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Sample records for determining rate constant

  1. On determining dose rate constants spectroscopically

    International Nuclear Information System (INIS)

    Rodriguez, M.; Rogers, D. W. O.

    2013-01-01

    Purpose: To investigate several aspects of the Chen and Nath spectroscopic method of determining the dose rate constants of 125 I and 103 Pd seeds [Z. Chen and R. Nath, Phys. Med. Biol. 55, 6089–6104 (2010)] including the accuracy of using a line or dual-point source approximation as done in their method, and the accuracy of ignoring the effects of the scattered photons in the spectra. Additionally, the authors investigate the accuracy of the literature's many different spectra for bare, i.e., unencapsulated 125 I and 103 Pd sources. Methods: Spectra generated by 14 125 I and 6 103 Pd seeds were calculated in vacuo at 10 cm from the source in a 2.7 × 2.7 × 0.05 cm 3 voxel using the EGSnrc BrachyDose Monte Carlo code. Calculated spectra used the initial photon spectra recommended by AAPM's TG-43U1 and NCRP (National Council of Radiation Protection and Measurements) Report 58 for the 125 I seeds, or TG-43U1 and NNDC(2000) (National Nuclear Data Center, 2000) for 103 Pd seeds. The emitted spectra were treated as coming from a line or dual-point source in a Monte Carlo simulation to calculate the dose rate constant. The TG-43U1 definition of the dose rate constant was used. These calculations were performed using the full spectrum including scattered photons or using only the main peaks in the spectrum as done experimentally. Statistical uncertainties on the air kerma/history and the dose rate/history were ⩽0.2%. The dose rate constants were also calculated using Monte Carlo simulations of the full seed model. Results: The ratio of the intensity of the 31 keV line relative to that of the main peak in 125 I spectra is, on average, 6.8% higher when calculated with the NCRP Report 58 initial spectrum vs that calculated with TG-43U1 initial spectrum. The 103 Pd spectra exhibit an average 6.2% decrease in the 22.9 keV line relative to the main peak when calculated with the TG-43U1 rather than the NNDC(2000) initial spectrum. The measured values from three different

  2. 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.

  3. 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.

  4. 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...

  5. 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 ...

  6. 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.

  7. 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.

  8. 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

  9. 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

  10. 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

  11. 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

  12. 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

  13. 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)

  14. 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.

  15. 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.

  16. 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.

  17. Photon spectrometry for the determination of the dose-rate constant of low-energy photon-emitting brachytherapy sources

    International Nuclear Information System (INIS)

    Chen, Zhe Jay; Nath, Ravinder

    2007-01-01

    Accurate determination of dose-rate constant (Λ) for interstitial brachytherapy sources emitting low-energy photons (<50 keV) has remained a challenge in radiation dosimetry because of the lack of a suitable absolute dosimeter for accurate measurement of the dose rates near these sources. Indeed, a consensus value of Λ taken as the arithmetic mean of the dose-rate constants determined by different research groups and dosimetry techniques has to be used at present for each source model in order to minimize the uncertainties associated with individual determinations of Λ. Because the dosimetric properties of a source are fundamentally determined by the characteristics of the photons emitted by the source, a new technique based on photon spectrometry was developed in this work for the determination of dose-rate constant. The photon spectrometry technique utilized a high-resolution gamma-ray spectrometer to measure source-specific photon characteristics emitted by the low-energy sources and determine their dose-rate constants based on the measured photon-energy spectra and known dose-deposition properties of mono-energetic photons in water. This technique eliminates many of the difficulties arising from detector size, the energy dependence of detector sensitivity, and the use of non-water-equivalent solid phantoms in absolute dose rate measurements. It also circumvents the uncertainties that might be associated with the source modeling in Monte Carlo simulation techniques. It was shown that the estimated overall uncertainty of the photon spectrometry technique was less than 4%, which is significantly smaller than the reported 8-10% uncertainty associated with the current thermo-luminescent dosimetry technique. In addition, the photon spectrometry technique was found to be stable and quick in Λ determination after initial setup and calibration. A dose-rate constant can be determined in less than two hours for each source. These features make it ideal to determine

  18. 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.

  19. 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...

  20. 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

  1. 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

  2. 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

  3. 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

  4. 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

  5. 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.

  6. Effect of improved TLD dosimetry on the determination of dose rate constants for 125I and 103Pd brachytherapy seeds

    International Nuclear Information System (INIS)

    Rodriguez, M.; Rogers, D. W. O.

    2014-01-01

    Purpose: To more accurately account for the relative intrinsic energy dependence and relative absorbed-dose energy dependence of TLDs when used to measure dose rate constants (DRCs) for 125 I and 103 Pd brachytherapy seeds, to thereby establish revised “measured values” for all seeds and compare the revised values with Monte Carlo and consensus values. Methods: The relative absorbed-dose energy dependence, f rel , for TLDs and the phantom correction, P phant , are calculated for 125 I and 103 Pd seeds using the EGSnrc BrachyDose and DOSXYZnrc codes. The original energy dependence and phantom corrections applied to DRC measurements are replaced by calculated (f rel ) −1 and P phant values for 24 different seed models. By comparing the modified measured DRCs to the MC values, an appropriate relative intrinsic energy dependence, k bq rel , is determined. The new P phant values and relative absorbed-dose sensitivities, S AD rel , calculated as the product of (f rel ) −1 and (k bq rel ) −1 , are used to individually revise the measured DRCs for comparison with Monte Carlo calculated values and TG-43U1 or TG-43U1S1 consensus values. Results: In general, f rel is sensitive to the energy spectra and models of the brachytherapy seeds. Values may vary up to 8.4% among 125 I and 103 Pd seed models and common TLD shapes. P phant values depend primarily on the isotope used. Deduced (k bq rel ) −1 values are 1.074 ± 0.015 and 1.084 ± 0.026 for 125 I and 103 Pd seeds, respectively. For (1 mm) 3 chips, this implies an overall absorbed-dose sensitivity relative to 60 Co or 6 MV calibrations of 1.51 ± 1% and 1.47 ± 2% for 125 I and 103 Pd seeds, respectively, as opposed to the widely used value of 1.41. Values of P phant calculated here have much lower statistical uncertainties than literature values, but systematic uncertainties from density and composition uncertainties are significant. Using these revised values with the literature’s DRC measurements, the

  7. 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

  8. Dose rate constants for new dose quantities

    International Nuclear Information System (INIS)

    Tschurlovits, M.; Daverda, G.; Leitner, A.

    1992-01-01

    Conceptual changes and new quantities made is necessary to reassess dose rate quantities. Calculations of the dose rate constant were done for air kerma, ambient dose equivalent and directional dose equivalent. The number of radionuclides is more than 200. The threshold energy is selected as 20 keV for the dose equivalent constants. The dose rate constant for the photon equivalent dose as used mainly in German speaking countries as a temporary quantity is also included. (Author)

  9. Spectrophotometric determination of association constant

    DEFF Research Database (Denmark)

    2016-01-01

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

  10. 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.

  11. Elongational flow of polymer melts at constant strain rate, constant stress and constant force

    Science.gov (United States)

    Wagner, Manfred H.; Rolón-Garrido, Víctor H.

    2013-04-01

    Characterization of polymer melts in elongational flow is typically performed at constant elongational rate or rarely at constant tensile stress conditions. One of the disadvantages of these deformation modes is that they are hampered by the onset of "necking" instabilities according to the Considère criterion. Experiments at constant tensile force have been performed even more rarely, in spite of the fact that this deformation mode is free from necking instabilities and is of considerable industrial relevance as it is the correct analogue of steady fiber spinning. It is the objective of the present contribution to present for the first time a full experimental characterization of a long-chain branched polyethylene melt in elongational flow. Experiments were performed at constant elongation rate, constant tensile stress and constant tensile force by use of a Sentmanat Extensional Rheometer (SER) in combination with an Anton Paar MCR301 rotational rheometer. The accessible experimental window and experimental limitations are discussed. The experimental data are modelled by using the Wagner I model. Predictions of the steady-start elongational viscosity in constant strain rate and creep experiments are found to be identical, albeit only by extrapolation of the experimental data to Hencky strains of the order of 6. For constant stress experiments, a minimum in the strain rate and a corresponding maximum in the elongational viscosity is found at a Hencky strain of the order of 3, which, although larger than the steady-state value, follows roughly the general trend of the steady-state elongational viscosity. The constitutive analysis also reveals that constant tensile force experiments indicate a larger strain hardening potential than seen in constant elongation rate or constant tensile stress experiments. This may be indicative of the effect of necking under constant elongation rate or constant tensile stress conditions according to the Considère criterion.

  12. Determination of the absolute second-order rate constant for the reaction Na + O3 → NaO + O2

    International Nuclear Information System (INIS)

    Husain, David; Marshall, Paul; Plane, J.M.C.

    1985-01-01

    The absolute second-order rate constant for the reaction Na + O 3 -> NaO + O 2 (k 1 ) has been determined by time-resolved atomic resonance absorption spectroscopy at lambda = 589 nm [Na(3 2 Psub(j)) 2 Ssub(1/2))] following pulsed irradiation, coupled with monitoring of O 3 by light absorption in the ultra-violet; this yields k 1 (500 K) = 4(+4,-2) x 10 -10 cm 3 molecule -1 s -1 , resolving large differences for various estimates of this important quantity used in modelling the sodium layer in the mesosphere. (author)

  13. 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.

  14. Inflation with a constant rate of roll

    International Nuclear Information System (INIS)

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

    2015-01-01

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

  15. 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)

  16. A systematic evaluation of the dose-rate constant determined by photon spectrometry for 21 different models of low-energy photon-emitting brachytherapy sources.

    Science.gov (United States)

    Chen, Zhe Jay; Nath, Ravinder

    2010-10-21

    The aim of this study was to perform a systematic comparison of the dose-rate constant (Λ) determined by the photon spectrometry technique (PST) with the consensus value ((CON)Λ) recommended by the American Association of Physicists in Medicine (AAPM) for 21 low-energy photon-emitting interstitial brachytherapy sources. A total of 63 interstitial brachytherapy sources (21 different models with 3 sources per model) containing either (125)I (14 models), (103)Pd (6 models) or (131)Cs (1 model) were included in this study. A PST described by Chen and Nath (2007 Med. Phys. 34 1412-30) was used to determine the dose-rate constant ((PST)Λ) for each source model. Source-dependent variations in (PST)Λ were analyzed systematically against the spectral characteristics of the emitted photons and the consensus values recommended by the AAPM brachytherapy subcommittee. The values of (PST)Λ for the encapsulated sources of (103)Pd, (125)I and (131)Cs varied from 0.661 to 0.678 cGyh(-1) U(-1), 0.959 to 1.024 cGyh(-1)U(-1) and 1.066 to 1.073 cGyh(-1)U(-1), respectively. The relative variation in (PST)Λ among the six (103)Pd source models, caused by variations in photon attenuation and in spatial distributions of radioactivity among the source models, was less than 3%. Greater variations in (PST)Λ were observed among the 14 (125)I source models; the maximum relative difference was over 6%. These variations were caused primarily by the presence of silver in some (125)I source models and, to a lesser degree, by the variations in photon attenuation and in spatial distribution of radioactivity among the source models. The presence of silver generates additional fluorescent x-rays with lower photon energies which caused the (PST)Λ value to vary from 0.959 to 1.019 cGyh(-1)U(-1) depending on the amount of silver used by a given source model. For those (125)I sources that contain no silver, their (PST)Λ was less variable and had values within 1% of 1.024 cGyh(-1)U(-1). For the 16

  17. The use of digital simulation to improve the cyclic voltammetric determination of rate constants for homogeneous chemical reactions following charge transfers

    International Nuclear Information System (INIS)

    Mozo, J.D.; Carbajo, J.; Sturm, J.C.; Nunez-Vergara, L.J.; Moscoso, R.; Squella, J.A.

    2011-01-01

    Cyclic voltammetry (CV) is a very useful electrochemical tool used to study reaction systems that include chemical steps that are coupled to electron transfers. This type of system generally involves the chemical reaction of an electrochemically generated free radical. Published methods exist that are used to determine the kinetics of electrochemically initiated chemical reactions from the measurements of the peak current ratio (i pa /i pc ) of a cyclic voltammogram. The published method requires working curves to relate a kinetic parameter to the peak current ratio. In the presented work, a digital simulation package was used to obtain improved working curves for specific working conditions. The curves were compared with the published results for the first- and second-order chemical reactions following the charge transfer step mechanisms. According to the presented results, the previously published working curve is reliable for a mechanism with a first-order chemical reaction; however, a change in the switching potential requires a recalculation of the curve. In the case of mechanisms with a second-order step (dimerisation and disproportionation), several different views exist on how the second-order chemical term should be expressed so that different values of the constant are obtained. Parameters such as electrode type, electrode area, electroactive species concentration, switching potential, scan rate and method for peak current ratio calculation modify the working curves and must always be specified. We propose a standardised method to obtain the most reliable kinetic constant values. The results of this work will permit researchers who handle simulation software to construct their own working curves. Additionally, those who do not have the simulation software could use the working curves described here. The revelations of the presented experiments may be useful to a broad chemistry audience because this study presents a simple and low-cost procedure for the

  18. 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 -

  19. 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)

  20. 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.

  1. 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)

  2. 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.

  3. On the determination of the Hubble constant

    International Nuclear Information System (INIS)

    Gurzadyan, V.G.; Harutyunyan, V.V.; Kocharyan, A.A.

    1990-10-01

    The possibility of an alternative determination of the distance scale of the Universe and the Hubble constant based on the numerical analysis of the hierarchical nature of the large scale Universe (galaxies, clusters and superclusters) is proposed. The results of computer experiments performed by means of special numerical algorithms are represented. (author). 9 refs, 7 figs

  4. 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.

  5. Direct determination of the rate constant of propagation by pseudo-stationary polymerization technique: screening investigation for the (implicit) penultimate effect

    International Nuclear Information System (INIS)

    Schnoll-Bitai, I.; Friedrich Olaj, O.; Liu Song Yu

    1999-01-01

    The systems styrene-p-methylstyrene, styrene-p-chlorostyrene, methyl methacrylate-p-methylstyrene and methyl methacrylate-p-chlorostyrene were polymerized under pseudo-stationary conditions (rotating sector or pulsed laser) at 25 degree C, 40 degree C and 50 degree C. The respective molecular weight distributions measured by GPC were analysed in order to derive directly the phenomenological rate constant of propagation, κ sub ρ. Copolymer compositions as a function of monomer feed could be described by the terminal model, whereas the kinetic results could only be interpreted in terms of the restricted penultimate model

  6. Planck Constant Determination from Power Equivalence

    Science.gov (United States)

    Newell, David B.

    2000-04-01

    Equating mechanical to electrical power links the kilogram, the meter, and the second to the practical realizations of the ohm and the volt derived from the quantum Hall and the Josephson effects, yielding an SI determination of the Planck constant. The NIST watt balance uses this power equivalence principle, and in 1998 measured the Planck constant with a combined relative standard uncertainty of 8.7 x 10-8, the most accurate determination to date. The next generation of the NIST watt balance is now being assembled. Modification to the experimental facilities have been made to reduce the uncertainty components from vibrations and electromagnetic interference. A vacuum chamber has been installed to reduce the uncertainty components associated with performing the experiment in air. Most of the apparatus is in place and diagnostic testing of the balance should begin this year. Once a combined relative standard uncertainty of one part in 10-8 has been reached, the power equivalence principle can be used to monitor the possible drift in the artifact mass standard, the kilogram, and provide an accurate alternative definition of mass in terms of fundamental constants. *Electricity Division, Electronics and Electrical Engineering Laboratory, Technology Administration, U.S. Department of Commerce. Contribution of the National Institute of Standards and Technology, not subject to copyright in the U.S.

  7. Time since death and decay rate constants of Norway spruce and European larch deadwood in subalpine forests determined using dendrochronology and radiocarbon dating

    Science.gov (United States)

    Petrillo, M.; Cherubini, P.; Fravolini, G.; Ascher, J.; Schärer, M.; Synal, H.-A.; Bertoldi, D.; Camin, F.; Larcher, R.; Egli, M.

    2015-09-01

    Due to the large size and highly heterogeneous spatial distribution of deadwood, the time scales involved in the coarse woody debris (CWD) decay of Picea abies (L.) Karst. and Larix decidua Mill. in Alpine forests have been poorly investigated and are largely unknown. We investigated the CWD decay dynamics in an Alpine valley in Italy using the five-decay class system commonly employed for forest surveys, based on a macromorphological and visual assessment. For the decay classes 1 to 3, most of the dendrochronological samples were cross-dated to assess the time that had elapsed since tree death, but for decay classes 4 and 5 (poorly preserved tree rings) and some others not having enough tree rings, radiocarbon dating was used. In addition, density, cellulose and lignin data were measured for the dated CWD. The decay rate constants for spruce and larch were estimated on the basis of the density loss using a single negative exponential model. In the decay classes 1 to 3, the ages of the CWD were similar varying between 1 and 54 years for spruce and 3 and 40 years for larch with no significant differences between the classes; classes 1-3 are therefore not indicative for deadwood age. We found, however, distinct tree species-specific differences in decay classes 4 and 5, with larch CWD reaching an average age of 210 years in class 5 and spruce only 77 years. The mean CWD rate constants were 0.012 to 0.018 yr-1 for spruce and 0.005 to 0.012 yr-1 for larch. Cellulose and lignin time trends half-lives (using a multiple-exponential model) could be derived on the basis of the ages of the CWD. The half-lives for cellulose were 21 yr for spruce and 50 yr for larch. The half-life of lignin is considerably higher and may be more than 100 years in larch CWD.

  8. Time since death and decay rate constants of Norway spruce and European larch deadwood in subalpine forests determined using dendrochronology and radiocarbon dating

    Science.gov (United States)

    Petrillo, Marta; Cherubini, Paolo; Fravolini, Giulia; Marchetti, Marco; Ascher-Jenull, Judith; Schärer, Michael; Synal, Hans-Arno; Bertoldi, Daniela; Camin, Federica; Larcher, Roberto; Egli, Markus

    2016-03-01

    Due to the large size (e.g. sections of tree trunks) and highly heterogeneous spatial distribution of deadwood, the timescales involved in the coarse woody debris (CWD) decay of Picea abies (L.) Karst. and Larix decidua Mill. in Alpine forests are largely unknown. We investigated the CWD decay dynamics in an Alpine valley in Italy using the chronosequence approach and the five-decay class system that is based on a macromorphological assessment. For the decay classes 1-3, most of the dendrochronological samples were cross-dated to assess the time that had elapsed since tree death, but for decay classes 4 and 5 (poorly preserved tree rings) radiocarbon dating was used. In addition, density, cellulose, and lignin data were measured for the dated CWD. The decay rate constants for spruce and larch were estimated on the basis of the density loss using a single negative exponential model, a regression approach, and the stage-based matrix model. In the decay classes 1-3, the ages of the CWD were similar and varied between 1 and 54 years for spruce and 3 and 40 years for larch, with no significant differences between the classes; classes 1-3 are therefore not indicative of deadwood age. This seems to be due to a time lag between the death of a standing tree and its contact with the soil. We found distinct tree-species-specific differences in decay classes 4 and 5, with larch CWD reaching an average age of 210 years in class 5 and spruce only 77 years. The mean CWD rate constants were estimated to be in the range 0.018 to 0.022 y-1 for spruce and to about 0.012 y-1 for larch. Snapshot sampling (chronosequences) may overestimate the age and mean residence time of CWD. No sampling bias was, however, detectable using the stage-based matrix model. Cellulose and lignin time trends could be derived on the basis of the ages of the CWD. The half-lives for cellulose were 21 years for spruce and 50 years for larch. The half-life of lignin is considerably higher and may be more than

  9. 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

  10. Determination of Peukert's Constant Using Impedance Spectroscopy: Application to Supercapacitors.

    Science.gov (United States)

    Mills, Edmund Martin; Kim, Sangtae

    2016-12-15

    Peukert's equation is widely used to model the rate dependence of battery capacity, and has recently attracted attention for application to supercapacitors. Here we present a newly developed method to readily determine Peukert's constant using impedance spectroscopy. Impedance spectroscopy is ideal for this purpose as it has the capability of probing electrical performance of a device over a wide range of time-scales within a single measurement. We demonstrate that the new method yields consistent results with conventional galvanostatic measurements through applying it to commercially available supercapacitors. Additionally, the novel method is much simpler and more precise, making it an attractive alternative for the determination of Peukert's constant.

  11. Biased Brownian dynamics for rate constant calculation.

    OpenAIRE

    Zou, G; Skeel, R D; Subramaniam, S

    2000-01-01

    An enhanced sampling method-biased Brownian dynamics-is developed for the calculation of diffusion-limited biomolecular association reaction rates with high energy or entropy barriers. Biased Brownian dynamics introduces a biasing force in addition to the electrostatic force between the reactants, and it associates a probability weight with each trajectory. A simulation loses weight when movement is along the biasing force and gains weight when movement is against the biasing force. The sampl...

  12. ADSORPTION RATE CONSTANTS OF EOSIN IN HUMIN

    OpenAIRE

    anshar, andi muhammad

    2015-01-01

    Eosin is one of the dyes commonly used in the industry and has the potential to cause pollution of the water environment. The Eosin pollution treatment methods used in this study was the adsorption method using humin fraction obtained from the peat land comes from Kalimantan. From the research data showed that the adsorption of eosin in humin result of washing with HCl / HF optimum at pH 4 and a contact time of 60 minutes with the adsorption-order rate was 8,4 x 10-3 min-1

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

    African Journals Online (AJOL)

    DR. AMINU

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

  14. Experimental Determination of the Avogadro Constant

    Indian Academy of Sciences (India)

    mental physical constant such as charge of an electron or the. Boltzmann constant ... ideas was that the number of particles or molecules in a gas of given volume could not ... knowledge of at least one property of a single molecule. Loschmidt ...

  15. 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.

  16. 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.

  17. Title: Elucidation of Environmental Fate of Artificial Sweeteners (Aspartame, Acesulfame K and Saccharin) by Determining Bimolecular Rate Constants with Hydroxyl Radical at Various pH and Temperature Conditions and Possible Reaction By-Products

    Science.gov (United States)

    Teraji, T.; Arakaki, T.; Suzuka, T.

    2012-12-01

    Use of artificial sweeteners in beverages and food has been rapidly increasing because of their non-calorie nature. In Japan, aspartame, acesulfame K and sucralose are among the most widely used artificial sweeteners. Because the artificial sweeteners are not metabolized in human bodies, they are directly excreted into the environment without chemical transformations. We initiated a study to better understand the fate of artificial sweeteners in the marine environment. The hydroxyl radical (OH), the most potent reactive oxygen species, reacts with various compounds and determines the environmental oxidation capacity and the life-time of many compounds. The steady-state OH concentration and the reaction rate constants between the compound and OH are used to estimate the life-time of the compound. In this study, we determine the bimolecular rate constants between aspartame, acefulfame K and saccharin and OH at various pH and temperature conditions using a competition kinetics technique. We use hydrogen peroxide as a photochemical source of OH. Bimolecular rate constant we obtained so far for aspartame was (2.6±1.2)×109 M-1 s-1 at pH = 3.0 and (4.9±2.3)×109 M-1 s-1 at pH = 5.5. Little effect was seen by changing the temperatures between 15 and 40 oC. Activation energy (Ea) was calculated to be -1.0 kJ mol-1 at pH = 3.0, +8.5 kJ mol-1 at pH = 5.5, which could be regarded as zero. We will report bimolecular rate constants at different pHs and temperatures for acesulfame K and saccharin, as well. Possible reaction by-products for aspartame will be also reported. We will further discuss the fate of aspartame in the coastal environment.

  18. 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

  19. FOREWORD: International determination of the Avogadro constant International determination of the Avogadro constant

    Science.gov (United States)

    Massa, Enrico; Nicolaus, Arnold

    2011-04-01

    This issue of Metrologia collects papers about the results of an international research project aimed at the determination of the Avogadro constant, NA, by counting the atoms in a silicon crystal highly enriched with the isotope 28Si. Fifty years ago, Egidi [1] thought about realizing an atomic mass standard. In 1965, Bonse and Hart [2] operated the first x-ray interferometer, thus paving the way to the achievement of Egidi's dream, and soon Deslattes et al [3] completed the first counting of the atoms in a natural silicon crystal. The present project, outlined by Zosi [4] in 1983, began in 2004 by combining the experiences and capabilities of the BIPM, INRIM, IRMM, NIST, NPL, NMIA, NMIJ and PTB. The start signal, ratified by a memorandum of understanding, was a contract for the production of a silicon crystal highly enriched with 28Si. The enrichment process was undertaken by the Central Design Bureau of Machine Building in St Petersburg. Subsequently, a polycrystal was grown in the Institute of Chemistry of High-Purity Substances of the Russian Academy of Sciences in Nizhny Novgorod and a 28Si boule was grown and purified by the Leibniz-Institut für Kristallzüchtung in Berlin. Isotope enrichment made it possible to apply isotope dilution mass spectroscopy, to determine the Avogadro constant with unprecedented accuracy, and to fulfil Egidi's dream. To convey Egidi's 'fantasy' into practice, two 28Si kilogram prototypes shaped as quasi-perfect spheres were manufactured by the Australian Centre for Precision Optics; their isotopic composition, molar mass, mass, volume, density and lattice parameter were accurately determined and their surfaces were chemically and physically characterized at the atomic scale. The paper by Andreas et al reviews the work carried out; it collates all the findings and illustrates how Avogadro's constant was obtained. Impurity concentration and gradients in the enriched crystal were measured by infrared spectroscopy and taken into

  20. Development of a chemical kinetic measurement apparatus and the determination of the reaction rate constants for lithium-lead/water interaction

    International Nuclear Information System (INIS)

    Biney, P.O.

    1993-04-01

    An experimental set-up for accurate measurement of hydrogen generation rate in Lithium-Lead (Li 17 Pb 83 ) Steam or water interactions has been designed. The most important features of the design include a pneumatic actuated quick opening and closing high temperature all stainless steel valve used to control the reaction time and the placement of most measuring devices below a water line to minimize leakage of the hydrogen collected. A PC based data acquisition and control system provides remote process sequencing, acquisition and control of all major components of the set-up. Initial tests indicate that the first design objective of maintaining leakproof gas collection chamber has been achieved. Initial pressure tests indicated that the pressure drop over a time span of 30 minutes was within the tolerance of the pressure transducer used to measure the pressure (within 0.690 kPa) at a nominal system pressure of 685 kPa. The experimental system hardware, data acquisition and control programs and data analysis program have been completed, tested and are currently functional

  1. 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

  2. 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...

  3. 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

  4. 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

  5. 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

  6. 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.

  7. 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 ...

  8. 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

  9. 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)

  10. Experimental determination of third-order elastic constants of diamond.

    Science.gov (United States)

    Lang, J M; Gupta, Y M

    2011-03-25

    To determine the nonlinear elastic response of diamond, single crystals were shock compressed along the [100], [110], and [111] orientations to 120 GPa peak elastic stresses. Particle velocity histories and elastic wave velocities were measured by using laser interferometry. The measured elastic wave profiles were used, in combination with published acoustic measurements, to determine the complete set of third-order elastic constants. These constants represent the first experimental determination, and several differ significantly from those calculated by using theoretical models.

  11. 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.)

  12. Rate constants for some electrophilic reactions of benzyl, benzhydryl, and trityl cations in solution

    International Nuclear Information System (INIS)

    Ujdak, R.J.; Jones, R.L.; Dorfman, L.M.

    1976-01-01

    Absolute rate constants have been determined by the pulse radiolysis technique for several electrophilic reactions of the benzyl, the benzhydryl, and the trityl cation in 1,2-dichloroethane solution. The rate constants for the reactions of these carbonium ions with chloride ion, with bromide ion, and with iodide ion are all very nearly the same, namely 6 x 10 10 M -1 s -1 at 24 0 C. The values very likely represent the diffusion controlled limit for the ion combination reactions. The rate constants for the reactions with triethylamine, tri-n-propylamine, and tri-n-butylamine range from 2.0 x 10 9 to 7 x 10 6 M -1 s -1 at 24 0 C. With increasing phenyl substitution, the decreasing trend in the magnitude of the rate constant is consistent with the combined electronic and steric effects. With increasing size of the amine, the decrease in the value of the rate constant seems to indicate that the steric effect predominates. The values of the rate constants for reactions of benzyl and benzhydryl cation with methanol, ethanol, and 2-propanol indicate the following. The rate constant is higher for reaction with the alcohol dimer in solution than with alcohol monomer. The rate constants for reaction with alcohol monomer have values of 1 x 10 8 M -1 s -1 or lower

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

    International Nuclear Information System (INIS)

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

    2003-01-01

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

  14. 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.

  15. 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

  16. 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.

  17. Procedures for determining MATMOD-4V material constants

    Energy Technology Data Exchange (ETDEWEB)

    Lowe, T.C.

    1993-11-01

    The MATMOD-4V constitutive relations were developed from the original MATMOD model to extend the range of nonelastic deformation behaviors represented to include transient phenomena such as strain softening. Improvements in MATMOD-4V increased the number of independent material constants and the difficulty in determining their values. Though the constitutive relations are conceptually simple, their form and procedures for obtaining their constants can be complex. This paper reviews in detail the experiments, numerical procedures, and assumptions that have been used to determine a complete set of MATMOD-4V constants for high purity aluminum.

  18. 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.

  19. Assessment of the analgesic potency of constant rate infusion of ...

    African Journals Online (AJOL)

    Parameters determined were heart and respiratory rates, blood glucose level, pain score and body weight. Results showed that mean heart rate, respiratory rate and body weight were not differed significantly (p > 0.05) within and among the groups. Mean blood glucose level of group 4 was significantly higher (p < 0.05) ...

  20. Problems of experimental determination of mononuclear hydroxocomplexes stability constants

    International Nuclear Information System (INIS)

    Davydov, Yu. P.; Davydov, D. Yu.

    2003-01-01

    In order to determine the stability constants of hydroxocomplexes a methodical approach has been developed that involves the following steps: (1) Determination of pH and concentration intervals in which a metal is present only in a form of mononuclear hydroxocomplex in solution; (2) determination of initial form of hydrated cation and conditions under which it occurs in solution; (3) Determination of the forms of mononuclear hydroxocomplexes and their stability constants by at least two independent methods. This paper illustrates application of the above approach for Fe(III) hydroxocomplex stability constant determination. The hydrolysis with formation of mononuclear species was studied at lower iron concentration since a pH interval is wider in that case (pH 3+ (H 2 O) 6 in the interval of pH 1.0 - 1.5. Further increase of pH (higher than 1.5) leads to hydrolysis of Fe with formation of mononuclear hydroxocomplexes. The results of ion exchange and spectrophotometry experiments showed that in a pH interval 1.5- 3.0 Fe(III) form only one complex Fe(OH)2+. The stability constant of iron first hydroxocomplex has been calculated. Applying the above approach for studying a series of cation we came to a conclusion that nearly in every case only the first hydroxocomplex stability stability constant can be experimentally determined. Only in the case of Pu(IV) it was possible to determine also the second constant. This paper demonstrates also application of the above approach for calculation of the Pu(IV) hydroxocomplexes stability constants. (authors)

  1. 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...

  2. Determination of the π3He3H coupling constant

    International Nuclear Information System (INIS)

    Nichitiu, F.; Sapozhnikov, M.G.

    1977-01-01

    Despersion relations for the real part of the antisymmetric amplitude of the π +-3 He scattering have been used in order to determine the π 3 He 3 H coupling constant. The coupling constant value determined by this method is larger than the elementary pion-nucleon coupling constant, but is in good agreement with the value obtained by another method. The obtained value is f 2 sub(π 3 He 3 H) = 0.12+-0.01. Shown is the importance of using the Coulomb corrections for dispersion relation calculations because the value of π 3 He 3 H coupling constant obtained with corrected total cross sections is larger by about 0.014 than the one obtained without these corrections. The best energy ranges for future π 3 He experiments are commented

  3. Divided Saddle Theory: A New Idea for Rate Constant Calculation.

    Science.gov (United States)

    Daru, János; Stirling, András

    2014-03-11

    We present a theory of rare events and derive an algorithm to obtain rates from postprocessing the numerical data of a free energy calculation and the corresponding committor analysis. The formalism is based on the division of the saddle region of the free energy profile of the rare event into two adjacent segments called saddle domains. The method is built on sampling the dynamics within these regions: auxiliary rate constants are defined for the saddle domains and the absolute forward and backward rates are obtained by proper reweighting. We call our approach divided saddle theory (DST). An important advantage of our approach is that it requires only standard computational techniques which are available in most molecular dynamics codes. We demonstrate the potential of DST numerically on two examples: rearrangement of alanine-dipeptide (CH3CO-Ala-NHCH3) conformers and the intramolecular Cope reaction of the fluxional barbaralane molecule.

  4. 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

  5. Determination of calibration constants for perturbing objects of cavity resonators

    International Nuclear Information System (INIS)

    Franco, M.A.R.; Serrao, V.A.; Fuhrmann, C.

    1989-05-01

    Using the Slater theorem, the calibrating constants for objects utilized in the tecnique of perturbing measurements of cavities electric and magnetic fields have been determined. Such perturbing objects are utilized in the measurements of the shunt impedance and electric field relative intensity ocurring in linac accelerating structures. To determine the calibrating constants of the perturbing objects, a cylindrical cavity of well know field pattern has been utilized. The cavity was excited in two differente modes of oscillation and the experimental results are in good aggrement with the theoretical values. (author) [pt

  6. Galvanic Cells and the Determination of Equilibrium Constants

    Science.gov (United States)

    Brosmer, Jonathan L.; Peters, Dennis G.

    2012-01-01

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

  7. Hydrogen molecular ions for improved determination of fundamental constants

    NARCIS (Netherlands)

    Karr, J.-P.; Hilico, L.; Koelemeij, J.C.J.; Korobov, V.I.

    2016-01-01

    The possible use of high-resolution rovibrational spectroscopy of the hydrogen molecular ions H-2(+) and HD+ for an independent determination of several fundamental constants is analyzed. While these molecules had been proposed for the metrology of nuclear-to-electron mass ratios, we show that they

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

    African Journals Online (AJOL)

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

  9. 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.

  10. The determination methods of the velocity constant for electrochemical reactions

    International Nuclear Information System (INIS)

    Molina, R.

    1963-01-01

    In a brief introduction are recalled the fundamental mechanisms of the electrochemical reaction and the definition of the intrinsic velocity constant of a such reaction. By the nature of the different parameters which enter in this definition are due some experimental problems which are examined. Then are given the principles of the measurement methods of the velocity constant. These methods are developed with the mathematical expression of the different rates of the mass transfer to an electrode. In each case are given the experimental limits of use of the methods and the size order of the velocity constant that can be reached. A list of fundamental works to be consulted conclude this work. (O.M.) [fr

  11. Determination of line broadening constants in high pressure discharge lamps

    International Nuclear Information System (INIS)

    Weiss, M; Schubert, H; Meier, S; Born, M; Reiter, D; Stroesser, M

    2005-01-01

    A numerical model of the radiative transfer in high pressure metal halide discharge lamps is used to determine line broadening parameters for atomic scandium lines. The determined broadening constants are in qualitative agreement with theoretical estimates in many cases, but significant deviations exist. The data obtained from this paper can, therefore, be used to further improve modelling of radiative contributions to the energy balance in such types of discharge lamps

  12. 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.

  13. 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.

  14. 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.

  15. Determination of the rate constants of the reactions CO/sub 2/+OH/sup -/ -> HCO/sub 3//sup -/ and barbituric acid -> barbiturate anion -> H/sup -/ using the pulse radiolyse technique

    Energy Technology Data Exchange (ETDEWEB)

    Schuchmann, M.N.; von Sonntag, C.

    1982-09-01

    The kinetics of the reactions of CO/sub 2/ + OH /sup -/-> HCO/sub 3//sup -/ (i) and barbituric acid -> barbiturate anion + H/sup +/ (ii) have been remeasured using as a new approach the pulse radiolysis technique with optical and conductivity detection. The rate constants obtained in the present study, ksub(j) (21/sup 0/C) = 6900 +- 700 M/sup -1/ s/sup -1/ and ksub(II) (19/sup 0/C) = 22 +- 2 s/sup -1/ agree within experimental errors with values obtained earlier by other methods.

  16. Atomic spectroscopy and highly accurate measurement: determination of fundamental constants

    International Nuclear Information System (INIS)

    Schwob, C.

    2006-12-01

    This document reviews the theoretical and experimental achievements of the author concerning highly accurate atomic spectroscopy applied for the determination of fundamental constants. A pure optical frequency measurement of the 2S-12D 2-photon transitions in atomic hydrogen and deuterium has been performed. The experimental setting-up is described as well as the data analysis. Optimized values for the Rydberg constant and Lamb shifts have been deduced (R = 109737.31568516 (84) cm -1 ). An experiment devoted to the determination of the fine structure constant with an aimed relative uncertainty of 10 -9 began in 1999. This experiment is based on the fact that Bloch oscillations in a frequency chirped optical lattice are a powerful tool to transfer coherently many photon momenta to the atoms. We have used this method to measure accurately the ratio h/m(Rb). The measured value of the fine structure constant is α -1 = 137.03599884 (91) with a relative uncertainty of 6.7*10 -9 . The future and perspectives of this experiment are presented. This document presented before an academic board will allow his author to manage research work and particularly to tutor thesis students. (A.C.)

  17. Determination of the pion-nucleon coupling constant

    International Nuclear Information System (INIS)

    Samaranayake, V.K.

    1977-06-01

    Forward dispersion relations are used to determine the pion-nucleon coupling constant and S-wave scattering lengths using a least squares fit with additional parameters introduced to take account of the uncertainties in the calculation of dispersion integrals. The values obtained are: f 2 = (78.0+- 2.1).10 -3 , a 1 -a 3 = (272.4+- 12.3).10 -3 , a 1 +2a 3 = (15.1+-10.4).10 -3

  18. Rapid and accurate determination of Stern-Volmer quenching constants

    International Nuclear Information System (INIS)

    Goodpaster, John V.; McGuffin, Victoria L.

    1999-01-01

    In this work, a novel system has been designed, characterized, and validated for the determination of fluorescence quenching constants. Capillary flow injection methods are used to automate the preparation and mixing of the fluorophore and quencher solutions. Because of the small diameter of the capillary (75-200 μm), fluorescence measurements can be made without corrections for primary and secondary absorbance effects. The fluorescence spectrometer is equipped with a charge-coupled device (CCD) that has a detection limit of 3.0x10 -9 M (2.3 ppb) and a linear dynamic range of 10 5 for integration times of 0.01-10 s. This spectrometer has a 300 nm spectral range with 1 nm resolution, allowing the fluorescence quenching constants to be calculated at single wavelengths or over integrated wavelength ranges. This system was validated by comparison to traditional methods for the determination of Stern-Volmer constants for alternant and nonalternant polycyclic aromatic hydrocarbons with nitromethane and triethylamine. (c) 2000 Society for Applied Spectroscopy

  19. Determination of the stability constants of uranium-tetracycline complexes

    International Nuclear Information System (INIS)

    Tarenzi, L.R.; Saiki, M.

    1983-01-01

    Stability constants of complexes formed with tetracycline (TC) and uranium have been determined by solvent extraction technique. The site on the tetracycline molecule at which uranyl ion may be bound has been studied by means of potentiometric titration and spectrophotometric techniques. The complex species with 1:1 and 1:2 for UO 2 : TC ratio have been identified by conductometric titration. Solvent extraction studies have also shown that the complexes are mononuclear of the type UO 2 (TC) sub (n) (n=1,2) and that no hidroxocomplexes or negatively charged complexes have been formed. Stability constant values have been calculated by numerical weighted least square method and by graphical methods of two parameters, of the average number of ligands and of the limiting value. (Author) [pt

  20. Determination of the gravitational constant with a beam balance

    International Nuclear Information System (INIS)

    Schlamminger, St.; Holzschuh, E.; Kuendig, W.

    2002-01-01

    The Newtonian gravitational constant G was determined by means of a novel beam-balance experiment with an accuracy comparable to that of the most precise torsion-balance experiments. The gravitational force of two stainless steel tanks filled with 13 521 kg mercury on 1.1 kg test masses was measured using a commercial mass comparator. A careful analysis of the data and the experimental error yields G=6.674 07(22)x10 -11 m 3 kg -1 s -2 . This value is in excellent agreement with most values previously obtained with different methods

  1. 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.

  2. Determination of sampling constants for selenium by cyclic INAA

    International Nuclear Information System (INIS)

    Chatt, A.; Jayawickreme, C.K.

    1988-01-01

    Biological reference materials of natural origin and certified elemental composition play an important role in not only evaluating the reliability of a new method but also assuring the quality of data produced in routine analysis. In fact, it has become a common practice to include an appropriate certified reference material (CRM) in every batch of samples analyzed for the purpose of quality assurance. One of the most important properties of a CRM or reference material (RM) should be its degree of homogeneity. For biological materials, inhomogeneity is inherently associated with their intricate structures. In order to justify the usage of a CRM or RM at a mass lower than that recommended by the issuing agency, is necessary to evaluate the homogeneity at lower mass ranges and to determine the sampling constant for the element of interest. The objectives of the present work are to investigate the homogeneity and to calculate the sampling constants for selenium in several biological CRM and RM that are frequently used to evaluate the accuracy of measurements

  3. Experimental determination of monoethanolamine protonation constant and its temperature dependency

    Directory of Open Access Journals (Sweden)

    Ma’mun Sholeh

    2017-01-01

    Full Text Available Carbon dioxide as one of the major contributors to the global warming problem is produced in large quantities by many important industries and its emission seems to rise from year to year. Aminebased absorption is one of the methods to capture CO2 from its sources. As a reactive system, mass transfer and chemical reaction take place simultaneously. In a vapor-liquid equilibrium model for the CO2-amine-water system, some parameters such as mass transfer coefficients and chemical equilibrium constants need to be known. However, some parameters could be determined experimentally and the rests could be regressed from the model. The protonation constant (pKa, as one of the model parameters, could then be measured experimentally. The purpose of this study is to measure the pKa of monoethanolamine (MEA at a range of temperatures from 303 to 330K by a potentiometric titration method. The experimental data obtained were in a good agreement with the literature data. The pKa data from this work together with those from the literature were then correlated in an empirical correlation to be used for future research.

  4. 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.

  5. Determination of constants of factorized pairing force from conservation laws

    International Nuclear Information System (INIS)

    Voronkov, Yu.P.; Mikhajlov, V.M.

    1975-01-01

    The constants of a factorized interaction in the particle-particle channel are evaluated on the basis of average field parameters and Cooper pairing. The relations between the constants of multipole particle-particle forces are derived for the spherical nuclei. The constants of the quadrupole pairing are obtained for deformed nuclei from the angular momentum conservation law. The calculated constants are compared with empiricalones

  6. 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.

  7. 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.

  8. Determination of stability constants of lanthanide complexes with tetracycline

    International Nuclear Information System (INIS)

    Saiki, Mitiko

    1975-01-01

    The stability constants of complexes compounds formed with tetracycline and lanthanides elements were determined for all lanthanides except promethium. The experimental procedure used was solvent extraction of the lanthanides labelled with their radioactive isotopes. It was shown that the formed complexes are mononuclear and that no hydroxo complexes or negatively charged complexes are formed in the experimental conditions of this work. Four methods of calculation were used for all complexes studied: the method of the average number of ligands, the method of limiting value, the method of two parameters and the method of weighted least squares. A comparison was made of the graphical methods with the method of least squares, showing the convenience of preceding least squares calculation by the graphical methods, in order to verify eventual mistakes of numerical data. It was shown the advantage of using radioisotopes of the elements for such a study, specially if the solvent extraction technique is used to-get the experimental data. (author)

  9. Impact of uncertainties in inorganic chemical rate constants on tropospheric composition and ozone radiative forcing

    Directory of Open Access Journals (Sweden)

    B. Newsome

    2017-12-01

    Full Text Available Chemical rate constants determine the composition of the atmosphere and how this composition has changed over time. They are central to our understanding of climate change and air quality degradation. Atmospheric chemistry models, whether online or offline, box, regional or global, use these rate constants. Expert panels evaluate laboratory measurements, making recommendations for the rate constants that should be used. This results in very similar or identical rate constants being used by all models. The inherent uncertainties in these recommendations are, in general, therefore ignored. We explore the impact of these uncertainties on the composition of the troposphere using the GEOS-Chem chemistry transport model. Based on the Jet Propulsion Laboratory (JPL and International Union of Pure and Applied Chemistry (IUPAC evaluations we assess the influence of 50 mainly inorganic rate constants and 10 photolysis rates on tropospheric composition through the use of the GEOS-Chem chemistry transport model. We assess the impact on four standard metrics: annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime. Uncertainty in the rate constants for NO2 + OH →M  HNO3 and O3 + NO  →  NO2 + O2 are the two largest sources of uncertainty in these metrics. The absolute magnitude of the change in the metrics is similar if rate constants are increased or decreased by their σ values. We investigate two methods of assessing these uncertainties, addition in quadrature and a Monte Carlo approach, and conclude they give similar outcomes. Combining the uncertainties across the 60 reactions gives overall uncertainties on the annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime of 10, 11, 16 and 16 %, respectively. These are larger than the spread between models in recent model intercomparisons. Remote

  10. 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...

  11. 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

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

    International Nuclear Information System (INIS)

    1989-01-01

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

  13. Note: Determination of torsional spring constant of atomic force microscopy cantilevers: Combining normal spring constant and classical beam theory

    DEFF Research Database (Denmark)

    Álvarez-Asencio, R.; Thormann, Esben; Rutland, M.W.

    2013-01-01

    A technique has been developed for the calculation of torsional spring constants for AFM cantilevers based on the combination of the normal spring constant and plate/beam theory. It is easy to apply and allow the determination of torsional constants for stiff cantilevers where the thermal power s...... spectrum is difficult to obtain due to the high resonance frequency and low signal/noise ratio. The applicability is shown to be general and this simple approach can thus be used to obtain torsional constants for any beam shaped cantilever. © 2013 AIP Publishing LLC....

  14. 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....

  15. Determination of the elastic constants of portlandite by Brillouin spectroscopy

    KAUST Repository

    Speziale, S.; Reichmann, H.J.; Schilling, F.R.; Wenk, H.R.; Monteiro, P.J.M.

    2008-01-01

    The single crystal elastic constants Cij and the shear and adiabatic bulk modulus of a natural portlandite (Ca(OH)2) crystal were determined by Brillouin spectroscopy at ambient conditions. The elastic constants, expressed in GPa, are: C11 = 102.0(± 2.0), C12 = 32.1(± 1.0), C13 = 8.4(± 0.4), C14 = 4.5(± 0.2), C33 = 33.6(± 0.7), C44 = 12.0(± 0.3), C66 = (C11-C12)/2 = 35.0(± 1.1), where the numbers in parentheses are 1σ standard deviations. The Reuss bounds of the adiabatic bulk and shear moduli are K0S = 26.0(± 0.3) GPa and G0 = 17.5(± 0.4) GPa, respectively, while the Voigt bounds of these moduli are K0S = 37.3(± 0.4) GPa and G0 = 24.4(± 0.3) GPa. The Reuss and Voigt bounds for the aggregate Young's modulus are 42.8(± 1.0) GPa and 60.0(± 0.8) GPa respectively, while the aggregate Poisson's ratio is equal to 0.23(± 0.01). Portlandite exhibits both large compressional elastic anisotropy with C11/C33 = 3.03(± 0.09) equivalent to that of the isostructural hydroxide brucite (Mg(OH)2), and large shear anisotropy with C66/C44 = 2.92(± 0.12) which is 11% larger than brucite. The comparison between the bulk modulus of portlandite and that of lime (CaO) confirms a systematic linear relationship between the bulk moduli of brucite-type simple hydroxides and the corresponding NaCl-type oxides. © 2008 Elsevier Ltd. All rights reserved.

  16. 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...

  17. An independent determination of the local Hubble constant

    Science.gov (United States)

    Fernández Arenas, David; Terlevich, Elena; Terlevich, Roberto; Melnick, Jorge; Chávez, Ricardo; Bresolin, Fabio; Telles, Eduardo; Plionis, Manolis; Basilakos, Spyros

    2018-02-01

    The relationship between the integrated H β line luminosity and the velocity dispersion of the ionized gas of H II galaxies and giant H II regions represents an exciting standard candle that presently can be used up to redshifts z ˜ 4. Locally it is used to obtain precise measurements of the Hubble constant by combining the slope of the relation obtained from nearby (z ≤ 0.2) H II galaxies with the zero-point determined from giant H II regions belonging to an `anchor sample' of galaxies for which accurate redshift-independent distance moduli are available. We present new data for 36 giant H II regions in 13 galaxies of the anchor sample that includes the megamaser galaxy NGC 4258. Our data are the result of the first 4 yr of observation of our primary sample of 130 giant H II regions in 73 galaxies with Cepheid determined distances. Our best estimate of the Hubble parameter is 71.0 ± 2.8(random) ± 2.1(systematic) km s- 1Mpc- 1. This result is the product of an independent approach and, although at present less precise than the latest SNIa results, it is amenable to substantial improvement.

  18. 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,

  19. Reaction rate constant for uranium in water and water vapor

    Energy Technology Data Exchange (ETDEWEB)

    TRIMBLE, D.J.

    1998-11-09

    The literature on uranium oxidation in water and oxygen free water vapor was reviewed. Arrhenius rate equations were developed from the review data. These data and equations will be used as a baseline from which to compare reaction rates measured for K Basin fuel.

  20. 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…

  1. 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.

  2. 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.

  3. 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.

  4. Determination of the elastic constants of portlandite by Brillouin spectroscopy

    KAUST Repository

    Speziale, S.

    2008-10-01

    The single crystal elastic constants Cij and the shear and adiabatic bulk modulus of a natural portlandite (Ca(OH)2) crystal were determined by Brillouin spectroscopy at ambient conditions. The elastic constants, expressed in GPa, are: C11 = 102.0(± 2.0), C12 = 32.1(± 1.0), C13 = 8.4(± 0.4), C14 = 4.5(± 0.2), C33 = 33.6(± 0.7), C44 = 12.0(± 0.3), C66 = (C11-C12)/2 = 35.0(± 1.1), where the numbers in parentheses are 1σ standard deviations. The Reuss bounds of the adiabatic bulk and shear moduli are K0S = 26.0(± 0.3) GPa and G0 = 17.5(± 0.4) GPa, respectively, while the Voigt bounds of these moduli are K0S = 37.3(± 0.4) GPa and G0 = 24.4(± 0.3) GPa. The Reuss and Voigt bounds for the aggregate Young\\'s modulus are 42.8(± 1.0) GPa and 60.0(± 0.8) GPa respectively, while the aggregate Poisson\\'s ratio is equal to 0.23(± 0.01). Portlandite exhibits both large compressional elastic anisotropy with C11/C33 = 3.03(± 0.09) equivalent to that of the isostructural hydroxide brucite (Mg(OH)2), and large shear anisotropy with C66/C44 = 2.92(± 0.12) which is 11% larger than brucite. The comparison between the bulk modulus of portlandite and that of lime (CaO) confirms a systematic linear relationship between the bulk moduli of brucite-type simple hydroxides and the corresponding NaCl-type oxides. © 2008 Elsevier Ltd. All rights reserved.

  5. A model for turbulent dissipation rate in a constant pressure ...

    Indian Academy of Sciences (India)

    J Dey

    the logarithmic region. However, measurement of the. Taylor microscale remains a difficult task, as it involves correlation function [1]. Consequently, an appreciation of the Taylor microscale, dissipation rate, etc., is lacking in practice due to complexity involved in estimating these quantities. Segalini et al [2] have proposed a ...

  6. 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

  7. 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.

  8. 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.

  9. The development of a chemical kinetic measurement apparatus and the determination of the reaction rate constants for lithium-lead/steam interaction. Final report 9-21-90--3-31-95

    International Nuclear Information System (INIS)

    Biney, P.O.

    1995-03-01

    The objective of this research to experimentally determine the hydrogen generation rate during the beginning and subsequent stages of liquid metal (Li 17 Pb 83 ) and water reaction. The experimental set-up has been built. It includes a metal sample preparation apparatus, a reaction system, a measurement system and a PC based data acquisition and control system. The most important feature of the reaction system is a pneumatic actuated quick opening and closing high temperature, all stainless steel valve used the system for reaction time control. The PC system provides remote process sequencing, acquisition and control of all the systems except the metal preparation apparatus. Due to the reactivity of the lithium, all the metal sampling, preparation and loading procedures are executed in a glove box under argon protection. The metal temperature was varied between 350 degrees C-650 degrees C and water temperature fixed at 60 degrees C during the experiments. A set of experimental procedures and two analyses methods: (1) thermodynamics method and (2) heat transfer method are discussed. All the measurements and data collections are executed under the PC system control. A data analysis program is used to calculate both the partial pressure of hydrogen and the hydrogen generation rate. The experiment results indicate that the amount of hydrogen generated is relate to the initial liquid metal temperature when the reaction surface is fixed. The mass of hydrogen generated as a function of initial liquid metal temperature and time of reaction is presented, The hydrogen generation over a time period of 240 seconds and the calculated errors are summarized in Table 1

  10. Constant temperatures and the rate of seed germination in maize ...

    African Journals Online (AJOL)

    The rate of germination of the NEM cultivar was faster than that of the QPM cultivar at all temperatures. The thermal times for median germination were 46 for QPM and 40.7 oCd for the NEM cultivar. The cardinal temperatures (base, Tb, optimum, To and ceiling, Tc) for the NEM cultivar were Tb: 7, To: 30 and Tc: 48.2 oC.

  11. Determinação das constantes cinéticas de degradação do ácido ascórbico em purê de pêssego: efeito da temperatura e concentração Determination of reaction rate constants for ascorbic acid degradation in peach pureé: effect of temperature and concentration

    Directory of Open Access Journals (Sweden)

    Ricardo Peraça Toralles

    2008-03-01

    Full Text Available O ácido ascórbico, vitamina C, é usado extensivamente na indústria de alimentos, não só devido ao seu valor nutricional, mas devido a suas contribuições funcionais na qualidade do produto. Existem muitos estudos sobre a estabilidade cinética do ácido ascórbico em bebidas, mas nenhum estudo foi encontrado sobre as constantes cinéticas de degradação do ácido ascórbico adicionado em purê de pêssego. Neste trabalho, estudou-se a cinética de degradação do ácido ascórbico em purê de pêssego da cultivar Jade, em condições anaeróbicas e na faixa de 70 a 90 °C. As concentrações de purês testadas foram 12, 22 e 32 °Brix. A análise cinética dos dados sugere que a degradação foi significativamente representada pelos modelos cinéticos de zero e primeira ordem. A velocidade de degradação do ácido ascórbico foi dependente da temperatura. A energia de ativação média foi de 45 kJ.mol-1 e independente da concentração de sólidos solúveis.Ascorbic acid (vitamin C is extensively used in the food industry, not only for its nutritional value, but also for its many functional contributions to product quality. There have been many studies on the stability of ascorbic acid in different beverages, but no study was found on the reaction rate constants for ascorbic acid degradation in peach purée. In this work, the degradation of ascorbic acid in Jade peach purée was studied in anaerobic conditions and from 70-90 °C. The peach purée concentrations tested were 12, 22 and 32 °Brix. The kinetic analysis of the data suggests that the degradation was significantly represented by zero and first-order kinetic models. The rate of ascorbic acid degradation in peach purée was temperature dependent. The average activation energy was 45 kJ.mol-1 and independent of the concentration of soluble solids.

  12. 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.

  13. 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.

  14. Determination of complex association constants from gas chromatograhic data

    NARCIS (Netherlands)

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

    1975-01-01

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

  15. DETERMINATION OF MIXED STABILITY CONSTANTS OF LEAD(II ...

    African Journals Online (AJOL)

    a

    stability constant values) at ionic strength 0.1 M and a temperature of 35 0C. ... biochemical aspects of sulphur containing amino acids have been reviewed by Jocelyn ... Electro-osmosis refers to the movement of liquid as a result of an applied ...

  16. DETERMINATION OF MIXED STABILITY CONSTANTS OF LEAD(II ...

    African Journals Online (AJOL)

    A method involving the use of paper ionophoresis is described for the study of equilibria in mixed – ligand complex systems in solution. The technique is based on the movement of a spot of metal ion under an electric field with the complexants added to the background electrolyte at pH 8.5. The stability constants of the ...

  17. 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

  18. 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

  19. Rate constants for the reaction of OH radicals with 1-chloroalkanes at 295 K

    DEFF Research Database (Denmark)

    Markert, F.; Nielsen, O.J.

    1992-01-01

    The rate constants for the reaction of OH radicals with a series of 1-chloroalkanes were measured at 295 K and at a total pressure of 1 atm. The rate constants were obtained by using the absolute technique of pulse radiolysis combined with kinetic UV-spectroscopy. The results are discussed in terms...

  20. 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

  1. 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.

  2. Direct determinations of the πNN coupling constants

    International Nuclear Information System (INIS)

    Ericson, T.E.O.; ); Loiseau, B.

    1998-01-01

    A novel extrapolation method has been used to deduce directly the charged πNN coupling constant from backward np differential scattering cross sections. The extracted value, g c 2 = 14.52(026)is higher than the indirectly deduced values obtained in nucleon-nucleon energy-dependent partial-wave analyses. Our preliminary direct value from a reanalysis of the GMO sum-rule points to an intermediate value of g c 2 about 13.97(30). (author)

  3. 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.

  4. Purohit's spectrophotometric method for determination of stability constants of complexes using Job's curves

    International Nuclear Information System (INIS)

    Purohit, D.N.; Goswami, A.K.; Chauhan, R.S.; Ressalan, S.

    1999-01-01

    A spectrophotometric method for determination of stability constants making use of Job's curves has been developed. Using this method stability constants of Zn(II), Cd(II), Mo(VI) and V(V) complexes of hydroxytriazenes have been determined. For the sake of comparison, values of the stability constants were also determined using Harvey and Manning's method. The values of the stability constants developed by two methods compare well. This new method has been named as Purohit's method. (author)

  5. 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.

  6. Spectrophotometric determination of the first hydrolysis constant of praseodymium (III)

    International Nuclear Information System (INIS)

    Gonzalez M, R.; Lopez G, H.; Rojas H, A.

    2010-01-01

    The behavior of the trivalent ion praseodymium in 2 M of NaCl at 303 K and in CO 2 free conditions, was studied. Spectrophotometric titrations of the soluble species were used, in order to obtain the value of the first hydrolysis constant of Pr(III). The data obtained were treated with both the program Squad and by a graphic method, respectively. The result obtained using Squad was log*β 1 = -8.94 ± 0.03, while it was log*β 1 = -8.77 ± 0.03, when calculated graphically. These results are similar to the value obtained previously with the potentiometric method. (Author)

  7. 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.

  8. Determination of the fine-structure constant {alpha} by measuring the quotient of the Planck constant and the neutron mass

    Energy Technology Data Exchange (ETDEWEB)

    Krueger, E; Nistler, W; Weirauch, W [Physikalisch-Technische Bundesanstalt, Braunschweig (Germany)

    1997-04-01

    Using a special high-precision apparatus at ILL the quotient h/m{sub n} (h Planck constant, m{sub n} neutron mass) has been measured. The value measured for h/m{sub n} leads to {alpha}{sup -1} = 137.03601082(524) (relative uncertainty: 3.9{center_dot}10{sup -8}) It was the first time that this fundamental constant has been determined by means of neutrons. The experiment, which had been running since 1981 in a preliminary version and since 1987 in the final version, which was finished in December 1996, is described. (author).

  9. 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.)

  10. 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.

  11. Geometrical determination of the constant of motion in General Relativity

    International Nuclear Information System (INIS)

    Catoni, F.; Cannata, R.; Zampetti, P.

    2009-01-01

    In recent time a theorem, due to E. Beltrami, through which the integration of the geodesic equations of a curved manifold is obtained by means of a merely geometric method, has been revisited. This way of dealing with the problem is well in accordance with the geometric spirit of the Theory of General Relativity. In this paper we show another relevant consequence of this method. Actually, the constants of the motion, introduced in this geometrical way that is completely independent of Newton theory, are related to the conservation laws for test particles in the Einstein theory. These conservation laws may be compared with the conservation laws of Newton. In particular, by the conservation of energy (E) and the L z component of angular momentum, the equivalence of the conservation laws for the Schwarzschild field is verified and the difference between Newton and Einstein theories for the rotating bodies (Kerr metric) is obtained in a straightforward way.

  12. Spectrophotometric determination of the first hydrolysis constant of praseodymium (III)

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez M, R.; Lopez G, H. [ININ, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico); Rojas H, A., E-mail: hilario.lopez@inin.gob.m [Universidad Autonoma Metropolitana, Unidad Iztapalapa, Departamento de Quimica, Av. San Rafael Atlixco No. 186, Col. Vicentina, 09340 Mexico D. F. (Mexico)

    2010-07-01

    The behavior of the trivalent ion praseodymium in 2 M of NaCl at 303 K and in CO{sub 2} free conditions, was studied. Spectrophotometric titrations of the soluble species were used, in order to obtain the value of the first hydrolysis constant of Pr(III). The data obtained were treated with both the program Squad and by a graphic method, respectively. The result obtained using Squad was log*{beta}{sub 1}= -8.94 {+-} 0.03, while it was log*{beta}{sub 1}= -8.77 {+-} 0.03, when calculated graphically. These results are similar to the value obtained previously with the potentiometric method. (Author)

  13. MAGIA - using atom interferometry to determine the Newtonian gravitational constant

    International Nuclear Information System (INIS)

    Stuhler, J; Fattori, M; Petelski, T; Tino, G M

    2003-01-01

    We describe our experiment MAGIA (misura accurata di G mediante interferometria atomica), in which we will use atom interferometry to perform a high precision measurement of the Newtonian gravitational constant G. Free-falling laser-cooled atoms in a vertical atomic fountain will be accelerated due to the gravitational potential of nearby source masses (SMs). Detecting this acceleration with techniques of Raman atom interferometry will enable us to assign a value to G. To suppress systematic effects we will implement a double-differential measurement. This includes launching two atom clouds in a gradiometer configuration and moving the SMs to different vertical positions. We briefly summarize the general idea of the MAGIA experiment and put it in the context of other high precision G-measurements. We present the current status of the experiment and report on analyses of the expected measurement accuracy

  14. 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)

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

    DEFF Research Database (Denmark)

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

    1976-01-01

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

  16. 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.

  17. 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.

  18. 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.

  19. 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

  20. Alternative method for determining the constant offset in lidar signal

    Science.gov (United States)

    Vladimir A. Kovalev; Cyle Wold; Alexander Petkov; Wei Min Hao

    2009-01-01

    We present an alternative method for determining the total offset in lidar signal created by a daytime background-illumination component and electrical or digital offset. Unlike existing techniques, here the signal square-range-correction procedure is initially performed using the total signal recorded by lidar, without subtraction of the offset component. While...

  1. 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)

  2. 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

  3. 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).

  4. 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

  5. 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)

  6. 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.

  7. Determination of sampling constants in NBS geochemical standard reference materials

    International Nuclear Information System (INIS)

    Filby, R.H.; Bragg, A.E.; Grimm, C.A.

    1986-01-01

    Recently Filby et al. showed that, for several elements, National Bureau of Standards (NBS) Fly Ash standard reference material (SRM) 1633a was a suitable reference material for microanalysis (sample weights 2 , and the mean sample weight, W vector, K/sub s/ = (S/sub s/%) 2 W vector, could not be determined from these data because it was not possible to quantitate other sources of error in the experimental variances. K/sub s/ values for certified elements in geochemical SRMs provide important homogeneity information for microanalysis. For mineralogically homogeneous SRMs (i.e., small K/sub s/ values for associated elements) such as the proposed clays, it is necessary to determine K/sub s/ by analysis of very small sample aliquots to maximize the subsampling variance relative to other sources of error. This source of error and the blank correction for the sample container can be eliminated by determining K/sub s/ from radionuclide activities of weighed subsamples of a preirradiated SRM

  8. Determination of Henry’s Law Constants Using Internal Standards with Benchmark Values

    Science.gov (United States)

    It is shown that Henry’s law constants can be experimentally determined by comparing headspace content of compounds with known constants to interpolate the constants of other compounds. Studies were conducted over a range of water temperatures to identify temperature dependence....

  9. 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.

  10. 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

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

    DEFF Research Database (Denmark)

    Pattison, D I; Davies, Michael Jonathan

    2001-01-01

    , absolute second-order rate constants for the reactions of HOCl with protein side chains, model compounds, and backbone amide (peptide) bonds have been determined at physiological pH values. The reactivity of HOCl with potential reactive sites in proteins is summarized by the series: Met (3.8 x 10(7) M(-1......Hypochlorous acid (HOCl) is a potent oxidant, which is produced in vivo by activated phagocytes. This compound is an important antibacterial agent, but excessive or misplaced production has been implicated in a number of human diseases, including atherosclerosis, arthritis, and some cancers....... Proteins are major targets for this oxidant, and such reaction results in side-chain modification, backbone fragmentation, and cross-linking. Despite a wealth of qualitative data for such reactions, little absolute kinetic data is available to rationalize the in vitro and in vivo data. In this study...

  12. 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

  13. Determination of the dynamic elastic constants of recycled aggregate concrete

    Science.gov (United States)

    Tsoumani, A. A.; Barkoula, N.-M.; Matikas, T. E.

    2015-03-01

    Nowadays, construction and demolition waste constitutes a major portion of the total solid waste production in the world. Due to both environmental and economical reasons, an increasing interest concerning the use of recycled aggregate to replace aggregate from natural sources is generated. This paper presents an investigation on the properties of recycled aggregate concrete. Concrete mixes are prepared using recycled aggregates at a substitution level between 0 and 100% of the total coarse aggregate. The influence of this replacement on strengthened concrete's properties is being investigated. The properties estimated are: density and dynamic modulus of elasticity at the age of both 7 and 28 days. Also, flexural strength of 28 days specimens is estimated. The determination of the dynamic elastic modulus was made using the ultrasonic pulse velocity method. The results reveal that the existence of recycled aggregates affects the properties of concrete negatively; however, in low levels of substitution the influence of using recycled aggregates is almost negligible. Concluding, the controlled use of recycled aggregates in concrete production may help solve a vital environmental issue apart from being a solution to the problem of inadequate concrete aggregates.

  14. Dose Rate Determination from Airborne Gamma-ray Spectra

    DEFF Research Database (Denmark)

    Bargholz, Kim

    1996-01-01

    The standard method for determination of ground level dose rates from airborne gamma-ray is the integral count rate which for a constant flying altitude is assumed proportional to the dose rate. The method gives reasonably results for natural radioactivity which almost always has the same energy...

  15. 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

  16. 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):

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

    Science.gov (United States)

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

    2016-01-01

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

  18. 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

  19. 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.

  20. 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

  1. Determination of the stability constants for the complexes of rare-earth elements and tetracycline

    International Nuclear Information System (INIS)

    Saiki, M.; Lima, F.W.

    1977-01-01

    Stability constants for the lanthanide elements complexes with tetracycline were determined by the methods of average number of ligands, the two parameters and by weighted least squares. The technique of solvent extraction was applied to obtain the values of the parameters required for the determination of the constants [pt

  2. Determination of low-energy constants of Wilson chiral perturbation theory

    International Nuclear Information System (INIS)

    Herdoiza, Gregorio; Univ. Autonoma de Madrid, Contoblanco; Univ. Autonoma de Madrid; Jansen, Karl; Univ. Cyprus, Nicosia; Michael, Chris; Ottnad, Konstantin; Urbach, Carsten; Univ. Bonn

    2013-03-01

    By matching Wilson twisted mass lattice QCD determinations of pseudoscalar meson masses to Wilson Chiral Perturbation Theory we determine the low-energy constants W 6 ' , W 8 ' and their linear combination c 2 . We explore the dependence of these low-energy constants on the choice of the lattice action and on the number of dynamical flavours.

  3. 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

  4. 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

  5. Massive graviton and determination of cosmological constant from gauge theory of gravity

    International Nuclear Information System (INIS)

    Mitrut, Alexandru

    2002-01-01

    The universe contains a lot more than the eye meets . Sophisticated experiments search diligently for this invisible dark matter. Here we will describe some theoretical implications of the gravitational gauge theory recently proposed by Ning Wu (hep-th/0112062), namely the possibility of the existence of massive gravitons which fill the intergalactic space. Dark matter is an important problem in cosmology. In gravitational gauge field theory, the following effects should be taken into account to solve this problem: 1) The existence of massive graviton will have some contribution to the dark matter; 2) If the gravitational magnetic field is strong inside a celestial system, the gravitational Lorentz force will provide additional centripetal force for circular motion of a celestial object; 3) The existence of a factor which violate inverse square law of classical gravity. Combining general relativity and gravitational gauge theory the cosmological constant is determined theoretically. The cosmological constant is related to the average vacuum energy of the gravitational gauge field. Because the vacuum energy of the gravitational gauge field is negative, the cosmological constant is positive what generates repulsive force on stars to make the expansion rate of the Universe accelerated. A rough estimation of it gives out its magnitude order 10 -52 m -2 , which is well consistent with experimental results. (authors)

  6. The determination methods of the velocity constant for electrochemical reactions; Les methodes de determination de la constante de vitesse des reactions electrochimiques

    Energy Technology Data Exchange (ETDEWEB)

    Molina, R

    1963-07-01

    In a brief introduction are recalled the fundamental mechanisms of the electrochemical reaction and the definition of the intrinsic velocity constant of a such reaction. By the nature of the different parameters which enter in this definition are due some experimental problems which are examined. Then are given the principles of the measurement methods of the velocity constant. These methods are developed with the mathematical expression of the different rates of the mass transfer to an electrode. In each case are given the experimental limits of use of the methods and the size order of the velocity constant that can be reached. A list of fundamental works to be consulted conclude this work. (O.M.) [French] Dans une breve introduction sont rappeles les mecanismes fondamentaux de la reaction electrochimique et la definition de la constante de vitesse intrinseque d'une telle reaction. De la nature des differents parametres qui entrent dans celle definition, decoulent un certain nombre de problemes experimentaux qui sont passes en revue. On donne ensuite les principes des methodes de mesure de la constante de vitesse. L'exposition de ces methodes est developpee a l'aide de l'expression mathematique des differents regimes de transfert de masse a une electrode. On s'attache dans chaque cas, a donner les limitations experimentales d'utilisation des methodes et l'ordre de grandeur de la constante de vitesse qu'elles permettent d'atteindre. Une liste des ouvrages fondamentaux a consulter conclut ce travail. (auteur)

  7. Determination of mass density, dielectric, elastic, and piezoelectric constants of bulk GaN crystal.

    Science.gov (United States)

    Soluch, Waldemar; Brzozowski, Ernest; Lysakowska, Magdalena; Sadura, Jolanta

    2011-11-01

    Mass density, dielectric, elastic, and piezoelectric constants of bulk GaN crystal were determined. Mass density was obtained from the measured ratio of mass to volume of a cuboid. The dielectric constants were determined from the measured capacitances of an interdigital transducer (IDT) deposited on a Z-cut plate and from a parallel plate capacitor fabricated from this plate. The elastic and piezoelectric constants were determined by comparing the measured and calculated SAW velocities and electromechanical coupling coefficients on the Z- and X-cut plates. The following new constants were obtained: mass density p = 5986 kg/m(3); relative dielectric constants (at constant strain S) ε(S)(11)/ε(0) = 8.6 and ε(S)(11)/ε(0) = 10.5, where ε(0) is a dielectric constant of free space; elastic constants (at constant electric field E) C(E)(11) = 349.7, C(E)(12) = 128.1, C(E)(13) = 129.4, C(E)(33) = 430.3, and C(E)(44) = 96.5 GPa; and piezoelectric constants e(33) = 0.84, e(31) = -0.47, and e(15) = -0.41 C/m(2).

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br

    Science.gov (United States)

    Hsu, K.-J.; Demore, W. B.

    1994-01-01

    Rate constants for the reactions of OH with CH3Cl, 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). Using absolute rate constants for HFC-152a and HFC-161, which we have determined relative to those for CH4, CH3CCl3, and C2H6, temperature dependent rate constants of both compounds were derived. The derived rate constant for CH3Br is in good agreement with recent absolute measurements. However, for the chloromethanes all the rate constants are lower at atmospheric temperatures than previously reported, especially for CH2Cl2 where the present rate constant is about a factor of 1.6 below the JPL 92-20 value. The new rate constant appears to resolve a discrepancy between the observed atmospheric concentrations and those calculated from the previous rate constant and estimated release rates.

  13. 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)

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

    Science.gov (United States)

    Nyasulu, Frazier; McMills, Lauren; Barlag, Rebecca

    2013-01-01

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

  15. 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)

  16. 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.

  17. 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

  18. 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

  19. 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

  20. 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 ...

  1. 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 ...

  2. 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).

  3. Atomic spectroscopy and highly accurate measurement: determination of fundamental constants; Spectroscopie atomique et mesures de grande precision: determination de constantes fonfamentales

    Energy Technology Data Exchange (ETDEWEB)

    Schwob, C

    2006-12-15

    This document reviews the theoretical and experimental achievements of the author concerning highly accurate atomic spectroscopy applied for the determination of fundamental constants. A pure optical frequency measurement of the 2S-12D 2-photon transitions in atomic hydrogen and deuterium has been performed. The experimental setting-up is described as well as the data analysis. Optimized values for the Rydberg constant and Lamb shifts have been deduced (R = 109737.31568516 (84) cm{sup -1}). An experiment devoted to the determination of the fine structure constant with an aimed relative uncertainty of 10{sup -9} began in 1999. This experiment is based on the fact that Bloch oscillations in a frequency chirped optical lattice are a powerful tool to transfer coherently many photon momenta to the atoms. We have used this method to measure accurately the ratio h/m(Rb). The measured value of the fine structure constant is {alpha}{sub -1} = 137.03599884 (91) with a relative uncertainty of 6.7*10{sup -9}. The future and perspectives of this experiment are presented. This document presented before an academic board will allow his author to manage research work and particularly to tutor thesis students. (A.C.)

  4. Detection of exudates in fundus imagery using a constant false-alarm rate (CFAR) detector

    Science.gov (United States)

    Khanna, Manish; Kapoor, Elina

    2014-05-01

    Diabetic retinopathy is the leading cause of blindness in adults in the United States. The presence of exudates in fundus imagery is the early sign of diabetic retinopathy so detection of these lesions is essential in preventing further ocular damage. In this paper we present a novel technique to automatically detect exudates in fundus imagery that is robust against spatial and temporal variations of background noise. The detection threshold is adjusted dynamically, based on the local noise statics around the pixel under test in order to maintain a pre-determined, constant false alarm rate (CFAR). The CFAR detector is often used to detect bright targets in radar imagery where the background clutter can vary considerably from scene to scene and with angle to the scene. Similarly, the CFAR detector addresses the challenge of detecting exudate lesions in RGB and multispectral fundus imagery where the background clutter often exhibits variations in brightness and texture. These variations present a challenge to common, global thresholding detection algorithms and other methods. Performance of the CFAR algorithm is tested against a publicly available, annotated, diabetic retinopathy database and preliminary testing suggests that performance of the CFAR detector proves to be superior to techniques such as Otsu thresholding.

  5. 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.

  6. 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.

  7. 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

  8. THz/Infrared Double Resonance Two-Photon Spectroscopy of HD+ for Determination of Fundamental Constants

    Directory of Open Access Journals (Sweden)

    Florin Lucian Constantin

    2017-10-01

    Full Text Available A double resonance two-photon spectroscopy scheme is discussed to probe jointly rotational and rovibrational transitions of ensembles of trapped HD+ ions. The two-photon transition rates and lightshifts are calculated with the two-photon tensor operator formalism. The rotational lines may be observed with sub-Doppler linewidth at the hertz level and good signal-to-noise ratio, improving the resolution in HD+ spectroscopy beyond the 10−12 level. The experimental accuracy, estimated at the 10−12 level, is comparable with the accuracy of theoretical calculations of HD+ energy levels. An adjustment of selected rotational and rovibrational HD+ lines may add clues to the proton radius puzzle, may provide an independent determination of the Rydberg constant, and may improve the values of proton-to-electron and deuteron-to-proton mass ratios beyond the 10−11 level.

  9. Determination of low-energy constants of Wilson chiral perturbation theory

    Energy Technology Data Exchange (ETDEWEB)

    Herdoiza, Gregorio [Mainz Univ. (Germany). Inst fuer Kernphysik, PRISMA Cluster of Excellence; Univ. Autonoma de Madrid, Contoblanco (Spain). Dept. de Fisica Teorica; Univ. Autonoma de Madrid (Spain). Inst. de Fisica Teorica UAM/CSIC; Jansen, Karl [Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany). John von Neumann-Inst. fuer Computing NIC; Univ. Cyprus, Nicosia (Cyprus). Dept. of Physics; Michael, Chris [Liverpool Univ. (United Kingdom). Theoretical Physics Division; Ottnad, Konstantin; Urbach, Carsten [Bonn Univ. (Germany). Helmholtz-Institut fuer Strahlen und Kernphysik; Univ. Bonn (Germany). Bethe Center for Theoretical Physics; Collaboration: European Twisted Mass Collaboration

    2013-03-15

    By matching Wilson twisted mass lattice QCD determinations of pseudoscalar meson masses to Wilson Chiral Perturbation Theory we determine the low-energy constants W{sub 6}{sup '}, W{sub 8}{sup '} and their linear combination c{sub 2}. We explore the dependence of these low-energy constants on the choice of the lattice action and on the number of dynamical flavours.

  10. 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.

  11. 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

  12. 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.

  13. 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)

  14. Determination of stability constants of aminoglycoside antibiotics with their metal complexes

    Science.gov (United States)

    Tiwow, Vanny M. A.

    2014-03-01

    One group of aminoglycoside antibiotics contains aminosugars. The aminosugar neomycin B with its derivate product neamine (2-Deoxy-4-0-(2,6-diamino-2,6-dideoxy-α-D-glucopyranosyl)-D-Streptamine) was identified as a free ligands and metal complexes. In particular, the stability constants of metal complexes by potentiometric titration techniques were investigated. Our previous study had determined the acid dissociation constants of these aminosugars with few metal complexes in fair depth. In this work, the complexation of two pyridine-containing amino alcohols and an amino sugar (neamine) have been measured potentiometrically. For instance, the stability constant of copper(II) complexation were determine and the model system generated an excellent fit. Stability constants with several metals have been determined and will be reported.

  15. 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.

  16. 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

  17. 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

  18. Determination of human albumin in serum and urine samples by constant-energy synchronous fluorescence method.

    Science.gov (United States)

    Madrakian, Tayyebeh; Bagheri, Habibollah; Afkhami, Abbas

    2015-08-01

    A sensitive spectrofluorimetric method using constant-energy synchronous fluorescence technique is proposed for the determination of human albumin without separation. In this method, no reagent was used for enhancement of the fluorescence signal of albumin in the solution. Effects of some parameters, such as energy difference between excitation and emission monochromators (ΔE), emission and excitation slit widths and scan rate of wavelength were studied and the optimum conditions were established. For this purpose factorial design and response surface method were employed for optimization of the effective parameters on the fluorescence signal. The results showed that the scan rate of the wavelength has no significant effect on the analytical signal. The calibration curve was linear in the range 0.1-220.0 µg mL(-1) of albumin with a detection limit of 7.0 × 10(-3)  µg mL(-1). The relative standard deviations (RSD) for six replicate measurements of albumin were calculated as 2.2%, 1.7% and 1.3% for 0.5, 10.0 and 100.0 µg mL(-1) albumin, respectively. Furthermore the proposed method has been employed for the determination of albumin in human serum and urine samples. Copyright © 2014 John Wiley & Sons, Ltd.

  19. 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.

  20. 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

  1. What Determines Star Formation Rates?

    Science.gov (United States)

    Evans, Neal John

    2017-06-01

    The relations between star formation and gas have received renewed attention. We combine studies on scales ranging from local (within 0.5 kpc) to distant galaxies to assess what factors contribute to star formation. These include studies of star forming regions in the Milky Way, the LMC, nearby galaxies with spatially resolved star formation, and integrated galaxy studies. We test whether total molecular gas or dense gas provides the best predictor of star formation rate. The star formation ``efficiency," defined as star formation rate divided by mass, spreads over a large range when the mass refers to molecular gas; the standard deviation of the log of the efficiency decreases by a factor of three when the mass of relatively dense molecular gas is used rather than the mass of all the molecular gas. We suggest ways to further develop the concept of "dense gas" to incorporate other factors, such as turbulence.

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

    KAUST Repository

    Badra, Jihad

    2014-01-01

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

  3. 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

    chemistry. For most determinations, a jet of water conditioned to the required chemistry but stripped of dissolved iron with ion-exchange is directed onto a pellet of magnetite and the dissolution monitored; the high velocity of the jet ensures that mass transfer effects are minimised. The magnetite is synthesised by a solid-state method involving heating a mixture of haematite and iron under vacuum at 600 deg. C, compacting under pressure and sintering into a pellet under argon at 1,100 deg. C. The product has an appropriate consistency and resistance to erosion. Most experiments have measured the average dissolution rate by estimating the amount of magnetite lost from the pellet by surface analysis and profilometry after exposure for a given time. Concomitant electrochemical information is obtained by electrically isolating the pellet from the loop and connecting it to a potentiostat, along with a counter-electrode and reference electrode strategically mounted in the loop test section. Detailed kinetic data are obtained by irradiating the magnetite before installation in the loop and monitoring on-line with gamma spectrometry the transport of dissolved, radioactive 59 Fe. Preliminary determinations had used radioactive magnetite precipitated under galvanostatic conditions from a solution of irradiated FeSO 4 in EDTA onto a platinum coupon. The coupon was then mounted axially in the loop test section and subjected to a range of imposed potentials during exposure; however, this coupon technique gave dissolution results confounded by the release of magnetite crystallites, so we concentrated on the pellet technique. The paper presents the results of exposures carried out over a range of temperatures and alkalinities at oxygen concentrations between 0 and 20 ppb. It shows how dissolution rate constants obtained under CANDU primary coolant conditions of 310 deg. C and pH 25C 10.5 (with LiOH) fall between published values, which were obtained with a different technique under

  4. 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

  5. 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.

  6. 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)

  7. 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...

  8. Spectroscopic determination of ionization constants of quinoline and 3-aminoquinoline at different temperature

    International Nuclear Information System (INIS)

    Indhar, H.A.B.

    2000-01-01

    Quinoline and its derivative are chemically and biologically important heterocylic compounds. Its ionization constant (pK/sub a/ values have been previously determined only at 18 or 20 deg. C. We have enhanced this work at different temperatures from 20-50 deg. C at the interval of 5 deg. C. The dissociation constants (pk/sub a/s), and Gibb's free energies of quinoline and 3-aminoquinoline have been determined by UV-Spectrophotometer (lambda 2) equipped with a temperature control of - + 0.1 deg. C at temperatures ranging from 20-50 deg. C in water. The experimental data have been used for the determination of thermodynamic ionization constants (pk /sub a //sup t/) sub t/, concentration ionization constants (pK/sub a//sup M/) and Gibbs's free energy values of pK/sub a/sup M/. The ionization constant values decrease with increase of temperature. The significance of relative magnitudes of the values is discussed and some useful generalization are obtained. The curves are parabolic. A computer program in GW-BASIC calculates the values of dissociation constants. From the pK/sub a/ values, Gibb's free energies are compared and discussed. (author)

  9. Precision determination of the strong coupling constant within a global PDF analysis

    NARCIS (Netherlands)

    Ball, Richard D.; Carrazza, Stefano; Debbio, Luigi Del; Forte, Stefano; Kassabov, Zahari; Rojo, Juan; Slade, Emma; Ubiali, Maria

    2018-01-01

    We present a determination of the strong coupling constant $\\alpha_s(m_Z)$ based on the NNPDF3.1 determination of parton distributions, which for the first time includes constraints from jet production, top-quark pair differential distributions, and the $Z$ $p_T$ distributions using exact NNLO

  10. Gas-phase reaction rate constants for atmospheric pressure ionization in ion-mobility spectrometry

    International Nuclear Information System (INIS)

    Vandiver, V.J.

    1987-01-01

    Ion-mobility spectrometry (IMS) is an instrumental technique in which gaseous ions are formed from neutral molecules by proton and charge transfer from reactant ions through collisional ionization. An abbreviated rate theory has been proposed for atmospheric pressure ionization (API) in IMS, but supporting experimental measurements have not been reported. The objectives of this thesis were (1) assessment of existing API rate theory using positive and negative product ions in IMS, (2) measurement of API equilibria and kinetics for binary mixtures, and (3) investigating of cross-ionizations with multiple-product ions in API reactions. Although IMS measurements and predictions from rate theory were comparable, shapes and slopes of response curves for both proton transfer and electron capture were not described exactly by existing theory. In particular, terms that are needed for calculation of absolute rate constants were unsuitable in the existing theory. These included recombination coefficients,initial number of reactant ions, and opposing ion densities

  11. Determination of the stability constants of lanthanum, praseodymium, europium, erbium and lutetium complexes with chloride ions

    International Nuclear Information System (INIS)

    Fernandez R, E.

    2008-01-01

    The stability constants of La 3+ , Pr 3+ , Eu 3+ , Er 3+ and Lu 3+ chloride complexes were determined in perchloric acid media using a liquid-liquid extraction method. The dinonyl napthalene sulfonic acid in n-heptane was used as extractant. The lanthanide (Ln) concentrations were measured by a radiochemical (Eu and Lu) and a spectrophotometric (La, Pr, and Er) methods. In the last method, xylenol orange was used for the determinations at ph 6. The stability constants of lanthanum, praseodymium, erbium and lutetium chloride complexes were determined in 2, 3 and 4 M ionic strength and europium in 1, 2 and 3 M, at 303 K. The fitting of experimental data to the equations for the calculation of the stability constants, was carry out considering both one chemical species (LnCl 2+ ) or two chemical species (LnCl 2+ and LnCl 2 + ). The Specific Ion Interaction Theory was applied to the values of log β I Ln , Cl and the first stability constants at zero ionic strength were calculated by extrapolation. The same theory could not be applied to the log β I Ln , 2Cl , due to its low abundance and the values determined for the stability constants were similar. The distribution diagrams of the chemical species were obtained using the program MEDUSA and considering log β I Ln , CI , log β I Ln , 2CI values obtained in this work and the hydrolysis constants taken from the literature. The lanthanide chloride complexes are present in solution at specific conditions of ionic strength, concentration and in the absence of hydrolysis. The log β I Ln , Cl data were related to the charge density and the corresponding equations were obtained. These equations could be used to determine the stability constants along the lanthanide series. (Author)

  12. 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.

  13. Stability constant determinations for technetium (IV) complexation with selected amino carboxylate ligands in high nitrate solutions

    Energy Technology Data Exchange (ETDEWEB)

    Omoto, Trevor; Wall, Nathalie A. [Washington State Univ., Pullman, WA (United States). Dept. of Chemistry

    2017-10-01

    The stability constants for Tc(IV) complexation with the ligands IDA, NTA, HEDTA, and DTPA were determined in varied nitrate concentrations using liquid-liquid extraction methods. The determined log β{sub 101} stability constants at 0.5 M NaNO{sub 3} were found to be 9.2±0.3, 10.3±0.3, and 15.3±0.3 for IDA, NTA, and HEDTA, respectively. The log β{sub 111} stability constant for DTPA was determined to be 22.0±0.6. These determined stability constants show a slight decrease in magnitude as a function of increasing NaNO{sub 3} concentration. These stability constants were used to model the total dissolution of Tc(IV) in acidic aqueous solutions in the presence of each ligand. The results of these predictive models indicate that amino carboxylic ligands have a high potential for increasing the aqueous dissolution of Tc(IV); at pH 2.3, 0.01 M ligand yield dissolved Tc(IV) concentrations of 1.42.10{sup -5} M, 1.33.10{sup -5} M, 6.07.10{sup -6} M, 9.65.10{sup -7} M, for DTPA, HEDTA, NTA, and IDA, respectively.

  14. Theory of space-charge polarization for determining ionic constants of electrolytic solutions

    Science.gov (United States)

    Sawada, Atsushi

    2007-06-01

    A theoretical expression of the complex dielectric constant attributed to space-charge polarization has been derived under an electric field calculated using Poisson's equation considering the effects of bound charges on ions. The frequency dependence of the complex dielectric constant of chlorobenzene solutions doped with tetrabutylammonium tetraphenylborate (TBATPB) has been analyzed using the theoretical expression, and the impact of the bound charges on the complex dielectric constant has been clarified quantitatively in comparison with a theory that does not consider the effect of the bound charges. The Stokes radius of TBA +(=TPB-) determined by the present theory shows a good agreement with that determined by conductometry in the past; hence, the present theory should be applicable to the direct determination of the mobility of ion species in an electrolytic solution without the need to measure ionic limiting equivalent conductance and transport number.

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

    International Nuclear Information System (INIS)

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

    1979-01-01

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

  16. 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.

  17. 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

  18. 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

  19. 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.

  20. 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....

  1. 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

  2. Surface acoustic waves and elastic constants of InN epilayers determined by Brillouin scattering

    Energy Technology Data Exchange (ETDEWEB)

    Jimenez-Rioboo, R.J.; Prieto, C. [Instituto de Ciencia de Materiales de Madrid, CSIC, Cantoblanco, Madrid (Spain); Cusco, R.; Domenech-Amador, N.; Artus, L. [Institut Jaume Almera, Consell Superior d' Investigacions Cientifiques (CSIC), Lluis Sole i Sabaris s.n., Barcelona, Catalonia (Spain); Yamaguchi, T.; Nanishi, Y. [Faculty of Science and Engineering, Ritsumeikan University, Noji-Higashi, Kusatsu, Shiga (Japan)

    2012-06-15

    The surface acoustic wave velocity in InN has been experimentally determined by means of Brillouin scattering experiments on c - and m -face epilayers. From simulations based on the Green's function formalism we determine the shear elastic constants c{sub 66} and c{sub 44} and propose a complete set of elastic constants for wurtzite InN. The analysis of the sagittal and azimuthal dependence of the surface acoustic wave velocity indicates a slightly different elastic behavior of the m -face sample that basically affects the c{sub 44} elastic constant. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  3. 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.

  4. Watt balance experiments for the determination of the Planck constant and the redefinition of the kilogram

    Science.gov (United States)

    Stock, M.

    2013-02-01

    Since 1889 the international prototype of the kilogram has served as the definition of the unit of mass in the International System of Units (SI). It is the last material artefact to define a base unit of the SI, and it influences several other base units. This situation is no longer acceptable in a time of ever increasing measurement precision. It is therefore planned to redefine the unit of mass by fixing the numerical value of the Planck constant. At the same time three other base units, the ampere, the kelvin and the mole, will be redefined. As a first step, the kilogram redefinition requires a highly accurate determination of the Planck constant in the present SI system, with a relative uncertainty of the order of 1 part in 108. The most promising experiment for this purpose, and for the future realization of the kilogram, is the watt balance. It compares mechanical and electrical power and makes use of two macroscopic quantum effects, thus creating a relationship between a macroscopic mass and the Planck constant. In this paper the background for the choice of the Planck constant for the kilogram redefinition is discussed and the role of the Planck constant in physics is briefly reviewed. The operating principle of watt balance experiments is explained and the existing experiments are reviewed. An overview is given of all presently available experimental determinations of the Planck constant, and it is shown that further investigation is needed before the redefinition of the kilogram can take place. This article is based on a lecture given at the International School of Physics ‘Enrico Fermi’, Course CLXXXV: Metrology and Physical Constants, held in Varenna on 17-27 July 2012. It will also be published in the proceedings of the school, edited by E Bava, M Kühne and A M Rossi (IOS Press, Amsterdam and SIF, Bologna).

  5. 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)

  6. Simultaneous Determination of Binding Constants for Multiple Carbohydrate Hosts in Complex Mixtures

    DEFF Research Database (Denmark)

    Meier, Sebastian; Beeren, Sophie

    2014-01-01

    We describe a simple method for the simultaneous determination of association constants for a guest binding to seven different hosts in a mixture of more than 20 different oligosaccharides. If the binding parameters are known for one component in the mixture, a single NMR titration suffices...

  7. A Methodology to Determine Self-Similarity, Illustrated by Example: Transient Heat Transfer with Constant Flux

    Science.gov (United States)

    Monroe, Charles; Newman, John

    2005-01-01

    This simple example demonstrates the physical significance of similarity solutions and the utility of dimensional and asymptotic analysis of partial differential equations. A procedure to determine the existence of similarity solutions is proposed and subsequently applied to transient constant-flux heat transfer. Short-time expressions follow from…

  8. Determination of stability constants of pyrophosphate complexes. 2. Influence of divalent cations: the magnesium

    International Nuclear Information System (INIS)

    Courriere, P.; Guillemart, A.; Besnard, J.-C.

    1978-01-01

    The stability constants of the complexes of pyrophosphate with magnesium have been determined directly from the titration curves of sodium pyrophosphate in presence of Mg 2+ with hydrochloric acid by a least-square iterative method at the temperature of 25 0 C and at a ionic strength adjusted to unity [fr

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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)

  17. 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.

  18. Determination of the Avogadro constant by the XRCD method using a 28Si-enriched sphere

    Science.gov (United States)

    Kuramoto, Naoki; Mizushima, Shigeki; Zhang, Lulu; Fujita, Kazuaki; Azuma, Yasushi; Kurokawa, Akira; Okubo, Sho; Inaba, Hajime; Fujii, Kenichi

    2017-10-01

    To determine the Avogadro constant N A by the x-ray crystal density method, the density of a 28Si-enriched crystal was determined by absolute measurements of the mass and volume of a 1 kg sphere manufactured from the crystal. The mass and volume were determined by an optical interferometer and a vacuum mass comparator, respectively. The sphere surface was characterized by x-ray photoelectron spectroscopy and spectroscopic ellipsometry to derive the mass and volume of the Si core of the sphere excluding the surface layers. From the mass and volume, the density of the Si core was determined with a relative standard uncertainty of 2.3  ×  10-8. By combining the Si core density with the lattice constant and the molar mass of the sphere reported by the International Avogadro Coordination (IAC) project in 2015, a new value of 6.022 140 84(15)  ×  1023 mol-1 was obtained for N A with a relative standard uncertainty of 2.4  ×  10-8. To make the N A value determined in this work usable for a future adjustment of the fundamental constants by the CODATA Task Group on Fundamental Constants, the correlation of the new N A value with the N A values determined in our previous works was examined. The correlation coefficients with the values of N A determined by IAC in 2011 and 2015 were estimated to be 0.07 and 0.28, respectively. The correlation of the new N A value with the N A value determined by IAC in 2017 using a different 28Si-enriched crystal was also examined, and the correlation coefficient was estimated to be 0.21.

  19. Reactor parameters and constants determination by using measurements in subcritical and exponential assembly

    International Nuclear Information System (INIS)

    Voi, Dante Luiz; Santos Bastos, Wilma dos

    1995-01-01

    Subcritical and exponential experiments are important for Reactor Physics integral parameter determinations both to validate and confirm theoretical models for reactor calculations. An exponential and subcritical facility has been constructed to be used on the internal thermal column of the Argonauta reactor at IEN-CNEN- Rio de Janeiro. An experimental research program has been developed for the determination of fundamental reactor constants as buckling, migration areas, resonance escape probabilities, thermal utilization, fast fission and fuel eta factors. (author) 23 refs

  20. 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

  1. Determination of alpha constant value for brazilian reality aiming de radiation protection optimization

    International Nuclear Information System (INIS)

    Teixeira, Pedro Barbosa

    2003-01-01

    This work aims to present a methodology for the calculation of the alpha constant taking into account the actual conditions in Brazil. This constant is used for the minimization of the worker doses meaning the optimization of radiation protection. The alpha constant represents a monetary value to establish the health detriment associated to the stochastic effects for unit of collective dose, and is directly related to the value of the human life. Along the years, several methods have been developed to obtain the most appropriate value for the alpha constant. These methods will be objects of analysis of this work. This work presents two methods for determination of the alpha constant: 'human capital' that is based on GDP of the country and 'willingness-to-pay' that is established for the value that the population would be willing to pay for the safety of the nuclear and radioactive facilities. A new methodology for the calculation of the alpha constant has been proposed in this study, that is the combination of two method previously mentioned, and recommends a new value of US$ 16,000.00 per man-sievert. Currently the value established by CNEN is US$ 10,000.00 per men sievert. This work also presents, in full details, the main mathematical tools for the elaboration of the optimization of the radiation protection: cost-benefit analysis, extended cost-benefit analysis and multi attribute utility analysis. An applied example, for an uranium mine radiation protection optimization was used to compare those two values of the alpha constant. (author)

  2. Technique for determination of the time constant for relay radioisotope instruments

    International Nuclear Information System (INIS)

    Gol'din, M.L.; Shestialtynov, V.K.

    1981-01-01

    A technique for calculating time constant of a gamma relay used in radio isotope automatics is suggested. It is shown that the time constant of a radioisotope relay device (RRD) mainly depends on parameters of the intergrating circuit ratemeter. Considering the ratemeter as a real communication channel with a limited transmission band, the equation for the active front duration at a ratemeter outlet when applying abrupt voltage to its inlet is obtained. From the complex transmission function of a ratemeter the upper boundary cyclic transmission frequency the substitution of which in the equation of the active front durationg ives the RRD time constant is determined. On the example of calculating the ratemeter for the GR-6 gamma relay a satisfactory coincidence of calculational results with the certificate data is shown [ru

  3. Invited Article: A precise instrument to determine the Planck constant, and the future kilogram

    International Nuclear Information System (INIS)

    Haddad, D.; Seifert, F.; Williams, C.; Chao, L. S.; Li, S.; Newell, D. B.; Pratt, J. R.; Schlamminger, S.

    2016-01-01

    A precise instrument, called a watt balance, compares mechanical power measured in terms of the meter, the second, and the kilogram to electrical power measured in terms of the volt and the ohm. A direct link between mechanical action and the Planck constant is established by the practical realization of the electrical units derived from the Josephson and the quantum Hall effects. We describe in this paper the fourth-generation watt balance at the National Institute of Standards and Technology (NIST), and report our initial determination of the Planck constant obtained from data taken in late 2015 and the beginning of 2016. A comprehensive analysis of the data and the associated uncertainties led to the SI value of the Planck constant, h = 6.626 069 83(22) × 10 −34 J s. The relative standard uncertainty associated with this result is 34 × 10 −9 .

  4. Invited Article: A precise instrument to determine the Planck constant, and the future kilogram

    Energy Technology Data Exchange (ETDEWEB)

    Haddad, D., E-mail: darine.haddad@nist.gov; Seifert, F.; Williams, C. [National Institute of Standards and Technology (NIST), 100 Bureau Drive Stop 8171, Gaithersburg, Maryland 20899 (United States); University of Maryland, Joint Quantum Institute, College Park, Maryland 20742 (United States); Chao, L. S.; Li, S.; Newell, D. B.; Pratt, J. R.; Schlamminger, S., E-mail: stephan.schlamminger@nist.gov [National Institute of Standards and Technology (NIST), 100 Bureau Drive Stop 8171, Gaithersburg, Maryland 20899 (United States)

    2016-06-15

    A precise instrument, called a watt balance, compares mechanical power measured in terms of the meter, the second, and the kilogram to electrical power measured in terms of the volt and the ohm. A direct link between mechanical action and the Planck constant is established by the practical realization of the electrical units derived from the Josephson and the quantum Hall effects. We describe in this paper the fourth-generation watt balance at the National Institute of Standards and Technology (NIST), and report our initial determination of the Planck constant obtained from data taken in late 2015 and the beginning of 2016. A comprehensive analysis of the data and the associated uncertainties led to the SI value of the Planck constant, h = 6.626 069 83(22) × 10{sup −34} J s. The relative standard uncertainty associated with this result is 34 × 10{sup −9}.

  5. 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

  6. Accurate determination of the Boltzmann constant by Doppler spectroscopy: Towards a new definition of the kelvin

    International Nuclear Information System (INIS)

    Darquie, B.; Mejri, S.; Sow, P. L. T.; Lemarchand, C.; Triki, M.; Tokunaga, S. K.; Borde, C. J.; Chardonnet, C.; Daussy, C.

    2013-01-01

    Accurate molecular spectroscopy in the mid-infrared region allows precision measurements of fundamental constants. For instance, measuring the linewidth of an isolated Doppler-broadened absorption line of ammonia around 10 μm enables a determination of the Boltzmann constant k B . We report on our latest measurements. By fitting this lineshape to several models which include Dicke narrowing or speed-dependent collisional effects, we find that a determination of k B with an uncertainty of a few ppm is reachable. This is comparable to the best current uncertainty obtained using acoustic methods and would make a significant contribution to any new value of k B determined by the CODATA. Furthermore, having multiple independent measurements at these accuracies opens the possibility of defining the kelvin by fixing k B , an exciting prospect considering the upcoming redefinition of the International System of Units. (authors)

  7. 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...

  8. 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.

  9. 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.

  10. 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)

  11. 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...

  12. 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....

  13. 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.)

  14. 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.

  15. Method for Determining the Time Constants Characterizing the Intensity of Steel Mixing in Continuous Casting Tundish

    Directory of Open Access Journals (Sweden)

    Pieprzyca J.

    2015-04-01

    Full Text Available A common method used in identification of hydrodynamics phenomena occurring in Continuous Casting (CC device's tundish is to determine the RTD curves of time. These curves allows to determine the way of the liquid steel flowing and mixing in the tundish. These can be identified either as the result of numerical simulation or by the experiments - as the result of researching the physical models. Special problem is to objectify it while conducting physical research. It is necessary to precisely determine the time constants which characterize researched phenomena basing on the data acquired in the measured change of the concentration of the tracer in model liquid's volume. The mathematical description of determined curves is based on the approximate differential equations formulated in the theory of fluid mechanics. Solving these equations to calculate the time constants requires a special software and it is very time-consuming. To improve the process a method was created to calculate the time constants with use of automation elements. It allows to solve problems using algebraic method, which improves interpretation of the research results of physical modeling.

  16. 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.

  17. Determination and analysis of dispersive optical constants of some organic thin films

    International Nuclear Information System (INIS)

    Kaya, Y.; Taysioglu, A. A.; Peksoez, A.; Irez, G.; Derebasi, N.; Kaynak, G.

    2010-01-01

    Schiff bases are an important class of ligands in coordination chemistry and find extensive application in different fields. Recently, increased interest in organic thin film materials has arisen due to their extensive applications in the fields of mechanics, flexible electronics and optics. Optoelectronics is the area in which organic films and organic-inorganic nanostructures have found their main applications in the last decade. These organic thin films have been also used in a wide variety of applications such as Schottky diodes, solid state devices and optical sensors. The optical constants (refractive index, n; extinction coefficient, k and dielectric constant, e) of some organic thin films were determined using reflectance and transmittance spectra. Analysis of the basis absorption spectra was also carried out to determine optical band gap (Eg) and Urbach parameter (E0). A surface observation of these thin films was also carried out by an Atomic Force Microscope.

  18. Determination of binding constants of cyclodextrin inclusion complexes with amino acids and dipeptides by potentiometric titration.

    Science.gov (United States)

    Kahle, Claudia; Holzgrabe, Ulrike

    2004-10-01

    Cyclodextrins are well known for their ability to separate enantiomers of drugs, natural products, and other chiral substances using HPLC, GC, or CE. The resolution of the enantiomers is due to the formation of diastereomeric complexes between the cyclodextrin and the pairs of enantiomers. The aim of this study was to determine the binding constants of the complexes between alpha- and beta-cyclodextrin and the enantiomers of a series of aliphatic and aromatic amino acids, and dipeptides, using a potentiometric titration method. The results of this method are compared to other methods, and correlated to findings in cyclodextrin-modified capillary electrophoresis and possible complex structures. Potentiometric titration was found to be an appropriate tool to determine the binding constants of cyclodextrin inclusion complexes.

  19. Determination of stability constants of lanthanide nitrate complex formation using a solvent extraction technique

    International Nuclear Information System (INIS)

    Andersson, S.; Ekberg, C.; Liljenzin, J.O.; Nilsson, M.; Skarnemark, G.; Eberhardt, K.

    2006-01-01

    For lanthanides and actinides, nitrate complex formation is an important factor with respect to the reprocessing of nuclear fuels and in studies that treat partitioning and transmutation/conditioning. Different techniques, including microcalorimetry, various kinds of spectroscopy, ion-exchange and solvent extraction, can be used to determine stability constants of nitrate complex formation. However, it is uncommon that all lanthanides are studied at the same time, using the same experimental conditions and technique. The strengths of the complexes are different for lanthanides and actinides, a feature that may assist in the separation of the two groups. This paper deals with nitrate complex formation of lanthanides using a solvent extraction technique. Trace amounts of radioactive isotopes of lanthanides were produced at the TRIGA Mainz research reactor and at the Institutt for Energiteknikk in Kjeller, Norway (JEEP II reactor). The extraction of lanthanide ions into an organic phase consisting of 2, 6-bis-(benzoxazolyl)-4-dodecyloxylpyridine, 2-bromodecanoic acid and tert-butyl benzene as a function of nitrate ion concentration in the aqueous phase was studied in order to estimate the stability constants of nitrate complex formation. When the nitrate ion concentration is increased in the aqueous phase, the nitrate complex formation starts to compete with the extraction of metal ions. Thus the stability constants of nitrate complex formation can be estimated by measuring the decrease in extraction and successive fitting of an appropriate model. Extraction curves for La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Dy, Ho and Er were obtained and stability constants for their nitrate complex formation were estimated. Tb, Tm, Yb and Lu were also investigated, but no stability constants could be determined. The distribution ratios for the metal ions at low nitrate ion concentration were obtained at the same time, showing the effect of lanthanide contraction resulting in decreasing

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

    Science.gov (United States)

    Eble, Johannes A

    2018-02-15

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

  1. Determination of sulfur in solids by constant current coulometric titration following combustion

    International Nuclear Information System (INIS)

    Monteiro, R.P.G.

    1986-01-01

    A method for determination of sulfur in solid materials by combustion in induction furnace, followed by constant current coulometric titration of the sulfur dioxide produced, is described. The method is applicable to samples with sulfur contents of 80 ppm to 20,000 ppm. Its feasibility was checked on the NBS and Leco steel samples. The results are in good agreement with the specified values. (author) [pt

  2. A Constant Rate of Spontaneous Mutation in DNA-Based Microbes

    Science.gov (United States)

    Drake, John W.

    1991-08-01

    In terms of evolution and fitness, the most significant spontaneous mutation rate is likely to be that for the entire genome (or its nonfrivolous fraction). Information is now available to calculate this rate for several DNA-based haploid microbes, including bacteriophages with single- or double-stranded DNA, a bacterium, a yeast, and a filamentous fungus. Their genome sizes vary by ≈6500-fold. Their average mutation rates per base pair vary by ≈16,000-fold, whereas their mutation rates per genome vary by only ≈2.5-fold, apparently randomly, around a mean value of 0.0033 per DNA replication. The average mutation rate per base pair is inversely proportional to genome size. Therefore, a nearly invariant microbial mutation rate appears to have evolved. Because this rate is uniform in such diverse organisms, it is likely to be determined by deep general forces, perhaps by a balance between the usually deleterious effects of mutation and the physiological costs of further reducing mutation rates.

  3. 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)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-06-15

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

  5. Constant current coulometric method for the determination of uranium in active process solutions

    International Nuclear Information System (INIS)

    Chitnis, R.T.; Talnikar, S.G.; Paranjape, A.H.

    1980-01-01

    The determination of uranium in the range of 2.5-5 mg by constant current coulometry is described. The procedure is based on the modified version of the DAVIES - GRAY method, wherein uranium, after the reduction step, is oxidized by adding a known amount of potassium dichromate, and the excess of dichromate is determined by titration with Fe 2+ solution. Fe 2+ ions needed for the titration are generated in situ with 100% current efficiency by electrolytic reduction of Fe 3+ . The method is found to be accurate with a coefficient of variation better than 0.2%. (author)

  6. Polarographic determination of stability constants of Eu(III) complexes with acrylic acid and crotonic acid

    Energy Technology Data Exchange (ETDEWEB)

    Rao, A L.J.; Makhan, S [Punjabi Univ., Patiala (India). Dept. of Chemistry

    1979-07-01

    Compositions and formation constants of Eu(III) complexes with acrylic acid and crotonic acid have been studied polarographically. The reductions are reversible and diffusion-controlled. The plot of Esub(1/2) versus -log Csub(x) is linear in the case of Eu(III)-acrylic acid system. The change in number of ligands bound to europium during reduction was found to be approximately equal to 1 and ratio of dissociation constants of Eu(III) and Eu(II) was found to be 40.76 x 10sup(-2). In the case of Eu(III)-crotonic acid system, composition and formation constants have been calculated by the method of Deford and Hume. Crotonic acid forms two complex species with europium (..beta../sub 1/, 60; ..beta../sub 2/, 4.2x10sup(+2)). The percentage distribution of various complex species as a function of ligand concentration has been calculated in the case of Eu(III)-crotonic acid system. A polarographic method for the determination of micro amounts of Eu(III) in the presence of diverse ions has been developed. Under optimum conditions Eu(III) in the concentration range 4x10sup(-4)-2x10sup(-3)M can be successfully determined in various mixtures.

  7. Polarographic determination of stability constants of Eu(III) complexes with acrylic and crotonic acid

    Energy Technology Data Exchange (ETDEWEB)

    Rao, A L.J.; Singh, Makhan [Punjabi Univ., Patiala (India). Dept. of Chemistry

    1979-07-01

    Compositions and formation constants of Eu(III) complexes with acrylic acid and crotonic acid have been studied polarographically. The reductions are reversible and diffusion-controlled. The plot of Esub(1/2) versus--log Csub(x) is linear in the case of Eu(III)-acrylic acid system. The change in number of ligands bound to europium during reduction was found to be approximately 1 and ratio of dissociation constants of Eu(III) and Eu(II) was found to be 40.76X10sup(-2). In the case of Eu(III)-crotonic acid system, composition and formation constants have been calculated by the method of Deford and Hume. Crotonic acid forms two complex species with europium (..beta../sub 1/,60; ..beta../sub 2/, 4.2x10sup(+2)). The percentage distribution of various complex species as a function of ligand concentration has been calculated in the case of Eu(III)-crotonic acid system. A polarographic method for the determination of micro amounts of Eu(III) in the presence of diverse ions has been developed. Under optimum conditions Eu(III) in the concentration range 4x19sup(-4)-2x10sup(-2)M can be successfully determined in various mixtures.

  8. 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

  9. Ultrasonic Determination of the Elastic Constants of Epoxy-natural Fiber Composites

    Science.gov (United States)

    Valencia, C. A. Meza; Pazos-Ospina, J. F.; Franco, E. E.; Ealo, Joao L.; Collazos-Burbano, D. A.; Garcia, G. F. Casanova

    This paper shows the applications ultrasonic through-transmission technique to determine the elastic constants of two polymer-natural fiber composite materials with potential industrial application and economic and environmental advantages. The transversely isotropic coconut-epoxy and fique-epoxy samples were analyzed using an experimental setup which allows the sample to be rotated with respect to transducers faces and measures the time-of-flight at different angles of incidence. Then, the elastic properties of the material were obtained by fitting the experimental data to the Christoffel equation. Results show a good agreement between the measured elastic constants and the values predicted by an analytical model. The velocities as a function of the incidence angle are reported and the effect of the natural fiber on the stiffness of the composite is discussed.

  10. Optimal determination of the elastic constants of composite materials from ultrasonic wave-speed measurements

    Science.gov (United States)

    Castagnède, Bernard; Jenkins, James T.; Sachse, Wolfgang; Baste, Stéphane

    1990-03-01

    A method is described to optimally determine the elastic constants of anisotropic solids from wave-speeds measurements in arbitrary nonprincipal planes. For such a problem, the characteristic equation is a degree-three polynomial which generally does not factorize. By developing and rearranging this polynomial, a nonlinear system of equations is obtained. The elastic constants are then recovered by minimizing a functional derived from this overdetermined system of equations. Calculations of the functional are given for two specific cases, i.e., the orthorhombic and the hexagonal symmetries. Some numerical results showing the efficiency of the algorithm are presented. A numerical method is also described for the recovery of the orientation of the principal acoustical axes. This problem is solved through a double-iterative numerical scheme. Numerical as well as experimental results are presented for a unidirectional composite material.

  11. Determination of the pairing-strength constants in the isovector plus isoscalar pairing case

    Science.gov (United States)

    Mokhtari, D.; Fellah, M.; Allal, N. H.

    2016-05-01

    A method for the determination of the pairing-strength constants, in the neutron-proton (n-p) isovector plus isoscalar pairing case, is proposed in the framework of the BCS theory. It is based on the fitting of these constants to reproduce the experimentally known pairing gap parameters as well as the root-mean-squared (r.m.s) charge radii values. The method is applied to some proton-rich even-even nuclei. The single-particle energies used are those of a deformed Woods-Saxon mean field. It is shown that the obtained value of the ratio GnpT=0/G npT=1 is of the same order as the ones, arbitrary chosen, of some previous works. The effect of the inclusion of the isoscalar n-p pairing in the r.m.s matter radii is then numerically studied for the same nuclei.

  12. Study on the stability of adrenaline and on the determination of its acidity constants

    Science.gov (United States)

    Corona-Avendaño, S.; Alarcón-Angeles, G.; Rojas-Hernández, A.; Romero-Romo, M. A.; Ramírez-Silva, M. T.

    2005-01-01

    In this work, the results are presented concerning the influence of time on the spectral behaviour of adrenaline (C 9H 13NO 3) (AD) and of the determination of its acidity constants by means of spectrophotometry titrations and point-by-point analysis, using for the latter freshly prepared samples for each analysis at every single pH. As the catecholamines are sensitive to light, all samples were protected against it during the course of the experiments. Each method rendered four acidity constants corresponding each to the four acid protons belonging to the functional groups present in the molecule; for the point-by-point analysis the values found were: log β 1=38.25±0.21 , log β 2=29.65±0.17 , log β 3=21.01±0.14 , log β 4=11.34±0.071 .

  13. Application of the pM'-pCH diagrams in the determination of hydrolysis constants of the lanthanides

    International Nuclear Information System (INIS)

    Lopez G, H.; Jimenez R, M.; Solache R, M.; Rojas H, A.

    2001-01-01

    The pM ' -pC H diagrams allowed to determine the saturation and non-saturation zones of Lu(OH) 3 in solid phase and those were applied for determining the hydrolysis and lutetium solubility constants, using the radioactive isotope Lu-177. The first constant of hydrolysis was also determined by the potentiometric method in absence of solid phase. (Author)

  14. 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.

  15. Antioxidant study of quercetin and their metal complex and determination of stability constant by spectrophotometry method.

    Science.gov (United States)

    Ravichandran, R; Rajendran, M; Devapiriam, D

    2014-03-01

    Quercetin found chelate cadmium ions, scavenge free radicals produced by cadmium. Hence new complex, quercetin with cadmium was synthesised, and the synthesised complex structures were determined by UV-vis spectrophotometry, infrared spectroscopy, thermogravimetry and differential thermal analysis techniques (UV-vis, IR, TGA and DTA). The equilibrium stability constants of quercetin-cadmium complex were determined by Job's method. The determined stability constant value of quercetin-cadminum complex at pH 4.4 is 2.27×10(6) and at pH 7.4 is 7.80×10(6). It was found that the quercetin and cadmium ion form 1:1 complex in both pH 4.4 and pH 7.4. The structure of the compounds was elucidated on the basis of obtained results. Furthermore, the antioxidant activity of the free quercetin and quercetin-cadmium complexes were determined by DPPH and ABTS assays. Copyright © 2013 Elsevier Ltd. All rights reserved.

  16. Determination and analysis of dispersive optical constants of CuIn3S5 thin films

    International Nuclear Information System (INIS)

    Khemiri, N.; Sinaoui, A.; Kanzari, M.

    2011-01-01

    CuIn 3 S 5 thin films were prepared from powder by thermal evaporation under vacuum (10 -6 mbar) onto glass substrates. The glass substrates were heated from 30 to 200 o C. The films were characterized for their optical properties using optical measurement techniques (transmittance and reflectance). We have determined the energy and nature of the optical transitions of films. The optical constants of the deposited films were determined in the spectral range 300-1800 nm from the analysis of transmission and reflection data. The Swanepoel envelope method was employed on the interference fringes of transmittance patterns for the determination of variation of refractive index with wavelength. Wemple-Di Domenico single oscillator model was applied to determine the optical constants such as oscillator energy E 0 and dispersion energy E d of the films deposited at different substrate temperatures. The electric free carrier susceptibility and the ratio of the carrier concentration to the effective mass were estimated according to the model of Spitzer and Fan.

  17. 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.

  18. 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.

  19. 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.

  20. Reaction paths and rate constants of the reaction of hydroxyl radicals with environmental species under tropospheric conditions

    International Nuclear Information System (INIS)

    Leonard, C.; Wahner, A.; Zetzsch, C.

    1987-01-01

    The uv-laser absorption technique in a multipath cell (with excimer-laser photolysis for radical production) is used to investigate the rate constants of the reaction of OH with carbon monoxide. The pressure dependence and the influence of collision partners (measurements in pure oxygen up to one atmosphere) of this important atmospheric chemical reaction are determined. In the kinetic measurements detection limits of 10 7 OH cm -3 are reached with millisecond time resolution. Furthermore the application of the cw-Laser for stationary OH measurements (for example in smog chambers or the free troposphere) is described. The possibilities and limits of different detection methods are discussed with respect to of noise spectra. Modifications of the apparatus with a frequency modulation technique are presented, with an extrapolated detection limit of 10 5 OH cm -3 . (orig.) With 43 refs., 16 figs [de

  1. 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.

  2. Effect of selecting a fixed dephosphorylation rate on the estimation of rate constants and rCMRGlu from dynamic [18F] fluorodeoxyglucose/PET data

    International Nuclear Information System (INIS)

    Dhawan, V.; Moeller, J.R.; Strother, S.C.; Evans, A.C.; Rottenberg, D.A.

    1989-01-01

    Several publications have discussed the estimation and physiologic significance of regional [ 18 F]fluorodeoxyglucose (FDG) rate constants and metabolic rates. Most of these studies analyzed dynamic data collected over 45-60 min; three rate constants (k1-k3) and blood volume (Vb) were estimated and the regional cerebral metabolic rate for glucose (rCMRGlu) was subsequently derived using the measured blood glucose value and a regionally invariant value of the lumped constant (LC). The dephosphorylation rate constant (k4) was either neglected, or a fixed value was used in the estimation procedure to obtain the remaining parameters. To compare the rate constants obtained by different authors using different values of k4 is impossible without knowledge of the effect of selecting different fixed values of k4 (including zero) on the estimated rate constants and rCMRGlu. Based on our analysis of FDG/PET data from nine normal volunteer subjects, we conclude that inclusion of a fixed value for k4, in spite of a scaling effect on the absolute values of model parameters, has no effect on the coefficient of variation (CV) of within- and between-subject parameter estimates and glucose metabolic rates

  3. Primary Gas Thermometry by Means of Laser-Absorption Spectroscopy: Determination of the Boltzmann Constant

    International Nuclear Information System (INIS)

    Casa, G.; Castrillo, A.; Galzerano, G.; Wehr, R.; Merlone, A.; Di Serafino, D.; Laporta, P.; Gianfrani, L.

    2008-01-01

    We report on a new optical implementation of primary gas thermometry based on laser-absorption spectrometry in the near infrared. The method consists in retrieving the Doppler broadening from highly accurate observations of the line shape of the R(12) ν 1 +2ν 2 0 +ν 3 transition in CO 2 gas at thermodynamic equilibrium. Doppler width measurements as a function of gas temperature, ranging between the triple point of water and the gallium melting point, allowed for a spectroscopic determination of the Boltzmann constant with a relative accuracy of ∼1.6x10 -4

  4. Primary Gas Thermometry by Means of Laser-Absorption Spectroscopy: Determination of the Boltzmann Constant

    Science.gov (United States)

    Casa, G.; Castrillo, A.; Galzerano, G.; Wehr, R.; Merlone, A.; di Serafino, D.; Laporta, P.; Gianfrani, L.

    2008-05-01

    We report on a new optical implementation of primary gas thermometry based on laser-absorption spectrometry in the near infrared. The method consists in retrieving the Doppler broadening from highly accurate observations of the line shape of the R(12) ν1+2ν20+ν3 transition in CO2 gas at thermodynamic equilibrium. Doppler width measurements as a function of gas temperature, ranging between the triple point of water and the gallium melting point, allowed for a spectroscopic determination of the Boltzmann constant with a relative accuracy of ˜1.6×10-4.

  5. Quantum size effects in Pb layers with absorbed Kondo adatoms: Determination of the exchange coupling constant

    KAUST Repository

    Schwingenschlö gl, Udo; Shelykh, I. A.

    2009-01-01

    We consider the magnetic interaction of manganese phtalocyanine (MnPc) absorbed on Pb layers that were grown on a Si substrate. We perform an ab initio calculation of the density of states and Kondo temperature as a function of the number of Pb monolayers. Comparison to experimental data [Y.-S. Fu et al., Phys. Rev. Lett. 99, 256601 (2007)] then allows us to determine the exchange coupling constant J between the spins of the adsorbed molecules and those of the Pb host. This approach gives rise to a general and reliable method for obtaining J by combining experimental and numerical results.

  6. Characterization and determination of the stability constant of lanthanide complexes with carbonates

    International Nuclear Information System (INIS)

    Bidoglio, G.; Marcandalli, B.

    1983-01-01

    The stability constants of Europium (III) complexes with carbonate and bicarbonate ions are measured at 22 0 C and at 0.5M ionic strength. Solvent extraction with 1.3-diphenyl 1.3-propanedione 5x10 -2 M in benzene is studied. The distribution between the organic and aqueous phases is determined by radioactive tracers. The limits of the spectrophotometric method and of the solubility in the evaluation of this type of complex are evidenced, mainly in the concentration range useful in geochemistry. Some results obtained with Nd and Am 241 are also given

  7. Interferometric method to determine the Kerr constant of perspex and ZnSe

    CSIR Research Space (South Africa)

    Govender, P

    2010-09-01

    Full Text Available , (1999). [2] T. K. Ishii and A. Griffis, “Measurement of electro-optic effects in acrylic plastic”, Microwave and Optical Technology Letters, 4, 387-389(1991). [3] W. Kucharczyk, M. J. Gunning, R. E. Raab and C. Graham, “Interferometric investigation... to Determine the Kerr Constant of Perspex Patricia Govender1, 2, Dr. V.W. Couling1 1 UKZN Pietermaritzburg, King Edward Avenue, Scottsville, Pietermaritzburg 2 CSIR, DPSS, 3Meiring Naude Avenue Patricia Govender e-mail address: pgovender...

  8. Bloch–Siegert shift in application to the astrophysical determination of the fundamental constants variation

    International Nuclear Information System (INIS)

    Solovyev, Dmitry

    2013-01-01

    We have evaluated the Bloch–Siegert shift for the different values of magnetic field's strengths defined at astrophysical conditions, i.e. when the stars with the strong surface magnetic fields are taken as a powerful pumping source of radiation. It is found that the additional shift of resonant frequency should be taken into account in the search for the time variation of the fundamental constants. The main conclusion is that the influence of the electromagnetic field should be considered carefully in each special case of the corresponding frequency determination

  9. Quantum size effects in Pb layers with absorbed Kondo adatoms: Determination of the exchange coupling constant

    KAUST Repository

    Schwingenschlögl, Udo

    2009-07-01

    We consider the magnetic interaction of manganese phtalocyanine (MnPc) absorbed on Pb layers that were grown on a Si substrate. We perform an ab initio calculation of the density of states and Kondo temperature as a function of the number of Pb monolayers. Comparison to experimental data [Y.-S. Fu et al., Phys. Rev. Lett. 99, 256601 (2007)] then allows us to determine the exchange coupling constant J between the spins of the adsorbed molecules and those of the Pb host. This approach gives rise to a general and reliable method for obtaining J by combining experimental and numerical results.

  10. Determination of the Boltzmann constant with cylindrical acoustic gas thermometry: new and previous results combined

    Science.gov (United States)

    Feng, X. J.; Zhang, J. T.; Lin, H.; Gillis, K. A.; Mehl, J. B.; Moldover, M. R.; Zhang, K.; Duan, Y. N.

    2017-10-01

    We report a new determination of the Boltzmann constant k B using a cylindrical acoustic gas thermometer. We determined the length of the copper cavity from measurements of its microwave resonance frequencies. This contrasts with our previous work (Zhang et al 2011 Int. J. Thermophys. 32 1297, Lin et al 2013 Metrologia 50 417, Feng et al 2015 Metrologia 52 S343) that determined the length of a different cavity using two-color optical interferometry. In this new study, the half-widths of the acoustic resonances are closer to their theoretical values than in our previous work. Despite significant changes in resonator design and the way in which the cylinder length is determined, the value of k B is substantially unchanged. We combined this result with our four previous results to calculate a global weighted mean of our k B determinations. The calculation follows CODATA’s method (Mohr and Taylor 2000 Rev. Mod. Phys. 72 351) for obtaining the weighted mean value of k B that accounts for the correlations among the measured quantities in this work and in our four previous determinations of k B. The weighted mean {{\\boldsymbol{\\hat{k}}}{B}} is 1.380 6484(28)  ×  10-23 J K-1 with the relative standard uncertainty of 2.0  ×  10-6. The corresponding value of the universal gas constant is 8.314 459(17) J K-1 mol-1 with the relative standard uncertainty of 2.0  ×  10-6.

  11. 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.

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

    Directory of Open Access Journals (Sweden)

    Borel B

    2016-11-01

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

  13. Rate Constant Change of Photo Reaction of Bacteriorhodopsin Observed in Trimeric Molecular System.

    Science.gov (United States)

    Tsujiuchi, Yutaka; Masumoto, Hiroshi; Goto, Takashi

    2016-04-01

    To elucidate the time evolution of photo reaction of bacteriorhodopsin in glycerol mixed purple membrane at around 196 K under irradiation by red light, a kinetic model was constructed. The change of absorption with irradiation at times of 560 nm and 412 nm was analyzed for the purpose of determining reaction rates of photo reaction of bacteriorhodopsin and its product M intermediate. In this study it is shown that reaction rates of conversion from bacteriorhodopsin to the M intermediate can be explained by a set of linear differential equations. This model analysis concludes that bacteriorhodopsin in which constitutes a trimer unit with other two bacteriorhodopsin molecules changes into M intermediates in the 1.73 of reaction rate, in the initial step, and according to the number of M intermediate in a trimer unit, from three to one, the reaction rate of bacteriorhodopsin into M intermediates smaller as 1.73, 0.80, 0.19 which caused by influence of inter-molecular interaction between bacteriorhodopsin.

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

    Science.gov (United States)

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

    2015-03-03

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

  15. The determinants of credit rating: brazilian evidence

    OpenAIRE

    MurciaI,Flávia Cruz de Souza; Dal-Ri Murcia,Fernando; Rover,Suliani; Borba,José Alonso

    2014-01-01

    This study attempts to identify the determinant factors of credit rating in Brazil. The relevance of this proposal is based on the importance of the subject as well as the uniqueness of the Brazilian market. As for originality, the great majority of previous studies regarding credit rating have been developed in the US, UK and Australia; therefore the effect on other markets is still unclear, especially in emerging markets, like Brazil. We’ve used a Generalized Estimating Equa...

  16. Study of supersonic flow in a constant rate of momentum change (CRMC) ejector with frictional effects

    International Nuclear Information System (INIS)

    Kumar, Virendra; Singhal, Gaurav; Subbarao, P.M.V.

    2013-01-01

    The constant rate of momentum change (CRMC) is a new approach towards design of supersonic ejectors. CRMC methodology was first proposed by Eames [1] in a study which was primarily based on isentropic flow inside the diffusing region of a supersonic ejector. The prime benefit that accrues from employing a CRMC ejector is that it can effectively eliminate the irreversibility associated with occurrence of thermodynamic shock process. The present study examines the supersonic flow in a CRMC ejector from the perspective of an adiabatic flow with frictional effects inside the variable cross-section of supersonic ejector, which is apparently more realistic. An analytical model has been discussed for the prediction of flow parameter variation in a space marching formulation taking into account change in localized frictional coefficient due to corresponding changes at each step. The analytical results have been validated by conducting a computational study based on 2-D axi-symmetric viscous compressible flow formulation with turbulence in FLUENT. The results are in good agreement at on-design conditions. The predictions especially for the recovered pressure made through the analytical formulation incorporating friction are found to be in significantly better agreement than the isentropic approach. The experimental validation for the approach has also been presented with the results being in close agreement with analytically predicted values. -- Highlights: • CRMC ejector eliminates the irreversibility due to occurrence of thermodynamic shock. • Frictional effect based apparently present more realistic solution for ejector. • Static pressure variation between proposed model and numerical study is nearly 2.29%. • Static pressure variation between analytical and experimental values is nearly 4%. • Experimentally observed entrainment ratio shows 3% variation w.r.t. design point value

  17. Use of the ion exchange method for determination of stability constants of uranyl ions with three soil humic acids

    International Nuclear Information System (INIS)

    Tao Zuyi; Du Jinzhou

    1994-01-01

    The ion exchange equilibrium method proposed by Ardakani and Stevenson has not been widely used to determine the stability constants of metal-soil organic matter complexes. In this paper the Ardakani-Stevenson's method has been modified and the stability constants of uranyl ion complexes with three soil humic acids were determined by using the modified Ardakani-Stevenson's method. (orig.)

  18. Dose-rate determination by radiochemical analysis

    International Nuclear Information System (INIS)

    Mangini, A.; Pernicka, E.; Wagner, G.A.

    1983-01-01

    At the previous TL Specialist Seminr we had suggested that α-counting is an unsuitable technique for dose-rate determination due to overcounting effects. This is confirmed by combining α-counting, neutron activation analysis, fission track counting, α-spectrometry on various pottery samples. One result of this study is that disequilibrium in the uranium decay chain alone cannot account for the observed discrepancies between α-counting and chemical analysis. Therefore we propose for routine dose-rate determination in TL dating to apply chemical analysis of the radioactive elements supplemented by an α-spectrometric equilibrium check. (author)

  19. Determination of material constants of vertically aligned carbon nanotube structures in compressions

    International Nuclear Information System (INIS)

    Li, Yupeng; Kang, Junmo; Choi, Jae-Boong; Nam, Jae-Do; Suhr, Jonghwan

    2015-01-01

    Different chemical vapour deposition (CVD) fabrication conditions lead to a wide range of variation in the microstructure and morphologies of carbon nanotubes (CNTs), which actually determine the compressive mechanical properties of CNTs. However, the underlying relationship between the structure/morphology and mechanical properties of CNTs is not fully understood. In this study, we characterized and compared the structural and morphological properties of three kinds of vertically aligned carbon nanotube (VACNT) arrays from different CVD fabrication methods and performed monotonic compressive tests for each VACNT array. The compressive stress–strain responses and plastic deformation were first compared and analyzed with nanotube buckling behaviours. To quantify the compressive properties of the VACNT arrays, a strain density energy function was used to determine their intrinsic material constants. Then, the structural and morphological effects on the quantified material constants of the VACNTs were statistically investigated and analogized to cellular materials with an open-cell model. The statistical analysis shows that density, defect degree, and the moment of inertia of the CNTs are key factors in the improvement of the compressive mechanical properties of VACNT arrays. This approach could allow a model-driven CNT synthesis for engineering their mechanical behaviours. (paper)

  20. Prompt Neutron Decay Constant Determination Of Silicide Transition Core Using Noise Method

    International Nuclear Information System (INIS)

    Jujuratisbela, Uju; Yulianto, Yusi Eko; Cahyana

    2001-01-01

    Chairman of BATAN had decided to replace the Oxide fuel element type of RSG-GAS into silicide element type step by step. The replacement will create core transitions. Kinetic characteristic of the transition cores have to be monitored in order to know the deviation of core behavior. For that reason, the kinetic parameters have to be measured. Prompt neutron decay constant (alpha) is one of the kinetic parameters that has to be monitored continuously in the transition cores. In order not to disturb the normal operation of reactor, alpha parameter should be measured by using noise analysis method. The voltage of neutron flux at power of 15 MW is connected to preamplifier and filter then to the Dynamic Signal Analyzer Version-2 and then the auto power spectral density (APSD) was determined by using Fast Fourier transform. From the APSD curve of each channel of JKT03, the cut off frequency of each channel can be determined by using linear regression technique such that the prompt neutron decay constant can be estimated

  1. Coulometric-potentiometric determination of autoprotolysis constant and relative acidity scale of water

    Directory of Open Access Journals (Sweden)

    Džudović Radmila M.

    2010-01-01

    Full Text Available The autoprotolysis constant and relative acidity scale of water were determined by applying the coulometric-potentiometric method and a hydrogen/palladium (H2/Pd generator anode. In the described procedure for the evaluation of autoprotolysis constant, a strong base generated coulometrically at the platinum cathode in situ in the electrolytic cell, in presence of sodium perchlorate as the supporting electrolyte, is titrated with hydrogen ions obtained by the anodic oxidation of hydrogen dissolved in palladium electrode. The titration was carried out with a glass-SCE electrode pair at 25.0±0.1°C. The value obtained pKw = 13.91 ± 0.06 is in agreement with literature data. The range of acidity scale of water is determined from the difference between the halfneutralization potentials of electrogenerated perchloric acid and that of sodium hydroxide in a sodium perchlorate medium. The halfneutralization potentials were measured using both a glass-SCE and a (H2/Pdind-SCE electrode pairs. A wider range of relative acidity scale of water was obtained with the glass-SCE electrode pair.

  2. Metrology of the hydrogen and deuterium atoms: determination of the Rydberg constant and Lamb shifts

    International Nuclear Information System (INIS)

    Beauvoir, B. de; Schwob, C.; Jozefowski, L.; Hilico, L.; Nez, F.; Julien, L.; Biraben, F.

    2000-01-01

    We present a detailed description of several experiments which have been previously reported in several letters: the determination of the 1S Lamb shift in hydrogen by a comparison of the frequencies of the 1S-3S and 2S-6S or 2S-6D two-photon transitions, and the measurement of the 2S-8S/D and 2S-12D optical frequencies. Following a complete study of the lineshape of the two-photon transitions, we provide the updated values of these frequencies which have been used in the 1998 adjustment of the fundamental constants. From an analysis taking into account these results and several other precise measurements by other authors, we show that the optical frequency measurements have superseded the microwave determination of the 2S Lamb shift and we deduce optimized values for the Rydberg constant, R ∞ =109737.31568550(84) cm -1 (relative uncertainty of 7.7 x 10 -12 ) and for the 1S and 2S Lamb shifts L(1S)=8172.840(22) MHz and L(2S-2P)=1 057.8450(29) MHz (respectively, 8183.970(22) MHz and 1059.2341(29) MHz for deuterium). These are now the most accurate values available. (orig.)

  3. Determination of the pion-nucleon coupling constant and scattering lengths

    CERN Document Server

    Ericson, Torleif Eric Oskar; Thomas, A W

    2002-01-01

    We critically evaluate the isovector GMO sum rule for forward pion-nucleon scattering using the recent precision measurements of negatively charged pion-proton and pion-deuteron scattering lengths from pionic atoms. We deduce the charged-pion-nucleon coupling constant, with careful attention to systematic and statistical uncertainties. This determination gives, directly from data a pseudoscalar coupling constant of 14.17+-0.05(statistical)+-0.19(systematic) or a pseudovector one of 0.0786(11). This value is intermediate between that of indirect methods and the direct determination from backward neutron-proton differential scattering cross sections. We also use the pionic atom data to deduce the coherent symmetric and antisymmetric sums of the negatively charged pion-proton and pion-neutron scattering lengths with high precision. The symmetric sum gives 0.0017+-0.0002(statistical)+-0.0008 (systematic) and the antisymmetric one 0.0900+-0.0003(statistical)+-0.0013(systematic), both in units of inverse charged pi...

  4. Determination of the kinetic and stoichiometric constant in a conventional bioreactor of activated sludge, to scale

    International Nuclear Information System (INIS)

    Rodriguez Chaparro, Tatiana; Perez Navarrete, Eddie Albert; Vivas Mora, Eneydi

    2003-01-01

    The activated sludge process is the one of the most efficient process, when it comes to removal of organic matter. Implementing in the lab is quite easy, economic technically feasible, and simultaneously offers the possibility of using the results obtained in the lab to be applied in field by determining the kinetic and stoichiometric constants. The activated sludge system was designed, built and operated in the water quality lab, at the Military University in Bogota, Colombia. The bioreactor has an aeration chamber, a sedimentation tank and a feeding source with wastewater taken from a meat packing plant in Bogota. The research was carried out for 3 months, in two stages as follows: in the first stage and in order to obtain a high concentration of biomass the acclimatizing process was carried out. This step allows the bioreactor to run in a continuous flow. In the second stage, the bioreactor was taken in to operation and fed with the acclimated sludge at different sludge ages. This would allow us to determine the kinetics, and the stoichiometric constants. The bioreactor was run with a hydraulic retention time of 8 hours and for different sludge ages (5, 10, and 15 days). The system was monitored with a daily grab samples, and pH, temperature as well as the DBO 5 and suspended volatile solids were terminated

  5. 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.

  6. Precision determination of uranium in uranium oxide by constant-current coulometry

    International Nuclear Information System (INIS)

    Xu Laili; Wang Chunhuan.

    1990-01-01

    A method of constant-current coulometric titration for determination of uranium in uranium oxide is described. This method involves preliminary reduction of U (VI) in H 2 SO 4 -H 3 PO 4 medium by Cr (II) as a reductant, followed by air oxidation of excess of Cr (II), addition of solid K 2 Cr 2 O 7 in quantity slightly more than that of the required for quantitative oxidation of U (IV) and final titration of excess of K 2 Cr 2 O 7 with the electrogenerated Fe (II). The endpoint is determined amperometrically. The effect of various factors on the sample treatment and reduction-oxidation processes has been examined. The precision of the method as indicated by the standard deviation of an individual observation is less than 0.01% for l gram uranium oxide

  7. 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

  8. 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.

  9. The determinants of exchange rate in Croatia

    Directory of Open Access Journals (Sweden)

    Manuel BENAZIC

    2016-06-01

    Full Text Available The dilemma for every country with an independent monetary policy is which kind of exchange rate arrangement should be applied. Through the exchange rate policy, countries can influence their economies, i.e. price stability and export competiveness. Croatia is a new EU member state, it has its own monetary policy and currency but it is on the way to euro introduction. Regarding the experiences from the beginning of the 1990s when Croatia was faced with serious monetary instabilities and hyperinflation, the goal of Croatian National Bank (CNB is to ensure price stability and one way to do so is through exchange rate policy. Croatia, as a small and open economy, has applied a managed floating exchange rate regime. The exchange rate is determined primarily by the foreign exchange supply and demand on the foreign exchange market, with occasional market interventions by the CNB. Therefore, in order to maintain exchange rate stability, policymakers must be able to recognize how changes in these factors affect changes in the exchange rate. This research aims to find a relationship among the main sources of foreign currency inflow and outflow and the level of exchange rate in Croatia. The analysis is carried out by using the bounds testing (ARDL approach for co-integration. The results indicate the existence of a stable co-integration relationship between the observed variables, whereby an increase in the majority of variables leads to an exchange rate appreciation.

  10. Nanometer diameter measurements on silicon for determination of the Avogadro constant

    International Nuclear Information System (INIS)

    Kenny, M.J.; Morris, E.C.

    1996-01-01

    Full text: The kilogram is the only remaining fundamental unit within the SI system which is defined in terms of an artefact ( a Pt-Ir cylinder kept in Paris). It is proposed in the medium term to redefine the kilogram in terms of the Avogadro constant. By definition an Avogadro number of 12 C atoms weigh exactly 12 g, so the kilogram could be defined as the mass of 1000/12 12 C atoms if the Avogadro constant is known to an accuracy of 1 x 10 -8 . The preferred method for determination of the Avogadro constant is to use a highly polished 1 kg silicon sphere manufactured with roundness to within ±30 nm. The parameters to be measured are lattice spacing and atoms per unit cell, mass and volume. It is also necessary to know the nature and composition of surface impurities such as oxide and water. The nominal diameter of a 1 kg Si sphere is 94 mm. In order to obtain an accuracy of 1 x l0 -8 in volume, the diameter must be known to ± 0.3 nm i.e. within one atom. This requires optical interferometry against a precision etalon using stabilised laser light. The measurements are sensitive to many parameters particularly temperature. An instability of ±5 mK will be sufficient to cause the silicon to expand and the refractive index of air to change beyond the accuracy limit. In addition alignment of all optical components is critical. The interference fringes are collected on the CCD of a video camera and transferred to computer for processing. An accuracy of ±1 millifringe is required. If the lattice parameters are known, the mass of an atom is simply the product of atomic volume by density. The Avogadro constant is the ratio of molar mass to atom mass. The paper describes the apparatus which is being set up for this series of measurements, the parameters which have to be considered and the role of surface impurities in the determination of the density

  11. 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.

  12. 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.

  13. Determination of the Conditional-Constant Component of the Bank’s Current Liabilities

    Directory of Open Access Journals (Sweden)

    Anatoly Pavlovich Vozhzhov

    2016-03-01

    Full Text Available The article deals with the questions of the definition of the semi-constant component of current liabilities of a bank. The purpose of this article is to develop a scientific and methodological approach to determine the semi-constant component of the current liabilities of a bank under the conditions of the complexity of data acquisition and processing of the data on factors that influence on demand deposits. The main hypothesis is the assumption of the heterogeneity of the variance of the daily cumulative sum of demand deposits. The analysis of scientific and methodological approaches that allow determining a stable component of current liabilities proves the need for further improvement of scientific instruments. In particular, a coefficient analysis that is proposed by some of the scholars, mainly, considers the average values of turnover on accounts, which in turn, can vary considerably throughout the calendar year. The use of the probability distributions to determine the expected value of the constant sum of deposits is possible only in the case of “ideal” financial conditions, when the impact of factors on the aggregate sum of deposits is not taken into account. The developed statistical models leave out the possible heterogeneity of the dispersion of this balance. In the article, it is proposed to apply econometric methods, namely, the methods of time series analysis to test the hypothesis of the variance heterogeneity of the cumulative sum of demand deposits, using daily data. In particular, the formalization and evaluation of EGARCH-model parameters are conducted. The EGARCH-model allows to take into account the non-linear, asymmetric effects of fluctuations in the financial series. The determination of the conditionalconstant component of demand deposits is proposed on the basis of the revealed regularities. The results of the research prove the hypothesis of the non-stationary character of the variance in daily balance of demand

  14. DETERMINATION OF THE SPECIFIC GROWTH RATE ON ...

    African Journals Online (AJOL)

    Sewage generation is one of the dense problems Nigerians encounter on daily bases, mostly at the urbanized area where factories and industries are located. This paper is aimed at determining the specific growth rate “K” of biological activities on cassava wastewater during degradation using Michaelis-Menten Equation.

  15. 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

  16. Mobility-based correction for accurate determination of binding constants by capillary electrophoresis-frontal analysis.

    Science.gov (United States)

    Qian, Cheng; Kovalchik, Kevin A; MacLennan, Matthew S; Huang, Xiaohua; Chen, David D Y

    2017-06-01

    Capillary electrophoresis frontal analysis (CE-FA) can be used to determine binding affinity of molecular interactions. However, its current data processing method mandate specific requirement on the mobilities of the binding pair in order to obtain accurate binding constants. This work shows that significant errors are resulted when the mobilities of the interacting species do not meet these requirements. Therefore, the applicability of CE-FA in many real word applications becomes questionable. An electrophoretic mobility-based correction method is developed in this work based on the flux of each species. A simulation program and a pair of model compounds are used to verify the new equations and evaluate the effectiveness of this method. Ibuprofen and hydroxypropyl-β-cyclodextrinare used to demonstrate the differences in the obtained binding constant by CE-FA when different calculation methods are used, and the results are compared with those obtained by affinity capillary electrophoresis (ACE). The results suggest that CE-FA, with the mobility-based correction method, can be a generally applicable method for a much wider range of applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. 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.

  18. Application of membrane LaF3 electrode in the determination of stability constants of Uranyl Fluoride complex in solution

    International Nuclear Information System (INIS)

    Muzakky; Iswani GS; Mintolo

    1996-01-01

    A membrane electrode LaF 3 has been applied in the determination of uranyl fluoride complex stability constant in solution. The determination is based on the detection of free F ion in solution as a result of hydrolysis reaction (process) of uranyl ions into the uranyl hydroxide form at low pH. The experiment results showed that there was no effect of ammonium carbonate 2 M titran, flow rate on the electrode response. The F release is optimum at pH 1. The free F ion in solution is calculated from the standard curve at pH 1, after the fluoride concentration at the same pH has been corrected. Using the plot of average number of ligand binding (n) versus minus log of free ligand (-log F) the value of β1 = 4.4, β2 = 7.48, β3=9.73, and β4 = 11.67

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

    Science.gov (United States)

    Qiang, Zhimin; Adams, Craig

    2004-07-01

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

  20. 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...

  1. Constant strain rate test and SCC-behaviour of stainless steels

    International Nuclear Information System (INIS)

    Krauss, H.; Speckhardt, H.

    1979-01-01

    In the present work, the stress corrosion cracking behaviour in boiling aqueous 35% magnesium chloride solution under conditions of no external current was investigated as a function of the defined extension rates for the two austenitic steels X 2 CrNi 189 and X 2 CrNiSi 1815, as well as for both ferritic austenitic steels X 6 CrNiMoCu 217 and X 2 CrNiMoN 225. The endurance time found until cracking, the maximum tensile stress, the sample stretching up to cracking and the relative rupture energy were determined for the evaluation, as well as metallographic investigations to describe the crack picture, test surface appearance and attack picture carried out. (orig.) 891 RW/orig. 892 BRE [de

  2. 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...

  3. Photometric method for determination of acidity constants through integral spectra analysis.

    Science.gov (United States)

    Zevatskiy, Yuriy Eduardovich; Ruzanov, Daniil Olegovich; Samoylov, Denis Vladimirovich

    2015-04-15

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

  4. 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.

  5. Determination and interpretation of the optical constants for solar cell materials

    Science.gov (United States)

    Fujiwara, Hiroyuki; Fujimoto, Shohei; Tamakoshi, Masato; Kato, Masato; Kadowaki, Hideyuki; Miyadera, Tetsuhiko; Tampo, Hitoshi; Chikamatsu, Masayuki; Shibata, Hajime

    2017-11-01

    Solar cell materials in thin film form often exhibit quite rough surface, which makes the accurate determination of the optical constants using spectroscopic ellipsometry (SE) quite difficult. In this study, we investigate the effect of the rough surface on the SE analysis and establish an analysis procedure, which is quite helpful for the correction of the underestimated roughness contribution. As examples, the roughness analyses for CuInSe2 and CH3NH3PbI3 hybrid-perovskite thin films are presented. Moreover, to interpret the dielectric functions of emerging solar cell materials, such as CH3NH3PbI3 and Cu2ZnSnSe4, the optical transition analyses are performed based on density functional theory (DFT). The excellent agreement observed between the experimental and DFT results allows the detailed assignment of the transition peaks, confirming the importance of DFT for revealing fundamental optical characteristics.

  6. Determination of the first hydrolysis constant of Europium (III) in 3 M of ionic strength

    International Nuclear Information System (INIS)

    Ramirez B, M.E.

    1994-01-01

    The first hydrolysis constant of Eu 3+ has been determined at 303 K and 3 M (NaCl) ionic strength. A solvent extraction method was used, the extractant was dibenzoylmethane in benzene and di glycolate anion in the aqueous phase provided competitive complexation. The tracer solution was 152m1 Eu (III) in water. The radioactive solution of europium was obtained by neutron irradiation of europium nitrate solutions at pH 3.0, in a TRIGA Mark III nuclear reactor at a neutron flux of 1 x 10 13 cm -2 s -1 . The half life of the produced isotope, 152m1 Eu (9.3 h), was verified by means of a Ge H detector and no interfering radiations were observed in the spectra. (Author)

  7. A micromorphic model for monolayer hexagonal boron nitride with determined constitutive constants by phonon dispersions

    International Nuclear Information System (INIS)

    Zhang, Bin; Yang, Gang

    2014-01-01

    A two dimensional (2D) micromorphic model is developed for monolayer hexagonal boron nitride (h-BN). Theoretical expressions of phonon dispersions for 2D crystals are derived based on the simplified governing equations of specialized three dimensional micromorphic crystals. The constitutive constants of governing equations of the h-BN micromorphic model are determined, which is performed by fitting the available phonon dispersions data of experimental measurements and first-principles calculations with our theoretical expressions. The obtained Young’s modulus and Poisson’s ratio of h-BN are comparable with the results of ab initio calculations and inelastic x-ray scattering experiments, thus the constitutive relations of the h-BN model are verified, which also indicates that mechanical properties of monolayer h-BN could be characterized by our 2D micromorphic model

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

    Science.gov (United States)

    Papanastasiou, G; Ziogas, I

    1995-06-01

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

  9. Surfactant media for constant-current coulometry. Application for the determination of antioxidants in pharmaceuticals

    Energy Technology Data Exchange (ETDEWEB)

    Ziyatdinova, Guzel, E-mail: Ziyatdinovag@mail.ru [Analytical Chemistry Department, A.M. Butlerov Institute of Chemistry, Kazan (Volga Region) Federal University, Kremlyevskaya, 18, Kazan 420008 (Russian Federation); Ziganshina, Endzhe; Budnikov, Herman [Analytical Chemistry Department, A.M. Butlerov Institute of Chemistry, Kazan (Volga Region) Federal University, Kremlyevskaya, 18, Kazan 420008 (Russian Federation)

    2012-09-26

    Highlights: Black-Right-Pointing-Pointer Applicability of surfactants in constant-current coulometry is shown for the first time. Black-Right-Pointing-Pointer Reactions of antioxidants with electrogenerated titrants in surfactant media are investigated. Black-Right-Pointing-Pointer Water insoluble antioxidants can be determined in water media with addition of surfactants. Black-Right-Pointing-Pointer Coulometric determination of antioxidants in pharmaceutical dosage forms using surfactants media is developed. - Abstract: Effect of surfactant presence on electrochemical generation of titrants has been evaluated and discussed for the first time. Cationic (1-dodecylpyridinium and cetylpyridinium bromide), anionic (sodium dodecyl sulfate) and nonionic (Triton X100 and Brij{sup Registered-Sign} 35) surfactants as well as nonionic high molecular weight polymer (PEG 4000) do not react with the electrogenerated bromine, iodine and hexacyanoferrate(III) ions. The electrogenerated chlorine chemically interact with Triton X100 and Brij{sup Registered-Sign} 35. The allowable range of surfactants concentrations providing 100% current yield has been found. Chain-breaking low molecular weight antioxidants (ascorbic acid, rutin, {alpha}-tocopherol and retinol) were determined by reaction with the electrogenerated titrants in surfactant media. Nonionic and cationic surfactants can be used for the determination of antioxidants by reaction with the electrogenerated halogens. On contrary, cationic surfactants gives significantly overstated results of antioxidants determination with electrogenerated hexacyanoferrate(III) ions. The use of surfactants in coulometry of {alpha}-tocopherol and retinol provides their solubilization and allows to perform titration in water media. Simple, express and reliable coulometric approach for determination of {alpha}-tocopherol, rutin and ascorbic acid in pharmaceuticals using surfactant media has been developed. The relative standard deviation of the

  10. 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).

  11. Palmitate and stearate binding to human serum albumin. Determination of relative binding constants

    DEFF Research Database (Denmark)

    Vorum, H; Fisker, K; Honoré, B

    1997-01-01

    Multiple binding equilibria of two apparently insoluble ligands, palmitate and stearate, to defatted human serum albumin were studied in a 66 mM sodium phosphate buffer (pH 7.4) at 37 degrees C, by determination of dialytic exchange rates of ligands among identical equilibrium solutions. The expe...

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

    Science.gov (United States)

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

    2015-08-10

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

  13. 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.

  14. Determination of diffuse double layer protonation constants for hydrous ferric oxide (HFO): supporting evidence for the Dzombak and Morel compilation

    CSIR Research Space (South Africa)

    Pretorius, PJ

    1998-01-01

    Full Text Available of the experimental system suggests that titration points below pH 4 should not be used for the determination of protonation constants because of potential HFO dissolution. Surface protonation constant, PZC and binding site estimates agree excellently with currently...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-07-01

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

  16. 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)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-08-14

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

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

    International Nuclear Information System (INIS)

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

    2009-01-01

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

  19. The Determinants of Credit Rating: Brazilian Evidence

    Directory of Open Access Journals (Sweden)

    Flávia Cruz de Souza Murcia

    2014-04-01

    Full Text Available This study attempts to identify the determinant factors of credit rating in Brazil. The relevance of this proposal is based on the importance of the subject as well as the uniqueness of the Brazilian market. As for originality, the great majority of previous studies regarding credit rating have been developed in the US, UK and Australia; therefore the effect on other markets is still unclear, especially in emerging markets, like Brazil. We’ve used a Generalized Estimating Equations (GEE model considering a panel structure with a categorical dependent variable (credit rating and ten independent variables: leverage, profitability, size, financial coverage, growth, liquidity, corporate governance, control, financial market performance and internationalization. The sample consisted of 153 rating observations during the period of 1997-2011 for a total of 49 public firms operating in the Brazilian Market. Results showed that leverage and internationalization are significant at the 1% level in explaining credit rating. Performance in the financial market was significant at a 5% level; profitability and growth were also statistically significant, but at a 10% significance level.

  20. Hybrid nanomembrane-based capacitors for the determination of the dielectric constant of semiconducting molecular ensembles

    Science.gov (United States)

    Petrini, Paula A.; Silva, Ricardo M. L.; de Oliveira, Rafael F.; Merces, Leandro; Bof Bufon, Carlos C.

    2018-06-01

    Considerable advances in the field of molecular electronics have been achieved over the recent years. One persistent challenge, however, is the exploitation of the electronic properties of molecules fully integrated into devices. Typically, the molecular electronic properties are investigated using sophisticated techniques incompatible with a practical device technology, such as the scanning tunneling microscopy. The incorporation of molecular materials in devices is not a trivial task as the typical dimensions of electrical contacts are much larger than the molecular ones. To tackle this issue, we report on hybrid capacitors using mechanically-compliant nanomembranes to encapsulate ultrathin molecular ensembles for the investigation of molecular dielectric properties. As the prototype material, copper (II) phthalocyanine (CuPc) has been chosen as information on its dielectric constant (k CuPc) at the molecular scale is missing. Here, hybrid nanomembrane-based capacitors containing metallic nanomembranes, insulating Al2O3 layers, and the CuPc molecular ensembles have been fabricated and evaluated. The Al2O3 is used to prevent short circuits through the capacitor plates as the molecular layer is considerably thin (electrical measurements of devices with molecular layers of different thicknesses, the CuPc dielectric constant has been reliably determined (k CuPc = 4.5 ± 0.5). These values suggest a mild contribution of the molecular orientation on the CuPc dielectric properties. The reported nanomembrane-based capacitor is a viable strategy for the dielectric characterization of ultrathin molecular ensembles integrated into a practical, real device technology.

  1. Determination of prompt neutron decay constant of the AP-600 reactor core

    International Nuclear Information System (INIS)

    Surbakti, T.

    1998-01-01

    Determination of prompt neutron decay constant of the AP-600 reactor core has been performed using combination of two codes WIMS/D4 and Batan-2DIFF. The calculation was done at beginning of cycle and all of control rods pulled out. Cell generation from various kinds of core materials was done with 4 neutron energy group in 1-D transport code (WIMS/D4). The cell is considered for 1/4 fuel assembly in cluster model with square pitch arrange and then, the dimension of its unit cell is calculated. The unit cell consist of a fuel and moderator unit. The unit cell dimension as input data of WIMS/D4 code, called it annulus, is obtained from the equivalent unit cell. Macroscopic cross sections as output was used as input on neutron diffusion code Batan-2DIFF for core calculation as appropriate with three enrichment regions of the fuel of AP-600 core, namely 2, 2.5, and 3%. From result of diffusion code ( Batan-2DIFF) is obtained the value of delayed neutron fraction of 6.932E-03 and average prompt neutron life-time of 26.38 μs, so that the value of prompt neutron decay constant is 262.8 s-1. If it is compared the calculation result with the design value, the deviation are, for the design value of delayed neutron fraction is 7.5E-03, about 8% and the design value of average prompt neutron life time is 19.6 μs, about 34% respectively. The deviation because there are still unknown several core components of AP-600, so it didn't include in calculation yet

  2. Hybrid nanomembrane-based capacitors for the determination of the dielectric constant of semiconducting molecular ensembles.

    Science.gov (United States)

    Petrini, Paula Andreia; Lopes da Silva, Ricardo Magno; de Oliveira, Rafael Furlan; Merces, Leandro; Bufon, Carlos César Bof

    2018-04-06

    Considerable advances in the field of molecular electronics have been achieved over the recent years. One persistent challenge, however, is the exploitation of the electronic properties of molecules fully integrated into devices. Typically, the molecular electronic properties are investigated using sophisticated techniques incompatible with a practical device technology, such as the scanning tunneling microscope (STM). The incorporation of molecular materials in devices is not a trivial task since the typical dimensions of electrical contacts are much larger than the molecular ones. To tackle this issue, we report on hybrid capacitors using mechanically-compliant nanomembranes to encapsulate ultrathin molecular ensembles for the investigation of molecular dielectric properties. As the prototype material, copper (II) phthalocyanine (CuPc) has been chosen as information on its dielectric constant (kCuPc) at the molecular scale is missing. Here, hybrid nanomembrane-based capacitors containing metallic nanomembranes, insulating Al2O3 layers, and the CuPc molecular ensemble have been fabricated and evaluated. The Al2O3 is used to prevent short circuits through the capacitor plates as the molecular layer is considerably thin (< 30 nm). From the electrical measurements of devices with molecular layers of different thicknesses, the CuPc dielectric constant has been reliably determined (kCuPc = 4.5 ± 0.5). These values suggest a mild contribution of molecular orientation in the CuPc dielectric properties. The reported nanomembrane-based capacitor is a viable strategy for the dielectric characterization of ultrathin molecular ensembles integrated into a practical, real device technology. © 2018 IOP Publishing Ltd.

  3. 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)

  4. Determination of the optical constants of polymer light-emitting diode films from single reflection measurements

    International Nuclear Information System (INIS)

    Zhu Dexi; Shen Weidong; Ye Hui; Liu Xu; Zhen Hongyu

    2008-01-01

    We present a simple and fast method to determine the optical constant and physical thickness of polymer films from a single reflectivity measurement. A self-consistent dispersion formula of the Forouhi-Bloomer model was introduced to fit the measured spectral curves by a modified 'Downhill' simplex algorithm. Four widely used polymer light-emitting diodes materials: poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylenevinylene], poly(9,9-dioctylfluoreny-2,7-diyl) (PFO), poly(N-vinyl carbazole) and poly(3,4-ethylene dioxythiophene) : poly(styrenesulfonate) were investigated by this technique. The refractive indices over the whole visible region as well as the optical band gap extracted by this method agree well with those reported in the literature. The determined physical thicknesses present a deviation less than 4% compared with the experimental values measured by the stylus profiler. The influence of scattering loss on the fitted results is discussed to demonstrate the applicability of this technology for polymer films.

  5. Determination of the Boltzmann constant using a quasi-spherical acoustic resonator.

    Science.gov (United States)

    Pitre, Laurent; Sparasci, Fernando; Truong, Daniel; Guillou, Arnaud; Risegari, Lara; Himbert, Marc E

    2011-10-28

    The paper reports a new experiment to determine the value of the Boltzmann constant, k(B)=1.3806477(17)×10(-23) J K(-1), with a relative standard uncertainty of 1.2 parts in 10(6). k(B) was deduced from measurements of the velocity of sound in argon, inside a closed quasi-spherical cavity at a temperature of the triple point of water. The shape of the cavity was achieved using an extremely accurate diamond turning process. The traceability of temperature measurements was ensured at the highest level of accuracy. The volume of the resonator was calculated from measurements of the resonance frequencies of microwave modes. The molar mass of the gas was determined by chemical and isotopic composition measurements with a mass spectrometer. Within combined uncertainties, our new value of k(B) is consistent with the 2006 Committee on Data for Science and Technology (CODATA) value: (k(B)(new)/k(B_CODATA)-1)=-1.96×10(-6), where the relative uncertainties are u(r)(k(B)(new))=1.2×10(-6) and u(r)(k(B_CODATA))=1.7×10(-6). The new relative uncertainty approaches the target value of 1×10(-6) set by the Consultative Committee on Thermometry as a precondition for redefining the unit of the thermodynamic temperature, the kelvin.

  6. Determination of the pion-nucleon coupling constant and scattering lengths

    International Nuclear Information System (INIS)

    Ericson, T.E.O.; Loiseau, B.; Thomas, A.W.

    2002-01-01

    We critically evaluate the isovector Goldberger-Miyazawa-Oehme (GMO) sum rule for forward πN scattering using the recent precision measurements of π - p and π - d scattering lengths from pionic atoms. We deduce the charged-pion-nucleon coupling constant, with careful attention to systematic and statistical uncertainties. This determination gives, directly from data, g c 2 (GMO)/4π=14.11±0.05(statistical)±0.19(systematic) or f c 2 /4π=0.0783(11). This value is intermediate between that of indirect methods and the direct determination from backward np differential scattering cross sections. We also use the pionic atom data to deduce the coherent symmetric and antisymmetric sums of the pion-proton and pion-neutron scattering lengths with high precision, namely, (a π - p +a π - n )/2=[-12±2(statistical)±8(systematic)]x10 -4 m π -1 and (a π - p -a π - n )/2=[895±3(statistical)±13 (systematic)]x10 -4 m π -1 . For the need of the present analysis, we improve the theoretical description of the pion-deuteron scattering length

  7. State of the art in the determination of the fine structure constant: test of Quantum Electrodynamics and determination of h/mu

    International Nuclear Information System (INIS)

    Bouchendira, Rym; Clade, Pierre; Nez, Francois; Biraben, Francois; Guellati-Khelifa, Saida

    2013-01-01

    The fine structure constant α has a particular status in physics. Its precise determination is required to test the quantum electrodynamics (QED) theory. The constant α is also a keystone for the determination of other fundamental physical constants, especially the ones involved in the framework of the future International System of units. This paper presents Paris experiment, where the fine structure constant is determined by measuring the recoil velocity of a rubidium atom when it absorbs a photon. The impact of the recent improvement of QED calculations of the electron moment anomaly and the recent measurement of the cesium atom recoil at Berkeley will be discussed. The opportunity to provide a precise value of the ratio h/m u between the Planck constant and the atomic mass constant will be investigated. (copyright 2013 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Determination of lutetium (III) hydrolysis constants in the middle of ion force 1M sodium chloride at 303 K

    International Nuclear Information System (INIS)

    Jimenez R, M.; Solache R, M.J.; Ramirez G, J.J.; Rojas H, A.

    1997-01-01

    With the purpose to complete information about the lutetium (III) hydrolysis constants here is used the potentiometric method to determine those in the middle of ion force 1M sodium chloride at 303 K. (Author)

  9. 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.

  10. Determination of time constants of reactor pressure and temperature sensors: the dynamic data system method

    International Nuclear Information System (INIS)

    Wu, S.M.; Hsu, M.C.; Chow, M.C.

    1979-01-01

    A new modeling technique is introduced for on-line sensor time constant identification, both for the resistance temperature detector (RTD) and for the pressure sensor using power plant operational data. The sensor's time constant is estimated from a real characteristic root of the fitted autoregressive moving average model. The RTD's time constant values were identified to be 8.4 s, with a standard deviation of 1.2 s. The pressure sensor time constant was identified to be 28.6 ms, with a standard deviation of 3.5 ms

  11. Elucidation of Environmental Fate of Artificial Sweetener, Aspartame by Determining Bimolecular Rate Constants with Hydroxyl Radical at Various pH and Temperature Conditions and Reaction By-Products Presentation type:Poster Section:Ocean Sciences Session:General Contribution Authors:Takashi Teraji (1) Takemitsu Arakaki (2) AGU# 10173629 (1) Graduate School of Engineering and Science, University of the Ryukyus, 1 Senbaru Nishihara-cho, Okinawa, 903-0123, Japan (a4269bj@yahoo.co.jp), (2) Department of Chemistry, Biology and Marine Science, Faculty of Science, University of the Ryukyus, 1 Senbaru Nishihara-cho, Okinawa, 903-0123, Japan (arakakit@sci.u-ryukyu.ac.jp)

    Science.gov (United States)

    Teraji, T.; Arakaki, T.

    2011-12-01

    Use of artificial sweeteners in drinks and food has been rapidly increasing because of their non-calorie nature. In Japan, aspartame, acesulfame K and sucralose are among the most widely used artificial sweeteners. Because the artificial sweeteners are not metabolized in human bodies, they are directly excreted into the environment without chemical transformations. We initiated a study to better understand the fate of artificial sweeteners in the marine environment. In particular, we focused on the fate of aspartame by determining its bimolecular rate constants with hydroxyl radicals at various pH and temperature conditions and reaction by-products. The hydroxyl radical (OH), the most potent reactive oxygen species, reacts with various compounds and determines the environmental oxidation capacity and the life-time of many compounds. The steady-state OH concentration and the reaction rate constants between the compound and OH are used to estimate the life-time of the compound. In this study, we determine the bimolecular rate constants between aspartame and OH at various pH and temperature conditions using a competition kinetics technique. We use hydrogen peroxide as a photochemical source of OH. Bimolecular rate constant we obtained so far was (2.6±1.2)×109 M-1 s-1 at pH = 3.0. Little effect was seen by changing the temperatures between 15 and 40 °C. Activation energy (Ea) was calculated to be -1.0 kJ mol-1 at pH = 3.0, which could be regarded as zero. We will report reaction rate constants at different pHs and reaction by-products which will be analyzed by GC-MS. We will further discuss the fate of aspartame in the coastal environment.

  12. 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...

  13. Application of Constant Rate of Supply model (CRS) in dating of Guanabara Bay sediments using 210Pb measures

    International Nuclear Information System (INIS)

    Braganca, Maura Julia Camara da Silva

    1992-09-01

    A geochronological study of the Guanabara Bay (Rio de Janeiro, Brazil) based on 210P b dating technique to determine sedimentation rates and using the Constant Rate of Supply model (CRS) is presented in this work. Sediment samples were collected from river-head of Estrela, Sao Joao de Meriti, Guapimirim, Guaxindiba e Imbuacu. A low energy gamma spectrometry ( 210P b, samples taken from the Estrela and Sao Joao de Meriti rivers. Radiochemical method was applied to determine the amount of 210P b in samples collected near Guapimirim, Guaxindiba and Imbuacu Rivers. Atomic absorption spectrometry with air-acetylene flame technique was used to determine the amount of copper in all these samples. Experimental data shown the following variation in the concentration levels of copper and 210P b: (i) copper; from 2.5 μg/g to 37.1 μg/g (Imbuacu River); from 3.6 to 228.1 μg/g (Estrela River); from 11.6 to 73.4 μg/g (Guapimirim River); from 12.0 to 52.9 μg/g (Guaxindiba River) and from 90.8 to to 237.7 μg/g (Sao Joao de Meriti River), (ti) 210P b; from 2.0 Bq/kg to 27.0 Bq/kg (Imbuacu River); from 25.2 to 136.6 Bq/kg (Estrela River); from 40.0 to 90.0 Bq/kg (Sao Joao de Meriti River); from 7.0 to 70.0 Bq/kg (Guapimirim River); from 10.0 to 48.0 Bq/kg (Guaxindiba River). The sedimentation rates ranged from 0.30 cm/y in the Imbuacu River for a depth below of 35 cm to 1.3 cm/y for 0-30 cm depth in Guaxindiba River. It was concluded that the experimental data found in this work are consistent with those published in the scientific literature and that they can be predicted by the CRS model. (author)

  14. Three Rate-Constant Kinetic Model for Permanganate Reactions Autocatalyzed by Colloidal Manganese Dioxide: The Oxidation of L-Phenylalanine.

    Science.gov (United States)

    Perez-Benito, Joaquin F; Ferrando, Jordi

    2014-12-26

    The reduction of permanganate ion to MnO(2)-Mn(2)O(3) soluble colloidal mixed oxide by l-phenylalanine in aqueous phosphate-buffered neutral solutions has been followed by a spectrophotometric method, monitoring the decay of permanganate ion at 525 nm and the formation of the colloidal oxide at 420 nm. The reaction is autocatalyzed by the manganese product, and three rate constants have been required to fit the experimental absorbance-time kinetic data. The reaction shows base catalysis, and the values of the activation parameters at different pHs have been determined. A mechanism including both the nonautocatalytic and the autocatalytic reaction pathways, and in agreement with the available experimental data, has been proposed. Some key features of this mechanism are the following: (i) of the two predominant forms of the amino acid, the anionic form exhibits a stronger reducing power than the zwitterionic form; (ii) the nonautocatalytic reaction pathway starts with the transfer of the hydrogen atom in the α position of the amino acid to permanganate ion; and (iii) the autocatalytic reaction pathway involves the reduction of Mn(IV) to Mn(II) by the amino acid and the posterior reoxidation of Mn(II) to Mn(IV) by permanganate ion.

  15. Dose rate constants for the quantity H{sub p}(3) for frequently used radionuclides in nuclear medicine

    Energy Technology Data Exchange (ETDEWEB)

    Szermerski, Bastian; Bruchmann, Iris; Geworski, Lilli [Medical School Hannover (Germany). Dept. for Radiation Protection and Medical Physics; Behrens, Rolf [Physikalisch-Technische Bundesanstalt (PTB), Braunschweig (Germany)

    2016-07-01

    According to recent studies, the human eye lens is more sensitive to ionising radiation than previously assumed. Therefore, the dose limit for personnel occupationally exposed to ionising radiation will be lowered from currently 150 mSv to 20 mSv per year. Currently, no data base for a reliable estimation of the dose to the lens of the eye is available for nuclear medicine. Furthermore, the dose is usually not monitored. The aim of this work was to determine dose rate constants for the quantity H{sub p}(3), which is supposed to estimate the dose to the lens of the eye. For this, H{sub p}(3)-dosemeters were fixed to an Alderson Phantom at different positions. The dosemeters were exposed to radiation from nuclides typically used in nuclear medicine in their geometries analog to their application in nuclear medicine, e.g. syringe or vial. The results show that the handling of high-energy beta (i.e. electron or positron) emitters may lead to a relevant dose to the lens of the eye. For low-energy beta emitters and gamma emitters, an exceeding of the lowered dose limit seems to be unlikely.

  16. Reversible conformational transition gives rise to 'zig-zag' temperature dependence of the rate constant of irreversible thermoinactivation of enzymes.

    Science.gov (United States)

    Levitsky VYu; Melik-Nubarov, N S; Siksnis, V A; Grinberg VYa; Burova, T V; Levashov, A V; Mozhaev, V V

    1994-01-15

    We have obtained unusual 'zig-zag' temperature dependencies of the rate constant of irreversible thermoinactivation (k(in)) of enzymes (alpha-chymotrypsin, covalently modified alpha-chymotrypsin, and ribonuclease) in a plot of log k(in) versus reciprocal temperature (Arrhenius plot). These dependencies are characterized by the presence of both ascending and descending linear portions which have positive and negative values of the effective activation energy (Ea), respectively. A kinetic scheme has been suggested that fits best for a description of these zig-zag dependencies. A key element of this scheme is the temperature-dependent reversible conformational transition of enzyme from the 'low-temperature' native state to a 'high-temperature' denatured form; the latter form is significantly more stable against irreversible thermoinactivation than the native enzyme. A possible explanation for a difference in thermal stabilities is that low-temperature and high-temperature forms are inactivated according to different mechanisms. Existence of the suggested conformational transition was proved by the methods of fluorescence spectroscopy and differential scanning calorimetry. The values of delta H and delta S for this transition, determined from calorimetric experiments, are highly positive; this fact underlies a conclusion that this heat-induced transition is caused by an unfolding of the protein molecule. Surprisingly, in the unfolded high-temperature conformation, alpha-chymotrypsin has a pronounced proteolytic activity, although this activity is much smaller than that of the native enzyme.

  17. The pulsed neutron method applied to the determination of the nuclear constants of graphite (1961); La methode des neutrons pulses appliquee a la determination des constantes nucleaires du graphite (1961)

    Energy Technology Data Exchange (ETDEWEB)

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

    1961-07-01

    A method for determining the nuclear constants {sigma}{sub a} and {lambda}{sub t} of a moderator is described. The disappearance of a burst of neutrons introduced into a finite medium is studied as a function of time. This decrease in the thermal neutron density is the product of two exponentials; one representing the absorption, the other the leakage. By varying one or other of these factors, the constants of the factor left unvaried can be determined, and from this the nuclear constant values are deduced. (author) [French] On decrit une methode permettant de determiner les constantes nucleaires {sigma}{sub a} et {lambda}{sub t} d'un moderateur. On etudie la decroissance dans le temps d'une bouffee de neutrons introduite dans un milieu fini. Cette decroissance de la densite en neutrons thermiques est le produit de deux exponentielles; l'une represente l'absorption, l'autre les fuites. Par variation de l'un ou l'autre de ces facteurs, on determine les constantes du facteur laisse invariant dont on deduit les valeurs des constantes nucleaires. (auteur)

  18. Determining the Optimal Values of Exponential Smoothing Constants--Does Solver Really Work?

    Science.gov (United States)

    Ravinder, Handanhal V.

    2013-01-01

    A key issue in exponential smoothing is the choice of the values of the smoothing constants used. One approach that is becoming increasingly popular in introductory management science and operations management textbooks is the use of Solver, an Excel-based non-linear optimizer, to identify values of the smoothing constants that minimize a measure…

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

    International Nuclear Information System (INIS)

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

    1990-01-01

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

  20. 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

  1. New determination of the gravitational constant G with time-of-swing method

    International Nuclear Information System (INIS)

    Tu Liangcheng; Li Qing; Wang Qinglan; Shao Chenggang; Yang Shanqing; Liu Linxia; Liu Qi; Luo Jun

    2010-01-01

    A new determination of the Newtonian gravitational constant G is presented by using a torsion pendulum with the time-of-swing method. Compared with our previous measurement with the same method, several improvements greatly reduced the uncertainties as follows: (i) two stainless steel spheres with more homogeneous density are used as the source masses instead of the cylinders used in the previous experiment, and the offset of the mass center from the geometric center is measured and found to be much smaller than that of the cylinders; (ii) a rectangular glass block is used as the main body of the pendulum, which has fewer vibration modes and hence improves the stability of the period and reduces the uncertainty of the moment of inertia; (iii) both the pendulum and source masses are placed in the same vacuum chamber to reduce the error of measuring the relative positions; (iv) changing the configurations between the ''near'' and ''far'' positions is remotely operated by using a stepper motor to lower the environmental disturbances; and (v) the anelastic effect of the torsion fiber is first measured directly by using two disk pendulums with the help of a high-Q quartz fiber. We have performed two independent G measurements, and the two G values differ by only 9 ppm. The combined value of G is (6.673 49±0.000 18)x10 -11 m 3 kg -1 s -2 with a relative uncertainty of 26 ppm.

  2. Determination of elastic constants of fuels plates based on uranium by ultrasound testing

    International Nuclear Information System (INIS)

    Moreira Castro, Martin Ignacio

    2015-01-01

    Current nuclear reactors use as U-235 U-enriched compounds enriched with U-235, requiring U-alloys that increase the amount of atoms available for nuclear fission in a convenient way. This study was carried out on fuel plates manufactured in the Chilean Nuclear Energy Commission, whose cores are composed of a dispersed mixture Al-U_3Si_2 and Al-U_7Mo, with different densities of uranium, covered by a coating of Al6061. The objective was to characterize elastically and classify the fuel plates analyzed. Specifically, five Al-U_3Si_2 fuel plates with 1.7 gU/cm"3, eight A-U_3Si_2 with 3.4 gU/cm"3, five of A-l U_3Si_2 with 4.8 gU/cm"3 were successfully studied. The apparent elastic constants (Young and Shear modules, and Poisson coefficient) were determined in the area where the fuel is located (MEAT) by means of an ultrasound sampling technique, thus being able to characterize them and classify them according to their composition. The behavior of the elastic constants generally shows a tendency to decrease as the amount of U_3Si_2 particles dispersed in the MEAT zone of the fuel plates increases. In addition, the non-destructive test method used made it possible to detect several differences between the fuel plates analyzed, such as the amount of reduction in rolling, among others. Additionally, six experimental fuel miniplates were analyzed whose meat were formed by a dispersion of the Al-UMo type, specifically: two of Al-U_7Mo with 6.0 gU/cm"3, two of Al-U_7Mo with 7.0 gU/ cm"3 and two of Al-U_7Mo with 8.0 gU/cm"3. The response of the U-Mo fuel miniplates against this technique was not good, so several ideas were proposed to improve this situation

  3. Apparatus and method for determining solids circulation rate

    Science.gov (United States)

    Ludlow, J Christopher [Morgantown, WV; Spenik, James L [Morgantown, WV

    2012-02-14

    The invention relates to a method of determining bed velocity and solids circulation rate in a standpipe experiencing a moving packed bed flow, such as the in the standpipe section of a circulating bed fluidized reactor The method utilizes in-situ measurement of differential pressure over known axial lengths of the standpipe in conjunction with in-situ gas velocity measurement for a novel application of Ergun equations allowing determination of standpipe void fraction and moving packed bed velocity. The method takes advantage of the moving packed bed property of constant void fraction in order to integrate measured parameters into simultaneous solution of Ergun-based equations and conservation of mass equations across multiple sections of the standpipe.

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

    NARCIS (Netherlands)

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

    2014-01-01

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

  5. Determination of Henry’s law constant of light hydrocarbon gases at low temperatures

    International Nuclear Information System (INIS)

    Mohebbi, V.; Naderifar, A.; Behbahani, R.M.; Moshfeghian, M.

    2012-01-01

    Highlights: ► Henry’s constants of light hydrocarbon gases are reported at low temperatures. ► Solubility of iso-butane in water at low temperatures (275 K to 293 K) was measured. ► An expression of Krichevsky–Kasarnovsky equation is reported. - Abstract: The solubility of i-butane in water at the low temperatures was measured (274 K to 293 K). Additionally, Henry’s law constants of light hydrocarbons (methane, ethane, propane, i-butane, and n-butane) in water at the low temperatures are reported. A modified equation based on Krichevsky–Kasarnovsky equation is proposed to consider the effect of pressure and temperature on the equation parameters. Results show that Henry’s law constant of the selected components depends on temperature. It is deduced that pressure has a considerable effect on Henry’s law constant for methane, ethane, and propane, whereas this dependency for butanes is negligible.

  6. Determining leach rates of monolithic waste forms

    International Nuclear Information System (INIS)

    Gilliam, T.M.; Dole, L.R.

    1986-01-01

    The ANS 16.1 Leach Procedure provides a conservative means of predicting long-term release from monolithic waste forms, offering a simple and relatively quick means of determining effective solid diffusion coefficients. As presented here, these coefficients can be used in a simple model to predict maximum release rates or be used in more complex site-specific models to predict actual site performance. For waste forms that pass the structural integrity test, this model also allows the prediction of EP-Tox leachate concentrations from these coefficients. Thus, the results of the ANS 16.1 Leach Procedure provide a powerful tool that can be used to predict the waste concentration limits in order to comply with the EP-Toxicity criteria for characteristically nonhazardous waste. 12 refs., 3 figs

  7. Determination of Ga-67 disintegration rate

    International Nuclear Information System (INIS)

    Fonseca, Katia A.; Koskinas, Maria F.; Dias, Mauro S.

    1996-01-01

    One of the consequences of the production by IPEN of new radioisotopes used in nuclear medicine, as the case of Ga-67, is the need of new standard sources of the radionuclide obtained in a fast and simple way. The Laboratorio de Metrologia de Radionuclideos at IPEN has a well-type ionization chamber system, the most suitable for this purpose. In order to calibrate this system it was necessary to standardize Ga-67 solutions by an absolute system. The present work gives details on the Ga-67 disintegration rate determination by an 4 π β-γ coincidence system, gamma spectrometry using an HPGe detector and measurements using a 1383A - type ionization chamber, in order to check the consistency in the adopted methodology. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-08-15

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

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

    International Nuclear Information System (INIS)

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

    2008-01-01

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

  10. Fast high-throughput method for the determination of acidity constants by capillary electrophoresis: I. Monoprotic weak acids and bases.

    Science.gov (United States)

    Fuguet, Elisabet; Ràfols, Clara; Bosch, Elisabeth; Rosés, Martí

    2009-04-24

    A new and fast method to determine acidity constants of monoprotic weak acids and bases by capillary zone electrophoresis based on the use of an internal standard (compound of similar nature and acidity constant as the analyte) has been developed. This method requires only two electrophoretic runs for the determination of an acidity constant: a first one at a pH where both analyte and internal standard are totally ionized, and a second one at another pH where both are partially ionized. Furthermore, the method is not pH dependent, so an accurate measure of the pH of the buffer solutions is not needed. The acidity constants of several phenols and amines have been measured using internal standards of known pK(a), obtaining a mean deviation of 0.05 pH units compared to the literature values.

  11. Determination of stability constants of lanthanides (III) with amino acids (Preprint No. AL-07)

    International Nuclear Information System (INIS)

    Patel, N.M.; Patel, P.M.; Patel, M.N.; Joshi, J.D.

    1989-01-01

    The present paper reports the stability constants of La(III), Ce(III), Pr(III), Nd(III), Sm(III) and Gd(III) with amino acids valine, serine, threonine, methionine and aspartic acid. The coordination of valine and aspartic acid have been discussed. The stability constants of trivalent lanthanide amino acid complexes were found to be in the order, La < Ce < Pr < Nd < Sm < Gd. (author). 5 refs

  12. Determination of acidity constants and ionic mobilities of polyprotic peptide hormones by CZE

    Czech Academy of Sciences Publication Activity Database

    Šolínová, Veronika; Kašička, Václav

    2013-01-01

    Roč. 34, č. 18 (2013), s. 2655-2665 ISSN 0173-0835 R&D Projects: GA ČR(CZ) GAP206/12/0453; GA ČR(CZ) GA13-17224S Institutional support: RVO:61388963 Keywords : acid dissociation constant * gonadotropin-releasing hormones * ionization constant * peptides * pK(a) Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 3.161, year: 2013

  13. 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.

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

    DEFF Research Database (Denmark)

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

    1993-01-01

    The rate constants for the reaction of NO with a series of peroxy radicals: CH3O2, C2H5O2, (CH3)3CCH2O2, (CH3)3CC(CH3)2CH2O2, CH2FO2, CH2ClO2, CH2BrO2, CHF2O2, CF2ClO2, CHF2CF2O2, CF3CF2O2, CFCl2CH2O2 and CF2ClCH2O2 were measured at 298 K and a total pressure of 1 atm. The rate constants were...

  15. A 2.4% DETERMINATION OF THE LOCAL VALUE OF THE HUBBLE CONSTANT

    Energy Technology Data Exchange (ETDEWEB)

    Riess, Adam G.; Scolnic, Dan; Jones, David O. [Department of Physics and Astronomy, Johns Hopkins University, Baltimore, MD (United States); Macri, Lucas M.; Hoffmann, Samantha L.; Yuan, Wenlong; Brown, Peter J. [George P. and Cynthia Woods Mitchell Institute for Fundamental Physics and Astronomy, Department of Physics and Astronomy, Texas A and M University, College Station, TX (United States); Casertano, Stefano [Space Telescope Science Institute, Baltimore, MD (United States); Filippenko, Alexei V.; Tucker, Brad E. [Department of Astronomy, University of California, Berkeley, CA (United States); Reid, Mark J.; Challis, Peter [Harvard-Smithsonian Center for Astrophysics, Cambridge, MA (United States); Silverman, Jeffrey M. [Department of Astronomy, University of Texas, Austin, TX (United States); Chornock, Ryan [Astrophysical Institute, Department of Physics and Astronomy, Ohio University, Athens, OH (United States); Foley, Ryan J., E-mail: ariess@stsci.edu [Department of Physics, University of Illinois at Urbana-Champaign, Urbana, IL (United States)

    2016-07-20

    We use the Wide Field Camera 3 (WFC3) on the Hubble Space Telescope (HST) to reduce the uncertainty in the local value of the Hubble constant from 3.3% to 2.4%. The bulk of this improvement comes from new near-infrared (NIR) observations of Cepheid variables in 11 host galaxies of recent type Ia supernovae (SNe Ia), more than doubling the sample of reliable SNe Ia having a Cepheid-calibrated distance to a total of 19; these in turn leverage the magnitude-redshift relation based on ∼300 SNe Ia at z < 0.15. All 19 hosts as well as the megamaser system NGC 4258 have been observed with WFC3 in the optical and NIR, thus nullifying cross-instrument zeropoint errors in the relative distance estimates from Cepheids. Other noteworthy improvements include a 33% reduction in the systematic uncertainty in the maser distance to NGC 4258, a larger sample of Cepheids in the Large Magellanic Cloud (LMC), a more robust distance to the LMC based on late-type detached eclipsing binaries (DEBs), HST observations of Cepheids in M31, and new HST -based trigonometric parallaxes for Milky Way (MW) Cepheids. We consider four geometric distance calibrations of Cepheids: (i) megamasers in NGC 4258, (ii) 8 DEBs in the LMC, (iii) 15 MW Cepheids with parallaxes measured with HST /FGS, HST /WFC3 spatial scanning and/or Hipparcos , and (iv) 2 DEBs in M31. The Hubble constant from each is 72.25 ± 2.51, 72.04 ± 2.67, 76.18 ± 2.37, and 74.50 ± 3.27 km s{sup 1} Mpc{sup 1}, respectively. Our best estimate of H {sub 0} = 73.24 ± 1.74 km s{sup 1} Mpc{sup 1} combines the anchors NGC 4258, MW, and LMC, yielding a 2.4% determination (all quoted uncertainties include fully propagated statistical and systematic components). This value is 3.4 σ higher than 66.93 ± 0.62 km s{sup 1} Mpc{sup 1} predicted by ΛCDM with 3 neutrino flavors having a mass of 0.06 eV and the new Planck data, but the discrepancy reduces to 2.1 σ relative to the prediction of 69.3 ± 0.7 km s{sup 1} Mpc{sup 1} based on the

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

    DEFF Research Database (Denmark)

    Sorvajärvi, Tapio; Viljanen, Jan; Toivonen, Juha

    2015-01-01

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

  17. 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...

  18. 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)

  19. 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

  20. How Precisely can we Determine the $\\piNN$ Coupling Constant from the Isovector GMO Sum Rule?

    CERN Document Server

    Loiseau, B; Thomas, A W

    1999-01-01

    The isovector GMO sum rule for zero energy forward pion-nucleon scattering iscritically studied to obtain the charged pion-nucleon coupling constant usingthe precise negatively charged pion-proton and pion-deuteron scattering lengthsdeduced recently from pionic atom experiments. This direct determination leadsto a pseudoscalar charged pion-nucleon coupling constant of 14.23 +- 0.09(statistic) +- 0.17 (systematic). We obtain also accurate values for thepion-nucleon scattering lengths.

  1. 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

  2. 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)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-07-16

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

  4. Geochronological study of the Guanabara Bay (Rio de Janeiro State, Brazil) using 2'10 Pb dating technique and the constant rate of supply model

    International Nuclear Information System (INIS)

    Silva Braganca, Maura Julia Camara da; Oliveira Godoy, Jose Marcos de

    1995-01-01

    A geochronological study of the Guanabara Bay (RJ, Brazil) based on 210 Pb dating technique using the Constant Rate of Supply Model CRS is presented. A low energy gamma spectrometry ( 210 Pb for samples collected from Estrela and Sao Joao de Meriti rivers. Radiochemical method was applied to determine the amount of 210 Pb in samples from Guapimirim, Guaxindiba and Imbuacu rivers. Atomic absorption spectrometry with air-acetylene flame technique was used to determine the amount of copper in all the samples. The CRS model showed adequate in this estuarine system. (author). 19 refs., 5 figs., 6 tabs

  5. 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)

  6. 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

  7. 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.

  8. Manifold adaptation for constant false alarm rate ship detection in South African oceans

    CSIR Research Space (South Africa)

    Schwegmann, CP

    2015-04-01

    Full Text Available prescreening method. It uses a scalar threshold value to determine how bright a pixel needs to be in order to be classified as a ship and thus inversely how many false alarms are permitted. This paper presents by a method of converting the scalar threshold...

  9. Slopes, nearly constant loss, universality, and hopping rates for dispersive ionic conduction

    International Nuclear Information System (INIS)

    Macdonald, J Ross; Ahmad, Mohamad M

    2007-01-01

    The title topics are investigated, discussed, and new insights provided by considering isothermal frequency response data for seven different materials having quite different conductivity spans and involving different electrode polarization effects and temperatures. These data sets were fitted using several different models, including the Kohlrausch-related K0 and K1 ones derived from stretched-exponential response in the temporal domain. The quasi-universal UN model, the K1 with its shape parameter, β 1 , fixed at 1/3, fitted most of the data very well, and its fits of such data were used to compare its predictions for hopping rate with those derived from fitting with the conventional 'universal dynamic response' Almond-West real-part-of-conductivity model. The K1-model theoretical hopping rate, involving the mean waiting time for a hop and derived from microscopic stochastic analysis, was roughly twice as large as the empirical Almond-West rate for most of the materials considered and should be used in place of it. Its use in a generalized Nernst-Einstein equation led to comparison of estimates of the concentration of fully dissociated mobile charge carriers in superionic PbSnF 4 with earlier estimates of Ahmad using an Almond-West hopping rate value. Agreement with an independent structure-derived value was relatively poor. Fitting results obtained using the K0 model, for Na 2 SO 4 data sets for two different polycrystalline material phases, and involving severely limited conductivity variation, were far superior to those obtained using the K1 model. The estimated values of the K0 shape parameter, β 0 , were close to 1/3 for both phases, strongly suggesting that the charge motion was one dimensional for each phase, even though they involved different crystalline structures

  10. Experimental determination of magnetocrystalline anisotropy constants and saturation magnetostriction constants of NiZn and NiZnCo ferrites intended to be used for antennas miniaturization

    Energy Technology Data Exchange (ETDEWEB)

    Mattei, Jean-Luc, E-mail: mattei@univ-brest.fr [Lab-STICC, Université de Bretagne Occidentale, CS 93837, 6 Avenue Le Gorgeu, 29238 Brest Cedex 3 (France); Le Guen, Emmanuel, E-mail: emmanuel.leguen@hotmail.fr [Lab-STICC, Université de Bretagne Occidentale, CS 93837, 6 Avenue Le Gorgeu, 29238 Brest Cedex 3 (France); IETR, Université de Rennes 1, 263 Avenue General Leclerc, 35042 Rennes Cedex (France); Chevalier, Alexis, E-mail: alexis.chevalier@univ-brest.fr [Lab-STICC, Université de Bretagne Occidentale, CS 93837, 6 Avenue Le Gorgeu, 29238 Brest Cedex 3 (France); Tarot, Anne-Claude, E-mail: anne-claude.tarot@univ-rennes1.fr [IETR, Université de Rennes 1, 263 Avenue General Leclerc, 35042 Rennes Cedex (France)

    2015-01-15

    This study investigates the magnetocrystalline anisotropy constants (K{sub 1}) and the saturation magnetostriction constants (λ{sub S}) of Ni{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} (NiZn) and Ni{sub 0.8−x}Zn{sub x}Co{sub 0.2}Fe{sub 1.98}O{sub 4−δ} (NiZnCo) ferrites intended to be used for antenna downsizing. Composite materials constituted of soft ferrite nanosized particles (NiZn or NiZnCo ferrites) embedded in an epoxy matrix are realized. Measurements of their magnetic permeability in the frequency range of 200 MHz–6 GHz are performed. The influence of compressive stress (in the range of 32–96 MPa) on their Ferrimagnetic Resonance (FMR) is demonstrated. An analytical modeling of stress-induced FMR changes is proposed that allows simultaneous determinations of the Natural Ferrimagnetic Resonance (NFMR, F{sub 0}), K{sub 1} and λ{sub S} of Ni{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} and Ni{sub 0.8−x}Zn{sub x}Co{sub 0.2}Fe{sub 1.98}O{sub 4−δ} ferrites. The obtained results for NiZn ferrites are in agreement with literature data, validating both the experimental process and the proposed modeling of the stress-induced FMR changes. Regarding NiZnCo ferrites, extended data on K{sub 1} and λ{sub S} are presented for the first time. Increasing zinc content (x) induces a spin disorder that reduces in a same time K{sub 1} and the magnetization at saturation M{sub S}. The rapid variation of K{sub 1}(x) is related to that of the magnetization M{sub S}(x) through a power law. The single-ion anisotropy model allows a satisfactory interpretation of K{sub 1} dependence on zinc content. The unexpected low values of λ{sub S} got for NiZnCo ferrites, compared to those got for NiZn ferrites, are also discussed. Application of compressive stress lowers noticeably magnetic losses of Ni{sub 0.6}Zn{sub 0.2}Co{sub 0.2}Fe{sub 1.98}O{sub 4−δ} at given frequency, thereby enhancing the ability of this spinel ferrite to be used as a substrate in the aim of antenna

  11. Experimental determination of magnetocrystalline anisotropy constants and saturation magnetostriction constants of NiZn and NiZnCo ferrites intended to be used for antennas miniaturization

    International Nuclear Information System (INIS)

    Mattei, Jean-Luc; Le Guen, Emmanuel; Chevalier, Alexis; Tarot, Anne-Claude

    2015-01-01

    This study investigates the magnetocrystalline anisotropy constants (K 1 ) and the saturation magnetostriction constants (λ S ) of Ni 1−x Zn x Fe 2 O 4 (NiZn) and Ni 0.8−x Zn x Co 0.2 Fe 1.98 O 4−δ (NiZnCo) ferrites intended to be used for antenna downsizing. Composite materials constituted of soft ferrite nanosized particles (NiZn or NiZnCo ferrites) embedded in an epoxy matrix are realized. Measurements of their magnetic permeability in the frequency range of 200 MHz–6 GHz are performed. The influence of compressive stress (in the range of 32–96 MPa) on their Ferrimagnetic Resonance (FMR) is demonstrated. An analytical modeling of stress-induced FMR changes is proposed that allows simultaneous determinations of the Natural Ferrimagnetic Resonance (NFMR, F 0 ), K 1 and λ S of Ni 1−x Zn x Fe 2 O 4 and Ni 0.8−x Zn x Co 0.2 Fe 1.98 O 4−δ ferrites. The obtained results for NiZn ferrites are in agreement with literature data, validating both the experimental process and the proposed modeling of the stress-induced FMR changes. Regarding NiZnCo ferrites, extended data on K 1 and λ S are presented for the first time. Increasing zinc content (x) induces a spin disorder that reduces in a same time K 1 and the magnetization at saturation M S . The rapid variation of K 1 (x) is related to that of the magnetization M S (x) through a power law. The single-ion anisotropy model allows a satisfactory interpretation of K 1 dependence on zinc content. The unexpected low values of λ S got for NiZnCo ferrites, compared to those got for NiZn ferrites, are also discussed. Application of compressive stress lowers noticeably magnetic losses of Ni 0.6 Zn 0.2 Co 0.2 Fe 1.98 O 4−δ at given frequency, thereby enhancing the ability of this spinel ferrite to be used as a substrate in the aim of antenna miniaturization. - Highlights: • We measure permeability of ferrite-based composites from 0.1 GHz to 6 GHz. • The influence of compressive stress on the FMR of

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

    Directory of Open Access Journals (Sweden)

    SLOBODAN K. MILONJIC

    2004-12-01

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

  13. Chromatographic determination of the rate and extent of absorption of air pollutants by sea water

    International Nuclear Information System (INIS)

    Nikolakaki, S.; Vassilakos, C.; Katsanos, N.A.

    1994-01-01

    A simple chromatographic method is developed to determine the rate constant for expulsion of an air pollutant from water or its diffusion parameter in the liquid, the rate constant for chemical reaction of the pollutant with water, its mass transfer coefficient in the liquid, and the partition coefficient between liquid water and air. From these physicochemical parameters, the absorption rate by sea water and, therefore, the depletion rate of a polluting substance from the air can be calculated, together with the equilibrium state of this absorption. The method has been applied to nitrogen dioxide being absorbed by triple-distilled water and by sea water, at various temperatures. From the temperature variation of the reaction rate constant and of the partition coefficient, the activation energy for the reaction and the differential heat of solution were determined. (orig.)

  14. Acidity Constants Determination of Triazine Dye Derivative in the presence of some Surfactants by Multiwavelength Spectrophotometric and Spectrofluorimetric

    Directory of Open Access Journals (Sweden)

    Ali Yeganeh Faal

    2014-03-01

    Full Text Available In this work, acidity constants protonated form of 4.4'-bis astilbene-2,2'-disulfonic-disodium salts (TRIAZ have been determined spectrophotometrically and spectrofluorimetrically at 25◦C and ionic strength of 0.1M KNO3. A program based on MCR-ALS applied for determination of acidity constants. The results show that the peak values of dye are influenced by the presence of anionic, cationic, and nonionic surfactants. The effects of sodium dodecyl sulfate (SDS, Triton X-100 (TX-100 and cetyl trimethyl ammonium bromide (CTAB as a surface-active agent on the acidic and basic forms, and the spectral properties of dye were studied. Also, we determined the critical micelle concentration (CMC for these surfactants by spectrophotometric and spectrofluorimetric triazine dye probes. In addition, by using of evolving factor analysis (EFA and multivariate curve resolution alternative least squares (MCR-ALS methods, acidity constants were acquired.

  15. Simple analytical approximation for rotationally inelastic rate constants based on the energy corrected sudden scaling law

    International Nuclear Information System (INIS)

    Smith, N.; Pritchard, D.E.

    1981-01-01

    We have recently demonstrated that the energy corrected sudden (ECS) scaling law of De Pristo et al. when conbined with the power law assumption for the basis rates k/sub l/→0proportional[l(l+1)]/sup -g/ can accurately fit a wide body of rotational energy transfer data. We develop a simple and accurate approximation to this fitting law, and in addition mathematically show the connection between it and our earlier proposed energy based law which also has been successful in describing both theoretical and experimental data on rotationally inelastic collisions

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

    DEFF Research Database (Denmark)

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

    2016-01-01

    in calculations of Gibbs free energies and reaction rates for the reaction between the OH radical and the DNA nucleobase adenine using Density Functional Theory at the ωB97X-D/6-311++G(2df,2pd) level with the Eckart tunneling correction. The solvent, water, has been included through either the implicit...... polarizable continuum model (PCM) or through explicit modelling of micro-solvation by a single water molecule at the site of reaction as well as the combination of both. Scrutiny of the thermodynamics and kinetics of the individual sub-reactions suggests that the qualitative differences introduced...

  17. Bioaccessibility of metal cations in soil is linearly related to its water exchange rate constant.

    Science.gov (United States)

    Laird, Brian D; Peak, Derek; Siciliano, Steven D

    2011-05-01

    Site-specific risk assessments often incorporate the concepts of bioaccessibility (i.e., contaminant fraction released into gastrointestinal fluids) or bioavailability (i.e., contaminant fraction absorbed into systemic circulation) into the calculation of ingestion exposure. We evaluated total and bioaccessible metal concentrations for 19 soil samples under simulated stomach and duodenal conditions using an in vitro gastrointestinal model. We demonstrated that the median bioaccessibility of 23 metals ranged between exchange rates of metal cations (k(H₂O)) indicated that desorption kinetics may influence if not control metal bioaccessibility.

  18. Diffraction and single-crystal elastic constants of Inconel 625 at room and elevated temperatures determined by neutron diffraction

    International Nuclear Information System (INIS)

    Wang, Zhuqing; Stoica, Alexandru D.; Ma, Dong; Beese, Allison M.

    2016-01-01

    In this work, diffraction and single-crystal elastic constants of Inconel 625 have been determined by means of in situ loading at room and elevated temperatures using time-of-flight neutron diffraction. Theoretical models proposed by Voigt, Reuss, and Kroner were used to determine single-crystal elastic constants from measured diffraction elastic constants, with the Kroner model having the best ability to capture experimental data. The magnitude of single-crystal elastic moduli, computed from single-crystal elastic constants, decreases and the single crystal anisotropy increases as temperature increases, indicating the importance of texture in affecting macroscopic stress at elevated temperatures. The experimental data reported here are of great importance in understanding additive manufacturing of metallic components as: diffraction elastic constants are required for computing residual stresses from residual lattice strains measured using neutron diffraction, which can be used to validate thermomechanical models of additive manufacturing, while single-crystal elastic constants can be used in crystal plasticity modeling, for example, to understand mechanical deformation behavior of additively manufactured components.

  19. Diffraction and single-crystal elastic constants of Inconel 625 at room and elevated temperatures determined by neutron diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhuqing [Department of Materials Science and Engineering, Pennsylvania State University, University Park, PA 16802 (United States); Stoica, Alexandru D. [Chemical and Engineering Materials Division, Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Ma, Dong, E-mail: dongma@ornl.gov [Chemical and Engineering Materials Division, Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Beese, Allison M., E-mail: amb961@psu.edu [Department of Materials Science and Engineering, Pennsylvania State University, University Park, PA 16802 (United States)

    2016-09-30

    In this work, diffraction and single-crystal elastic constants of Inconel 625 have been determined by means of in situ loading at room and elevated temperatures using time-of-flight neutron diffraction. Theoretical models proposed by Voigt, Reuss, and Kroner were used to determine single-crystal elastic constants from measured diffraction elastic constants, with the Kroner model having the best ability to capture experimental data. The magnitude of single-crystal elastic moduli, computed from single-crystal elastic constants, decreases and the single crystal anisotropy increases as temperature increases, indicating the importance of texture in affecting macroscopic stress at elevated temperatures. The experimental data reported here are of great importance in understanding additive manufacturing of metallic components as: diffraction elastic constants are required for computing residual stresses from residual lattice strains measured using neutron diffraction, which can be used to validate thermomechanical models of additive manufacturing, while single-crystal elastic constants can be used in crystal plasticity modeling, for example, to understand mechanical deformation behavior of additively manufactured components.

  20. 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.

  1. Determination of the static spring constant of electrically-driven quartz tuning forks with two freely oscillating prongs

    International Nuclear Information System (INIS)

    González, Laura; Oria, Roger; Botaya, Luis; Puig-Vidal, Manel; Otero, Jorge

    2015-01-01

    Quartz tuning forks have become popular in nanotechnology applications, especially as sensors for scanning probe microscopy. The sensor’s spring constant and the oscillation amplitude are required parameters to evaluate the tip-sample forces; however, there is certain controversy within the research community as to how to arrive at a value for the static spring constant of the device when working in shear mode. Here, we present two different methods based on finite element simulations, to determine the value of the spring constant of the sensors: the amplitude and Cleveland methods. The results obtained using these methods are compared to those using the geometrical method, and show that the latter overestimates the spring constant of the device. (paper)

  2. Analysis of neutron leakage effect in the determination of macrogroup constants

    International Nuclear Information System (INIS)

    Martinez, A.S.; Vieira, H.D.

    1986-01-01

    A method to include the neutron leakage in the macrogroup constants calculation is presented. The method leads to independent equations for neutron flux and neutron current density. The results that have been gotten with the present method are very precise despite its simplicity. (Author) [pt

  3. Determination of the stability constants for cobalt, nickel and palladium homogeneous catalyst complexes containing triphenylphosphine ligands

    NARCIS (Netherlands)

    Djekic, T.; Zivkovic, Z.; van der Ham, Aloysius G.J.; de Haan, A.B.

    2006-01-01

    Homogeneous catalysts are complex compounds that are always in equilibrium with their free metal, free ligand and other forms of complexes. The ratios between different species are defined by the stability constants, which are influenced by different parameters such as the type of metal, ligand,

  4. 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

  5. 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.

  6. Points of Interest: What Determines Interest Rates?

    Science.gov (United States)

    Schilling, Tim

    Interest rates can significantly influence people's behavior. When rates decline, homeowners rush to buy new homes and refinance old mortgages; automobile buyers scramble to buy new cars; the stock market soars, and people tend to feel more optimistic about the future. But even though individuals respond to changes in rates, they may not fully…

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

    International Nuclear Information System (INIS)

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

    1976-01-01

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

  8. Accurate Determination of the Values of Fundamental Physical Constants: The Basis of the New "Quantum" SI Units

    Science.gov (United States)

    Karshenboim, S. G.

    2018-03-01

    The metric system appeared as the system of units designed for macroscopic (laboratory scale) measurements. The progress in accurate determination of the values of quantum constants (such as the Planck constant) in SI units shows that the capabilities in high-precision measurement of microscopic and macroscopic quantities in terms of the same units have increased substantially recently. At the same time, relative microscopic measurements (for example, the comparison of atomic transition frequencies or atomic masses) are often much more accurate than relative measurements of macroscopic quantities. This is the basis for the strategy to define units in microscopic phenomena and then use them on the laboratory scale, which plays a crucial role in practical methodological applications determined by everyday life and technologies. The international CODATA task group on fundamental constants regularly performs an overall analysis of the precision world data (the so-called Adjustment of the Fundamental Constants) and publishes their recommended values. The most recent evaluation was based on the data published by the end of 2014; here, we review the corresponding data and results. The accuracy in determination of the Boltzmann constant has increased, the consistency of the data on determination of the Planck constant has improved; it is these two dimensional constants that will be used in near future as the basis for the new definition of the kelvin and kilogram, respectively. The contradictions in determination of the Rydberg constant and the proton charge radius remain. The accuracy of determination of the fine structure constant and relative atomic weight of the electron has improved. Overall, we give a detailed review of the state of the art in precision determination of the values of fundamental constants. The mathematical procedure of the Adjustment, the new data and results are considered in detail. The limitations due to macroscopic properties of material

  9. Measuring in-stream retention of copper by means of constant-rate additions.

    Science.gov (United States)

    Serra, A; Guasch, H; Martí, E; Geiszinger, A

    2009-06-01

    Human practices entail inputs of nutrients and toxicants such as heavy metals to the fluvial ecosystems. While nutrient dynamics in fluvial ecosystems have been widely studied for over three decades, dynamics of toxicants still remain unclear. In this investigation, the nutrient spiraling concept and associated methodologies to quantify nutrient retention in streams were applied to study copper (Cu) dynamics in streams. The present study aimed to quantify total dissolved Cu retention using a simplified system of indoor channels colonized with fluvial biofilms. Cu retention was studied at sub-toxic concentrations to avoid negative/lethal effects on biota. In addition, Cu retention was compared with retention estimates of a macronutrient, phosphate (PO(4)(3-)), which has been widely studied within the context of the nutrient spiraling concept. The methodology used allowed a successful quantification of Cu and PO(4)(3-) retention. The results showed higher retention efficiency for PO(4)(3-) than for Cu. The biofilm played a key role in retaining both solutes. Although retention efficiency for both solutes was higher in the experiments with colonized substrata compared to uncolonized substrata, we found a positive relationship between uptake rate and chlorophyll-a only for PO(4)(3-). Finally, retention efficiency for both solutes was influenced by water discharge, showing lower retention efficiencies under higher flow conditions. These results suggest that the fate and toxic effects of copper on stream biota may be strongly influenced by the prevailing environmental conditions. Our results indicate that the experimental approach considered can provide new insights into the investigation of retention of toxic compounds in fluvial systems and their controlling mechanisms.

  10. 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.

  11. 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)

  12. Multi-wavelength spectrophotometric determination of acidity constant of some newly synthesized Schiff bases and their QSPR study

    Science.gov (United States)

    Hemmateenejad, Bahram; Emami, Leila; Sharghi, Hashem

    2010-01-01

    The acidity constants of some newly synthesized Schiff base derivatives were determined by hard-model based multivariate data analysis of the spectrophotometric data in the course of pH-metric titration in 50% (v/v) methanol-water binary solvent. The employed data analysis method was also able to extract the pure spectra and pH-dependent concentration profiles of the acid-base species. The molecules that possess different substituents (both electron donating and withdrawing) on the ortho-, meta- and para-positions of one of the phenyl ring showed variable acidity constants ranging from 8.77 to 11.07 whereas the parent molecule had an acidity constant of 10.25. To investigate the quantitative effects of changing of substitution pattern on the acidity constant, a quantitative structure-property relation analysis was conducted using substituent constants and molecular descriptor. Some models with high statistical quality (measured by cross-validation Q2) were obtained. It was found that the acidity constant of the studied molecules in the methanol-water mixed solvent not only is affected by electronic features of the solutes but also by the lipophilic interaction between methanol part of solvent and the deprotonated solutes.

  13. Application of quantitative structure-activity relationship to the determination of binding constant based on fluorescence quenching

    Energy Technology Data Exchange (ETDEWEB)

    Wen Yingying [Department of Applied Chemistry, Yantai University, Yantai 264005 (China); Liu Huitao, E-mail: liuht-ytu@163.co [Department of Applied Chemistry, Yantai University, Yantai 264005 (China); Luan Feng; Gao Yuan [Department of Applied Chemistry, Yantai University, Yantai 264005 (China)

    2011-01-15

    Quantitative structure-activity relationship (QSAR) model was used to predict and explain binding constant (log K) determined by fluorescence quenching. This method allowed us to predict binding constants of a variety of compounds with human serum albumin (HSA) based on their structures alone. Stepwise multiple linear regression (MLR) and nonlinear radial basis function neural network (RBFNN) were performed to build the models. The statistical parameters provided by the MLR model (R{sup 2}=0.8521, RMS=0.2678) indicated satisfactory stability and predictive ability while the RBFNN predictive ability is somewhat superior (R{sup 2}=0.9245, RMS=0.1736). The proposed models were used to predict the binding constants of two bioactive components in traditional Chinese medicines (isoimperatorin and chrysophanol) whose experimental results were obtained in our laboratory and the predicted results were in good agreement with the experimental results. This QSAR approach can contribute to a better understanding of structural factors of the compounds responsible for drug-protein interactions, and can be useful in predicting the binding constants of other compounds. - Research Highlights: QSAR models for binding constants of some compounds to HSA were developed. The models provide a simple and straightforward way to predict binding constant. QSAR can give some insight into structural features related to binding behavior.

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

    Czech Academy of Sciences Publication Activity Database

    Lišková, A.; Křivánková, Ludmila

    2005-01-01

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

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

    Czech Academy of Sciences Publication Activity Database

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

    2015-01-01

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

  16. 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.

  17. The Determinants of Country Risk Ratings

    OpenAIRE

    Jean-Claude Cosset; Jean Roy

    1991-01-01

    The purpose of this paper is to replicate Euromoney's and Institutional Investor's country risk ratings on the basis of economic and political variables. The evidence reveals that country risk ratings respond to some of the variables suggested by the theory. In particular, both the level of per capita income and propensity to invest affect positively the rating of a country. In addition, high-ranking countries are less indebted than low-ranking countries. It also appears that the ability of t...

  18. 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.

  19. Determination of association constants between steroid compounds and albumins by partial-filling ACE.

    Science.gov (United States)

    Amundsen, Lotta K; Sirén, Heli

    2007-10-01

    ACE is a popular technique for evaluating association constants between drugs and proteins. However, ACE has not previously been applied to study the association between electrically neutral biomolecules and plasma proteins. We studied the affinity between human and bovine serum albumins (HSA and BSA, respectively) and three neutral endogenous steroid hormones (testosterone, epitestosterone and androstenedione) and two synthetic analogues (methyltestosterone and fluoxymesterone) by applying the partial-filling technique in ACE (PF-ACE). From the endocrinological point of view, the distribution of endogenous steroids among plasma components is of great interest. Strong interactions with albumins suppress the biological activity of steroids. Notable differences in the association constants were observed. In the case of the endogenous steroids, the interactions between testosterone and the albumins were strongest, and those between androstenedione and the albumins were substantially weaker. The association constants, K(b), for testosterone, epitestosterone and androstenedione and HSA at 37 degrees C were 32 100 +/- 3600, 21 600 +/- 1500 and 13 300 +/- 1300 M(-1), respectively, while the corresponding values for the steroids and BSA were 18 800 +/- 1500, 14 000 +/- 400 and 7800 +/- 900 M(-1). Methyltestosterone was bound even more strongly than testosterone, while fluoxymesterone was only weakly bound by the albumins. Finally, the steroids were separated by PF-ACE with HSA and BSA used as resolving components.

  20. Hydrogen Balmer series measurements and determination of Rydberg's constant using two different spectrometers

    International Nuclear Information System (INIS)

    Amrani, D

    2014-01-01

    This paper investigates the use of two different methods, the optical and the computer-aided diffraction-grating spectrometer, to measure the wavelength of visible lines of Balmer series from the hydrogen atomic spectrum and estimate the value of Rydberg's constant. Analysis and interpretation of data showed that both methods, despite their difference in terms of the type of equipment used, displayed good performance in terms of precision of measurements of wavelengths of spectral lines. A comparison was carried out between the experimental value of Rydberg's constant obtained with both methods and the accepted value. The results of Rydberg's constant obtained with both the optical and computer-aided spectrometers were 1.099 28 × 10 −7  m −1  and 1.095 13 × 10 −7  m −1  with an error difference of 0.17% and 0.20% compared to the accepted value 1.097 373 × 10 −7  m −1 , respectively. (paper)

  1. Heat release determination in a constant volume combustion chamber from the instantaneous cylinder pressure

    International Nuclear Information System (INIS)

    Lapuerta, Magín; Sanz-Argent, Josep; Raine, Robert

    2014-01-01

    A diagnostic method has been developed to interpret the results of basic combustion studies with diesel-like fuels performed in a constant volume reactor originally conceived for cetane number measurements. The main target of the method is to calculate the instantaneous heat release over time from the chamber pressure experimental signal. The method incorporates filtering of the raw data to eliminate the oscillations recorded as a consequence of the location of the pressure sensor. It considers homogeneity of the gaseous mixture (single zone model) and change in its composition due to the combustion process. A semi-empirical heat transfer model was also proposed and its coefficients were fitted from experimental results obtained in the constant volume chamber using diesel fuel. -- Highlights: • A diagnostic model for constant volume reactors has been developed and tested. • Updating the gas composition after combustion improves accuracy of the method. • Heat transfer coefficients are used for the fulfillment of boundary conditions. • The model provides a deeper insight than the apparent heat release analysis

  2. The D(+) + H2 reaction: differential and integral cross sections at low energy and rate constants at low temperature.

    Science.gov (United States)

    González-Lezana, Tomás; Scribano, Yohann; Honvault, Pascal

    2014-08-21

    The D(+) + H2 reaction is investigated by means of a time independent quantum mechanical (TIQM) and statistical quantum mechanical (SQM) methods. Differential cross sections and product rotational distributions obtained with these two theoretical approaches for collision energies between 1 meV and 0.1 eV are compared to analyze the dynamics of the process. The agreement observed between the TIQM differential cross sections and the SQM predictions as the energy increases revealed the role played by the complex-forming mechanism. The importance of a good description of the asymptotic regions is also investigated by calculating rate constants for the title reaction at low temperature.

  3. 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

  4. 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.

  5. 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)

  6. On the determination of the vertex constants and asymptotic normalization coefficients

    International Nuclear Information System (INIS)

    Blokhintsev, L.D.; Yeremenko, V.O.

    2006-01-01

    Full text: The nuclear vertex constant (VC) G abc is the on-shell matrix element of the virtual decay (or synthesis) of a composite system into fragments b and c: a↔ b+c. It is proportional to the asymptotic normalization coefficient (ANC) of the wave function of the system a in the b+c channel. VC's and ANC's are important nuclear characteristics. They determine the cross sections of low-energy nuclear reactions with charged particles, in particular, of the peripheral astrophysical nuclear reactions [1]. There are different methods to obtain information on the values of VC's and ANC's, either from the analysis of experimental data or by calculating them using approaches of nuclear structure theory. Some of these methods are described in the review article [2]. In the given work, the new method of determining VC's is suggested, which makes use both of the experimental information and of the analytical properties of the scattering amplitudes. We consider two integrals over k of the partial wave amplitude f l (k) of the elastic b+c scattering in the complex k plane, k being the relative momentum of b and c. In the first integral (I 1 ) f l (k) is integrated along the real k axis where its values could be in principle taken from the phase-shift analysis of the corresponding data. The integration path of the second integral (I 2 ) is chosen along the dynamical cut of f l (k), which is situated on the positive imaginary k semi-axis. The integrand of I 2 is the discontinuity of f l (k)on this cut. Its explicit form follows from the analytical properties of f l (k). If there exists the bound state a with the angular momentum l in the b+c system, then, according to the Cauchy theorem, the sum I 1 +I 2 is equal to 2πi res f 1 (k), where res f 1 (k) is the residue of f l (k) at the pole corresponding to the binding energy of a in the b+c channel. This residue is expressed directly in terms of the sought-for VC G abc [2]. The integration limits of I 1 and I 2 are infinite

  7. Optimal determination of the elastic constants of woven 2D SiC/SiC composite materials

    International Nuclear Information System (INIS)

    Mouchtachi, A; Guerjouma, R El; Baboux, J C; Rouby, D; Bouami, D

    2004-01-01

    For homogeneous materials, the ultrasonic immersion method, associated with a numerical optimization process mostly based on Newton's algorithm, allows the determination of elastic constants for various synthetic and natural composite materials. Nevertheless, a principal limitation of the existing optimization procedure occurs when the considered material is at the limit of the homogeneous hypothesis. Such is the case of the woven bidirectional SiC matrix and SiC fibre composite material. In this study, we have developed two numerical methods for the determination of the elastic constants of the 2D SiC/SiC composite material (2D SiC/SiC). The first one is based on Newton's algorithm: the elastic constants are obtained by minimizing the square deviation between experimental and calculated velocities. The second method is based on the Levenberg-Marquardt algorithm. We show that these algorithms give the same results in the case of homogeneous anisotropic composite materials. For the 2D SiC/SiC composite material, the two methods, using the same measured velocities, give different sets of elastic constants. We then note that the Levenberg-Marquardt algorithm enables a better convergence towards a global set of elastic constants in good agreement with the elastic properties, which can be measured using classical quasi-static methods

  8. Determining a Solubility Product Constant by Potentiometric Titration to Increase Students' Conceptual Understanding of Potentiometry and Titrations

    Science.gov (United States)

    Grabowski, Lauren E.; Goode, Scott R.

    2017-01-01

    Potentiometric titrations are widely taught in first-year undergraduate courses to connect electrochemistry, stoichiometry, and equilibria and to reinforce acid-base titrations. Students perform a potentiometric titration that is then analyzed to determine analyte concentrations and the solubility product constant of the solid species.

  9. Determination of the ratio of axial-vector-to-vector weak coupling constants for beta decay of triton

    CERN Document Server

    Akulov, Y A

    2002-01-01

    Data on the chemical shifts of half-lives for atomic and molecular tritium were used to determine the ratio of axial-vector-to-vector weak coupling constants for beta decay of triton (G sub A /G sub V) sub t = -1.2646 +- 0.0035

  10. 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.

  11. 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

  12. Two-dimensional analytical solutions for chemical transport in aquifers. Part 1. Simplified solutions for sources with constant concentration. Part 2. Exact solutions for sources with constant flux rate

    International Nuclear Information System (INIS)

    Shan, C.; Javandel, I.

    1996-05-01

    Analytical solutions are developed for modeling solute transport in a vertical section of a homogeneous aquifer. Part 1 of the series presents a simplified analytical solution for cases in which a constant-concentration source is located at the top (or the bottom) of the aquifer. The following transport mechanisms have been considered: advection (in the horizontal direction), transverse dispersion (in the vertical direction), adsorption, and biodegradation. In the simplified solution, however, longitudinal dispersion is assumed to be relatively insignificant with respect to advection, and has been neglected. Example calculations are given to show the movement of the contamination front, the development of concentration profiles, the mass transfer rate, and an application to determine the vertical dispersivity. The analytical solution developed in this study can be a useful tool in designing an appropriate monitoring system and an effective groundwater remediation method

  13. 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.

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

    Science.gov (United States)

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

    2010-10-15

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

  15. 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.

  16. Determination of stability constants of iron(III and chromium(III-nitrilotriacetate-methyl cysteine mixed complexes by electrophoretic technique

    Directory of Open Access Journals (Sweden)

    Brij Bhushan Tewari

    2004-06-01

    Full Text Available The stability constants of Fe(III and Cr(III with methyl cysteine and nitrilotriacetate (NTA were determined by paper electrophoretic technique. Beside binary ternary complexes have also been studied, in which nitrilotriacetate and methyl cysteine acts as primary and secondary ligand, respectively. The stability constants of mixed ligand complexes metal (M-nitrilotriacetate-methyl cysteine have been found to be 5.72 plus or minus 0.09 and 5.54 plus or minus 0.11 (log K values for Fe(III and Cr(III complexes, respectively, at 35 oC and ionic strength 0.1 M.

  17. Determination of temperature dependence of full matrix material constants of PZT-8 piezoceramics using only one sample.

    Science.gov (United States)

    Zhang, Yang; Tang, Liguo; Tian, Hua; Wang, Jiyang; Cao, Wenwu; Zhang, Zhongwu

    2017-08-15

    Resonant ultrasound spectroscopy (RUS) was used to determine the temperature dependence of full matrix material constants of PZT-8 piezoceramics from room temperature to 100 °C. Property variations from sample to samples can be eliminated by using only one sample, so that data self-consistency can be guaranteed. The RUS measurement system error was estimated to be lower than 2.35%. The obtained full matrix material constants at different temperatures all have excellent self-consistency, which can help accurately predict device performance at high temperatures using finite element simulations.

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

    Czech Academy of Sciences Publication Activity Database

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

    2008-01-01

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

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

    Science.gov (United States)

    Bonham, Russell A.

    1998-05-01

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

  20. The possibility to determine a constant of spin-orbit interaction by scanning tunneling microscopy method

    International Nuclear Information System (INIS)

    Khotkevich, N.V.; Kolesnichenko, Yu.A.; Vovk, N.P.

    2016-01-01

    The electron tunneling from the quasi-two-dimensional (surface) states with the spin-orbit interaction into bulk-mode states is studied in the framework of a model of an infinitely thin inhomogeneous tunnel magnetic barrier. The influence of the scattering of quasi-two-dimensional electrons by a single magnetic defect on the tunnel current is analyzed. Analytic formulas for the conductance of a tunnel point-contact as a function of its distance from the defect are obtained. It is shown that the analysis of the local magnetization density around the defect by means of spin-polarized scanning tunneling microscopy allows finding the constant of spin orbit interaction.

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

    Science.gov (United States)

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

    2013-12-03

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

  2. Line-focus acoustic microscopy of Ti-6242 α/β single colony: determination of elastic constants

    International Nuclear Information System (INIS)

    Kim, J.-Y.; Yakovlev, V.; Rokhlin, S.I.

    2002-01-01

    Time-resolved line-focus acoustic microscopy is performed for determining elastic constants of Ti-6242 α/β-single colony and Ti-6 α-phase single crystal. Surface acoustic wave (SAW) velocities are obtained as a function of the propagation angle from measured time-delays of SAW signals. The propagation of surface waves in a semi-infinite half space formed by anisotropic layers inclined arbitrarily to the sample surface is studied to model a quasi-random lamellar structure of the Ti-6242 α/β-single colony. Effective elastic constants of the multilayered structure are derived and verified through the comparison with exact ones, based on which SAW velocities in non-principal planes are calculated. Effective and constituent elastic constants of the α/β-single colony and the α-phase single crystal are inversely determined from the measured and calculated SAW velocities. The α- and β-phase elastic constants from the α/β-single colony so determined are compared with those from the α-single crystal and data in the literature

  3. 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).

  4. How precisely can the difference method determine the $\\pi$NN coupling constant?

    CERN Document Server

    Loiseau, B

    2000-01-01

    The Coulomb-like backward peak of the neutron-proton scattering differentialcross section is due to one-pion exchange. Extrapolation to the pion pole ofprecise data should allow to obtain the value of the charged pion-nucleoncoupling constant. This was classically attempted by the use of a smoothphysical function, the Chew function, built from the cross section. To improveaccuracy of such an extrapolation one has introduced a difference method. Itconsists of extrapolating the difference between the Chew function based onexperimental data and that built from a model where the pion-nucleon couplingis exactly known. Here we cross-check to which precision can work this novelextrapolation method by applying it to differences between models and betweendata and models. With good reference models and for the 162 MeV neutron-protonUppsala single energy precise data with a normalisation error of 2.3 , thevalue of the charged pion-nucleon coupling constant is obtained with anaccuracy close to 1.8

  5. Standard Glbbs Energy of Formation of the Hydroxyl Radical in Aqueous Solution. Rate Constants for the Reaction C102- -t O3 S 03- -t CIO,

    DEFF Research Database (Denmark)

    Klaning, U. K.; Sehested, Knud; Holcman, J.

    1985-01-01

    The rate constants of the following reactions were determined by pulse radiolysis and stopped-flow experiments: C102- + O3 + C102 + 03-(k f= (4 f 1) X lo6 dm3 mol-' s-', k, = (1.8 f 0.2) X lo5 dm3 mol-' s-]); C102 + OH - C103- + H+ (k = (4.0 * 0.4) X lo9 dm3 mol-' s-l); C102 + 0- - C103- (k = (2.......7 * 0.4) X lo9 dm3 mol-' s-l); and O3 + C102 - C103 + O2 (k = (1.05 f 0.10) X lo3 dm3 mol-l s-'), where kf is the forward rate of reaction and k, is the reverse rate of reaction. The standard Gibbs energy of formation of OH in aqueous solution A&O,,(OH) and the corresponding standard oxidation potential...

  6. 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.

  7. 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.

  8. MONETARY MODELS AND EXCHANGE RATE DETERMINATION ...

    African Journals Online (AJOL)

    Power Party [PPP] based on the law of one price asserts that the change in the exchange rate between .... exchange in international economic transactions has made it vitally evident that the management of ... One lesson from this episode is to ...

  9. Pulsed neutron determination of anisotropic diffusion constants in multi-layered slabs

    International Nuclear Information System (INIS)

    Sri Ram, K.

    1978-01-01

    Anisotropic neutron diffusion parameters for graphite and plexiglas slab assemblies were calculated using one-dimensional discrete ordinates code ANISN, and also Case's eigenfunction expansion technique as suggested by Leonard. These calculated values were checked with the pulsed neutron experimental results as well as simple diffusion theory calculations of Spinrad. Relatively little experimental work has been done with heterogeneous assemblies which do not contain voids. The present comparison shows that the experimental results agree well with transport theory calculations. It appears from the results and inter-comparison of this work in simple geometries, that the pulsed neutron method can yield accurate experimental anisotropic diffusion constants, and can therefore be applied to more complicated geometries which may be difficult to calculate. (author)

  10. Precision determination of the $\\pi N$ scattering lengths and the charged $\\pi NN$ coupling constant

    CERN Document Server

    Ericson, Torleif Eric Oskar; Thomas, A W

    2000-01-01

    We critically evaluate the isovector GMO sumrule for the charged $\\pi N N$ coupling constant using recent precision data from $\\pi ^-$p and $\\pi^-$d atoms and with careful attention to systematic errors. From the $\\pi ^-$d scattering length we deduce the pion-proton scattering lengths ${1/2}(a_{\\pi ^-p}+a_{\\pi ^-n})=(-20\\pm 6$(statistic)$ \\pm 10$ (systematic))~$\\cdot 10^{-4}m_{\\pi_c}^{-1}$ and ${1/2}(a_{\\pi ^-p}-a_{\\pi ^-n})=(903 \\pm 14)\\cdot 10^{-4}m_{\\pi_c}^{-1}$. From this a direct evaluation gives $g^2_c(GMO) =14.20\\pm 0.07$(statistic)$\\pm 0.13$(systematic) or $f^2_c= 0.0786\\pm 0.0008$.

  11. Enzymatic spectrophotometric reaction rate determination of aspartame

    Directory of Open Access Journals (Sweden)

    Trifković Kata T.

    2015-01-01

    Full Text Available Aspartame is an artificial sweetener of low caloric value (approximately 200 times sweeter than sucrose. Aspartame is currently permitted for use in food and beverage production in more than 90 countries. The application of aspartame in food products requires development of rapid, inexpensive and accurate method for its determination. The new assay for determination of aspartame was based on set of reactions that are catalyzed by three different enzymes: α-chymotrypsin, alcohol oxidase and horseradish peroxidase. Optimization of the proposed method was carried out for: (i α-chymotrypsin activity; (ii time allowed for α-chymotrypsin action, (iii temperature. Evaluation of the developed method was done by determining aspartame content in “diet” drinks, as well as in artificial sweetener pills. [Projekat Ministarstva nauke Republike Srbije, br. III46010

  12. Probing the probe: AFM tip-profiling via nanotemplates to determine Hamaker constants from phase–distance curves

    International Nuclear Information System (INIS)

    Rodriguez, Raul D.; Lacaze, Emmanuelle; Jupille, Jacques

    2012-01-01

    A method to determine the van der Waals forces from phase–distance curves recorded by atomic force microscopy (AFM) in tapping mode is presented. The relationship between the phase shift and the tip–sample distance is expressed as a function of the product of the Hamaker constant by tip radius. Silica-covered silicon tips are used to probe silica-covered silicon substrate in dry conditions to avoid capillary effects. Tips being assumed spherical, radii are determined in situ by averaging profiles recorded in different directions on hematite nanocrystals acting as nanotemplates, thus accounting for tip anisotropy. Through a series of reproducible measurements performed with tips of various radii (including the in-situ characterization of a damaged tip), a value of (6.3±0.4)×10 −20 J is found for the Hamaker constant of interacting silica surfaces in air, in good agreement with tabulated data. The results demonstrate that the onset of the tip–surface interaction is dominated by the van der Waals forces and that the total force can be modeled in the framework of the harmonic approximation. Based on the tip radius and the Hamaker constant associated to the tip–substrate system, the model is quite flexible. Once the Hamaker constant is known, a direct estimate of the tip size can be achieved whereas when the tip size is known, a quantitative evaluation of the van der Waals force becomes possible on different substrates with a spatial resolution at the nanoscale. -- Highlights: ► Van der Waal forces in tapping mode atomic force microscopy. ► Harmonic approximation model of phase–distance curves probed by simulations. ► Silica tips and surfaces as a model case. ► Tip geometry determined in situ by nanoparticles as nanotemplates. ► Method to derive the Hamaker constant for any tip/surface system.

  13. Experimental determination of the spin-rotation coupling constant in the Cs129Xe and K129Xe molecules

    International Nuclear Information System (INIS)

    Wu, Z.; Happer, W.

    1984-01-01

    Since alkali-noble gas van der Waals molecules are involved in the spin transfer process, the physics can be naturally divided into two parts. One of them is to study the formation and break-up rates of the molecules, the chemical equilibrium constant, etc. The other aspect of this problem is to study how the individual angular momenta evolve during the lifetime of the molecule. The experiments described address the second aspect

  14. 7 CFR 1714.5 - Determination of interest rates on municipal rate loans.

    Science.gov (United States)

    2010-01-01

    ... 7 Agriculture 11 2010-01-01 2010-01-01 false Determination of interest rates on municipal rate... General § 1714.5 Determination of interest rates on municipal rate loans. (a) RUS will post on the RUS website, Electric Program HomePage, a schedule of interest rates for municipal rate loans at the beginning...

  15. Calculated Third Order Rate Constants for Interpreting the Mechanisms of Hydrolyses of Chloroformates, Carboxylic Acid Halides, Sulfonyl Chlorides and Phosphorochloridates

    Directory of Open Access Journals (Sweden)

    T. William Bentley

    2015-05-01

    Full Text Available Hydrolyses of acid derivatives (e.g., carboxylic acid chlorides and fluorides, fluoro- and chloroformates, sulfonyl chlorides, phosphorochloridates, anhydrides exhibit pseudo-first order kinetics. Reaction mechanisms vary from those involving a cationic intermediate (SN1 to concerted SN2 processes, and further to third order reactions, in which one solvent molecule acts as the attacking nucleophile and a second molecule acts as a general base catalyst. A unified framework is discussed, in which there are two reaction channels—an SN1-SN2 spectrum and an SN2-SN3 spectrum. Third order rate constants (k3 are calculated for solvolytic reactions in a wide range of compositions of acetone-water mixtures, and are shown to be either approximately constant or correlated with the Grunwald-Winstein Y parameter. These data and kinetic solvent isotope effects, provide the experimental evidence for the SN2-SN3 spectrum (e.g., for chloro- and fluoroformates, chloroacetyl chloride, p-nitrobenzoyl p-toluenesulfonate, sulfonyl chlorides. Deviations from linearity lead to U- or V-shaped plots, which assist in the identification of the point at which the reaction channel changes from SN2-SN3 to SN1-SN2 (e.g., for benzoyl chloride.

  16. 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.

  17. 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.

  18. Loss of incoherence and determination of coupling constants in quantum gravity

    International Nuclear Information System (INIS)

    Giddings, S.B.; Strominger, A.

    1988-01-01

    The wave function of an interacting 'family' of one large 'parent' and many Planck-sized 'baby' universes is computed in a semiclassical approximation using an adaptation of Hartle-Hawking initial conditions. A recently discovered gravitational instanton which exists for general relativity coupled to axions is employed. The outcome of a single experiment in the parent universe is in general described by a mixed state, even if the initial state is pure. However, a sequence of measurements rapidly collapses the wave function of the family of universes into one of an infinite number of 'coherent' states for which quantum incoherence is not observed in the parent universe. This provides a concrete illustration of an unexpected phenomena whose existence has been argued for on quite general grounds by Coleman: Quantum incoherence due to information loss to baby universes is not experimentally observable. We further argue that all coupling constants governing dynamics in the parent universe depend on the parameters describing the particular coherent state into which the family wave function collapses. In particular, generically terms that violate any global symmetries will be induced in the effective action for the parent universe. These last results have much broader applicability than our specific model. (orig.)

  19. Supersymmetry breaking and determination of the unification gauge coupling constant in string theories

    International Nuclear Information System (INIS)

    Carlos, B. de; Casas, J.A.; Munoz, C.

    1993-01-01

    We study in a systematic and modular invariant way gaugino condensation in the hidden sector as a potential source of hierarchical supersymmetry breaking and a non-trivial potential for the dilaton S whose real part corresponds to the tree-level gauge coupling constant (Re S∝g gut -2 ). For the case of pure Yang-Mills condensation, we show that no realistic results (in particular no reasonable values for Re S) can emerge, even if the hidden gauge group is not simple. However, in the presence of hidden matter (i.e. the most frequent case) there arises a very interesting class of scenarios with two or more hidden condensing groups for which the dilaton dynamically acquires a reasonable value (Re S∝2) and supersymmetry is broken at the correct scale (m 3/2 ∝10 3 GeV) with no need of fine-tuning. Actually, good values for Re S and m 3/2 are correlated. We make an exhaustive classification of the working possibilities. Remarkably, the results are basically independent from the value of δ GS (the contributions from the Green-Schwarz mechanism). The radius of the compactified space also acquires an expectation value, breaking duality spontaneously. (orig.)

  20. The effect of surfaces on AGR coolant chemistry: critical assessment of gas-phase rate constants relevant to ethane pyrolysis

    International Nuclear Information System (INIS)

    Gonzales, M.D.U.; Norfolk, D.J.

    1988-02-01

    Previous work has shown the ability of a chemical kinetic model, applied using the FACSIMILE computer code, to predict the thermal decomposition of ethane in a silica flow reactor. To optimise the performance of the model, the present report reviews the literature data on the twenty reactions which it incorporates. Critical assessment has shown some discrepancies in the previously used rate constants, especially those leading to ethyne formation. Table 2 of the report gives the kinetic data which, as a result of the present evaluation, are recommended for future work. Use of these data gives significantly improved agreement between the model and the experimental results, particularly for ethyne formation, which had previously been underestimated. (author)

  1. Determination of Conditional Stability Constants for Metal Ions with Humic Acid using Chemically Immobilised Humic Acid on Silica Gel

    Energy Technology Data Exchange (ETDEWEB)

    Szabo, G.; Guszi, J. [Frederic Joliot-Curie' National Research Inst. for Rad iobiology and Radiohygiene, Budapest, H-1775 (Hungary)]. e-mail: szabogy@hp.osski.hu; Miyajima, T. [Dept. of Chemistry, Faculty of Science and Engineering, Saga Univ ., 1-Honjo, Saga (Japan); Geckeis, H. [Forschungszentrum Karlsruhe, Inst. fuer Nuk leare Entsorgung, 76021 Karlsruhe (Germany); Reiller, P. [Commissariat a l' Energie A tomique, CE Saclay, Laboratoire de Speciation des Radionucleides et des Molecule s, F-91191 Gif-sur-Yvette (France); Bulman, R.A. [Radiation Protection Div., Health Protection Agency, Chilton, Didcot (United Kingdom)

    2007-06-15

    Limitations on aqueous solution chemistries of humic acid, and also hydrolysis of some cationic species, restrict measurement of conditional stability constants of 4f- and 5f-series elements as humate complexes. Reported log {beta} values are determined by using non-linear regression binding isotherms, of Am(III) and Th(IV), and also Ag(I) and Sr(II), bound by a humic acid composite.

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

    International Nuclear Information System (INIS)

    Wiesehahn, G.; Hearst, J.E.

    1978-01-01

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

  3. 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.

  4. 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.

  5. 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.

  6. 5 CFR 304.104 - Determining rate of pay.

    Science.gov (United States)

    2010-01-01

    ... 5 Administrative Personnel 1 2010-01-01 2010-01-01 false Determining rate of pay. 304.104 Section... CONSULTANT APPOINTMENTS § 304.104 Determining rate of pay. (a) The rate of basic pay for experts and... appropriate rate of basic pay on an hourly or daily basis, subject to the limitations described in section 304...

  7. Determination of formation constants of hydroxo carbonate complexes of Pr3+ in 2M NaCl at 303 K

    International Nuclear Information System (INIS)

    Lopez G, H.D.

    1996-01-01

    The hydrolysis of Praseodymium III in 2M sodium chloride at 303 K was studied. Two methods were used: pH titration followed by a computational refinement and solvent extraction in the presence of a competitive ligand. The hydrolysis constants obtained by pH titration were: log β 1,H = -7.68 ± 0.07, log β 1,2H = -15.10 ± 0.03, and β 1,3H -23.8 ± 0.04. The stability constants of Praseodymium carbonates were determined by pH titration as well and were: log β 1,CO3 2- = 5.94 ± 0.08 and log β 1,2CO3 2- = 11.15 ± 0.15. Praseodymium carbonate species were taken into consideration for calculating the first hydrolysis constants by the solvent extraction method and the value obtained was: log β 1,H = -7.69 ± 0.27. The values for log β 1,H attained by both methods are the same. The species-distribution diagram was obtained from the stability constants of Praseodymium carbonates and hydrolysis products in the conditions of the present work. (Author)

  8. 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.

  9. Effects of a constant rate infusion of detomidine on cardiovascular function, isoflurane requirements and recovery quality in horses.

    Science.gov (United States)

    Schauvliege, Stijn; Marcilla, Miguel Gozalo; Verryken, Kirsten; Duchateau, Luc; Devisscher, Lindsey; Gasthuys, Frank

    2011-11-01

    To examine the influence of a detomidine constant rate infusion (CRI) on cardiovascular function, isoflurane requirements and recovery quality in horses undergoing elective surgery. Prospective, randomized, blinded, clinical trial. Twenty adult healthy horses. After sedation (detomidine, 10 μg kg(-1) intravenously [IV]) and induction of anaesthesia (midazolam 0.06 mg kg(-1) , ketamine 2.2 mg kg(-1) IV), anaesthesia was maintained with isoflurane in oxygen/air (inspiratory oxygen fraction 55%). When indicated, the lungs were mechanically ventilated. Dobutamine was administered when MAPdetomidine (5 μg kg(-1)  hour(-1) ) (D) or saline (S) CRI, with the anaesthetist unaware of the treatment. Monitoring included end-tidal isoflurane concentration, arterial pH, PaCO(2) , PaO(2) , dobutamine administration rate, heart rate (HR), arterial pressure, cardiac index (CI), systemic vascular resistance (SVR), stroke index and oxygen delivery index (ḊO(2) I). For recovery from anaesthesia, all horses received 2.5 μg kg(-1) detomidine IV. Recovery quality and duration were recorded in each horse. For statistical analysis, anova, Pearson chi-square and Wilcoxon rank sum tests were used as relevant. Heart rate (p=0.0176) and ḊO(2) I (p= 0.0084) were lower and SVR higher (p=0.0126) in group D, compared to group S. Heart rate (p=0.0011) and pH (p=0.0187) increased over time. Significant differences in isoflurane requirements were not detected. Recovery quality and duration were comparable between treatments. A detomidine CRI produced cardiovascular effects typical for α(2) -agonists, without affecting isoflurane requirements, recovery duration or recovery quality. © 2011 The Authors. Veterinary Anaesthesia and Analgesia. © 2011 Association of Veterinary Anaesthetists and the American College of Veterinary Anesthesiologists.

  10. DETERMINING STAR FORMATION RATES FOR INFRARED GALAXIES

    International Nuclear Information System (INIS)

    Rieke, G. H.; Weiner, B. J.; Perez-Gonzalez, P. G.; Donley, J. L.; Alonso-Herrero, A.; Blaylock, M.; Marcillac, D.

    2009-01-01

    We show that measures of star formation rates (SFRs) for infrared galaxies using either single-band 24 μm or extinction-corrected Paα luminosities are consistent in the total infrared luminosity = L(TIR) ∼ 10 10 L sun range. MIPS 24 μm photometry can yield SFRs accurately from this luminosity upward: SFR(M sun yr -1 ) = 7.8 x 10 -10 L(24 μm, L sun ) from L(TIR) = 5x 10 9 L sun to 10 11 L sun and SFR = 7.8 x 10 -10 L(24 μm, L sun )(7.76 x 10 -11 L(24)) 0.048 for higher L(TIR). For galaxies with L(TIR) ≥ 10 10 L sun , these new expressions should provide SFRs to within 0.2 dex. For L(TIR) ≥ 10 11 L sun , we find that the SFR of infrared galaxies is significantly underestimated using extinction-corrected Paα (and presumably using any other optical or near-infrared recombination lines). As a part of this work, we constructed spectral energy distribution templates for eleven luminous and ultraluminous purely star forming infrared galaxies and over the spectral range 0.4 μm to 30 cm. We use these templates and the SINGS data to construct average templates from 5 μm to 30 cm for infrared galaxies with L(TIR) = 5x 10 9 to 10 13 L sun . All of these templates are made available online.

  11. 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

  12. 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

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

    Science.gov (United States)

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

    2017-12-01

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

  14. 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

  15. Optimizing the solar photo-Fenton process in the treatment of contaminated water. Determination of intrinsic kinetic constants for scale-up

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez, Miguel [Universidad de Los Andes, Escuela Basica de Ingenieria, La Hechicera, Merida (Venezuela); Malato, Sixto [Plataforma Solar de Almeria, Tabernas (PSA) (Spain); Pulgarin, Cesar [Institute of Environmental Engineering, Laboratory for Environmental Biotechnology, Swiss Federal Institute of Technology (EPFL), CH-1015 Lausanne (Switzerland); Contreras, Sandra; Curco, David; Gimenez, Jaime; Esplugas, Santiago [Department d' Enginyeria Quimica i Metallurgia, Universitat de Barcelona, Marti i Franques 1, 08028 Barcelona (Spain)

    2005-10-01

    The elimination of aromatic compounds present in surface water by photo-Fenton with sunlight as the source of radiation was studied. The concentrations of Fe{sup 3+} and H{sub 2}O{sub 2} are key factors for this process. A solar simulator and a prototype parabolic collector were used as laboratory-scale reactors to find the parameters of those key factors to be used in the CPC (compound parabolic collector) pilot plant reactor. The initial mineralization rate constant (k{sub obs}) was determined and evaluated at different Fe{sup 3+} and H{sub 2}O{sub 2} concentrations to find the best values for maximum efficiency. In all the experiments the mineralization of an aqueous phenol solution was described by assuming a pseudo-first-order reaction. The intrinsic kinetic constants not dependent on the lighting conditions were also estimated for scale-up. (author)

  16. Evaporation Kinetics of Polyol Droplets: Determination of Evaporation Coefficients and Diffusion Constants

    Science.gov (United States)

    Su, Yong-Yang; Marsh, Aleksandra; Haddrell, Allen E.; Li, Zhi-Ming; Reid, Jonathan P.

    2017-11-01

    In order to quantify the kinetics of mass transfer between the gas and condensed phases in aerosol, physicochemical properties of the gas and condensed phases and kinetic parameters (mass/thermal accommodation coefficients) are crucial for estimating mass fluxes over a wide size range from the free molecule to continuum regimes. In this study, we report measurements of the evaporation kinetics of droplets of 1-butanol, ethylene glycol (EG), diethylene glycol (DEG), and glycerol under well-controlled conditions (gas flow rates and temperature) using the previously developed cylindrical electrode electrodynamic balance technique. Measurements are compared with a model that captures the heat and mass transfer occurring at the evaporating droplet surface. The aim of these measurements is to clarify the discrepancy in the reported values of mass accommodation coefficient (αM, equals to evaporation coefficient based on microscopic reversibility) for 1-butanol, EG, and DEG and improve the accuracy of the value of the diffusion coefficient for glycerol in gaseous nitrogen. The uncertainties in the thermophysical and experimental parameters are carefully assessed, the literature values of the vapor pressures of these components are evaluated, and the plausible ranges of the evaporation coefficients for 1-butanol, EG, and DEG as well as uncertainty in diffusion coefficient for glycerol are reported. Results show that αM should be greater than 0.4, 0.2, and 0.4 for EG, DEG, and 1-butanol, respectively. The refined values are helpful for accurate prediction of the evaporation/condensation rates.

  17. Energy dependence of the reaction rate constants of Ar+, Ar++ and N2+ ions with Cl2

    International Nuclear Information System (INIS)

    Lukac, P.; Holubcik, L.; Morva, I.; Lindinger, W.

    2002-01-01

    Dry etching processes using low temperature plasmas in Cl 2 and in Cl 2 -noble gas or nitrogen mixtures are common in the manufacture of semiconductor devices, but their chemical mechanisms are often poorly understood. Results are given for the reaction rate constant measurements of Ar + , Ar ++ , N 2 + ions with chlorine as a function of mean relative kinetic energy. The experiments were performed by using the innsbruck flow drift tube (IFDT) apparatus. Measurements were done at various E/N values, where E is the electric field strength and N the buffer gas density in the drift section. The mean relative kinetic energy KE CM between the ions and the neutral chlorine Cl 2 was calculated using the Wanniers formula. It was found that The N 2 + , Ar + and Ar ++ positive ions react with chlorine Cl 2 very fast and the corresponding reaction rate coefficients depend on the mean relative kinetic energy. For the reaction of Ar - with Cl 2 , its reaction coefficient depends also on the buffer gas. It can imply the enhancement of Cl 2 + ions during etching of Si in the Ar/Cl 2 mixtures. (nevyjel)

  18. Determination of complex formation constants by phase sensitive alternating current polarography: Cadmium-polymethacrylic acid and cadmium-polygalacturonic acid.

    Science.gov (United States)

    Garrigosa, Anna Maria; Gusmão, Rui; Ariño, Cristina; Díaz-Cruz, José Manuel; Esteban, Miquel

    2007-10-15

    The use of phase sensitive alternating current polarography (ACP) for the evaluation of complex formation constants of systems where electrodic adsorption is present has been proposed. The applicability of the technique implies the previous selection of the phase angle where contribution of capacitive current is minimized. This is made using Multivariate Curve Resolution by Alternating Least Squares (MCR-ALS) in the analysis of ACP measurements at different phase angles. The method is checked by the study of the complexation of Cd by polymethacrylic (PMA) and polygalacturonic (PGA) acids, and the optimal phase angles have been ca. -10 degrees for Cd-PMA and ca. -15 degrees for Cd-PGA systems. The goodness of phase sensitive ACP has been demonstrated comparing the determined complex formation constants with those obtained by reverse pulse polarography, a technique that minimizes the electrode adsorption effects on the measured currents.

  19. Determination of the Axial-Vector Weak Coupling Constant with Ultracold Neutrons

    International Nuclear Information System (INIS)

    Liu, J.; Mendenhall, M. P.; Carr, R.; Filippone, B. W.; Hickerson, K. P.; Perez Galvan, A.; Russell, R.; Holley, A. T.; Hoagland, J.; VornDick, B.; Back, H. O.; Pattie, R. W. Jr.; Young, A. R.; Bowles, T. J.; Clayton, S.; Currie, S.; Hogan, G. E.; Ito, T. M.; Makela, M.; Morris, C. L.

    2010-01-01

    A precise measurement of the neutron decay β asymmetry A 0 has been carried out using polarized ultracold neutrons from the pulsed spallation ultracold neutron source at the Los Alamos Neutron Science Center. Combining data obtained in 2008 and 2009, we report A 0 =-0.119 66±0.000 89 -0.00140 +0.00123 , from which we determine the ratio of the axial-vector to vector weak coupling of the nucleon g A /g V =-1.275 90 -0.00445 +0.00409 .

  20. 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