for long-period variables

International Nuclear Information System (INIS)

Fox, M.W.; Wood, P.R.

1982-01-01

Theoretical values of the growth rate, period, and pulsation constant for the first three radial pulsation modes in red giants (Population II and galactic disk) and supergiants have been derived in the linear, nonadiabatic approximation. The effects of altering the surface boundary conditions, the effective temperature (or mixing length), and the opacity in the outer layers have been explored. In the standard models, the Q-value for the first overtone can be much larger (Q 1 1 roughly-equal0.04); in addition, the Q-value for the fundamental mode is reduced from previous values, as is the period ratio P 0 /P 1 . The growth rate for the fundamental mode is found to increase with luminosity on the giant branch while the growth rate for the first overtone decreases. Dynamical instabilities found in previous adiabatic models of extreme red giants do not occur when nonadiabatic effects are included in the models. In some massive, luminous models, period ratios P 0 /P 1 approx.7 occur when P 0 approx.2000--5000 days; it is suggested that the massive galactic supergiants and carbon stars which have secondary periods Papprox.2000--7000 days and primary periods Papprox.300--700 days are first-overtone pulsators in which the long secondary periods are due to excitation of the fundamental mode. Some other consequences of the present results are briefly discussed, with particular emphasis on the mode of pulsation of the Mira variables. Subject headings: stars: long-period variables: stars: pulsation: stars: supergiants

Dynamic Monte Carlo rate constants for magnetic Hamiltonians coupled to a phonon bath

Science.gov (United States)

Solomon, Lazarus; Novotny, Mark

2007-03-01

For quantitative comparisons between experimental time- dependent measurements and dynamic Monte Carlo simulations, a relation between the time constant in the simulation and real time is necessary. We calculate the transition rate for spin S system using the lattice frame method for a rigid spin cluster in an elastic medium [1]. We compare this with the transition rate for an Ising spin 12 system using the quantum- mechanical density-matrix method [2] with the results of ref [1,3]. These transition probabilities are different from those of either the Glauber or the Metropolis dynamics, and reflect the properties of the bosonic bath. Comparison with recent experiments [4] will be discussed. [1] E. M. Chudnovsky, D. A. Garanin, and R. Schilling (PRB 72, 2006) [2] K. Park, M. A. Novotny, and P. A. Rikvold (PRE 66, 2002) [3] K Saito, S. Takesue, and S. Miyashita, (PRE 61, 2002) [4] T. Meunier et al (Condensed Matter, 2006)

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

Science.gov (United States)

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

1987-01-01

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

Dynamic Characteristics of The DSI-Type Constant-Flow Valves

Science.gov (United States)

Kang, Yuan; Hu, Sheng-Yan; Chou, Hsien-Chin; Lee, Hsing-Han

Constant flow valves have been presented in industrial applications or academic studies, which compensate recess pressures of a hydrostatic bearing to resist load fluctuating. The flow rate of constant-flow valves can be constant in spite of the pressure changes in recesses, however the design parameters must be specified. This paper analyzes the dynamic responses of DSI-type constant-flow valves that is designed as double pistons on both ends of a spool with single feedback of working pressure and regulating restriction at inlet. In this study the static analysis presents the specific relationships among design parameters for constant flow rate and the dynamic analyses give the variations around the constant flow rate as the working pressure fluctuates.

Direct and Indirect Determinations of Elementary Rate Constants H + O2: Chain Branching; the Dehydration of tertiary-Butanol; the Retro Diels-Alder Reaction of Cyclohexene; the Dehydration of Isopropanol

Science.gov (United States)

Heyne, Joshua S.

Due to growing environmental concern over the continued use of fossil fuels, methods to limit emissions and partially replace fossil fuel use with renewable biofuels are of considerable interest. Developing chemical kinetic models for the chemistry that affects combustion properties is important to understanding how new fuels affect combustion energy conversion processes in transportation devices. This thesis reports the experimental study of several important reactions (the H + O2 branching reaction, the key decomposition reactions of tertiary-butanol, the dehydration reaction of isopropanol, and the retro Diels-Alder reaction of cyclohexene) and develops robust analysis methods to estimate the absolute uncertainties of specific elementary rate constants derived from the experimental data. In the study of the above reactions, both a direct and indirect rate constant determination technique with associated uncertainty estimation methodologies are developed. In the study of the decomposition reactions, a direct determination technique is applied to experimental data gathered in preparation of this thesis. In the case of the dehydration reaction of tertiary-butanol and the retro Diels-Alder reaction of cyclohexene, both of which are used as internal standards for relative rate studies (Herzler et al. 1997) and chemical thermometry (Rosado-Reyes et al. 2013) , analysis showed an ˜20 K difference in the reaction rate between the reported results and the previous recommendations. In light of these discrepancies, an uncertainty estimation of previous recommendations illuminated an uncertainty of at least 20 K for the dehydration reaction of tertiary-butanol and the retro Diels-Alder reaction of cyclohexene, thus resolving the discrepancies. The determination of the H + O2 branching reaction and decomposition reactions of isopropanol used an indirect determination technique. The uncertainty of the H + O2 branching reaction rate is shown to be underestimated by previous

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

Science.gov (United States)

Clarke, William T; Robson, Matthew D; Neubauer, Stefan; Rodgers, Christopher T

2017-07-01

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

Absolute nuclear material assay

Science.gov (United States)

Prasad, Manoj K [Pleasanton, CA; Snyderman, Neal J [Berkeley, CA; Rowland, Mark S [Alamo, CA

2010-07-13

A method of absolute nuclear material assay of an unknown source comprising counting neutrons from the unknown source and providing an absolute nuclear material assay utilizing a model to optimally compare to the measured count distributions. In one embodiment, the step of providing an absolute nuclear material assay comprises utilizing a random sampling of analytically computed fission chain distributions to generate a continuous time-evolving sequence of event-counts by spreading the fission chain distribution in time.

Effect of the absolute statistic on gene-sampling gene-set analysis methods.

Science.gov (United States)

Nam, Dougu

2017-06-01

Gene-set enrichment analysis and its modified versions have commonly been used for identifying altered functions or pathways in disease from microarray data. In particular, the simple gene-sampling gene-set analysis methods have been heavily used for datasets with only a few sample replicates. The biggest problem with this approach is the highly inflated false-positive rate. In this paper, the effect of absolute gene statistic on gene-sampling gene-set analysis methods is systematically investigated. Thus far, the absolute gene statistic has merely been regarded as a supplementary method for capturing the bidirectional changes in each gene set. Here, it is shown that incorporating the absolute gene statistic in gene-sampling gene-set analysis substantially reduces the false-positive rate and improves the overall discriminatory ability. Its effect was investigated by power, false-positive rate, and receiver operating curve for a number of simulated and real datasets. The performances of gene-set analysis methods in one-tailed (genome-wide association study) and two-tailed (gene expression data) tests were also compared and discussed.

Bimolecular Rate Constants for FAD-Dependent Glucose Dehydrogenase from Aspergillus terreus and Organic Electron Acceptors.

Science.gov (United States)

Tsuruoka, Nozomu; Sadakane, Takuya; Hayashi, Rika; Tsujimura, Seiya

2017-03-10

The flavin adenine dinucleotide-dependent glucose dehydrogenase (FAD-GDH) from Aspergillus species require suitable redox mediators to transfer electrons from the enzyme to the electrode surface for the application of bioelectrical devices. Although several mediators for FAD-GDH are already in use, they are still far from optimum in view of potential, kinetics, sustainability, and cost-effectiveness. Herein, we investigated the efficiency of various phenothiazines and quinones in the electrochemical oxidation of FAD-GDH from Aspergillus terreus . At pH 7.0, the logarithm of the bimolecular oxidation rate constants appeared to depend on the redox potentials of all the mediators tested. Notably, the rate constant of each molecule for FAD-GDH was approximately 2.5 orders of magnitude higher than that for glucose oxidase from Aspergillus sp. The results suggest that the electron transfer kinetics is mainly determined by the formal potential of the mediator, the driving force of electron transfer, and the electron transfer distance between the redox active site of the mediator and the FAD, affected by the steric or chemical interactions. Higher k ₂ values were found for ortho-quinones than for para-quinones in the reactions with FAD-GDH and glucose oxidase, which was likely due to less steric hindrance in the active site in the case of the ortho-quinones.

Bimolecular Rate Constants for FAD-Dependent Glucose Dehydrogenase from Aspergillus terreus and Organic Electron Acceptors

Directory of Open Access Journals (Sweden)

Nozomu Tsuruoka

2017-03-01

Full Text Available The flavin adenine dinucleotide-dependent glucose dehydrogenase (FAD-GDH from Aspergillus species require suitable redox mediators to transfer electrons from the enzyme to the electrode surface for the application of bioelectrical devices. Although several mediators for FAD-GDH are already in use, they are still far from optimum in view of potential, kinetics, sustainability, and cost-effectiveness. Herein, we investigated the efficiency of various phenothiazines and quinones in the electrochemical oxidation of FAD-GDH from Aspergillus terreus. At pH 7.0, the logarithm of the bimolecular oxidation rate constants appeared to depend on the redox potentials of all the mediators tested. Notably, the rate constant of each molecule for FAD-GDH was approximately 2.5 orders of magnitude higher than that for glucose oxidase from Aspergillus sp. The results suggest that the electron transfer kinetics is mainly determined by the formal potential of the mediator, the driving force of electron transfer, and the electron transfer distance between the redox active site of the mediator and the FAD, affected by the steric or chemical interactions. Higher k2 values were found for ortho-quinones than for para-quinones in the reactions with FAD-GDH and glucose oxidase, which was likely due to less steric hindrance in the active site in the case of the ortho-quinones.

Thermodynamics of negative absolute pressures

International Nuclear Information System (INIS)

Lukacs, B.; Martinas, K.

1984-03-01

The authors show that the possibility of negative absolute pressure can be incorporated into the axiomatic thermodynamics, analogously to the negative absolute temperature. There are examples for such systems (GUT, QCD) processing negative absolute pressure in such domains where it can be expected from thermodynamical considerations. (author)

The Planck Constant, the International System of Units, and the 2012 North American Watt Balance Absolute Gravity Comparison

Science.gov (United States)

Newell, D. B.

2012-12-01

As outlined in Resolution 1 of the 24th Meeting of the General Conference on Weights and Measures (CGPM) on the future revision of the International System of Units (SI) [1], the current four SI base units the kilogram, the ampere, the kelvin and the mole, will be redefined in terms of invariants of nature. The new definitions will be based on fixed numerical values of the Planck constant (h), the elementary charge (e), the Boltzmann constant (k), and the Avogadro constant (NA), respectively. While significant progress has been made towards providing the necessary experimental results for the redefinition, some disagreement among the relevant data remain. Among the set of discrepant data towards the redefinition of the SI are the determinations of the Planck constant from the National Institute of Standards and Technology (NIST) watt balance [2] and the recent result from the National Research Council Canada (NRC) watt balance [3], with the discrepancy of roughly 2.5 parts in 107 being significantly outside the reported uncertainties. Of major concern is that the watt balance experiment is seen as a key component of a mise en pratique for the new kilogram definition, once such a redefinition takes place. The basic operational principle of a watt balance relates the Planck constant to mass, length, and time through h = mgvC, where m is the mass of an artifact mass standard, g is the local acceleration of gravity, v is a velocity, and C is a combination of frequencies and scalar constants. With the total uncertainty goal for the watt balance on the order of a few parts in 108, g needs to be determined at the location of the mass standard to parts in 109 such that its uncertainty is negligible in the final watt balance result. NIST and NRC have formed a collaborative effort to reconcile the relevant discrepant data and provide further progress towards preparing and testing a mise en pratique for the new kilogram definition. As an initial step, direct comparisons of

The constant failure rate model for fault tree evaluation as a tool for unit protection reliability assessment

International Nuclear Information System (INIS)

Vichev, S.; Bogdanov, D.

2000-01-01

The purpose of this paper is to introduce the fault tree analysis method as a tool for unit protection reliability estimation. The constant failure rate model applies for making reliability assessment, and especially availability assessment. For that purpose an example for unit primary equipment structure and fault tree example for simplified unit protection system is presented (author)

Hysteresis behaviour of silver sputtered in different plasma atmospheres at constant flow rates

International Nuclear Information System (INIS)

Rizk, A.; Makar, L.N.; Rizk, N.S.; Shinoda, R.

1990-01-01

The effects of ion bombardment on sputtering behaviour of pure silver targets in inert and active gas atmospheres were investigated, using a dc planar magnetron sputtering system. The obtained current-voltage characteristics showed the formation of hysteresis loops without noticeable sharp transitions. Redeposited layers of silver nitride or silver oxide on the target surface when using nitrogen or oxygen in the glow discharge, residual ionization when using dry argon atmosphere were considered the main reasons for the occurrence of these loops. The results indicate that films of AgN x and AgO x can be deposited with controlled x in the range 0 ≤ x ≤ 1 using voltage control at constant gas flow rates. (author)

Constant strain rate and peri-implant bone modeling: an in vivo longitudinal micro-CT analysis.

Science.gov (United States)

De Smet, Els; Jaecques, Siegfried V N; Wevers, Martine; Sloten, Jos Vander; Naert, Ignace E

2013-06-01

Strain, frequency, loading time, and strain rate, among others, determine mechanical parameters in osteogenic loading. We showed a significant osteogenic effect on bone mass (BM) by daily peri-implant loading at 1.600µε.s(-1) after 4 weeks. To study the peri-implant osteogenic effect of frequency and strain in the guinea pig tibia by in vivo longitudinal micro-computed tomography (CT) analysis. One week after implant installation in both hind limb tibiae, one implant was loaded daily for 10' during 4 weeks, while the other served as control. Frequencies (3, 10, and 30Hz) and strains varied alike in the three series to keep the strain rate constant at 1.600µε.s(-1) . In vivo micro-CT scans were taken of both tibiae: 1 week after implantation but before loading (v1) and after 2 (v2) and 4 weeks (v3) of loading as well as postmortem (pm). BM (BM (%) bone-occupied area fraction) was calculated as well as the difference between test and control sides (delta BM) RESULTS: All implants (n=78) were clinically stable at 4 weeks. Significant increase in BM was measured between v1 and v2 (pimplant marrow 500 Region of Interest already 2 weeks after loading (p=.01) and was significantly larger (11%) in series 1 compared with series 2 (p=.006) and 3 (p=.016). Within the constraints of constant loading time and strain rate, the effect of early implant loading on the peri-implant bone is strongly dependent on strain and frequency. This cortical bone model has shown to be most sensitive for high force loading at low frequency. © 2011 Wiley Periodicals, Inc.

Absolute analytical prediction of photonic crystal guided mode resonance wavelengths

International Nuclear Information System (INIS)

Hermannsson, Pétur Gordon; Vannahme, Christoph; Smith, Cameron L. C.; Kristensen, Anders

2014-01-01

A class of photonic crystal resonant reflectors known as guided mode resonant filters are optical structures that are widely used in the field of refractive index sensing, particularly in biosensing. For the purposes of understanding and design, their behavior has traditionally been modeled numerically with methods such as rigorous coupled wave analysis. Here it is demonstrated how the absolute resonance wavelengths of such structures can be predicted by analytically modeling them as slab waveguides in which the propagation constant is determined by a phase matching condition. The model is experimentally verified to be capable of predicting the absolute resonance wavelengths to an accuracy of within 0.75 nm, as well as resonance wavelength shifts due to changes in cladding index within an accuracy of 0.45 nm across the visible wavelength regime in the case where material dispersion is taken into account. Furthermore, it is demonstrated that the model is valid beyond the limit of low grating modulation, for periodically discontinuous waveguide layers, high refractive index contrasts, and highly dispersive media.

Is there a rule of thumb for absolute purchasing power parity to hold?

OpenAIRE

Zhang, Zhibai

2014-01-01

We find an example where real exchange rate (RER) is stationary and the nominal exchange rate and the price levels are cointegrated but purchasing power parity (PPP) does not hold, which reveals a fault of the unit root and cointegration tests in this use. We argue that the distribution of an RER misalignment can be used in testing absolute PPP. Then we apply this new test and the coefficient restriction test to study the validity of absolute PPP in 40 main countries and areas (versus the US)...

Absolute photoabsorption cross-sections (oscillator strengths) for hydrogen chloride, hydrogen bromide and hydrogen iodide

International Nuclear Information System (INIS)

Brion, C.E.; Dyck, M.; Cooper, G.

2004-01-01

Full text: Absolute photoabsorption cross-sections (oscillator strengths) for the free molecules HCl, HBr and HI have been measured in the valence and selected in- ner shell regions. The experimental technique used for these studies is dipole (e,e) spectroscopy [1-3] which is not affected by line saturation effects (i.e. bandwidth interactions) which can complicate direct photoabsorption methods using the Beer- Lambert law. The dipole (e,e) method is also not subject to the effects of higher order radiation. In the dipole (e,e) method relative intensities obtained in fast (3 keV) for- ward scattered electron energy loss spectra are converted to relative dipole oscillator strengths (i.e. photoabsorption spectra) using the known Bethe-Born factors for the instrument as a function of photon energy (i.e. energy loss). The target pressure is constant at 10 - 5 torr, but it is not necessary to know the absolute target density. The absolute oscillator strength scale for HCl is determined from Bethe-Born converted, wide range dipole (e,e) spectra using the Thomas-Reiche-Kuhn (TRK) sum rule. For HBr and HI the absolute oscillator strength scales have been established using the S(-2) Sum Rule and literature values of the static dipole polarizability

Direct quantum mechanical calculation of the F + H{sub 2} {yields} HF + H thermal rate constant

Energy Technology Data Exchange (ETDEWEB)

Moix, Marc [Computer Simulation and Modeling (COSMO) Lab, Parc Cientific de Barcelona, Josep Samitier 5, 08028 Barcelona (Spain); Institut de Quimica Teorica i Computacional de la UB (IQTCUB), Universitat de Barcelona (Spain); Huarte-Larranaga, Fermin [Computer Simulation and Modeling (COSMO) Lab, Parc Cientific de Barcelona, Josep Samitier 5, 08028 Barcelona (Spain); Institut de Quimica Teorica i Computacional de la UB (IQTCUB), Universitat de Barcelona (Spain)], E-mail: fhuarte@pcb.ub.es

2008-07-03

Accurate full-dimensional quantum mechanical thermal rate constant values have been calculated for the F+H{sub 2}{yields}HF+H reaction on the Stark-Werner ab initio potential energy surface. These calculations are based on a flux correlation functions and employ a rigorous statistical sampling scheme to account for the overall rotation and the MCTDH scheme for the wave packet propagation. Our results shed some light on discrepancies on the thermal rate found for previous flux correlation based calculations with respect to accurate reactive scattering results. The resonance pattern of the all-J cumulative reaction probability is analyzed in terms of the partial wave contributions.

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

Directory of Open Access Journals (Sweden)

Youhua Chen

2014-01-01

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

Effects of Water Molecule on CO Oxidation by OH: Reaction Pathways, Kinetic Barriers, and Rate Constants.

Science.gov (United States)

Zhang, Linyao; Yang, Li; Zhao, Yijun; Zhang, Jiaxu; Feng, Dongdong; Sun, Shaozeng

2017-07-06

The water dilute oxy-fuel combustion is a clean combustion technology for near-zero emission power; and the presence of water molecule could have both kinetic and dynamic effects on combustion reactions. The reaction OH + CO → CO 2 + H, one of the most important elementary reactions, has been investigated by extensive electronic structure calculations. And the effects of a single water molecule on CO oxidation have been studied by considering the preformed OH(H 2 O) complex reacts with CO. The results show little change in the reaction pathways, but the additional water molecule actually increases the vibrationally adiabatic energy barriers (V a G ). Further thermal rate constant calculations in the temperature range of 200 to 2000 K demonstrate that the total low-pressure limit rate constant for the water assisted OH(H 2 O) + CO → CO 2 + H 2 O + H reaction is 1-2 orders lower than that of the water unassisted one, which is consistent with the change of V a G . Therefore, the hydrated radical OH(H 2 O) would actually slow down the oxidation of CO. Meanwhile, comparisons show that the M06-2X/aug-cc-pVDZ method gives a much better estimation in energy and thus is recommended to be employed for direct dynamics simulations.

Simultaneous measurement of glucose blood–brain transport constants and metabolic rate in rat brain using in-vivo 1H MRS

Science.gov (United States)

Du, Fei; Zhang, Yi; Zhu, Xiao-Hong; Chen, Wei

2012-01-01

Cerebral glucose consumption and glucose transport across the blood–brain barrier are crucial to brain function since glucose is the major energy fuel for supporting intense electrophysiological activity associated with neuronal firing and signaling. Therefore, the development of noninvasive methods to measure the cerebral metabolic rate of glucose (CMRglc) and glucose transport constants (KT: half-saturation constant; Tmax: maximum transport rate) are of importance for understanding glucose transport mechanism and neuroenergetics under various physiological and pathological conditions. In this study, a novel approach able to simultaneously measure CMRglc, KT, and Tmax via monitoring the dynamic glucose concentration changes in the brain tissue using in-vivo 1H magnetic resonance spectroscopy (MRS) and in plasma after a brief glucose infusion was proposed and tested using an animal model. The values of CMRglc, Tmax, and KT were determined to be 0.44±0.17 μmol/g per minute, 1.35±0.47 μmol/g per minute, and 13.4±6.8 mmol/L in the rat brain anesthetized with 2% isoflurane. The Monte-Carlo simulations suggest that the measurements of CMRglc and Tmax are more reliable than that of KT. The overall results indicate that the new approach is robust and reliable for in-vivo measurements of both brain glucose metabolic rate and transport constants, and has potential for human application. PMID:22714049

Constant conditional entropy and related hypotheses

International Nuclear Information System (INIS)

Ferrer-i-Cancho, Ramon; Dębowski, Łukasz; Moscoso del Prado Martín, Fermín

2013-01-01

Constant entropy rate (conditional entropies must remain constant as the sequence length increases) and uniform information density (conditional probabilities must remain constant as the sequence length increases) are two information theoretic principles that are argued to underlie a wide range of linguistic phenomena. Here we revise the predictions of these principles in the light of Hilberg’s law on the scaling of conditional entropy in language and related laws. We show that constant entropy rate (CER) and two interpretations for uniform information density (UID), full UID and strong UID, are inconsistent with these laws. Strong UID implies CER but the reverse is not true. Full UID, a particular case of UID, leads to costly uncorrelated sequences that are totally unrealistic. We conclude that CER and its particular cases are incomplete hypotheses about the scaling of conditional entropies. (letter)

Estimating reaction rate constants from a two-step reaction: a comparison between two-way and three-way methods

NARCIS (Netherlands)

Bijlsma, S.; Smilde, A. K.

2000-01-01

In this paper, two different spectral datasets are used in order to estimate reaction rate constants using different algorithms. Dataset 1 consists of short-wavelength near-infrared (SW NIR) spectra taken in time of the two-step epoxidation of 2,5-di-tert-butyl-1,4-benzoquinone using tert-butyl

Regional Distribution of Epifascial Swelling and Epifascial Lymph Drainage Rate Constants in Breast Cancer-Related Lymphedema

OpenAIRE

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...

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

Energy Technology Data Exchange (ETDEWEB)

Greene, Samuel M., E-mail: samuel.greene@chem.ox.ac.uk; Shan, Xiao, E-mail: xiao.shan@chem.ox.ac.uk; Clary, David C., E-mail: david.clary@chem.ox.ac.u [Physical and Theoretical Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QZ (United Kingdom)

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.

UNBIASED MOMENT-RATE SPECTRA AND ABSOLUTE SITE EFFECTS IN THE KACHCHH BASIN, INDIA, FROM THE ANALYSIS OF THE AFTERSHOCKS OF THE 2001 Mw 7.6 BHUJ EARTHQUAKE

Energy Technology Data Exchange (ETDEWEB)

Malagnini, L; Bodin, P; Mayeda, K; Akinci, A

2005-05-04

What can be learned about absolute site effects on ground motions and about earthquake source spectra from recordings at temporary seismic stations, none of which could be considered a 'reference' (hard rock) site, for which no geotechnical information is available, in a very poorly instrumented region? This challenge motivated our current study of aftershocks of the 2001 Mw 7.6 Bhuj earthquake, in Western India. Crustal attenuation and spreading relationships based on the same data used here were determined in an earlier study. In this paper we decouple the ambiguity between absolute source radiation and site effects by first computing robust estimates of moment-rate spectra of about 200 aftershocks in each of two depth ranges. Using these new estimates of sourcespectra, and our understanding of regional wave propagation, we extract the absolute site terms of the sites of the temporary deployment. Absolute site terms (one for each component of the ground motion, for each station) are computed in an average sense, via an L{sub 1}-norm minimization, and results for each site are averaged over wide ranges of azimuths and takeoff angles. The Bhuj deployment is characterized by a variable shallow geology, mostly of soft sedimentary units. Vertical site terms in the region were observed to be almost featureless and slightly < 1.0 within wide frequency ranges. As a result, H/V spectral ratios mimic the absolute behaviors of absolute horizontal site terms, and they generally overpredict them. On the contrary, with respect to the results for sedimentary rock sites (limestone, dolomite) obtained by Malagnini et al. (2004), H/V spectral ratios in their study did not have much in common with absolute horizontal site terms. Spectral ratios between the vector sum of the computed horizontal site terms for the temporary deployment with respect to the same quantity computed at the hardest rock station available, BAC1, are seriously biased by its non-flat, non

Danish Towns during Absolutism

DEFF Research Database (Denmark)

This anthology, No. 4 in the Danish Urban Studies Series, presents in English recent significant research on Denmark's urban development during the Age of Absolutism, 1660-1848, and features 13 articles written by leading Danish urban historians. The years of Absolutism were marked by a general...

Absolute humidity and the seasonal onset of influenza in the continental United States.

Directory of Open Access Journals (Sweden)

Jeffrey Shaman

2010-02-01

Full Text Available Much of the observed wintertime increase of mortality in temperate regions is attributed to seasonal influenza. A recent reanalysis of laboratory experiments indicates that absolute humidity strongly modulates the airborne survival and transmission of the influenza virus. Here, we extend these findings to the human population level, showing that the onset of increased wintertime influenza-related mortality in the United States is associated with anomalously low absolute humidity levels during the prior weeks. We then use an epidemiological model, in which observed absolute humidity conditions temper influenza transmission rates, to successfully simulate the seasonal cycle of observed influenza-related mortality. The model results indicate that direct modulation of influenza transmissibility by absolute humidity alone is sufficient to produce this observed seasonality. These findings provide epidemiological support for the hypothesis that absolute humidity drives seasonal variations of influenza transmission in temperate regions.

Ab initio calculation of the transition-state properties and addition rate constants for H + C2H2 and selected isotopic analogues

International Nuclear Information System (INIS)

Harding, L.B.; Wagner, A.F.; Bowman, J.M.; Schatz, G.C.; Christoffel, K.

1982-01-01

GVB-POL-CI ab initio calculations of the geometries, energetics, and normal mode frequencies of C 2 H 2 , C 2 H 3 , and the transition state for the addition reaction of H + C 2 H 2 are presented. In addition, normal mode frequencies for the isotopic variants D + C 2 D 2 , D + C 2 H 2 , and H + C 2 D 2 are preented. These results are compared to experimental values for C 2 H 2 and to ab initio values of Hagase and Kern, and semiempirical values of Keil, Lynch, Cowfer, and Michael. The results are also used to calculate the apparent bimolecular addition rate constant using conventional RRKM theory for chemical activation. The calculated rate constants and their isotopic variants are compared as a function of temperature and pressure to available experimental information. The agreement is little different from that obtained by Keil et al. with a similar calculation using semiempirical values for acetylene, transition-state, and vinyl radical properties. In particular, the calculated high-pressure limit of the rate constant appears to be at least 1 order of magnitude higher than the experimental limit. Several possible reasons for this discrepancy are discussed

Assessment of volumetric-modulated arc therapy for constant and variable dose rates

Directory of Open Access Journals (Sweden)

Mariluz De Ornelas-Couto

2017-01-01

Full Text Available Purpose: The aim of this study is to compare the effects of dose rate on volumetric-modulated arc therapy plans to determine optimal dose rates for prostate and head and neck (HN cases. Materials and Methods: Ten prostate and ten HN cases were retrospectively studied. For each case, seven plans were generated: one variable dose rate (VDR and six constant dose rate (CDR (100–600 monitor units [MUs]/min plans. Prescription doses were: 80 Gy to planning target volume (PTV for the prostate cases, and 70, 60, and 54 Gy to PTV1, PTV2, and PTV3, respectively, for HN cases. Plans were normalized to 95% of the PTV and PTV1, respectively, with the prescription dose. Plans were assessed using Dose-Volume-Histogram metrics, homogeneity index, conformity index, MUs, and delivery time. Results: For the prostate cases, significant differences were found for rectum D35 between VDR and all CDR plans, except CDR500. Furthermore, VDR was significantly different than CDR100 and 200 for bladder D50. Delivery time for all CDR plans and MUs for CDR400–600 were significantly higher when compared to VDR. HN cases showed significant differences between VDR and CDR100, 500 and 600 for D2 to the cord and brainstem. Significant differences were found for delivery time and MUs for all CDR plans, except CDR100 for number of MUs. Conclusion: The most significant differences were observed in delivery time and number of MUs. All-in-all, the best CDR for prostate cases was found to be 300 MUs/min and 200 or 300 MUs/min for HN cases. However, VDR plans are still the choice in terms of MU efficiency and plan quality.

Dynamic Analysis of Offshore Oil Pipe Installation Using the Absolute Nodal Coordinate Formulation

DEFF Research Database (Denmark)

Nielsen, Jimmy D; Madsen, Søren B; Hyldahl, Per Christian

2013-01-01

The Absolute Nodal Coordinate Formulation (ANCF) has shown promising results in dynamic analysis of structures that undergo large deformation. The method relaxes the assumption of infinitesimal rotations. Being based in a fixed inertial reference frame leads to a constant mass matrix and zero......, are included to mimic the external forces acting on the pipe during installation. The scope of this investigation is to demonstrate the ability using the ANCF to analyze the dynamic behavior of an offshore oil pipe during installation...

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

Directory of Open Access Journals (Sweden)

Andreas Gansäuer

2013-08-01

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

Effects of Warmness and Spatial Nonuniformity of the Plasma Waveguide on Periodic Absolute Parametric Instability

International Nuclear Information System (INIS)

Zaki, N.G.; Bekheit, A.H.

2011-01-01

The periodic absolute parametric instability (API) of the low-frequency oscillations excited by a monochromatic pumping field of arbitrary amplitude in a warm I-D nonuniform magneto active plasma is investigated. One can use the separation method to solve the two-fluid plasma equations which describe the system. The method used enables us to determine the frequencies and growth rates of unstable modes and the self-consistent electric field. Plasma electrons are considered to have a thermal velocity. One can examine different solutions for the spatial equation in the following cases: A) API in uniform Plasma B) API in nonuniform plasma, we study this case for two variants: B.1) Exact harmonic oscillator and B.2) Bounded harmonic oscillator (bounded plasma). Increment is found in the buildup of the oscillations, and it is shown that the spatial nonuniformity of the plasma exerts a stabilizing effect on the parametric instability. It is shown that the growth rate of API in warm plasma is reduced compared to cold plasma. It is found also that the warmness of the plasma has no effect on the solution of the space part of the problem ( only through the separation constant )

Time-Dependent Quantum Wave Packet Study of the Si + OH → SiO + H Reaction: Cross Sections and Rate Constants.

Science.gov (United States)

Rivero Santamaría, Alejandro; Dayou, Fabrice; Rubayo-Soneira, Jesus; Monnerville, Maurice

2017-03-02

The dynamics of the Si( 3 P) + OH(X 2 Π) → SiO(X 1 Σ + ) + H( 2 S) reaction is investigated by means of the time-dependent wave packet (TDWP) approach using an ab initio potential energy surface recently developed by Dayou et al. ( J. Chem. Phys. 2013 , 139 , 204305 ) for the ground X 2 A' electronic state. Total reaction probabilities have been calculated for the first 15 rotational states j = 0-14 of OH(v=0,j) at a total angular momentum J = 0 up to a collision energy of 1 eV. Integral cross sections and state-selected rate constants for the temperature range 10-500 K were obtained within the J-shifting approximation. The reaction probabilities display highly oscillatory structures indicating the contribution of long-lived quasibound states supported by the deep SiOH/HSiO wells. The cross sections behave with collision energies as expected for a barrierless reaction and are slightly sensitive to the initial rotational excitation of OH. The thermal rate constants show a marked temperature dependence below 200 K with a maximum value around 15 K. The TDWP results globally agree with the results of earlier quasi-classical trajectory (QCT) calculations carried out by Rivero-Santamaria et al. ( Chem. Phys. Lett. 2014 , 610-611 , 335 - 340 ) with the same potential energy surface. In particular, the thermal rate constants display a similar temperature dependence, with TDWP values smaller than the QCT ones over the whole temperature range.

Absolute exposure determination of cobalt-60 gamma radiation

International Nuclear Information System (INIS)

Ahmad, S.S.; Ali, A.; Orfi, S.D.

1986-02-01

The report describes the procedure for the determination of absolute exposure for Cobalt-60 gamma radiation. A graphite cavity chamber, nominal volume of 1 cm 3 , manufactured by Austrian Research Centre Seibersdorf has been used. The exposure rate at reference distance determined with the graphite chamber was compared with mean exposure rate measured with NPL-Therapy level X-ray exposure meter normalized to same date. An agreement of 0.39% was found between the two measuring systems, which seems to be very encouraging and quite satisfactory. (authors)

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

Directory of Open Access Journals (Sweden)

Afshin Taghva Manesh

2017-02-01

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

Absolute beam-charge measurement for single-bunch electron beams

International Nuclear Information System (INIS)

Suwada, Tsuyoshi; Ohsawa, Satoshi; Furukawa, Kazuro; Akasaka, Nobumasa

2000-01-01

The absolute beam charge of a single-bunch electron beam with a pulse width of 10 ps and that of a short-pulsed electron beam with a pulse width of 1 ns were measured with a Faraday cup in a beam test for the KEK B-Factory (KEKB) injector linac. It is strongly desired to obtain a precise beam-injection rate to the KEKB rings, and to estimate the amount of beam loss. A wall-current monitor was also recalibrated within an error of ±2%. This report describes the new results for an absolute beam-charge measurement for single-bunch and short-pulsed electron beams, and recalibration of the wall-current monitors in detail. (author)

Reaction kinetics aspect of U3O8 kernel with gas H2 on the characteristics of activation energy, reaction rate constant and O/U ratio of UO2 kernel

International Nuclear Information System (INIS)

Damunir

2007-01-01

The reaction kinetics aspect of U 3 O 8 kernel with gas H 2 on the characteristics of activation energy, reaction rate constant and O/U ratio of UO 2 kernel had been studied. U 3 O 8 kernel was reacted with gas H 2 in a reduction furnace at varied reaction time and temperature. The reaction temperature was varied at 600, 700, 750 and 850 °C with a pressure of 50 mmHg for 3 hours in gas N 2 atmosphere. The reation time was varied at 1, 2, 3 and 4 hours at a temperature of 750 °C using similar conditions. The reaction product was UO 2 kernel. The reaction kinetic aspect between U 3 O 8 and gas H 2 comprised the minimum activation energy (ΔE), the reaction rate constant and the O/U ratio of UO 2 kernel. The minimum activation energy was determined from a straight line slope of equation ln [{D b . R o {(1 - (1 - X b ) ⅓ } / (b.t.Cg)] = -3.9406 x 10 3 / T + 4.044. By multiplying with the straight line slope -3.9406 x 10 3 , the ideal gas constant (R) 1.985 cal/mol and the molarity difference of reaction coefficient 2, a minimum activation energy of 15.644 kcal/mol was obtained. The reaction rate constant was determined from first-order chemical reaction control and Arrhenius equation. The O/U ratio of UO 2 kernel was obtained using gravimetric method. The analysis result of reaction rate constant with chemical reaction control equation yielded reaction rate constants of 0.745 - 1.671 s -1 and the Arrhenius equation at temperatures of 650 - 850 °C yielded reaction rate constants of 0.637 - 2.914 s -1 . The O/U ratios of UO 2 kernel at the respective reaction rate constants were 2.013 - 2.014 and the O/U ratios at reaction time 1 - 4 hours were 2.04 - 2.011. The experiment results indicated that the minimum activation energy influenced the rate constant of first-order reaction and the O/U ratio of UO 2 kernel. The optimum condition was obtained at reaction rate constant of 1.43 s -1 , O/U ratio of UO 2 kernel of 2.01 at temperature of 750 °C and reaction time of 3

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

KAUST Repository

Sudhakaran, Sairam

2013-03-01

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

Parametric imaging of the rate constant K[sub i] using 18Fluoro-L-dopa positron emission tomography in progressive supranuclear palsy

Energy Technology Data Exchange (ETDEWEB)

Cordes, M. (Neurodegenerative Disorders Centre, Univ. Hospital, Univ. of British Columbia, Vancouver, BC (Canada) Strahlenklinik und Poliklinik, Universitaetsklinikum Rudolf-Virchow, Berlin (Germany)); Snow, B.J. (Neurodegenerative Disorders Centre, Univ. Hospital, Univ. of British Columbia, Vancouver, BC (Canada)); Morrison, S. (TRIUMF, Univ. of British Columbia, Vancouver, BC (Canada)); Sossi, V. (TRIUMF, Univ. of British Columbia, Vancouver, BC (Canada)); Ruth, T.J. (TRIUMF, Univ. of British Columbia, Vancouver, BC (Canada)); Calne, D.B. (Neurodegenerative Disorders Centre, Univ. Hospital, Univ. of British Columbia, Vancouver, BC (Canada))

1993-01-01

Positron emission tomography (PET) studies using 18F-L-dopa were carried out in 9 patients with supranuclear palsy and 13 controls. For quantification of PET data a rate constant K[sub i] was calculated for the radiotracer using a graphical method. Corrections for nonspecific activity were performed in both arterial plasma and brain tissue. The purpose of this study was to test the hypothesis that parametric images of the rate constant K mapping can be obtained on a pixel-by-pixel basis using an appropriate mathematical algorithm. K[sub i] values from these parametric images and the graphical approach were compared. Both correlated closely, with y=0.013+0.947[sup *]x, r=0.992 and y=-0.052+1.048[sup *]x, r=0.965 in patients and controls, respectively. Contrast measurements were also performed and showed a striking increase in contrast on parametric images. K mapping offers several advantages over the graphical approach, since parametric images are time-independent, i.e. one image represents the quantitative result of the study. In addition, parmetric images of the rate constant are normalized to arterial plasma radioactivity and corrected for tissue metabolites. Thus, parametric images of K[sub i] in different individuals can be compared directly without further processing in order to assess the nigrostriatal integrity. (orig.)

Effects of warmness and spatial nonuniformity of plasma waveguide on periodic absolute parametric instability

International Nuclear Information System (INIS)

Zaki, N.G.; Bekheit, A.H.

2011-01-01

The periodic absolute parametric instability (API) of the low-frequency oscillations excited by a monochromatic pumping field of an arbitrary amplitude in a warm 1-D (one-dimensional) nonuniform magnetoactive plasma is investigated. The separation method can be used for solving the two-fluid plasma equations describing the system. By applying this method we were able to determine the frequencies and growth rates of unstable modes and the self-consistent electric field. Plasma electrons are considered to have a thermal velocity. Different solutions for the spatial equation can be obtained the following cases: A) API in a uniform plasma, B) API in a nonuniform plasma. The latter has been studied here for two cases: B.1) the exact harmonic oscillator and B.2) the bounded harmonic oscillator (a bounded plasma). An increment has been found in the build-up of the oscillations, and it has been shown that the spatial nonuniformity of the plasma exerts the stabilizing effect on the parametric instability. A reduced growth rate of API in the warm plasma, in comparison to the cold plasma, is reported. It has also been found that the warmness of the plasma has no effect on the solution of the space part of the problem (only through the separation constant). (authors)

Radionuclide mass transfer rates from a pinhole in a waste container for an inventory-limited and a constant concentration source

International Nuclear Information System (INIS)

LeNeveu, D.M.

1996-03-01

Analytical solutions for transient and steady state diffusive mass transfer rates from a pinhole in a waste container are developed for constant concentration and inventory-limited source conditions. Mass transport in three media are considered, inside the pinhole (medium 2), outside the container (medium 3) and inside the container (medium 1). Simple equations are developed for radionuclide mass transfer rates from a pinhole. It is shown that the medium with the largest mass transfer resistance need only be considered to provide a conservative estimate of mass transfer rates. (author) 11 refs., 3 figs

Indirectly estimated absolute lung cancer mortality rates by smoking status and histological type based on a systematic review

International Nuclear Information System (INIS)

Lee, Peter N; Forey, Barbara A

2013-01-01

National smoking-specific lung cancer mortality rates are unavailable, and studies presenting estimates are limited, particularly by histology. This hinders interpretation. We attempted to rectify this by deriving estimates indirectly, combining data from national rates and epidemiological studies. We estimated study-specific absolute mortality rates and variances by histology and smoking habit (never/ever/current/former) based on relative risk estimates derived from studies published in the 20 th century, coupled with WHO mortality data for age 70–74 for the relevant country and period. Studies with populations grossly unrepresentative nationally were excluded. 70–74 was chosen based on analyses of large cohort studies presenting rates by smoking and age. Variations by sex, period and region were assessed by meta-analysis and meta-regression. 148 studies provided estimates (Europe 59, America 54, China 22, other Asia 13), 54 providing estimates by histology (squamous cell carcinoma, adenocarcinoma). For all smoking habits and lung cancer types, mortality rates were higher in males, the excess less evident for never smokers. Never smoker rates were clearly highest in China, and showed some increasing time trend, particularly for adenocarcinoma. Ever smoker rates were higher in parts of Europe and America than in China, with the time trend very clear, especially for adenocarcinoma. Variations by time trend and continent were clear for current smokers (rates being higher in Europe and America than Asia), but less clear for former smokers. Models involving continent and trend explained much variability, but non-linearity was sometimes seen (with rates lower in 1991–99 than 1981–90), and there was regional variation within continent (with rates in Europe often high in UK and low in Scandinavia, and higher in North than South America). The indirect method may be questioned, because of variations in definition of smoking and lung cancer type in the

Indirectly estimated absolute lung cancer mortality rates by smoking status and histological type based on a systematic review

Science.gov (United States)

2013-01-01

Background National smoking-specific lung cancer mortality rates are unavailable, and studies presenting estimates are limited, particularly by histology. This hinders interpretation. We attempted to rectify this by deriving estimates indirectly, combining data from national rates and epidemiological studies. Methods We estimated study-specific absolute mortality rates and variances by histology and smoking habit (never/ever/current/former) based on relative risk estimates derived from studies published in the 20th century, coupled with WHO mortality data for age 70–74 for the relevant country and period. Studies with populations grossly unrepresentative nationally were excluded. 70–74 was chosen based on analyses of large cohort studies presenting rates by smoking and age. Variations by sex, period and region were assessed by meta-analysis and meta-regression. Results 148 studies provided estimates (Europe 59, America 54, China 22, other Asia 13), 54 providing estimates by histology (squamous cell carcinoma, adenocarcinoma). For all smoking habits and lung cancer types, mortality rates were higher in males, the excess less evident for never smokers. Never smoker rates were clearly highest in China, and showed some increasing time trend, particularly for adenocarcinoma. Ever smoker rates were higher in parts of Europe and America than in China, with the time trend very clear, especially for adenocarcinoma. Variations by time trend and continent were clear for current smokers (rates being higher in Europe and America than Asia), but less clear for former smokers. Models involving continent and trend explained much variability, but non-linearity was sometimes seen (with rates lower in 1991–99 than 1981–90), and there was regional variation within continent (with rates in Europe often high in UK and low in Scandinavia, and higher in North than South America). Conclusions The indirect method may be questioned, because of variations in definition of smoking and

Reaction of H2 with O2 in Excited Electronic States: Reaction Pathways and Rate Constants.

Science.gov (United States)

Pelevkin, Alexey V; Loukhovitski, Boris I; Sharipov, Alexander S

2017-12-21

Comprehensive quantum chemical analysis with the use of the multireference state-averaged complete active space self-consistent field approach was carried out to study the reactions of H 2 with O 2 in a 1 Δ g , b 1 Σ g + , c 1 Σ u - , and A' 3 Δ u electronically excited states. The energetically favorable reaction pathways and possible intersystem crossings have been revealed. The energy barriers were refined employing the extended multiconfiguration quasi-degenerate second-order perturbation theory. It has been shown that the interaction of O 2 (a 1 Δ g ) and O 2 (A' 3 Δ u ) with H 2 occurs through the H-abstraction process with relatively low activation barriers that resulted in the formation of the HO 2 molecule in A″ and A' electronic states, respectively. Meanwhile, molecular oxygen in singlet sigma states (b 1 Σ g + and c 1 Σ u - ) was proved to be nonreactive with respect to the molecular hydrogen. Appropriate rate constants for revealed reaction and quenching channels have been estimated using variational transition-state theory including corrections for the tunneling effect, possible nonadiabatic transitions, and anharmonicity of vibrations for transition states and reactants. It was demonstrated that the calculated reaction rate constant for the H 2 + O 2 (a 1 Δ g ) process is in reasonable agreement with known experimental data. The Arrhenius approximations for these processes have been proposed for the temperature range T = 300-3000 K.

NVU dynamics. I. Geodesic motion on the constant-potential-energy hypersurface

DEFF Research Database (Denmark)

Ingebrigtsen, Trond; Toxværd, Søren; Heilmann, Ole

2011-01-01

that ensures potential-energy and step-length conservation; center-of-mass drift is also eliminated. Analytical arguments confirmed by simulations demonstrate that the modified NVU algorithm is absolutely stable. Finally, we present simulations showing that the NVU algorithm and the standard leap-frog NVE......An algorithm is derived for computer simulation of geodesics on the constant-potential-energy hypersurface of a system of N classical particles. First, a basic time-reversible geodesic algorithm is derived by discretizing the geodesic stationarity condition and implementing the constant......-potential-energy constraint via standard Lagrangian multipliers. The basic NVU algorithm is tested by single-precision computer simulations of the Lennard-Jones liquid. Excellent numerical stability is obtained if the force cutoff is smoothed and the two initial configurations have identical potential energy within machine...

Measurement of nucleotide exchange rate constants in single rabbit soleus myofibrils during shortening and lengthening using a fluorescent ATP analog.

Science.gov (United States)

Shirakawa, I; Chaen, S; Bagshaw, C R; Sugi, H

2000-02-01

The kinetics of displacement of a fluorescent nucleotide, 2'(3')-O-[N[2-[[Cy3]amido]ethyl]carbamoyl]-adenosine 5'-triphosphate (Cy3-EDA-ATP), bound to rabbit soleus muscle myofibrils were studied using flash photolysis of caged ATP. Use of myofibrils from this slow twitch muscle allowed better resolution of the kinetics of nucleotide exchange than previous studies with psoas muscle myofibrils (, Biophys. J. 73:2033-2042). Soleus myofibrils in the presence of Cy3-EDA-nucleotides (Cy3-EDA-ATP or Cy3-EDA-ADP) showed selective fluorescence staining of the A-band. The K(m) for Cy3-EDA-ATP and the K(d) for Cy3-EDA-ADP binding to the myofibril A-band were 1.9 microM and 3.8 microM, respectively, indicating stronger binding of nucleotide to soleus cross-bridges compared to psoas cross-bridges (2.6 microM and 50 microM, respectively). After flash photolysis of caged ATP, the A-band fluorescence of the myofibril in the Cy3-EDA-ATP solution under isometric conditions decayed exponentially with a rate constant of 0.045 +/- 0.007 s(-1) (n = 32) at 10 degrees C, which was about seven times slower than that for psoas myofibrils. When a myofibril was allowed to shorten with a constant velocity, the nucleotide displacement rate constant increased from 0.066 s(-1) (isometric) to 0.14 s(-1) at 20 degrees C with increasing shortening velocity up to 0.1 myofibril length/s (V(max), the shortening velocity under no load was approximately 0. 2 myofibril lengths/s). The rate constant was not significantly affected by an isovelocity stretch of up to 0.1 myofibril lengths/s. These results suggest that the cross-bridge kinetics are not significantly affected at higher strain during lengthening but depend on the lower strain during shortening. These data also indicate that the interaction distance between a cross-bridge and the actin filament is at least 16 nm for a single cycle of the ATPase.

Near threshold absolute TDCS: First results

International Nuclear Information System (INIS)

Roesel, T.; Schlemmer, P.; Roeder, J.; Frost, L.; Jung, K.; Ehrhardt, H.

1992-01-01

A new method, and first results for an impact energy 2 eV above the threshold of ionisation of helium, are presented for the measurement of absolute triple differential cross sections (TDCS) in a crossed beam experiment. The method is based upon measurement of beam/target overlap densities using known absolute total ionisation cross sections and of detection efficiencies using known absolute double differential cross sections (DDCS). For the present work the necessary absolute DDCS for 1 eV electrons had also to be measured. Results are presented for several different coplanar kinematics and are compared with recent DWBA calculations. (orig.)

Absolute entropy of ions in methanol

International Nuclear Information System (INIS)

Abakshin, V.A.; Kobenin, V.A.; Krestov, G.A.

1978-01-01

By measuring the initial thermoelectromotive forces of chains with bromo-silver electrodes in tetraalkylammonium bromide solutions the absolute entropy of bromide-ion in methanol is determined in the 298.15-318.15 K range. The anti Ssub(Brsup(-))sup(0) = 9.8 entropy units value is used for calculation of the absolute partial molar entropy of alkali metal ions and halogenide ions. It has been found that, absolute entropy of Cs + =12.0 entropy units, I - =14.0 entropy units. The obtained ion absolute entropies in methanol at 298.15 K within 1-2 entropy units is in an agreement with published data

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...... transition state machine that allows to decrease power consumption on the mobile device....

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

Science.gov (United States)

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

1994-01-01

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

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...

Fingerprints of flower absolutes using supercritical fluid chromatography hyphenated with high resolution mass spectrometry.

Science.gov (United States)

Santerre, Cyrille; Vallet, Nadine; Touboul, David

2018-06-02

Supercritical fluid chromatography hyphenated with high resolution mass spectrometry (SFC-HRMS) was developed for fingerprint analysis of different flower absolutes commonly used in cosmetics field, especially in perfumes. Supercritical fluid chromatography-atmospheric pressure photoionization-high resolution mass spectrometry (SFC-APPI-HRMS) technique was employed to identify the components of the fingerprint. The samples were separated with a porous graphitic carbon (PGC) Hypercarb™ column (100 mm × 2.1 mm, 3 μm) by gradient elution using supercritical CO 2 and ethanol (0.0-20.0 min (2-30% B), 20.0-25.0 min (30% B), 25.0-26.0 min (30-2% B) and 26.0-30.0 min (2% B)) as mobile phase at a flow rate of 1.5 mL/min. In order to compare the SFC fingerprints between five different flower absolutes: Jasminum grandiflorum absolutes, Jasminum sambac absolutes, Narcissus jonquilla absolutes, Narcissus poeticus absolutes, Lavandula angustifolia absolutes from different suppliers and batches, the chemometric procedure including principal component analysis (PCA) was applied to classify the samples according to their genus and their species. Consistent results were obtained to show that samples could be successfully discriminated. Copyright © 2018 Elsevier B.V. All rights reserved.

Reactor group constants and benchmark test

Energy Technology Data Exchange (ETDEWEB)

Takano, Hideki [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

2001-08-01

The evaluated nuclear data files such as JENDL, ENDF/B-VI and JEF-2 are validated by analyzing critical mock-up experiments for various type reactors and assessing applicability for nuclear characteristics such as criticality, reaction rates, reactivities, etc. This is called Benchmark Testing. In the nuclear calculations, the diffusion and transport codes use the group constant library which is generated by processing the nuclear data files. In this paper, the calculation methods of the reactor group constants and benchmark test are described. Finally, a new group constants scheme is proposed. (author)

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

International Nuclear Information System (INIS)

Olid, Carolina; Diego, David; Garcia-Orellana, Jordi; Cortizas, Antonio Martínez; Klaminder, Jonatan

2016-01-01

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 210 Pb 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 Pb xs ) 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. - Highlights: • Accurate age dating of peat and sediment cores is critical for evaluating change. • A new 210 Pb dating model that includes vertical transport of 210 Pb was developed. • The IP-CRS model provided consistent peat accumulation rates. • The IP-CRS ages were consistent with independent chronological markers. • The IP-CRS model derives peat ages where downward 210 Pb transport is evidenced.

Fitting the elementary rate constants of the P-gp transporter network in the hMDR1-MDCK confluent cell monolayer using a particle swarm algorithm.

Directory of Open Access Journals (Sweden)

Deep Agnani

Full Text Available P-glycoprotein, a human multidrug resistance transporter, has been extensively studied due to its importance to human health and disease. In order to understand transport kinetics via P-gp, confluent cell monolayers overexpressing P-gp are widely used. The purpose of this study is to obtain the mass action elementary rate constants for P-gp's transport and to functionally characterize members of P-gp's network, i.e., other transporters that transport P-gp substrates in hMDR1-MDCKII confluent cell monolayers and are essential to the net substrate flux. Transport of a range of concentrations of amprenavir, loperamide, quinidine and digoxin across the confluent monolayer of cells was measured in both directions, apical to basolateral and basolateral to apical. We developed a global optimization algorithm using the Particle Swarm method that can simultaneously fit all datasets to yield accurate and exhaustive fits of these elementary rate constants. The statistical sensitivity of the fitted values was determined by using 24 identical replicate fits, yielding simple averages and standard deviations for all of the kinetic parameters, including the efflux active P-gp surface density. Digoxin required additional basolateral and apical transporters, while loperamide required just a basolateral tranporter. The data were better fit by assuming bidirectional transporters, rather than active importers, suggesting that they are not MRP or active OATP transporters. The P-gp efflux rate constants for quinidine and digoxin were about 3-fold smaller than reported ATP hydrolysis rate constants from P-gp proteoliposomes. This suggests a roughly 3∶1 stoichiometry between ATP hydrolysis and P-gp transport for these two drugs. The fitted values of the elementary rate constants for these P-gp substrates support the hypotheses that the selective pressures on P-gp are to maintain a broad substrate range and to keep xenobiotics out of the cytosol, but not out of the

Site-Specific Rate Constant Measurements for Primary and Secondary H- and D-Abstraction by OH Radicals: Propane and n -Butane

KAUST Repository

Badra, Jihad; Nasir, Ehson F.; Farooq, Aamir

2014-01-01

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.

Theoretical study and rate constant calculation for the reactions of SH (SD) with Cl2, Br2, and BrCl.

Science.gov (United States)

Wang, Li; Liu, Jing-Yao; Li, Ze-Sheng; Sun, Chia-Chung

2005-01-30

The mechanisms of the SH (SD) radicals with Cl2 (R1), Br2 (R2), and BrCl (R3) are investigated theoretically, and the rate constants are calculated using a dual-level direct dynamics method. The optimized geometries and frequencies of the stationary points are calculated at the MP2/6-311G(d,p) and MPW1K/6-311G(d,p) levels. Higher-level energies are obtained at the approximate QCISD(T)/6-311++G(3df, 2pd) level using the MP2 geometries as well as by the multicoefficient correlation method based on QCISD (MC-QCISD) using the MPW1K geometries. Complexes with energies less than those of the reactants or products are located at the entrance or the exit channels of these reactions, which indicate that the reactions may proceed via an indirect mechanism. The enthalpies of formation for the species XSH/XSD (X = Cl and Br) are evaluated using hydrogenation working reactions method. By canonical variational transition-state theory (CVT), the rate constants of SH and SD radicals with Cl2, Br2, and BrCl are calculated over a wide temperature range of 200-2000 K at the a-QCISD(T)/6-311++G(3df, 2pd)//MP2/6-311G(d, p) level. Good agreement between the calculated and experimental rate constants is obtained in the measured temperature range. Our calculations show that for SH (SD) + BrCl reaction bromine abstraction (R3a or R3a') leading to the formation of BrSH (BrSD) + Cl in a barrierless process dominants the reaction with the branching ratios for channels 3a and 3a' of 99% at 298 K, which is quite different from the experimental result of k3a'/k3' = 54 +/- 10%. Negative activation energies are found at the higher level for the SH + Br2 and SH + BrCl (Br-abstraction) reactions; as a result, the rate constants show a slightly negative temperature dependence, which is consistent with the determination in the literature. The kinetic isotope effects for the three reactions are "inverse". The values of kH/kD are 0.88, 0.91, and 0.69 at room temperature, respectively, and they increase

Site-Specific Rate Constant Measurements for Primary and Secondary H- and D-Abstraction by OH Radicals: Propane and n -Butane

KAUST Repository

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.

Surface hopping, transition state theory, and decoherence. II. Thermal rate constants and detailed balance

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.

Validation of absolute axial neutron flux distribution calculations with MCNP with 197Au(n,γ)198Au reaction rate distribution measurements at the JSI TRIGA Mark II reactor.

Science.gov (United States)

Radulović, Vladimir; Štancar, Žiga; Snoj, Luka; Trkov, Andrej

2014-02-01

The calculation of axial neutron flux distributions with the MCNP code at the JSI TRIGA Mark II reactor has been validated with experimental measurements of the (197)Au(n,γ)(198)Au reaction rate. The calculated absolute reaction rate values, scaled according to the reactor power and corrected for the flux redistribution effect, are in good agreement with the experimental results. The effect of different cross-section libraries on the calculations has been investigated and shown to be minor. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

Science.gov (United States)

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

2017-06-14

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

A constant velocity Moessbauer spectrometer free of long-term instrumental drifts in the count rate

International Nuclear Information System (INIS)

Sarma, P.R.; Sharma, A.K.; Tripathi, K.C.

1979-01-01

Two new control circuits to be used with a constant velocity Moessbauer spectrometer with a loud-speaker drive have been described. The wave-forms generated in the circuits are of the stair-case type instead of the usual square wave-form, so that in each oscillation of the source it remains stationary for a fraction of the time-period. The gamma-rays counted during this period are monitored along with the positive and negative velocity counts and are used to correct any fluctuation in the count rate by feeding these pulses into the timer. The associated logic circuits have been described and the statistical errors involved in the circuits have been computed. (auth.)

Projective absoluteness for Sacks forcing

NARCIS (Netherlands)

Ikegami, D.

2009-01-01

We show that Sigma(1)(3)-absoluteness for Sacks forcing is equivalent to the nonexistence of a Delta(1)(2) Bernstein set. We also show that Sacks forcing is the weakest forcing notion among all of the preorders that add a new real with respect to Sigma(1)(3) forcing absoluteness.

Forecasting Error Calculation with Mean Absolute Deviation and Mean Absolute Percentage Error

Science.gov (United States)

Khair, Ummul; Fahmi, Hasanul; Hakim, Sarudin Al; Rahim, Robbi

2017-12-01

Prediction using a forecasting method is one of the most important things for an organization, the selection of appropriate forecasting methods is also important but the percentage error of a method is more important in order for decision makers to adopt the right culture, the use of the Mean Absolute Deviation and Mean Absolute Percentage Error to calculate the percentage of mistakes in the least square method resulted in a percentage of 9.77% and it was decided that the least square method be worked for time series and trend data.

Development and application of a detector for absolute measurement of neutron fluence rate in MeV region

International Nuclear Information System (INIS)

Silva Dias, M. da.

1988-01-01

The development and performance of the DTS (Dual Thin Scintillator) for the absolute measurement of the neutron fluence rate between 1 and 15 MeV is decribed. The DTS detector consists of a pair of organic scintillators in a dual configuration, where the incident produces a proton-recoil which is detected in a 2Π geometry therefore avoiding the effect of the escape of protons. Thin scintillators are used resulting in small multiple scattering corrections. The theoretical caluclations of detector efficiency and proton-recoil spectrum were performed by means of a Monte Carlos code - CARLO DTS. The calculated efficiency was compared to the experimental one at two neutron energies namely 2.446 MeV and 14.04 MeV applying the Time Correlated Associated Particle technique. The theoretical and experimental efficiencies agreed within the experimental uncertainties of 1.44% and 0.77%, respectively. The performance of the DTS has been verified in an absolute 235 U(n,f) cross section measurement between 1 and 6 MeV neutron energy. The cross section results were compared to those obtained replacing the DTS detector by the NBS (National Bureau of Standards, USA) Black Neutron Detector. The agreement was excellent in the overlapping energy interval of the two experiments (between 1 and 3 MeV), within the estimated uncertainly in the range of 1,0 to 1,7%. The agreement with the most recent evaluation from the ENDF/B-VI was excellent in almost all the energy range between 1 and 6 MeV. The 235 U(n,f) cross section, average over the 252 Cf fission neutron spectrum has been evaluated. The result including the cross section values of the present work was 1220 mb, in excellent agreement with the average value among the most recent measurements, 1227 +- 12 mb, and with the value 1213 mb, using the ENDF/B-VI data. (author) [pt

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

Science.gov (United States)

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

1988-01-01

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

Optimal mutation rates for the (1+λ) EA on OneMax

DEFF Research Database (Denmark)

Gießen, Christian; Witt, Carsten

2016-01-01

We study the (1 + λ) EA with mutation probability c/n, where c > 0 is a constant, on the ONEMAX problem. Using an improved variable drift theorem, we show that upper and lower bounds on the expected runtime of the (1+λ) EA obtained from variable drift theorems are at most apart by a small lower...... mutation rates for the (1+λ) EA for various parameter settings of c and λ and also for moderate sizes of n. This makes the need for potentially lengthy and costly experiments in order to optimize the parameters unnecessary. Interestingly, even for moderate n and not too small λ it turns out that mutation...... rates up to 10% larger than the asymptotically optimal rate 1/n minimize the expected runtime. However, in absolute terms the expected runtime does not change by much when replacing 1/n with the optimal mutation rate....

Fine-structure constant: Is it really a constant

International Nuclear Information System (INIS)

Bekenstein, J.D.

1982-01-01

It is often claimed that the fine-structure ''constant'' α is shown to be strictly constant in time by a variety of astronomical and geophysical results. These constrain its fractional rate of change alpha-dot/α to at least some orders of magnitude below the Hubble rate H 0 . We argue that the conclusion is not as straightforward as claimed since there are good physical reasons to expect alpha-dot/α 0 . We propose to decide the issue by constructing a framework for a variability based on very general assumptions: covariance, gauge invariance, causality, and time-reversal invariance of electromagnetism, as well as the idea that the Planck-Wheeler length (10 -33 cm) is the shortest scale allowable in any theory. The framework endows α with well-defined dynamics, and entails a modification of Maxwell electrodynamics. It proves very difficult to rule it out with purely electromagnetic experiments. In a cosmological setting, the framework predicts an alpha-dot/α which can be compatible with the astronomical constraints; hence, these are too insensitive to rule out α variability. There is marginal conflict with the geophysical constraints: however, no firm decision is possible because of uncertainty about various cosmological parameters. By contrast the framework's predictions for spatial gradients of α are in fatal conflict with the results of the Eoetvoes-Dicke-Braginsky experiments. Hence these tests of the equivalence principle rule out with confidence spacetime variability of α at any level

Temperature dependence of the rate constant for reactions of hydrated electrons with H, OH and H2O2

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......-1 and E(A) = 15.6 kJ mol-1 (3.7 kcal mol-1) measured from 5-150-degrees-C. Thus, the activation energy for all three fast reactions is close to that expected for diffusion controlled reactions. As phosphates were used as buffer system, the rate constant and activation energy for the reaction......(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...

New perspectives on constant-roll inflation

Science.gov (United States)

Cicciarella, Francesco; Mabillard, Joel; Pieroni, Mauro

2018-01-01

We study constant-roll inflation using the β-function formalism. We show that the constant rate of the inflaton roll is translated into a first order differential equation for the β-function which can be solved easily. The solutions to this equation correspond to the usual constant-roll models. We then construct, by perturbing these exact solutions, more general classes of models that satisfy the constant-roll equation asymptotically. In the case of an asymptotic power law solution, these corrections naturally provide an end to the inflationary phase. Interestingly, while from a theoretical point of view (in particular in terms of the holographic interpretation) these models are intrinsically different from standard slow-roll inflation, they may have phenomenological predictions in good agreement with present cosmological data.

Comparison of the rate constants for energy transfer in the light-harvesting protein, C-phycocyanin, calculated from Foerster`s theory and experimentally measured by time-resolved fluorescence spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Debreczeny, Martin Paul [Univ. of California, Berkeley, CA (United States)

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.

PC based system for absolute neutron flux-spectrum measurements. Final report for the period 1 April 1994 - 15 December 1997

International Nuclear Information System (INIS)

Dobrea, D.

1998-01-01

When measuring absolute neutron flux-spectra, thin detector foils are irradiated in a neutron field. The absolute activity of isotopes generated by activation or fission reactions (fission products) is then measured, using an efficiency calibrated high resolution gamma-ray spectroscopy system, and the absolute reaction rates for their production is determined. Finally the flux-spectrum is determined based upon the reaction rate values. A general method to obtain flux-spectra from the reaction rate is the unfolding method. The above process involves computations of photopeak area, reaction rate, flux perturbation corrections and flux-spectrum. The PC's are well suited for the data processing system outlined above. Using available interfaces, the PC's can be involved even in the data acquisition. Graphical facilities allow decision upon the data processing flow

Commissioning of the Absolute Luminosity For ATLAS detector at the LHC

CERN Document Server

Jakobsen, Sune; Hansen, Peter; Hansen, Jørgen Beck

The startup of the LHC (Large Hadron Collider) has initialized a new era in particle physics. The standard model of particle physics has for the last 40 years with tremendous success described all measurements with phenomenal precision. The experiments at the LHC are testing the standard model in a new energy regime. To normalize the measurements and understand the potential discoveries of the LHC experiments it is often crucial to know the interaction rate - the absolute luminosity. The ATLAS (A Toroidal LHC ApparatuS) detector will measure luminosity by numerous methods. But for most of the methods only the relative luminosity is measured with good precision. The absolute scale has to be provided from elsewhere. ATLAS is like the other LHC experiments mainly relying of absolute luminosity calibration from van der Meer scans (beam separation scans). To cross check and maybe even improve the precision; ATLAS has built a sub-detector to measure the flux of protons scattered under very small angles as this flux...

Comparative study of sclerotherapy of venous malformation in children using absolute ethanol and pingyangmycin

International Nuclear Information System (INIS)

Zhang Jing; Li Haobo; Zhou Shaoyi; Chen Kunshan; Niu Chuanqiang; Tan Xiaoyun; Jiang Yizhou; Lin Queqing

2012-01-01

Objective: To evaluate and compare the curative effect and the safety of sclerotherapy of venous malformation in children using absolute ethanol and pingyangmycin. Methods: Eighty children with venous malformation were treated by sclerotherapy with absolute ethanol or pingyangmycin under general anesthesia during February of 2009 to May of 2011. Diagnostic criteria included the presence of a blue-colored lesion at birth, with gradual increase in its size associated with a positive postural test. MRI showed characteristic imaging features. Eighty patients were divided into two groups by randomization. Forty patients were treated with absolute ethanol, and the remaining 40 patients with pingyangmycin. The therapeutic effects and side effects were observed and recorded during a follow-up period of 6 to 24 months (average 15 months). Treatment results were divided into four categories: cure, basic cure, effective, and ineffective, and the former three categories were considered effective in treatment. Chi-square test was used to compare the rate of effective treatment and rate of complications in these two groups. Results: The effective patients treated with absolute ethanol was 38 (95.0%, 38/40), and the effective patients with pingyangmycin was 26 (65.0%, 26/40), χ 2 test (χ 2 =11.25, P<0.01) difference was statistically significant. Eight patients developed skin necrosis; 4 patients serious local swelling, 2 patients muscle fibrosis, 1 patient cerebral embolism in the absolute alcohol group. Two patients developed postoperative fever and vomiting and 2 skin necrosis in the pingyangmycin group,the difference was statistically significant (χ 2 =12.29, P<0.01). Conclusions: Sclerotherapy is effective for the treatment of venous malformations in children. Absolute ethanol is more effective, but associated with more complications, such as skin necrosis or as serious as cerebral embolism, than pingyangmycin. (authors)

Constant mortality and fertility over age in Hydra

DEFF Research Database (Denmark)

Schaible, R.; Scheuerlein, A.; Danko, M. J.

2015-01-01

that 2,256 Hydra from two closely related species in two laboratories in 12 cohorts, with cohort age ranging from 0 to more than 41 y, have extremely low, constant rates of mortality. Fertility rates for Hydra did not systematically decline with advancing age. This falsifies the universality......Senescence, the increase in mortality and decline in fertility with age after maturity, was thought to be inevitable for all multicellular species capable of repeated breeding. Recent theoretical advances and compilations of data suggest that mortality and fertility trajectories can go up or down......, or remain constant with age, but the data are scanty and problematic. Here, we present compelling evidence for constant age-specific death and reproduction rates in Hydra, a basal metazoan, in a set of experiments comprising more than 3.9 million days of observations of individual Hydra. Our data show...

USING IN VIVO GAS UPDATE STUDIES TO ESTIMATE METABOLIC RATE CONSTANTS FOR CCL CHEMICALS: 1,1-DICHLOROPROPANE AND 2,2-DICHLOROPROPANE

Science.gov (United States)

USING IN VIVO GAS UPTAKE STUDIES TO ESTIMATE METABOLIC RATE CONSTANTS FOR CCL CHEMICALS: 1,1-DICHLOROPROPENE AND 2,2-DICHLOROPROPANE. Mitchell, C T, Evans, M V, Kenyon, E M. NHEERL, U.S. EPA, ORD, ETD, RTP, NC The Safe Drinking Water Act Amendments of 1996 required ...

Direct Dynamics Simulation of the Thermal 3CH2 + 3O2 Reaction. Rate Constant and Product Branching Ratios.

Science.gov (United States)

Lakshmanan, Sandhiya; Pratihar, Subha; Machado, Francisco Bolivar Correto; Hase, William Louis

2018-04-26

The reaction of 3CH2 with 3O2 is of fundamental importance in combustion and the reaction is complex as a result of multiple extremely exothermic product channels. In the present study, direct dynamics simulations were performed to study the reaction on both the singlet and triplet potential energy surfaces (PESs). The simulations were performed at the UM06/6-311++G(d,p) level of theory. Trajectories were calculated at a temperature of 300 K and all reactive trajectories proceeded through the carbonyl oxide Criegee intermediate, CH2OO, on both the singlet and triplet PESs. The triplet surface leads to only one product channel, H2CO + O(3P), while the singlet surface leads to 8 product channels with their relative importance as: CO + H2O > CO + OH + H ~ H2CO + O(1D) > HCO + OH ~ CO2 + H2 ~ CO + H2 + O(1D) > CO2 + H + H > HCO + O(1D) + H. Reaction on the singlet PES is barrierless, consistent with experiment and the total rate constant on the singlet surface is 0.93 ± 0.22 x 10-12 cm3molecule-1s-1 in comparison to the recommended experimental rate constant of 3.3 x 10-12 cm3molecule-1s-1. The simulation product yields for the singlet PES are compared with experiment and the most significant differences are for H, CO2, and H2O. Reaction on the triplet surface is also barrierless, inconsistent with experiment. A discussion is given of the need for future calculations to address the: (1) barrier on the triplet PES for 3CH2 + 3O2 → 3CH2OO; (2) temperature dependence of the 3CH2 + 3O2 reaction rate constant and product branching ratios; and (3) possible non-RRKM dynamics of the 1CH2OO Criegee intermediate.

Variance computations for functional of absolute risk estimates.

Science.gov (United States)

Pfeiffer, R M; Petracci, E

2011-07-01

We present a simple influence function based approach to compute the variances of estimates of absolute risk and functions of absolute risk. We apply this approach to criteria that assess the impact of changes in the risk factor distribution on absolute risk for an individual and at the population level. As an illustration we use an absolute risk prediction model for breast cancer that includes modifiable risk factors in addition to standard breast cancer risk factors. Influence function based variance estimates for absolute risk and the criteria are compared to bootstrap variance estimates.

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

Directory of Open Access Journals (Sweden)

Perumal Puvanasvaran

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.

Absolute determination of the deuterium content of heavy water, measurement of absolute density

International Nuclear Information System (INIS)

Ceccaldi, M.; Riedinger, M.; Menache, M.

1975-01-01

The absolute density of two heavy water samples rich in deuterium (with a grade higher than 99.9%) was determined with the hydrostatic method. The exact isotopic composition of this water (hydrogen and oxygen isotopes) was very carefully studied. A theoretical estimate enabled us to get the absolute density value of isotopically pure D 2 16 O. This value was found to be 1104.750 kg.m -3 at t 68 =22.3 0 C and under the pressure of one atmosphere. (orig.) [de

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

International Nuclear Information System (INIS)

Nesseris, Savvas; Blake, Chris; Davis, Tamara; Parkinson, David

2011-01-01

We constrain the evolution of Newton's constant using the growth rate of large-scale structure measured by the WiggleZ Dark Energy Survey in the redshift range 0.1 m (assuming General Relativity), and use this to construct a diagnostic to detect the presence of an evolving Newton's constant. Secondly we directly measure the evolution of Newton's constant, G eff , that appears in Modified Gravity theories, without assuming General Relativity to be true. The novelty of these approaches are that, contrary to other methods, they do not require knowledge of the expansion history of the Universe, H(z), making them model independent tests. Our constraints for the second derivative of Newton's constant at the present day, assuming it is slowly evolving as suggested by Big Bang Nucleosynthesis constraints, using the WiggleZ data is G double-dot eff (t 0 ) = −1.19 ± 0.95·10 −20 h 2 yr −2 , where h is defined via H 0 = 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-dot eff (t 0 ) = −3.6 ± 6.8·10 −21 h 2 yr −2 , both being consistent with General Relativity. Finally, our constraint for the rms mass fluctuation σ 8 using the WiggleZ data is σ 8 = 0.75 ± 0.08, while using both the WiggleZ and the SDSS LRG data σ 8 = 0.77 ± 0.07, both in good agreement with the latest measurements from the Cosmic Microwave Background radiation

The absolute environmental performance of buildings

DEFF Research Database (Denmark)

Brejnrod, Kathrine Nykjær; Kalbar, Pradip; Petersen, Steffen

2017-01-01

Our paper presents a novel approach for absolute sustainability assessment of a building's environmental performance. It is demonstrated how the absolute sustainable share of the earth carrying capacity of a specific building type can be estimated using carrying capacity based normalization factors....... A building is considered absolute sustainable if its annual environmental burden is less than its share of the earth environmental carrying capacity. Two case buildings – a standard house and an upcycled single-family house located in Denmark – were assessed according to this approach and both were found...... to exceed the target values of three (almost four) of the eleven impact categories included in the study. The worst-case excess was for the case building, representing prevalent Danish building practices, which utilized 1563% of the Climate Change carrying capacity. Four paths to reach absolute...

Constant strain rate experiments and constitutive modeling for a class of bitumen

Science.gov (United States)

Reddy, Kommidi Santosh; Umakanthan, S.; Krishnan, J. Murali

2012-08-01

The mechanical properties of bitumen vary with the nature of the crude source and the processing methods employed. To understand the role of the processing conditions played in the mechanical properties, bitumen samples derived from the same crude source but processed differently (blown and blended) are investigated. The samples are subjected to constant strain rate experiments in a parallel plate rheometer. The torque applied to realize the prescribed angular velocity for the top plate and the normal force applied to maintain the gap between the top and bottom plate are measured. It is found that when the top plate is held stationary, the time taken by the torque to be reduced by a certain percentage of its maximum value is different from the time taken by the normal force to decrease by the same percentage of its maximum value. Further, the time at which the maximum torque occurs is different from the time at which the maximum normal force occurs. Since the existing constitutive relations for bitumen cannot capture the difference in the relaxation times for the torque and normal force, a new rate type constitutive model, incorporating this response, is proposed. Although the blended and blown bitumen samples used in this study correspond to the same grade, the mechanical responses of the two samples are not the same. This is also reflected in the difference in the values of the material parameters in the model proposed. The differences in the mechanical properties between the differently processed bitumen samples increase further with aging. This has implications for the long-term performance of the pavement.

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-01-15

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

40 CFR 1065.644 - Vacuum-decay leak rate.

Science.gov (United States)

2010-07-01

... criterion specified in § 1065.345(e). ER06MY08.028 Where: V vac = geometric volume of the vacuum-side of the sampling system. R = molar gas constant. p 2 = Vacuum-side absolute pressure at time t2. T 2 = Vacuum-side...

A Simulation Analysis of Errors in the Measurement of Standard Electrochemical Rate Constants from Phase-Selective Impedance Data.

Science.gov (United States)

1987-09-30

RESTRICTIVE MARKINGSC Unclassif ied 2a SECURIly CLASSIFICATION ALIIMOA4TY 3 DIS1RSBj~jiOAVAILAB.I1Y OF RkPORI _________________________________ Approved...of the AC current, including the time dependence at a growing DME, at a given fixed potential either in the presence or the absence of an...the relative error in k b(app) is ob relatively small for ks (true) : 0.5 cm s-, and increases rapidly for ob larger rate constants as kob reaches the

Systematics of constant roll inflation

Science.gov (United States)

Anguelova, Lilia; Suranyi, Peter; Wijewardhana, L. C. R.

2018-02-01

We study constant roll inflation systematically. This is a regime, in which the slow roll approximation can be violated. It has long been thought that this approximation is necessary for agreement with observations. However, recently it was understood that there can be inflationary models with a constant, and not necessarily small, rate of roll that are both stable and compatible with the observational constraint ns ≈ 1. We investigate systematically the condition for such a constant-roll regime. In the process, we find a whole new class of inflationary models, in addition to the known solutions. We show that the new models are stable under scalar perturbations. Finally, we find a part of their parameter space, in which they produce a nearly scale-invariant scalar power spectrum, as needed for observational viability.

The role of serum non-cholesterol sterols as surrogate markers of absolute cholesterol synthesis and absorption.

Science.gov (United States)

Miettinen, T A; Gylling, H; Nissinen, M J

2011-10-01

To study the whole-body cholesterol metabolism in man, cholesterol synthesis and absorption need to be measured. Because of the complicated methods of the measurements, new approaches were developed including the analysis of serum non-cholesterol sterols. In current lipidologic papers and even in intervention studies, serum non-cholesterol sterols are frequently used as surrogate markers of cholesterol metabolism without any validation to the absolute metabolic variables. The present review compares serum non-cholesterol sterols with absolute measurements of cholesterol synthesis and absorption in published papers to find out whether the serum markers are valid indicators of cholesterol metabolism in various conditions. During statin treatment, during interventions of dietary fat, and in type 2 diabetes the relative and absolute variables of cholesterol synthesis and absorption were frequently but not constantly correlated with each other. In some occasions, especially in subjects with apolipoprotein E3/4 and E4/4 phenotypes, the relative metabolic markers were even more sensitive than the absolute ones to reflect changes in cholesterol metabolism during dietary interventions. Even in general population at very high absorption the homeostasis of cholesterol metabolism is disturbed damaging the validity of the serum markers. It is worth using several instead of only one precursor and absorption sterol marker for making conclusions of altered synthesis or absorption of cholesterol, and even then the presence of at least some absolute measurement is valuable. During consumption of plant sterol-enriched diets and in situations of interfered cholesterol homeostasis the relative markers do not adequately reflect cholesterol metabolism. Accordingly, the validity of the relative markers of cholesterol metabolism should not be considered as self-evident. Copyright © 2011 Elsevier B.V. All rights reserved.

Absolute Summ

Science.gov (United States)

Phillips, Alfred, Jr.

Summ means the entirety of the multiverse. It seems clear, from the inflation theories of A. Guth and others, that the creation of many universes is plausible. We argue that Absolute cosmological ideas, not unlike those of I. Newton, may be consistent with dynamic multiverse creations. As suggested in W. Heisenberg's uncertainty principle, and with the Anthropic Principle defended by S. Hawking, et al., human consciousness, buttressed by findings of neuroscience, may have to be considered in our models. Predictability, as A. Einstein realized with Invariants and General Relativity, may be required for new ideas to be part of physics. We present here a two postulate model geared to an Absolute Summ. The seedbed of this work is part of Akhnaton's philosophy (see S. Freud, Moses and Monotheism). Most important, however, is that the structure of human consciousness, manifest in Kenya's Rift Valley 200,000 years ago as Homo sapiens, who were the culmination of the six million year co-creation process of Hominins and Nature in Africa, allows us to do the physics that we do. .

Absolute Gravimetry in Fennoscandia

DEFF Research Database (Denmark)

Pettersen, B. R; TImmen, L.; Gitlein, O.

The Fennoscandian postglacial uplift has been mapped geometrically using precise levelling, tide gauges, and networks of permanent GPS stations. The results identify major uplift rates at sites located around the northern part of the Gulf of Bothnia. The vertical motions decay in all directions...... motions) has its major axis in the direction of southwest to northeast and covers a distance of about 2000 km. Absolute gravimetry was made in Finland and Norway in 1976 with a rise-and fall instrument. A decade later the number of gravity stations was expanded by JILAg-5, in Finland from 1988, in Norway...... time series of several years are now available. Along the coast there are nearby tide gauge stations, many of which have time series of several decades. We describe the observing network, procedures, auxiliary observations, and discuss results obtained for selected sites. We compare the gravity results...

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

KAUST Repository

Sudhakaran, Sairam; Amy, Gary L.

2013-01-01

. 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

Rate constants for the slow Mu + propane abstraction reaction at 300 K by diamagnetic RF resonance.

Science.gov (United States)

Fleming, Donald G; Cottrell, Stephen P; McKenzie, Iain; Ghandi, Khashayar

2015-08-14

The study of kinetic isotope effects for H-atom abstraction rates by incident H-atoms from the homologous series of lower mass alkanes (CH4, C2H6 and, here, C3H8) provides important tests of reaction rate theory on polyatomic systems. With a mass of only 0.114 amu, the most sensitive test is provided by the rates of the Mu atom. Abstraction of H by Mu can be highly endoergic, due to the large zero-point energy shift in the MuH bond formed, which also gives rise to high activation energies from similar zero-point energy corrections at the transition state. Rates are then far too slow near 300 K to be measured by conventional TF-μSR techniques that follow the disappearance of the spin-polarised Mu atom with time. Reported here is the first measurement of a slow Mu reaction rate in the gas phase by the technique of diamagnetic radio frequency (RF) resonance, where the amplitude of the MuH product formed in the Mu + C3H8 reaction is followed with time. The measured rate constant, kMu = (6.8 ± 0.5) × 10(-16) cm(3) s(-1) at 300 K, is surprisingly only about a factor of three slower than that expected for H + C3H8, indicating a dominant contribution from quantum tunneling in the Mu reaction, consistent with elementary transition state theory calculations of the kMu/kH kinetic isotope effect.

A new variable interval schedule with constant hazard rate and finite time range.

Science.gov (United States)

Bugallo, Mehdi; Machado, Armando; Vasconcelos, Marco

2018-05-27

We propose a new variable interval (VI) schedule that achieves constant probability of reinforcement in time while using a bounded range of intervals. By sampling each trial duration from a uniform distribution ranging from 0 to 2 T seconds, and then applying a reinforcement rule that depends linearly on trial duration, the schedule alternates reinforced and unreinforced trials, each less than 2 T seconds, while preserving a constant hazard function. © 2018 Society for the Experimental Analysis of Behavior.

Absolute flux scale for radioastronomy

International Nuclear Information System (INIS)

Ivanov, V.P.; Stankevich, K.S.

1986-01-01

The authors propose and provide support for a new absolute flux scale for radio astronomy, which is not encumbered with the inadequacies of the previous scales. In constructing it the method of relative spectra was used (a powerful tool for choosing reference spectra). A review is given of previous flux scales. The authors compare the AIS scale with the scale they propose. Both scales are based on absolute measurements by the ''artificial moon'' method, and they are practically coincident in the range from 0.96 to 6 GHz. At frequencies above 6 GHz, 0.96 GHz, the AIS scale is overestimated because of incorrect extrapolation of the spectra of the primary and secondary standards. The major results which have emerged from this review of absolute scales in radio astronomy are summarized

Realization of a frequency standard at 778 nm: absolute frequency measurement of the 2S-8S/D transitions in hydrogen and deuterium and determination of the Rydberg constant; Realisation d'un etalon de frequence a 778 nm: mesure absolue des frequences 2S-8S/D des atomes d'hydrogene et de deuterium et determination de la constante de rydberg

Energy Technology Data Exchange (ETDEWEB)

Beauvoir, B. de

1996-12-15

The purpose of this work is to design a 778 nm standard laser for performing an absolute measurement of 2S-8S/D frequencies of hydrogen and deuterium atoms. This frequency calibration is based on a 5S-5D two-photon transition of the rubidium atom. Metrological performance of this laser is 10 times as good as that of He-Ne laser calibrated on iodine. It has been shown that the passage of a laser radiation through an optic fiber does not deteriorate its metrological properties. 2S-8S/8D transitions have been excited in an atomic jet by a titanium-sapphire laser. Spurious effects can shift and broaden lines. In order to prevent these effects, a theoretical line has been shaped and adjusted on experimental signals. The frequency comparison between the excitation laser and the standard laser has led to the measurement of the absolute frequency of the line concerned. The value of the Rydberg constant has been deduced: R{sub {infinity}} = 109737.3156859 (10) cm{sup -1}. The comparison of experimental data between deuterium and hydrogen has allowed us to determine the value of the Lamb shift of the 2S state of deuterium: L(2S-2P) = 1059,230 (9) MHz.

Transition probabilities and radiative decay constants of the excited levels of Ne

International Nuclear Information System (INIS)

Wosinski, L.

1981-01-01

Transition probabilities for eight optical transitions between the 3p and 3d neon levels have been measured by the ''plasma transparency method''. The transitions probabilities are placed on an absolute scale by use of the recently reported values for the 4p→3s transitions. The measurements of induced changes in populations allowed the determination of the ratios of the radiative decay constants for the 4p and 3d levels. The experimental results are compared with the theoretically calculated transitions probabilities of Murphy and Lilly. (author)

Discovery of a Significant Acetone•Hydroperoxy Adduct Chaperone Effect and Its Impact on the Determination of Room Temperature Rate Constants for Acetonylperoxy/Hydroperoxy Self-Reactions and Cross Reaction Via Infrared Kinetic Spectroscopy.

Science.gov (United States)

Grieman, F. J.; Hui, A. O.; Okumura, M.; Sander, S. P.

2017-12-01

In order to model the upper troposphere/lower stratosphere in regions containing acetone properly, the kinetics of the acetonylperoxy/hydroperoxy self-reactions and cross reaction have been studied over a wide temperature range using Infrared Kinetic Spectroscopy. We report here the determination of different rate constants for the acetonylperoxy chemistry that we obtained at 298 K compared to currently accepted values. A considerable increase in the observed HO2 self-reaction rate constant due to rate enhancement via the chaperone effect from the reaction between HO2 and the (CH3)2CO•HO2 hydrogen-bonded adduct, even at room temperature, was discovered that was previously ignored. Correct determination of the acetonylperoxy and hydroperoxy kinetics must include this dependence of the HO2 self-reaction rate on acetone concentration. Via excimer laser flash photolysis to create the radical reactants, HO2 absorption was monitored in the infrared by diode laser wavelength modulation detection simultaneously with CH3C(O)CH2O2absorption monitored in the ultraviolet at 300 nm as a function of time. Resulting decay curves were fit concurrently first over a short time scale to obtain the rate constants minimizing subsequent product reactions. Modeling/fitting with a complete reaction scheme was then performed to refine the rate constants and test their veracity. Experiments were carried out over a variety of concentrations of acetone and methanol. Although no effect due to methanol concentration was found at room temperature, the rate constant for the hydroperoxy self-reaction was found to increase linearly with acetone concentration which is interpreted as the adduct being formed and resulting in a chaperone mechanism that enhances the self-reaction rate: (CH3)2CO·HO2 + HO2 → H2O2 + O2 + (CH3)2CO Including this effect, the resulting room temperature rate constants for the cross reaction and the acetonylperoxy self-reaction were found to be 2-3 times smaller than

Quantum mechanical calculations of state-to-state cross sections and rate constants for the F + DCl → Cl + DF reaction.

Science.gov (United States)

Bulut, Niyazi; Kłos, Jacek; Roncero, Octavio

2015-06-07

We present accurate state-to-state quantum wave packet calculations of integral cross sections and rate constants for the title reaction. Calculations are carried out on the best available ground 1(2)A' global adiabatic potential energy surface of Deskevich et al. [J. Chem. Phys. 124, 224303 (2006)]. Converged state-to-state reaction cross sections have been calculated for collision energies up to 0.5 eV and different initial rotational and vibrational excitations, DCl(v = 0, j = 0 - 1; v = 1, j = 0). Also, initial-state resolved rate constants of the title reaction have been calculated in a temperature range of 100-400 K. It is found that the initial rotational excitation of the DCl molecule does not enhance reactivity, in contract to the reaction with the isotopologue HCl in which initial rotational excitation produces an important enhancement. These differences between the isotopologue reactions are analyzed in detail and attributed to the presence of resonances for HCl(v = 0, j), absent in the case of DCl(v = 0, j). For vibrational excited DCl(v = 1, j), however, the reaction cross section increases noticeably, what is also explained by another resonance.

Gender equality and women's absolute status: a test of the feminist models of rape.

Science.gov (United States)

Martin, Kimberly; Vieraitis, Lynne M; Britto, Sarah

2006-04-01

Feminist theory predicts both a positive and negative relationship between gender equality and rape rates. Although liberal and radical feminist theory predicts that gender equality should ameliorate rape victimization, radical feminist theorists have argued that gender equality may increase rape in the form of male backlash. Alternatively, Marxist criminologists focus on women's absolute socioeconomic status rather than gender equality as a predictor of rape rates, whereas socialist feminists combine both radical and Marxist perspectives. This study uses factor analysis to overcome multicollinearity limitations of past studies while exploring the relationship between women's absolute and relative socioeconomic status on rape rates in major U.S. cities using 2000 census data. The findings indicate support for both the Marxist and radical feminist explanations of rape but no support for the ameliorative hypothesis. These findings support a more inclusive socialist feminist theory that takes both Marxist and radical feminist hypotheses into account.

A global algorithm for estimating Absolute Salinity

Science.gov (United States)

McDougall, T. J.; Jackett, D. R.; Millero, F. J.; Pawlowicz, R.; Barker, P. M.

2012-12-01

The International Thermodynamic Equation of Seawater - 2010 has defined the thermodynamic properties of seawater in terms of a new salinity variable, Absolute Salinity, which takes into account the spatial variation of the composition of seawater. Absolute Salinity more accurately reflects the effects of the dissolved material in seawater on the thermodynamic properties (particularly density) than does Practical Salinity. When a seawater sample has standard composition (i.e. the ratios of the constituents of sea salt are the same as those of surface water of the North Atlantic), Practical Salinity can be used to accurately evaluate the thermodynamic properties of seawater. When seawater is not of standard composition, Practical Salinity alone is not sufficient and the Absolute Salinity Anomaly needs to be estimated; this anomaly is as large as 0.025 g kg-1 in the northernmost North Pacific. Here we provide an algorithm for estimating Absolute Salinity Anomaly for any location (x, y, p) in the world ocean. To develop this algorithm, we used the Absolute Salinity Anomaly that is found by comparing the density calculated from Practical Salinity to the density measured in the laboratory. These estimates of Absolute Salinity Anomaly however are limited to the number of available observations (namely 811). In order to provide a practical method that can be used at any location in the world ocean, we take advantage of approximate relationships between Absolute Salinity Anomaly and silicate concentrations (which are available globally).

Constant extension rate testing of Type 304L stainless steel in simulated waste tank environments

International Nuclear Information System (INIS)

Wiersma, B.J.

1992-01-01

New tanks for storage of low level radioactive wastes will be constructed at the Savannah River Site (SRS) of AISI Type 304L stainless steel (304L). The presence of chlorides and fluorides in the wastes may induce Stress Corrosion Cracking (SCC) in 304L. Constant Extension Rate Tests (CERT) were performed to determine the susceptibility of 304L to SCC in simulated wastes. In five of the six tests conducted thus far 304L was not susceptible to SCC in the simulated waste environments. Conflicting results were obtained in the final test and will be resolved by further tests. For comparison purposes the CERT tests were also performed with A537 carbon steel, a material similar to that utilized for the existing nuclear waste storage tanks at SRS

Constant-roll (quasi-)linear inflation

Science.gov (United States)

Karam, A.; Marzola, L.; Pappas, T.; Racioppi, A.; Tamvakis, K.

2018-05-01

In constant-roll inflation, the scalar field that drives the accelerated expansion of the Universe is rolling down its potential at a constant rate. Within this framework, we highlight the relations between the Hubble slow-roll parameters and the potential ones, studying in detail the case of a single-field Coleman-Weinberg model characterised by a non-minimal coupling of the inflaton to gravity. With respect to the exact constant-roll predictions, we find that assuming an approximate slow-roll behaviour yields a difference of Δ r = 0.001 in the tensor-to-scalar ratio prediction. Such a discrepancy is in principle testable by future satellite missions. As for the scalar spectral index ns, we find that the existing 2-σ bound constrains the value of the non-minimal coupling to ξphi ~ 0.29–0.31 in the model under consideration.

Ideal Gas with a Varying (Negative Absolute) Temperature: an Alternative to Dark Energy?

Science.gov (United States)

Saha, Subhajit; Mondal, Anindita; Corda, Christian

2018-02-01

The present work is an attempt to investigate whether the evolutionary history of the Universe from the offset of inflation can be described by assuming the cosmic fluid to be an ideal gas with a specific gas constant but a varying negative absolute temperature (NAT). The motivation of this work is to search for an alternative to the "exotic" and "supernatural" dark energy (DE). In fact, the NAT works as an "effective quintessence" and there is need to deal neither with exotic matter like DE nor with modified gravity theories. For the sake of completeness, we release some clarifications on NATs in Section 3 of the paper.

Determination of the rate constant for neuronal and extra-neuronal monoamine oxidase

International Nuclear Information System (INIS)

Cassis, L.; Ludwig, J.; Trendelenburg, U.

1986-01-01

In the rat vas deferens, neuronal deamination of 3 H-(-) noradrenaline ( 3 H-NA) to 3 H-dihydroxyphenethylglycol ( 3 HDOPEG) cannot be inhibited by pretreatment with a monoamine oxidase (MAO) inhibitor. However, in the extraneuronal compartment of the rat heart, inhibition of MAO abolishes the formation of 3 HDOPEG. To clarify this discrepancy, the authors determined the rate constant for MAO (/sup k/mao/) neuronally (rat vas deferens) and extraneuronally (rat heart). For neuronal /sup k/mao, vasa deferentia were incubated with 3 HNA for 300 minutes, and the cumulative formation of 3 HDOPEG measured. The delay in time before 3 HDOPEG achieves steady state (/sup tau/system), is inversely proportional to /sup k/mao. Because /sup tau/system is very short for neuronal MAO, an appreciable delay was only achieved after partial inhibition of MAO with various parglyline concentrations. To relate to the uninhibited enzyme, the percentage inhibition by pargyline was then determined in homogenate preparations. For extraneuronal MAO, a similar procedure was performed in perfused rat hearts. Results show a significantly greater /sup k/mao of neuronal origin, (/sup k/mao = .57min - 1) which when related to the fractional size of the neuronal compartment suggests a very high activity of neuronal MAO

Fractional order absolute vibration suppression (AVS) controllers

Science.gov (United States)

Halevi, Yoram

2017-04-01

Absolute vibration suppression (AVS) is a control method for flexible structures. The first step is an accurate, infinite dimension, transfer function (TF), from actuation to measurement. This leads to the collocated, rate feedback AVS controller that in some cases completely eliminates the vibration. In case of the 1D wave equation, the TF consists of pure time delays and low order rational terms, and the AVS controller is rational. In all other cases, the TF and consequently the controller are fractional order in both the delays and the "rational parts". The paper considers stability, performance and actual implementation in such cases.

Direct measurements of rate constants for the reactions of CH3 radicals with C2H6, C2H4, and C2H2 at high temperatures.

Science.gov (United States)

Peukert, S L; Labbe, N J; Sivaramakrishnan, R; Michael, J V

2013-10-10

The shock tube technique has been used to study the reactions CH3 + C2H6 → C2H4 + CH4 + H (1), CH3 + C2H4 → Products + H (2), and CH3 + C2H2 → Products + H (3). Biacetyl, (CH3CO)2, was used as a clean high temperature thermal source for CH3-radicals for all the three reactions studied in this work. For reaction 1, the experiments span a T-range of 1153 K ≤ T ≤ 1297 K, at P ~ 0.4 bar. The experiments on reaction 2 cover a T-range of 1176 K ≤ T ≤ 1366 K, at P ~ 1.0 bar, and those on reaction 3 a T-range of 1127 K ≤ T ≤ 1346 K, at P ~ 1.0 bar. Reflected shock tube experiments performed on reactions 1-3, monitored the formation of H-atoms with H-atom Atomic Resonance Absorption Spectrometric (ARAS). Fits to the H-atom temporal profiles using an assembled kinetics model were used to make determinations for k1, k2, and k3. In the case of C2H6, the measurements of [H]-atoms were used to derive direct high-temperature rate constants, k1, that can be represented by the Arrhenius equation k1(T) = 5.41 × 10(-12) exp(-6043 K/T) cm(3) molecules(-1) s(-1) (1153 K ≤ T ≤ 1297 K) for the only bimolecular process that occurs, H-atom abstraction. TST calculations based on ab initio properties calculated at the CCSD(T)/CBS//M06-2X/cc-pVTZ level of theory show excellent agreement, within ±20%, of the measured rate constants. For the reaction of CH3 with C2H4, the present rate constant results, k2', refer to the sum of rate constants, k(2b) + k(2c), from two competing processes, addition-elimination, and the direct abstraction CH3 + C2H4 → C3H6 + H (2b) and CH3 + C2H4 → C2H2 + H + CH4 (2c). Experimental rate constants for k2' can be represented by the Arrhenius equation k2'(T) = 2.18 × 10(-10) exp(-11830 K/T) cm(3) molecules(-1) s(-1) (1176 K ≤ T ≤ 1366 K). The present results are in excellent agreement with recent theoretical predictions. The present study provides the only direct measurement for the high-temperature rate constants for these channels

Evaluation of Chemical Kinetic for Mathematics Model Reduction of Cadmium Reaction Rate, Constant and Reaction Orde in to Electrochemical Process

International Nuclear Information System (INIS)

Prayitno

2007-01-01

The experiment was reduction of cadmium rate with electrochemical influenced by time process, concentration, current strength and type of electrode plate. The aim of the experiment was to know the influence, mathematic model reduction of cadmium the reaction rate, reaction rate constant and reaction orde influenced by time process, concentration, current strength and type of electrode plate. Result of research indicate the time processing if using plate of copper electrode is during 30 minutes and using plate of aluminium electrode is during 20 minutes. Condition of strong current that used in process of electrochemical is only 0.8 ampere and concentration effective is 5.23 mg/l. The most effective type Al of electrode plate for reduction from waste and the efficiency of reduction is 98 %. (author)

Water Exchange Rate Constant as a Biomarker of Treatment Efficacy in Patients With Brain Metastases Undergoing Stereotactic Radiosurgery

International Nuclear Information System (INIS)

Mehrabian, Hatef; Desmond, Kimberly L.; Chavez, Sofia; Bailey, Colleen; Rola, Radoslaw; Sahgal, Arjun; Czarnota, Gregory J.; Soliman, Hany; Martel, Anne L.; Stanisz, Greg J.

2017-01-01

Purpose: This study was designed to evaluate whether changes in metastatic brain tumors after stereotactic radiosurgery (SRS) can be seen with quantitative MRI early after treatment. Methods and Materials: Using contrast-enhanced MRI, a 3-water-compartment tissue model consisting of intracellular (I), extracellular-extravascular (E), and vascular (V) compartments was used to assess the intra–extracellular water exchange rate constant (k IE ), efflux rate constant (k ep ), and water compartment volume fractions (M 0,I , M 0,E , M 0,V ). In this prospective study, 19 patients were MRI-scanned before treatment and 1 week and 1 month after SRS. The change in model parameters between the pretreatment and 1-week posttreatment scans was correlated to the change in tumor volume between pretreatment and 1-month posttreatment scans. Results: At 1 week k IE differentiated (P<.001) tumors that had partial response from tumors with stable and progressive disease, and a high correlation (R=−0.76, P<.001) was observed between early changes in the k IE and tumor volume change 1 month after treatment. Other model parameters had lower correlation (M 0,E ) or no correlation (k ep , M 0,V ). Conclusions: This is the first study that measured k IE early after SRS, and it found that early changes in k IE (1 week after treatment) highly correlated with long-term tumor response and could predict the extent of tumor shrinkage at 1 month after SRS.

Lifetime of titanium filament at constant current

International Nuclear Information System (INIS)

Chou, T.S.; Lanni, C.

1981-01-01

Titanium Sublimation Pump (TSP) represents the most efficient and the least expensive method to produce Ultra High Vacuum (UHV) in storage rings. In ISABELLE, a proton storage accelerator under construction at Brookhaven National Laboratory, for example, TSP provides a pumping speed for hydrogen of > 2 x 10 6 l/s. Due to the finite life of titanium filaments, new filaments have to be switched in before the end of filament burn out, to ensure smooth operation of the accelerator. Therefore, several operational modes that can be used to activate the TSP were studied. The constant current mode is a convenient way of maintaining constant evaporating rate by increasing the power input while the filament diameter decreases as titanium evaporates. The filaments used in this experiment were standard Varian 916-0024 filaments made of Ti 85%, Mo 15% alloy. During their lifetime at a constant current of 48 amperes, the evaporation rate rose to a maximum at about 10% of their life and then flattened out to a constant value, 0.25 g/hr. The maximum evaporation rate occurs coincidently with the recrystallization of 74% Ti 26% Mo 2 from microstructure crystalline at higher titanium concentration to macrostructure crystalline at lower titanium concentration. As the macrocrystal grows, the slip plane develops at the grain boundary resulting in high resistance at the slip plane which will eventually cause the filament burn out due to local heating

Determination of first order rate constants by natural logarithm of the slope plot exemplified by analysis of Aspergillus niger in batch culture

NARCIS (Netherlands)

Poulsen, B.R.; Ruiter, G.; Visser, J.; Iversen, J.J.L.

2003-01-01

Finding rate constants from experimental data is often difficult because of offset and noise. A computer program was developed to average experimental data points, reducing the effect of noise, and to produce a loge of slope plot - a plot of the natural logarithm of the slope of a curve -

Constant physics and characteristics of fundamental constant

International Nuclear Information System (INIS)

Tarrach, R.

1998-01-01

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

Interaction of hydrated electron with dietary flavonoids and phenolic acids. Rate constants and transient spectra studied by pulse radiolysis

International Nuclear Information System (INIS)

Cai, Zhongli; Li, Xifeng; Katsumura, Yosuke

2000-01-01

The reaction rate constants and transient spectra of 11 flavonoids and 4 phenolic acids reacting with e aq - at neutral pH were measured. The results suggest that C 4 keto group is the active site for e aq - to attack on flavonoids and phenolic acids, while the o-dihydroxy structure in B-ring, the C 2,3 double bond, the C 3 -OH group and glycosylation have little effects on the e aq - scavenging activities. (author)

40 CFR Appendix I to Subpart A of... - Global Warming Potentials (Mass Basis), Referenced to the Absolute GWP for the Adopted Carbon...

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 17 2010-07-01 2010-07-01 false Global Warming Potentials (Mass Basis), Referenced to the Absolute GWP for the Adopted Carbon Cycle Model CO2 Decay Response and Future CO2 Atmospheric Concentrations Held Constant at Current Levels. (Only Direct Effects Are Considered.) I Appendix I to Subpart A of Part 82 Protection o...

A global algorithm for estimating Absolute Salinity

Directory of Open Access Journals (Sweden)

T. J. McDougall

2012-12-01

Full Text Available The International Thermodynamic Equation of Seawater – 2010 has defined the thermodynamic properties of seawater in terms of a new salinity variable, Absolute Salinity, which takes into account the spatial variation of the composition of seawater. Absolute Salinity more accurately reflects the effects of the dissolved material in seawater on the thermodynamic properties (particularly density than does Practical Salinity.

When a seawater sample has standard composition (i.e. the ratios of the constituents of sea salt are the same as those of surface water of the North Atlantic, Practical Salinity can be used to accurately evaluate the thermodynamic properties of seawater. When seawater is not of standard composition, Practical Salinity alone is not sufficient and the Absolute Salinity Anomaly needs to be estimated; this anomaly is as large as 0.025 g kg⁻¹ in the northernmost North Pacific. Here we provide an algorithm for estimating Absolute Salinity Anomaly for any location (x, y, p in the world ocean.

To develop this algorithm, we used the Absolute Salinity Anomaly that is found by comparing the density calculated from Practical Salinity to the density measured in the laboratory. These estimates of Absolute Salinity Anomaly however are limited to the number of available observations (namely 811. In order to provide a practical method that can be used at any location in the world ocean, we take advantage of approximate relationships between Absolute Salinity Anomaly and silicate concentrations (which are available globally.

Can climate models be tuned to simulate the global mean absolute temperature correctly?

Science.gov (United States)

Duan, Q.; Shi, Y.; Gong, W.

2016-12-01

The Inter-government Panel on Climate Change (IPCC) has already issued five assessment reports (ARs), which include the simulation of the past climate and the projection of the future climate under various scenarios. The participating models can simulate reasonably well the trend in global mean temperature change, especially of the last 150 years. However, there is a large, constant discrepancy in terms of global mean absolute temperature simulations over this period. This discrepancy remained in the same range between IPCC-AR4 and IPCC-AR5, which amounts to about 3oC between the coldest model and the warmest model. This discrepancy has great implications to the land processes, particularly the processes related to the cryosphere, and casts doubts over if land-atmosphere-ocean interactions are correctly considered in those models. This presentation aims to explore if this discrepancy can be reduced through model tuning. We present an automatic model calibration strategy to tune the parameters of a climate model so the simulated global mean absolute temperature would match the observed data over the last 150 years. An intermediate complexity model known as LOVECLIM is used in the study. This presentation will show the preliminary results.

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

Science.gov (United States)

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

2017-04-01

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

Flux and permanence of risk perceptions: Tourists' perception of the relative and absolute risk for various destinations.

Science.gov (United States)

Wolff, Katharina; Larsen, Svein

2016-12-01

The present investigation is a cross-sectional, multi-national, quantitative, and quasi-experimental comparison of tourists' risk perceptions regarding different destinations throughout the past decade. Over 10,000 tourists to Norway from 89 different countries filled in a questionnaire rating the perceived risk for various destinations. Data were collected during 2004, 2010, 2011, 2012, 2013 and 2015 and allow for a comparison of perceived risk across time, place and nationality. Results show that while absolute risk judgments for different destinations fluctuate somewhat over the years, relative risk judgments remain constant. Findings also reveal a "home-is-safer-then-abroad-bias" with tourists consistently perceiving their home country among the safest destinations. The current investigation is rare because it looks at more than one destination at a time. Insights gained from the present findings diverge from what would have been concluded from employing case studies, that is, looking at one destination at a time. © 2016 The Authors. Scandinavian Journal of Psychology published by Scandinavian Psychological Associations and John Wiley & Sons Ltd.

Invariant and Absolute Invariant Means of Double Sequences

Directory of Open Access Journals (Sweden)

Abdullah Alotaibi

2012-01-01

Full Text Available We examine some properties of the invariant mean, define the concepts of strong σ-convergence and absolute σ-convergence for double sequences, and determine the associated sublinear functionals. We also define the absolute invariant mean through which the space of absolutely σ-convergent double sequences is characterized.

Determination of rate constants of N-alkylation of primary amines by 1H NMR spectroscopy.

Science.gov (United States)

Li, Chenghong

2013-09-05

Macromolecules containing N-diazeniumdiolates of secondary amines are proposed scaffolds for controlled nitrogen oxide (NO) release medical applications. Preparation of these compounds often involves converting primary amine groups to secondary amine groups through N-alkylation. However, N-alkylation results in not only secondary amines but tertiary amines as well. Only N-diazeniumdiolates of secondary amines are suitable for controlled NO release; therefore, the yield of secondary amines is crucial to the total NO load of the carrier. In this paper, (1)H NMR spectroscopy was used to estimate the rate constants for formation of secondary amine (k1) and tertiary amine (k2) for alkylation reagents such as propylene oxide (PO), methyl acrylate (MA), and acrylonitrile (ACN). At room temperature, the ratio of k2/k1 for the three reactions was found to be around 0.50, 0.026, and 0.0072.

The effect of addition of primary positive salts, complex salt, on the ionic strength and rate constant at various temperatures by reaction kinetics

Science.gov (United States)

Kurade, S. S.; Ramteke, A. A.

2018-05-01

In this work, we have investigated the rate of reaction by using ionic strength at different temperatures. The main goal of this experiment is to determine the relation between ionic strength with reaction rate, reaction time and rate constant with temperature. It is observed that the addition of positive salt indicate the increasing ionic strength with increase in run time at various temperatures. Thus the temperature affects the speed of reaction and mechanism by which chemical reaction occurs and time variable plays vital role in the progress of reaction at different temperatures.

Cryogenic, Absolute, High Pressure Sensor

Science.gov (United States)

Chapman, John J. (Inventor); Shams. Qamar A. (Inventor); Powers, William T. (Inventor)

2001-01-01

A pressure sensor is provided for cryogenic, high pressure applications. A highly doped silicon piezoresistive pressure sensor is bonded to a silicon substrate in an absolute pressure sensing configuration. The absolute pressure sensor is bonded to an aluminum nitride substrate. Aluminum nitride has appropriate coefficient of thermal expansion for use with highly doped silicon at cryogenic temperatures. A group of sensors, either two sensors on two substrates or four sensors on a single substrate are packaged in a pressure vessel.

Determination of constant of chemical reaction rate in the process of steel treatment in the endothermal atmosphere

International Nuclear Information System (INIS)

Gyulikhandanov, E.L.; Kislenkov, V.V.

1978-01-01

The high-temperature method was applied to measuring a relative variation in the electrical resistance of a thin steel foil prepared from the 12KhN3A, 18Kh2N4VA, 20KhGNR, and 20Kh3MVF steels during its carburization and decarburization, and determined was the temperature dependence of the reaction rate of the interaction of the endothermal atmosphere of different compositions with the analloyed γ-Fe. A connection has been established between the reaction rate constant and the thermodynamic activity of carbon in the alloyed austenite at the temperature of about 925 deg C, corresponding to the cementation temperature. This provides the quantitative estimation of the above value for any alloyed steels and with the presence of numerical values of diffusion coefficients; this also enables one to carry out an accurate calculation of the distribution of carbon throughout the depth of a layer when effecting the cementation in the endothermal atmosphere

Determination of the stability constants of a number of metal fluoride complexes and their rates of formation

International Nuclear Information System (INIS)

Hammer, R.R.

1979-08-01

The stability constants of the fluoride complexes of Al +3 , H 3 BO 3 , Cr +3 , Cr +6 , Fe +3 , Gd +3 , Nb +5 , UO 2 +2 , and Zr +4 were determined in 0.96 and 2.88 M HNO 3 solutions in the temperature range 25 to 60 0 C with a fluoride specific ion electrode. These data can be used to calculate the concentration of chemical species in solution and will be used to correlate solution properties with solution composition. The solubilities of some fluoride precipitates were also measured in nitric acid solutions. The rates of formation of the fluoborates, aluminum fluoride, and zirconium fluoride complexes were measured with a fluoride specific ion electrode at 25, 35, and 45 0 C. The rates of formation of all complexes, except BF 4 - , AlF +2 , and a fluoride complex with aluminum containing more than three fluorides associated with it, were too fast to measure with the instrumentation used

A developmental study of latent absolute pitch memory.

Science.gov (United States)

Jakubowski, Kelly; Müllensiefen, Daniel; Stewart, Lauren

2017-03-01

The ability to recall the absolute pitch level of familiar music (latent absolute pitch memory) is widespread in adults, in contrast to the rare ability to label single pitches without a reference tone (overt absolute pitch memory). The present research investigated the developmental profile of latent absolute pitch (AP) memory and explored individual differences related to this ability. In two experiments, 288 children from 4 to12 years of age performed significantly above chance at recognizing the absolute pitch level of familiar melodies. No age-related improvement or decline, nor effects of musical training, gender, or familiarity with the stimuli were found in regard to latent AP task performance. These findings suggest that latent AP memory is a stable ability that is developed from as early as age 4 and persists into adulthood.

Rate constant and mechanism of the reaction Cl + CFCl₂H → CFCl₂ + HCl over the temperature range 298-670 K in N₂ or N₂/O₂ diluent.

Science.gov (United States)

Kaiser, E W; Jawad, Khadija M

2014-05-08

The rate constant of the reaction Cl + CFCl2H (k1) has been measured relative to the established rate constant for the reaction Cl + CH4 (k2) at 760 Torr. The measurements were carried out in Pyrex reactors using a mixture of CFCl2H, CH4, and Cl2 in either N2 or N2/O2 diluent. Reactants and products were quantified by GC/FID analysis. Cl atoms were generated by irradiation of the mixture with 360 nm light to dissociate the Cl2 for temperatures up to ~550 K. At higher temperature, the Cl2 dissociated thermally, and no irradiation was used. Over the temperature range 298-670 K, k1 is consistently a factor of ~5 smaller than that of k2 with a nearly identical temperature dependence. The optimum non-Arrhenius rate constant is represented by the expression k1 = 1.14 × 10(-22) T(3.49) e(-241/T) cm(3) molecule(-1) s(-1) with an estimated uncertainty of ±15% including uncertainty in the reference reaction. CFCl3 formed from the reaction CFCl2 + Cl2 (k3) is the sole product in N2 diluent. In ~20% O2 at 298 K, the CFCl3 product is suppressed. The rate constant of reaction 3 was measured relative to that of reaction 4 [CFCl2 + O2 (k4)] giving the result k3/k4 = 0.0031 ± 0.0005 at 298 K. An earlier experiment by others observed C(O)FCl to be the major product of reaction channel 4 [formed via the sequence, CFCl2(O2) → CFCl2O → C(O)FCl + Cl]. Our current experiments verified that there is a Cl atom chain reaction in the presence of O2 as required by this mechanism.

The dissolution rate constant of magnetite in water at different temperatures and pH conditions

International Nuclear Information System (INIS)

Mohajery, Khatereh; Deydier de Pierrefeu, Laurent; Lister, Derek H.

2012-09-01

Under the nominal conditions of power system coolants, the corrosion of components made of carbon steel is limited by the magnetite films that develop on surfaces. In some situations, the magnetite film loses much of its protective ability and corrosion and loss of iron to the system are exacerbated. Common examples of such situations occur when the system is non-isothermal so that temperature gradients cause differences in magnetite solubility around the circuit; the resulting areas of under-saturation in iron give rise to dissolution of normally protective films. Condensing steam in two-phase systems may also promote oxide dissolution. When the turbulence in the system is high, oxide degradation is aggravated and flow-accelerated corrosion (FAC) results. The subsequent increased loading of systems with iron leads to fouling of flow passages and heat transfer surfaces and in reactor primary coolants to rising radiation fields, while FAC can have disastrous results in terms of pipe wall thinning and eventual rupture. Magnetite dissolution is clearly a key contributor to these processes. Thus, the conventional mechanistic description of FAC postulates magnetite dissolution in series with mass transfer of iron from the film to the bulk coolant. In the resulting equations, if the dissolution rate constant is considerably less than the mass transfer coefficient for a particular situation, dissolution will control and flow should have no effect. This is clearly untenable for FAC, so it is often assumed that mass transfer controls and the contribution from oxide dissolution is ignored - on occasion when data on dissolution kinetics are available and sometimes when those data show that dissolution should control. In most cases, however, dissolution rate constants for magnetite are not available. At UNB Nuclear we have a research program using a high-temperature loop to measure dissolution rates of magnetite in water under various conditions of flow, temperature and

Water Exchange Rate Constant as a Biomarker of Treatment Efficacy in Patients With Brain Metastases Undergoing Stereotactic Radiosurgery

Energy Technology Data Exchange (ETDEWEB)

Mehrabian, Hatef, E-mail: hatef.mehrabian@sri.utoronto.ca [Medical Biophysics, University of Toronto, Toronto, Ontario (Canada); Physical Sciences, Sunnybrook Research Institute, Toronto, Ontario (Canada); Desmond, Kimberly L. [Physical Sciences, Sunnybrook Research Institute, Toronto, Ontario (Canada); Chavez, Sofia [Research Imaging Centre, Centre for Addiction and Mental Health, Toronto, Ontario (Canada); Bailey, Colleen [Computer Science Department, University College London, London (United Kingdom); Rola, Radoslaw [Neurosurgery and Pediatric Neurosurgery, Medical University, Lublin (Poland); Sahgal, Arjun [Physical Sciences, Sunnybrook Research Institute, Toronto, Ontario (Canada); Radiation Oncology, Sunnybrook Health Sciences Centre, Toronto, Ontario (Canada); Czarnota, Gregory J. [Medical Biophysics, University of Toronto, Toronto, Ontario (Canada); Physical Sciences, Sunnybrook Research Institute, Toronto, Ontario (Canada); Radiation Oncology, Sunnybrook Health Sciences Centre, Toronto, Ontario (Canada); Soliman, Hany [Radiation Oncology, Sunnybrook Health Sciences Centre, Toronto, Ontario (Canada); Martel, Anne L. [Medical Biophysics, University of Toronto, Toronto, Ontario (Canada); Physical Sciences, Sunnybrook Research Institute, Toronto, Ontario (Canada); Stanisz, Greg J. [Medical Biophysics, University of Toronto, Toronto, Ontario (Canada); Physical Sciences, Sunnybrook Research Institute, Toronto, Ontario (Canada); Neurosurgery and Pediatric Neurosurgery, Medical University, Lublin (Poland)

2017-05-01

Purpose: This study was designed to evaluate whether changes in metastatic brain tumors after stereotactic radiosurgery (SRS) can be seen with quantitative MRI early after treatment. Methods and Materials: Using contrast-enhanced MRI, a 3-water-compartment tissue model consisting of intracellular (I), extracellular-extravascular (E), and vascular (V) compartments was used to assess the intra–extracellular water exchange rate constant (k{sub IE}), efflux rate constant (k{sub ep}), and water compartment volume fractions (M{sub 0,I}, M{sub 0,E}, M{sub 0,V}). In this prospective study, 19 patients were MRI-scanned before treatment and 1 week and 1 month after SRS. The change in model parameters between the pretreatment and 1-week posttreatment scans was correlated to the change in tumor volume between pretreatment and 1-month posttreatment scans. Results: At 1 week k{sub IE} differentiated (P<.001) tumors that had partial response from tumors with stable and progressive disease, and a high correlation (R=−0.76, P<.001) was observed between early changes in the k{sub IE} and tumor volume change 1 month after treatment. Other model parameters had lower correlation (M{sub 0,E}) or no correlation (k{sub ep}, M{sub 0,V}). Conclusions: This is the first study that measured k{sub IE} early after SRS, and it found that early changes in k{sub IE} (1 week after treatment) highly correlated with long-term tumor response and could predict the extent of tumor shrinkage at 1 month after SRS.

Chandra Independently Determines Hubble Constant

Science.gov (United States)

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

Advancing Absolute Calibration for JWST and Other Applications

Science.gov (United States)

Rieke, George; Bohlin, Ralph; Boyajian, Tabetha; Carey, Sean; Casagrande, Luca; Deustua, Susana; Gordon, Karl; Kraemer, Kathleen; Marengo, Massimo; Schlawin, Everett; Su, Kate; Sloan, Greg; Volk, Kevin

2017-10-01

We propose to exploit the unique optical stability of the Spitzer telescope, along with that of IRAC, to (1) transfer the accurate absolute calibration obtained with MSX on very bright stars directly to two reference stars within the dynamic range of the JWST imagers (and of other modern instrumentation); (2) establish a second accurate absolute calibration based on the absolutely calibrated spectrum of the sun, transferred onto the astronomical system via alpha Cen A; and (3) provide accurate infrared measurements for the 11 (of 15) highest priority stars with no such data but with accurate interferometrically measured diameters, allowing us to optimize determinations of effective temperatures using the infrared flux method and thus to extend the accurate absolute calibration spectrally. This program is integral to plans for an accurate absolute calibration of JWST and will also provide a valuable Spitzer legacy.

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

Directory of Open Access Journals (Sweden)

Petros Damos

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

Dynamics of the cosmological and Newton’s constant

International Nuclear Information System (INIS)

Smolin, Lee

2016-01-01

A modification of general relativity is presented in which Newton’s constant, G, and the cosmological constant, Λ, become a conjugate pair of dynamical variables. These are functions of a global time, hence the theory is presented in the framework of shape dynamics, which trades many-fingered time for a local scale invariance and an overall reparametrization of the global time. As a result, due to the fact that these global dynamical variables are canonically conjugate, the field equations are consistent. The theory predicts a relationship with no free parameters between the rates of change of Newton’s constant and the cosmological constant, in terms of the spatial average of the matter Lagrangian density. (paper)

Interaction of hydrated electron with dietary flavonoids and phenolic acids. Rate constants and transient spectra studied by pulse radiolysis

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)

Predicting the Rate Constant of Electron Tunneling Reactions at the CdSe-TiO2 Interface.

Science.gov (United States)

Hines, Douglas A; Forrest, Ryan P; Corcelli, Steven A; Kamat, Prashant V

2015-06-18

Current interest in quantum dot solar cells (QDSCs) motivates an understanding of the electron transfer dynamics at the quantum dot (QD)-metal oxide (MO) interface. Employing transient absorption spectroscopy, we have monitored the electron transfer rate (ket) at this interface as a function of the bridge molecules that link QDs to TiO2. Using mercaptoacetic acid, 3-mercaptopropionic acid, 8-mercaptooctanoic acid, and 16-mercaptohexadecanoic acid, we observe an exponential attenuation of ket with increasing linker length, and attribute this to the tunneling of the electron through the insulating linker molecule. We model the electron transfer reaction using both rectangular and trapezoidal barrier models that have been discussed in the literature. The one-electron reduction potential (equivalent to the lowest unoccupied molecular orbital) of each molecule as determined by cyclic voltammetry (CV) was used to estimate the effective barrier height presented by each ligand at the CdSe-TiO2 interface. The electron transfer rate (ket) calculated for each CdSe-ligand-TiO2 interface using both models showed the results in agreement with the experimentally determined trend. This demonstrates that electron transfer between CdSe and TiO2 can be viewed as electron tunneling through a layer of linking molecules and provides a useful method for predicting electron transfer rate constants.

Quantum chemical and conventional TST calculations of rate constants for the OH + alkane reaction

International Nuclear Information System (INIS)

Bravo-Perez, Graciela; Alvarez-Idaboy, J. Raul; Jimenez, Annia Galano; Cruz-Torres, Armando

2005-01-01

Reactions of OH with methane, ethane, propane, i-butane, and n-butane have been modeled using ab initio (MP2) and hybrid DFT (BHandHLYP) methods, and the 6-311G(d,p) basis set. Furthermore, single-point calculations at the CCSD(T) level were carried out at the optimized geometries. The rate constants have been calculated using the conventional transition-state theory (CTST). Arrhenius equations are proposed in the temperature range of 250-650 K. Hindered Internal Rotation partition functions calculations were explicitly carried out and included in the total partition functions. These corrections showed to be relevant in the determination of the pre-exponential parameters, although not so important as in the NO 3 + alkane reactions [G. Bravo-Perez, J.R. Alvarez-Idaboy, A. Cruz-Torres, M.E. Ruiz, J. Phys. Chem. A 106 (2002) 4645]. The explicit participation of the tunnel effect has been taken into account. The calculated rate coefficients provide a very good agreement with the experimental data. The best agreement for the overall alkane + OH reactions seemed to occur when the BHandHLYP geometries and partition functions are used. For propane and i-butane, in addition to the respective secondary and tertiary H-abstraction channels, the primary one has been considered. These pathways are confirmed to be significant in spite of the large differences in activation energies between primary and secondary or primary and tertiary channels, respectively of propane and i-butane reactions and should not be disregarded

Entrenched geographical and socioeconomic disparities in child mortality: trends in absolute and relative inequalities in Cambodia.

Directory of Open Access Journals (Sweden)

Eliana Jimenez-Soto

Full Text Available BACKGROUND: Cambodia has made considerable improvements in mortality rates for children under the age of five and neonates. These improvements may, however, mask considerable disparities between subnational populations. In this paper, we examine the extent of the country's child mortality inequalities. METHODS: Mortality rates for children under-five and neonates were directly estimated using the 2000, 2005 and 2010 waves of the Cambodian Demographic Health Survey. Disparities were measured on both absolute and relative scales using rate differences and ratios, and where applicable, slope and relative indices of inequality by levels of rural/urban location, regions and household wealth. FINDINGS: Since 2000, considerable reductions in under-five and to a lesser extent in neonatal mortality rates have been observed. This mortality decline has, however, been accompanied by an increase in relative inequality in both rates of child mortality for geography-related stratifying markers. For absolute inequality amongst regions, most trends are increasing, particularly for neonatal mortality, but are not statistically significant. The only exception to this general pattern is the statistically significant positive trend in absolute inequality for under-five mortality in the Coastal region. For wealth, some evidence for increases in both relative and absolute inequality for neonates is observed. CONCLUSION: Despite considerable gains in reducing under-five and neonatal mortality at a national level, entrenched and increased geographical and wealth-based inequality in mortality, at least on a relative scale, remain. As expected, national progress seems to be associated with the period of political and macroeconomic stability that started in the early 2000s. However, issues of quality of care and potential non-inclusive economic growth might explain remaining disparities, particularly across wealth and geography markers. A focus on further addressing key

THE ABSOLUTE MAGNITUDES OF TYPE Ia SUPERNOVAE IN THE ULTRAVIOLET

International Nuclear Information System (INIS)

Brown, Peter J.; Roming, Peter W. A.; Ciardullo, Robin; Gronwall, Caryl; Hoversten, Erik A.; Pritchard, Tyler; Milne, Peter; Bufano, Filomena; Mazzali, Paolo; Elias-Rosa, Nancy; Filippenko, Alexei V.; Li Weidong; Foley, Ryan J.; Hicken, Malcolm; Kirshner, Robert P.; Gehrels, Neil; Holland, Stephen T.; Immler, Stefan; Phillips, Mark M.; Still, Martin

2010-01-01

We examine the absolute magnitudes and light-curve shapes of 14 nearby (redshift z = 0.004-0.027) Type Ia supernovae (SNe Ia) observed in the ultraviolet (UV) with the Swift Ultraviolet/Optical Telescope. Colors and absolute magnitudes are calculated using both a standard Milky Way extinction law and one for the Large Magellanic Cloud that has been modified by circumstellar scattering. We find very different behavior in the near-UV filters (uvw1 rc covering ∼2600-3300 A after removing optical light, and u ∼ 3000-4000 A) compared to a mid-UV filter (uvm2 ∼2000-2400 A). The uvw1 rc - b colors show a scatter of ∼0.3 mag while uvm2-b scatters by nearly 0.9 mag. Similarly, while the scatter in colors between neighboring filters is small in the optical and somewhat larger in the near-UV, the large scatter in the uvm2 - uvw1 colors implies significantly larger spectral variability below 2600 A. We find that in the near-UV the absolute magnitudes at peak brightness of normal SNe Ia in our sample are correlated with the optical decay rate with a scatter of 0.4 mag, comparable to that found for the optical in our sample. However, in the mid-UV the scatter is larger, ∼1 mag, possibly indicating differences in metallicity. We find no strong correlation between either the UV light-curve shapes or the UV colors and the UV absolute magnitudes. With larger samples, the UV luminosity might be useful as an additional constraint to help determine distance, extinction, and metallicity in order to improve the utility of SNe Ia as standardized candles.

Greater absolute risk for all subtypes of breast cancer in the US than Malaysia.

Science.gov (United States)

Horne, Hisani N; Beena Devi, C R; Sung, Hyuna; Tang, Tieng Swee; Rosenberg, Philip S; Hewitt, Stephen M; Sherman, Mark E; Anderson, William F; Yang, Xiaohong R

2015-01-01

Hormone receptor (HR) negative breast cancers are relatively more common in low-risk than high-risk countries and/or populations. However, the absolute variations between these different populations are not well established given the limited number of cancer registries with incidence rate data by breast cancer subtype. We, therefore, used two unique population-based resources with molecular data to compare incidence rates for the 'intrinsic' breast cancer subtypes between a low-risk Asian population in Malaysia and high-risk non-Hispanic white population in the National Cancer Institute's surveillance, epidemiology, and end results 18 registries database (SEER 18). The intrinsic breast cancer subtypes were recapitulated with the joint expression of the HRs (estrogen receptor and progesterone receptor) and human epidermal growth factor receptor-2 (HER2). Invasive breast cancer incidence rates overall were fivefold greater in SEER 18 than in Malaysia. The majority of breast cancers were HR-positive in SEER 18 and HR-negative in Malaysia. Notwithstanding the greater relative distribution for HR-negative cancers in Malaysia, there was a greater absolute risk for all subtypes in SEER 18; incidence rates were nearly 7-fold higher for HR-positive and 2-fold higher for HR-negative cancers in SEER 18. Despite the well-established relative breast cancer differences between low-risk and high-risk countries and/or populations, there was a greater absolute risk for HR-positive and HR-negative subtypes in the US than Malaysia. Additional analytical studies are sorely needed to determine the factors responsible for the elevated risk of all subtypes of breast cancer in high-risk countries like the United States.

Absolutely nondestructive discrimination of Huoshan Dendrobium nobile species with miniature near-infrared (NIR) spectrometer engine.

Science.gov (United States)

Hu, Tian; Yang, Hai-Long; Tang, Qing; Zhang, Hui; Nie, Lei; Li, Lian; Wang, Jin-Feng; Liu, Dong-Ming; Jiang, Wei; Wang, Fei; Zang, Heng-Chang

2014-10-01

As one very precious traditional Chinese medicine (TCM), Huoshan Dendrobium has not only high price, but also significant pharmaceutical efficacy. However, different species of Huoshan Dendrobium exhibit considerable difference in pharmaceutical efficacy, so rapid and absolutely non-destructive discrimination of Huoshan Dendrobium nobile according to different species is crucial to quality control and pharmaceutical effect. In this study, as one type of miniature near-infrared (NIR) spectrometer, MicroNIR 1700 was used for absolutely nondestructive determination of NIR spectra of 90 batches of Dendrobium from five species of differ- ent commodity grades. The samples were intact and not smashed. Soft independent modeling of class analogy (SIMCA) pattern recognition based on principal component analysis (PCA) was used to classify and recognize different species of Dendrobium samples. The results indicated that the SIMCA qualitative models established with pretreatment method of standard normal variate transformation (SNV) in the spectra range selected by Qs method had 100% recognition rates and 100% rejection rates. This study demonstrated that a rapid and absolutely non-destructive analytical technique based on MicroNIR 1700 spectrometer was developed for successful discrimination of five different species of Huoshan Dendrobium with acceptable accuracy.

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

International Nuclear Information System (INIS)

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

2009-01-01

Single-arc intensity-modulated arc therapy (IMAT) has gained worldwide interest in both research and clinical implementation due to its superior plan quality and delivery efficiency. Single-arc IMAT techniques such as the Varian RapidArc(TM) deliver conformal dose distributions to the target in one single gantry rotation, resulting in a delivery time in the order of 2 min. The segments in these techniques are evenly distributed within an arc and are allowed to have different monitor unit (MU) weightings. Therefore, a variable dose-rate (VDR) is required for delivery. Because the VDR requirement complicates the control hardware and software of the linear accelerators (linacs) and prevents most existing linacs from delivering IMAT, we propose an alternative planning approach for IMAT using constant dose-rate (CDR) delivery with variable angular spacing. We prove the equivalence by converting VDR-optimized RapidArc plans to CDR plans, where the evenly spaced beams in the VDR plan are redistributed to uneven spacing such that the segments with larger MU weighting occupy a greater angular interval. To minimize perturbation in the optimized dose distribution, the angular deviation of the segments was restricted to ≤± 5 deg. This restriction requires the treatment arc to be broken into multiple sectors such that the local MU fluctuation within each sector is reduced, thereby lowering the angular deviation of the segments during redistribution. The converted CDR plans were delivered with a single gantry sweep as in the VDR plans but each sector was delivered with a different value of CDR. For four patient cases, including two head-and-neck, one brain and one prostate, all CDR plans developed with the variable spacing scheme produced similar dose distributions to the original VDR plans. For plans with complex angular MU distributions, the number of sectors increased up to four in the CDR plans in order to maintain the original plan quality. Since each sector was

Evolution of the solar constant

International Nuclear Information System (INIS)

Newman, M.J.

1978-01-01

The ultimate source of the energy utilized by life on Earth is the Sun, and the behavior of the Sun determines to a large extent the conditions under which life originated and continues to thrive. What can be said about the history of the Sun. Has the solar constant, the rate at which energy is received by the Earth from the Sun per unit area per unit time, been constant at its present level since Archean times. Three mechanisms by which it has been suggested that the solar energy output can vary with time are discussed, characterized by long (approx. 10 9 years), intermediate (approx. 10 8 years), and short (approx. years to decades) time scales

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

Science.gov (United States)

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

2009-01-01

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

NGS Absolute Gravity Data

Data.gov (United States)

National Oceanic and Atmospheric Administration, Department of Commerce — The NGS Absolute Gravity data (78 stations) was received in July 1993. Principal gravity parameters include Gravity Value, Uncertainty, and Vertical Gradient. The...

Cosmological Hubble constant and nuclear Hubble constant

International Nuclear Information System (INIS)

Horbuniev, Amelia; Besliu, Calin; Jipa, Alexandru

2005-01-01

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

Absolute isotopic abundances of Ti in meteorites

International Nuclear Information System (INIS)

Niederer, F.R.; Papanastassiou, D.A.; Wasserburg, G.J.

1985-01-01

The absolute isotope abundance of Ti has been determined in Ca-Al-rich inclusions from the Allende and Leoville meteorites and in samples of whole meteorites. The absolute Ti isotope abundances differ by a significant mass dependent isotope fractionation transformation from the previously reported abundances, which were normalized for fractionation using 46 Ti/ 48 Ti. Therefore, the absolute compositions define distinct nucleosynthetic components from those previously identified or reflect the existence of significant mass dependent isotope fractionation in nature. We provide a general formalism for determining the possible isotope compositions of the exotic Ti from the measured composition, for different values of isotope fractionation in nature and for different mixing ratios of the exotic and normal components. The absolute Ti and Ca isotopic compositions still support the correlation of 50 Ti and 48 Ca effects in the FUN inclusions and imply contributions from neutron-rich equilibrium or quasi-equilibrium nucleosynthesis. The present identification of endemic effects at 46 Ti, for the absolute composition, implies a shortfall of an explosive-oxygen component or reflects significant isotope fractionation. Additional nucleosynthetic components are required by 47 Ti and 49 Ti effects. Components are also defined in which 48 Ti is enhanced. Results are given and discussed. (author)

Absolute magnitude estimation and relative judgement approaches to subjective workload assessment

Science.gov (United States)

Vidulich, Michael A.; Tsang, Pamela S.

1987-01-01

Two rating scale techniques employing an absolute magnitude estimation method, were compared to a relative judgment method for assessing subjective workload. One of the absolute estimation techniques used was an unidimensional overall workload scale and the other was the multidimensional NASA-Task Load Index technique. Thomas Saaty's Analytic Hierarchy Process was the unidimensional relative judgment method used. These techniques were used to assess the subjective workload of various single- and dual-tracking conditions. The validity of the techniques was defined as their ability to detect the same phenomena observed in the tracking performance. Reliability was assessed by calculating test-retest correlations. Within the context of the experiment, the Saaty Analytic Hierarchy Process was found to be superior in validity and reliability. These findings suggest that the relative judgment method would be an effective addition to the currently available subjective workload assessment techniques.

RATE CONSTANTS FOR THE REACTIONS OF OH RADICALS AND CL ATOMS WITH DI-N-PROPYL ETHER AND DI-N-BUTYL ETHER AND THEIR DEUTERATED ANALOGS. (R825252)

Science.gov (United States)

Using relative rate methods, rate constants for the gas-phase reactions of OH radicals and Cl atoms with di-n-propyl ether, di-n-propyl ether-d14, di-n-butyl ether and di-n-butyl ether-d18 have been measured at 296 ? 2 K and atmos...

Microfabricated Collector-Generator Electrode Sensor for Measuring Absolute pH and Oxygen Concentrations.

Science.gov (United States)

Dengler, Adam K; Wightman, R Mark; McCarty, Gregory S

2015-10-20

Fast-scan cyclic voltammetry (FSCV) has attracted attention for studying in vivo neurotransmission due to its subsecond temporal resolution, selectivity, and sensitivity. Traditional FSCV measurements use background subtraction to isolate changes in the local electrochemical environment, providing detailed information on fluctuations in the concentration of electroactive species. This background subtraction removes information about constant or slowly changing concentrations. However, determination of background concentrations is still important for understanding functioning brain tissue. For example, neural activity is known to consume oxygen and produce carbon dioxide which affects local levels of oxygen and pH. Here, we present a microfabricated microelectrode array which uses FSCV to detect the absolute levels of oxygen and pH in vitro. The sensor is a collector-generator electrode array with carbon microelectrodes spaced 5 μm apart. In this work, a periodic potential step is applied at the generator producing transient local changes in the electrochemical environment. The collector electrode continuously performs FSCV enabling these induced changes in concentration to be recorded with the sensitivity and selectivity of FSCV. A negative potential step applied at the generator produces a transient local pH shift at the collector. The generator-induced pH signal is detected using FSCV at the collector and correlated to absolute solution pH by postcalibration of the anodic peak position. In addition, in oxygenated solutions a negative potential step at the generator produces hydrogen peroxide by reducing oxygen. Hydrogen peroxide is detected with FSCV at the collector electrode, and the magnitude of the oxidative peak is proportional to absolute oxygen concentrations. Oxygen interference on the pH signal is minimal and can be accounted for with a postcalibration.

Determination of H-atom reaction rate constants by the competition kinetic technique using riboflavin as a standard solute [Paper No. RD-7

International Nuclear Information System (INIS)

Kishore, Kamal; Moorthy, P.N.; Rao, K.N.

1982-01-01

Riboflavin has been used as a standard solute to evaluate H-atom rate constants of other solutes by steady state radiolytic competition kinetic method. The bleaching of absorbance of riboflavin at 445 nm as a result of its reaction with H-atoms is made use of in estimating its decomposition. The merits and demerits of this method are discussed. (author)

Bioclimatic Thresholds, Thermal Constants and Survival of Mealybug, Phenacoccus solenopsis (Hemiptera: Pseudococcidae) in Response to Constant Temperatures on Hibiscus

Science.gov (United States)

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 ( Hibiscus rosa -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. PMID:24086597

Bioclimatic thresholds, thermal constants and survival of mealybug, Phenacoccus solenopsis (hemiptera: pseudococcidae) in response to constant temperatures on hibiscus.

Science.gov (United States)

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 Importance of the Dissociation Rate in Ion Channel Blocking

Directory of Open Access Journals (Sweden)

Hugo Zeberg

2018-02-01

Full Text Available Understanding the relationships between the rates and dynamics of current wave forms under voltage clamp conditions is essential for understanding phenomena such as state-dependence and use-dependence, which are fundamental for the action of drugs used as anti-epileptics, anti-arrhythmics, and anesthetics. In the present study, we mathematically analyze models of blocking mechanisms. In previous experimental studies of potassium channels we have shown that the effect of local anesthetics can be explained by binding to channels in the open state. We therefore here examine models that describe the effect of a blocking drug that binds to a non-inactivating channel in its open state. Such binding induces an inactivation-like current decay at higher potential steps. The amplitude of the induced peak depends on voltage and concentration of blocking drug. In the present study, using analytical methods, we (i derive a criterion for the existence of a peak in the open probability time evolution for a model with an arbitrary number of closed states, (ii derive formula for the relative height of the peak amplitude, and (iii determine the voltage dependence of the relative peak height. Two findings are apparent: (1 the dissociation (unbinding rate constant is important for the existence of a peak in the current waveform, while the association (binding rate constant is not, and (2 for a peak to exist it suffices that the dissociation rate must be smaller than the absolute value of all eigenvalues to the kinetic matrix describing the model.

Acceleration and sensitivity analysis of lattice kinetic Monte Carlo simulations using parallel processing and rate constant rescaling.

Science.gov (United States)

Núñez, M; Robie, T; Vlachos, D G

2017-10-28

Kinetic Monte Carlo (KMC) simulation provides insights into catalytic reactions unobtainable with either experiments or mean-field microkinetic models. Sensitivity analysis of KMC models assesses the robustness of the predictions to parametric perturbations and identifies rate determining steps in a chemical reaction network. Stiffness in the chemical reaction network, a ubiquitous feature, demands lengthy run times for KMC models and renders efficient sensitivity analysis based on the likelihood ratio method unusable. We address the challenge of efficiently conducting KMC simulations and performing accurate sensitivity analysis in systems with unknown time scales by employing two acceleration techniques: rate constant rescaling and parallel processing. We develop statistical criteria that ensure sufficient sampling of non-equilibrium steady state conditions. Our approach provides the twofold benefit of accelerating the simulation itself and enabling likelihood ratio sensitivity analysis, which provides further speedup relative to finite difference sensitivity analysis. As a result, the likelihood ratio method can be applied to real chemistry. We apply our methodology to the water-gas shift reaction on Pt(111).

Investigating Absolute Value: A Real World Application

Science.gov (United States)

Kidd, Margaret; Pagni, David

2009-01-01

Making connections between various representations is important in mathematics. In this article, the authors discuss the numeric, algebraic, and graphical representations of sums of absolute values of linear functions. The initial explanations are accessible to all students who have experience graphing and who understand that absolute value simply…

Rate Constants of PSII Photoinhibition and its Repair, and PSII Fluorescence Parameters in Field Plants in Relation to their Growth Light Environments.

Science.gov (United States)

Miyata, Kazunori; Ikeda, Hiroshi; Nakaji, Masayoshi; Kanel, Dhana Raj; Terashima, Ichiro

2015-09-01

The extent of photoinhibition of PSII is determined by a balance between the rate of photodamage to PSII and that of repair of the damaged PSII. It has already been indicated that the rate constants of photodamage (kpi) and repair (krec) of the leaves differ depending on their growth light environment. However, there are no studies using plants in the field. We examined these rate constants and fluorescence parameters of several field-grown plants to determine inter-relationships between these values and the growth environment. The kpi values were strongly related to the excess energy, EY, of the puddle model and non-regulated energy dissipation, Y(NO), of the lake model, both multiplied by the photosynthetically active photon flux density (PPFD) level during the photoinhibitory treatment. In contrast, the krec values corrected against in situ air temperature were very strongly related to the daily PPFD level. The plants from the fields showed higher NPQ than the chamber-grown plants, probably because these field plants acclimated to stronger lightflecks than the averaged growth PPFD. Comparing chamber-grown plants and the field plants, we showed that kpi is determined by the incident light level and the photosynthetic capacities such as in situ rate of PSII electron transport and non-photochemical quenching (NPQ) [e.g. Y(NO)×PPFD] and that krec is mostly determined by the growth light and temperature levels. © The Author 2015. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Determination of the rate constant for the OH(X2Π) + OH(X2Π) → H2O + O(3P) reaction over the temperature range 295 to 701 K.

Science.gov (United States)

Altinay, Gokhan; Macdonald, R Glen

2014-01-09

The rate constant for the radical-radical reaction OH(X(2)Π) + OH(X(2)Π) → H2O + O((3)P) has been measured over the temperature and pressure ranges 295-701 K and 2-12 Torr, respectively, in mixtures of CF4, N2O, and H2O. The OH radical was produced by the 193 nm laser photolysis of N2O. The resulting O((1)D) atoms reacted rapidly with H2O to produce the OH radical. The OH radical was detected by high-resolution time-resolved infrared absorption spectroscopy using a single Λ-doublet component of the OH(1,0) P1e/f(4.5) fundamental vibrational transition. A detailed kinetic model was used to determine the reaction rate constant as a function of temperature. These experiments were conducted in a new temperature controlled reaction chamber. The values of the measured rate constants are quite similar to the previous measurements from this laboratory of Bahng and Macdonald (J. Phys. Chem. A 2007 , 111 , 3850 - 3861); however, they cover a much larger temperature range. The results of the present work do not agree with recent measurements of Sangwan and Krasnoperov (J. Phys. Chem. A 2012 , 116 , 11817 - 11822). At 295 K the rate constant of the title reaction was found to be (2.52 ± 0.63) × 10(-12) cm(3) molecule(-1) s(-1), where the uncertainty includes both experimental scatter and an estimate of systematic errors at the 95% confidence limit. Over the temperature range of the experiments, the rate constant can be represented by k1a = 4.79 × 10(-18)T(1.79) exp(879.0/T) cm(3) molecule(-1) s(-1) with a uncertainty of ±24% at the 2σ level, including experimental scatter and systematic error.

Photometric method for determination of acidity constants through integral spectra analysis

Science.gov (United States)

Zevatskiy, Yuriy Eduardovich; Ruzanov, Daniil Olegovich; Samoylov, Denis Vladimirovich

2015-04-01

An express method for determination of acidity constants of organic acids, based on the analysis of the integral transmittance vs. pH dependence is developed. The integral value is registered as a photocurrent of photometric device simultaneously with potentiometric titration. The proposed method allows to obtain pKa using only simple and low-cost instrumentation. The optical part of the experimental setup has been optimized through the exclusion of the monochromator device. Thus it only takes 10-15 min to obtain one pKa value with the absolute error of less than 0.15 pH units. Application limitations and reliability of the method have been tested for a series of organic acids of various nature.

Approach To Absolute Zero

Indian Academy of Sciences (India)

more and more difficult to remove heat as one approaches absolute zero. This is the ... A new and active branch of engineering ... This temperature is called the critical temperature, Te' For sulfur dioxide the critical ..... adsorbent charcoal.

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

Science.gov (United States)

Shibata, Katsumi; Fukuwatari, Tsutomu

2014-01-01

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

Ablation of tumor and inflammatory tissue with absolute ethanol

Energy Technology Data Exchange (ETDEWEB)

Uflacker, R.; Paolini, R.M.; Nobrega, M.

Absolute ethanol was used to ablate tumors, inflammatory lesions, and end-stage nephrosclerotic kidneys in 38 patients. Thirty patients had various types of renal tumors, and 3 had chronic end-stage renal failure with malignant hypertension. One patient had a fibrosarcoma of the right leg and one had a metastatis in the humerus from a renal carcinoma. A large adrenal carcinoma was treated with absolute ethanol in a patient who had liver metastases that were ablated one year after the first procedure. An additional patient had metastatic liver disease from a non-functioning adrenal carcinoma. The remaining patient had an extensive hypervascular inflammatory lesion (tuberculosis and aspergilloma) of the right upper pulmonary lobe. In addition to ethanol, coils were introduced in one patient and Gelfoam in another. The amount of ethanol used ranged from 5 to 50 ml. Twenty-two patients suffered from considerable transient pain during ethanol injection, but sedation was necessary in only 3 of them. Skin necrosis appeared in 2 patients requiring plastic reconstruction in one of them. Two patients died within 5 days of the procedure unrelated to the ablation. Two patients presented upper gastrointestinal bleeding within 2 days of the ethanol injection and one of these died in acute renal failure. One patient suffered from left colonic infarction after left renal tumor ablation, but survived for several months. Absolute ethanol was a useful and efficient sclerosing agent causing extensive tumor destruction and marked reduction of the vascularity in tumor and inflammatory lesions, but caused an 18% complication rate.

Design and construction of a cryogenic facility providing absolute measurements of radon 222 activity for developing a primary standard

International Nuclear Information System (INIS)

Picolo, Jean-Louis

1995-06-01

Radon 222 metrology is required to obtain higher accuracy in assessing human health risks from exposure to natural radiation. This paper describes the development of a cryogenic facility that allows absolute measurements of radon 222 in order to obtain a primary standard. The method selected is the condensation of a radon 222 sample on a geometrically defined cold surface with a constant, well known and adjustable temperature and facing an alpha particles detector. Counting of the alpha particles reaching the detector and the precisely known detection geometry provide an absolute measurement of the source activity. After describing the cryogenic facility, the measurement accuracy and precision are discussed and a comparison made with other measurement systems. The relative uncertainty is below 1 pc (1 σ). The facility can also be used to improve our knowledge of the nuclear properties of radon 222 and to produce secondary standards. (author) [fr

Constant Proportion Debt Obligations (CPDOs)

DEFF Research Database (Denmark)

Cont, Rama; Jessen, Cathrine

2012-01-01

be made arbitrarily small—and thus the credit rating arbitrarily high—by increasing leverage, but the ratings obtained strongly depend on assumptions on the credit environment (high spread or low spread). More importantly, CPDO loss distributions are found to exhibit a wide range of tail risk measures......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...

Constant Fault Slip-Rates Over Hundreds of Millenia Constrained By Deformed Quaternary Palaeoshorelines: the Vibo and Capo D'Orlando Faults, Southern Italy.

Science.gov (United States)

Meschis, M.; Roberts, G.; Robertson, J.; Houghton, S.; Briant, R. M.

2017-12-01

Whether slip-rates on active faults accumulated over multiple seismic events is constant or varying over tens to hundreds of millenia timescales is an open question that can be addressed through study of deformed Quaternary palaeoshorelines. It is important to know the answer so that one can judge whether shorter timescale measurements (e.g. Holocene palaeoseismology or decadal geodesy) are suitable for determining earthquake recurrence intervals for Probabilistic Seismic Hazard Assessment or more suitable for studying temporal earthquake clustering. We present results from the Vibo Fault and the Capo D'Orlando Fault, that lie within the deforming Calabrian Arc, which has experienced damaging seismic events such as the 1908 Messina Strait earthquake ( Mw 7) and the 1905 Capo Vaticano earthquake ( Mw 7). These normal faults deform uplifted Late Quaternary palaeoshorelines, which outcrop mainly within their hangingwalls, but also partially in their footwalls, showing that a regional subduction and mantle-related uplift outpaces local fault-related subsidence. Through (1) field and DEM-based mapping of palaeoshorelines, both up flights of successively higher, older inner edges, and along the strike of the faults, and (2) utilisation of synchronous correlation of non-uniformly-spaced inner edge elevations with non-uniformly spaced sea-level highstand ages, we show that slip-rates decrease towards fault tips and that slip-rates have remained constant since 340 ka (given the time resolution we obtain). The slip-rates for the Capo D'Orlando Fault and Vibo Fault are 0.61mm/yr and 1mm/yr respectively. We show that the along-strike gradients in slip-rate towards fault tips differ for the two faults hinting at fault interaction and also discuss this in terms of other regions of extension like the Gulf of Corinth, Greece, where slip-rate has been shown to change through time through the Quaternary. We make the point that slip-rates may change through time as fault systems grow

Absolute spectrophotometry of Nova Cygni 1975

International Nuclear Information System (INIS)

Kontizas, E.; Kontizas, M.; Smyth, M.J.

1976-01-01

Radiometric photoelectric spectrophotometry of Nova Cygni 1975 was carried out on 1975 August 31, September 2, 3. α Lyr was used as reference star and its absolute spectral energy distribution was used to reduce the spectrophotometry of the nova to absolute units. Emission strengths of Hα, Hβ, Hγ (in W cm -2 ) were derived. The Balmer decrement Hα:Hβ:Hγ was compared with theory, and found to deviate less than had been reported for an earlier nova. (author)

The Pragmatics of "Unruly" Dative Absolutes in Early Slavic

Directory of Open Access Journals (Sweden)

Daniel E. Collins

2011-08-01

Full Text Available This chapter examines some uses of the dative absolute in Old Church Slavonic and in early recensional Slavonic texts that depart from notions of how Indo-European absolute constructions should behave, either because they have subjects coreferential with the (putative main-clause subjects or because they function as if they were main clauses in their own right. Such "noncanonical" absolutes have generally been written off as mechanistic translations or as mistakes by scribes who did not understand the proper uses of the construction. In reality, the problem is not with literalistic translators or incompetent scribes but with the definition of the construction itself; it is quite possible to redefine the Early Slavic dative absolute in a way that accounts for the supposedly deviant cases. While the absolute is generally dependent semantically on an adjacent unit of discourse, it should not always be regarded as subordinated syntactically. There are good grounds for viewing some absolutes not as dependent clauses but as independent sentences whose collateral character is an issue not of syntax but of the pragmatics of discourse.

Development of Monopole Interaction Models for Ionic Compounds. Part I: Estimation of Aqueous Henry’s Law Constants for Ions and Gas Phase pKa Values for Acidic Compounds

Science.gov (United States)

The SPARC (SPARC Performs Automated Reasoning in Chemistry) physicochemical mechanistic models for neutral compounds have been extended to estimate Henry’s Law Constant (HLC) for charged species by incorporating ionic electrostatic interaction models. Combinations of absolute aq...

Automated absolute activation analysis with californium-252 sources

International Nuclear Information System (INIS)

MacMurdo, K.W.; Bowman, W.W.

1978-09-01

A 100-mg 252 Cf neutron activation analysis facility is used routinely at the Savannah River Laboratory for multielement analysis of many solid and liquid samples. An absolute analysis technique converts counting data directly to elemental concentration without the use of classical comparative standards and flux monitors. With the totally automated pneumatic sample transfer system, cyclic irradiation-decay-count regimes can be pre-selected for up to 40 samples, and samples can be analyzed with the facility unattended. An automatic data control system starts and stops a high-resolution gamma-ray spectrometer and/or a delayed-neutron detector; the system also stores data and controls output modes. Gamma ray data are reduced by three main programs in the IBM 360/195 computer: the 4096-channel spectrum and pertinent experimental timing, counting, and sample data are stored on magnetic tape; the spectrum is then reduced to a list of significant photopeak energies, integrated areas, and their associated statistical errors; and the third program assigns gamma ray photopeaks to the appropriate neutron activation product(s) by comparing photopeak energies to tabulated gamma ray energies. Photopeak areas are then converted to elemental concentration by using experimental timing and sample data, calculated elemental neutron capture rates, absolute detector efficiencies, and absolute spectroscopic decay data. Calculational procedures have been developed so that fissile material can be analyzed by cyclic neutron activation and delayed-neutron counting procedures. These calculations are based on a 6 half-life group model of delayed neutron emission; calculations include corrections for delayed neutron interference from 17 O. Detection sensitivities of 239 Pu were demonstrated with 15-g samples at a throughput of up to 140 per day. Over 40 elements can be detected at the sub-ppM level

Virtual Instrument for Determining Rate Constant of Second-Order Reaction by pX Based on LabVIEW 8.0.

Science.gov (United States)

Meng, Hu; Li, Jiang-Yuan; Tang, Yong-Huai

2009-01-01

The virtual instrument system based on LabVIEW 8.0 for ion analyzer which can measure and analyze ion concentrations in solution is developed and comprises homemade conditioning circuit, data acquiring board, and computer. It can calibrate slope, temperature, and positioning automatically. When applied to determine the reaction rate constant by pX, it achieved live acquiring, real-time displaying, automatical processing of testing data, generating the report of results; and other functions. This method simplifies the experimental operation greatly, avoids complicated procedures of manual processing data and personal error, and improves veracity and repeatability of the experiment results.

Absolutyzm i pluralizm (ABSOLUTISM AND PLURALISM

Directory of Open Access Journals (Sweden)

Renata Ziemińska

2005-06-01

Full Text Available Alethic absolutism is a thesis that propositions can not be more or less true, that they are true or false for ever (if true at all and that their truth is independent on any circumstances of their assertion. In negative version, easier to defend, alethic absolutism claims the very same proposition can not be both true and false relative to circumstances of its assertion. Simple alethic pluralism is a thesis that we have many concepts of truth. It is a very good way to dissolve the controversy between alethic relativism and absolutism. Many philosophical concepts of truth are the best reason for such pluralism. If concept is meaning of a name, we have many concepts of truth because the name 'truth' was understood in many ways. The variety of meanings however can be superficial. Under it we can find one idea of truth expressed in correspondence truism or schema (T. The content of the truism is too poor to be content of anyone concept of truth, so it usually is connected with some picture of the world (ontology and we have so many concepts of truth as many pictures of the world. The authoress proposes the hierarchical pluralism with privileged classic (or correspondence in weak sense concept of truth as absolute property.Other author's publications:

Rate Constants for the Reactions of OH with CH(sub 3)Cl, CH(sub 2) C1(sub 2), CHC1(sub 3)and CH(sub 3)Br

Science.gov (United States)

Hsu, H-J.; DeMore, W.

1994-01-01

Rate constants for the reactions of OH with CH3C1, CH2Cl2, CHCl3 and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2)and for CH2Cl2, HFC-161 (CH3CH2F).

Application of the constant rate of pressure change method to improve jet pump performance

International Nuclear Information System (INIS)

Long, X P; Yang, X L

2012-01-01

This paper adopts a new method named the constant rate of pressure change (CRPC) to improve the jet pump performance. The main contribution of this method is that the diffuser generates uniform pressure gradient. The performance of the jet pump with new diffusers designed by the CRPC method, obtained by CFD methods, was compared with that of the jet pump with traditional conical diffusers. It is found that the CRPC diffuser produces a linear pressure increase indeed. The higher friction loss and the separation decrease the CRPC diffuser efficiency and then lower the pump efficiency. The pump with shorter throats has higher efficiency at small flow ratio while its efficiency is lower than the original pump at lager flow ratio and the peak efficiency of the pumps with the throat length of 5-6 Dt is higher than that of the pumps with other throat length. When the throat length is less than 4 Dt, the CRPC diffuser efficiency is higher than the conical diffuser. The CRPC method could also be used to design the nozzle and other situations needing the pressure change gradually.

Introducing the Mean Absolute Deviation "Effect" Size

Science.gov (United States)

Gorard, Stephen

2015-01-01

This paper revisits the use of effect sizes in the analysis of experimental and similar results, and reminds readers of the relative advantages of the mean absolute deviation as a measure of variation, as opposed to the more complex standard deviation. The mean absolute deviation is easier to use and understand, and more tolerant of extreme…

Absolute Quantification of Human Liver Phosphorus-Containing Metabolites In Vivo Using an Inhomogeneous Spoiling Magnetic Field Gradient

Science.gov (United States)

Bashir, Adil; Gropler, Robert; Ackerman, Joseph

2015-01-01

Purpose Absolute concentrations of high-energy phosphorus (31P) metabolites in liver provide more important insight into physiologic status of liver disease compared to resonance integral ratios. A simple method for measuring absolute concentrations of 31P metabolites in human liver is described. The approach uses surface spoiling inhomogeneous magnetic field gradient to select signal from liver tissue. The technique avoids issues caused by respiratory motion, chemical shift dispersion associated with linear magnetic field gradients, and increased tissue heat deposition due to radiofrequency absorption, especially at high field strength. Methods A method to localize signal from liver was demonstrated using superficial and highly non-uniform magnetic field gradients, which eliminate signal(s) from surface tissue(s) located between the liver and RF coil. A double standard method was implemented to determine absolute 31P metabolite concentrations in vivo. 8 healthy individuals were examined in a 3 T MR scanner. Results Concentrations of metabolites measured in eight healthy individuals are: γ-adenosine triphosphate (ATP) = 2.44 ± 0.21 (mean ± sd) mmol/l of wet tissue volume, α-ATP = 3.2 ± 0.63 mmol/l, β-ATP = 2.98 ± 0.45 mmol/l, inorganic phosphates (Pi) = 1.87 ± 0.25 mmol/l, phosphodiesters (PDE) = 10.62 ± 2.20 mmol/l and phosphomonoesters (PME) = 2.12 ± 0.51 mmol/l. All are in good agreement with literature values. Conclusions The technique offers robust and fast means to localize signal from liver tissue, allows absolute metabolite concentration determination, and avoids problems associated with constant field gradient (linear field variation) localization methods. PMID:26633549

Absolute Determination of High DC Voltages by Means of Frequency Measurement

Science.gov (United States)

Peier, Dirk; Schulz, Bernd

1983-01-01

A novel absolute measuring procedure is presented for the definition of fixed points of the voltage in the 100 kV range. The method is based on transit time measurements with accelerated electrons. By utilizing the selective interaction of a monoenergetic electron beam with the electromagnetic field of a special cavity resonator, the voltage is referred to fundamental constants and the base unit second. Possible balance voltages are indicated by a current detector. Experimental investigations are carried out with resonators in the normal conducting range. With a copper resonator operating at the temperature of boiling nitrogen (77 K), the relative uncertainty of the voltage points is estimated to be +/- 4 × 10-4. The technically realizable uncertainty can be reduced to +/- 1 × 10-5 by the proposed application of a superconducting niobium resonator. Thus this measuring device becomes suitable as a primary standard for the high-voltage range.

Absolute calibration in vivo measurement systems

International Nuclear Information System (INIS)

Kruchten, D.A.; Hickman, D.P.

1991-02-01

Lawrence Livermore National Laboratory (LLNL) is currently investigating a new method for obtaining absolute calibration factors for radiation measurement systems used to measure internally deposited radionuclides in vivo. Absolute calibration of in vivo measurement systems will eliminate the need to generate a series of human surrogate structures (i.e., phantoms) for calibrating in vivo measurement systems. The absolute calibration of in vivo measurement systems utilizes magnetic resonance imaging (MRI) to define physiological structure, size, and composition. The MRI image provides a digitized representation of the physiological structure, which allows for any mathematical distribution of radionuclides within the body. Using Monte Carlo transport codes, the emission spectrum from the body is predicted. The in vivo measurement equipment is calibrated using the Monte Carlo code and adjusting for the intrinsic properties of the detection system. The calibration factors are verified using measurements of existing phantoms and previously obtained measurements of human volunteers. 8 refs

Dissociative Recombination and Excitation of CH+5 : Absolute Cross Sections and Branching Fractions

International Nuclear Information System (INIS)